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Zeolite-based Fenton-like catalysis for pollutant removal and reclamation from wastewater
Zichen Shangguan, Xingzhong Yuan, Longbo Jiang, Yanlan Zhao, Lei Qin, Xuerong Zhou, Yan Wu, Jia Wei Chew, Hou Wang
2022, 33(11): 4719-4731  doi: 10.1016/j.cclet.2022.01.001
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Wastewater treatment and reclamation from wastewater are essential for the sustainable use of water resource. Zeolite-based heterogeneous catalysis shows great potential in circumventing the current limitations on pollutant removal and transformation to useful chemicals, inspiring advancements towards practical water treatment. This paper summarizes the methods for synthesizing zeolite-based catalyst, and the corresponding advantages and disadvantages. In comparison with traditional Fenton-like reaction, the superiority of zeolite-based catalysis lies in less sludge, wide pH range and easy recyclability. Accordingly, applications of zeolite-based Fenton-like catalysis (ZFCs) in pollutant removal and reclamation of wastewater were reviewed. Emphasis was placed on the methodological strategies in improving ZFCs, including the combination of external driving force (e.g., photocatalysis or electrochemistry), as well as the introduction of various transition metals into zeolite-based catalyst. Possible challenges and future perspectives for ZFCs were proposed.
1,n-Thiosulfonylation using thiosulfonates as dual functional reagents
Danhua Ge, Jia-Wei Chen, Pei Xu, Jinyin Pan, Xue-Qiang Chu
2022, 33(11): 4732-4739  doi: 10.1016/j.cclet.2022.02.019
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In recent years, the direct introduction of sulfonyl and sulfenyl groups into unsaturated substrates by using thiosulfonates as unique dual functional reagents has inarguably provided chemists a new platform for the diverse synthesis of important S-containing derivatives. These 1,n-thiosulfonylation reactions usually feature simple procedures, 100% atom economy, and high regioselectivity. This review focuses on the recent advancements in the transformations of thiosulfonates through 1,n-thiosulfonylation involving the formation of two distinct C-S bonds under transition-metal-catalyzed or metal-free conditions, where thiosulfonates act as both a sulfonyl and a sulfenyl component.
Degradation of florfenicol in a flow-through electro-Fenton system enhanced by wood-derived block carbon (WBC) cathode
Li Tian, Qiongfang Zhuo, Jincheng Lu, Jingjing Liu, Xiaofeng Xu, Xiaolin You, Manman Xu, Bo Yang, Junfeng Niu
2022, 33(11): 4740-4745  doi: 10.1016/j.cclet.2021.12.083
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The flow-through electro-Fenton (EF-T) reactor with WBC cathode was designed to remove florfenicol (FF). The activated WBC cathode was prepared by facile carbonization and activation methods, and featured high specific surface area, natural multi-channel structure, abundant oxygen-containing groups, good hydrophilicity, and excellent O2 reducing capacity. WBC cathode was located above Ti/Ru-IrO2 mesh anode. O2 evolved at the anode was carried to the inner wall of channel of WBC by the force of buoyancy and water flow, which increases oxygen source of H2O2 generation at the cathode. The flow-through system by using WBC electrode promote the mass transfer of O2 and FF. The production amount of H2O2 at activated WBC was 32.2 mg/L, which was almost twice as much as that at non-activated WBC (15.0 mg/L). FF removal ratio in EF-T system was 98%, which was much higher than that of traditional flow-by electro-Fenton (EF-B, 33%) or single electrooxidation system (EO, 16%). EF-T system has the lowest energy consumption (4.367 kWh/kg) among the three electrochemical systems. The cathodic adsorption, anodic electrooxidation, and EF reaction are responsible for the degradation of FF. After five consecutive cycle experiments, FF removal ratio was still 98%, indicating WBC has the good stability.
Simultaneous determination of indole metabolites of tryptophan in rat feces by chemical labeling assisted liquid chromatography-tandem mass spectrometry
Qin-Feng Zhang, Hua-Ming Xiao, Jin-Tao Zhan, Bi-Feng Yuan, Yu-Qi Feng
2022, 33(11): 4746-4749  doi: 10.1016/j.cclet.2022.01.004
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As the connecting part of diet and host physiology, intestinal microbes can convert the ingested diet into a huge number of physiologically active small molecules. Indole metabolites of tryptophan are precursors or signal molecules for many biologically active substances, which are involved in serotonin and microbial catabolism pathways. To understand the influence of tryptophan metabolism in the intestinal environment on the neurological and immune systems at the molecular level, it is important to establish a high-coverage analytical method to comprehensively analyze the metabolites involved in tryptophan metabolism. However, due to a small molecular weight and poor response during mass spectrometry analysis, as well as weak retention on the reversed-phase chromatography, determination of indole metabolites of tryptophan is challenging. Here, we proposed a method for the simultaneous determination of 20 indole metabolites of tryptophan in a single run on reversed-phase chromatography by chemical labeling coupled to liquid chromatography-tandem mass spectrometry analysis. 4-(Dimethylamino)benzaldehyde (DMAB) was used for the labeling of indole metabolites of tryptophan, which could significantly improve the detection sensitivities and retention of these metabolites on reversed-phase chromatography. With the developed method, we realized the sensitive detection and comprehensive analysis of 15 endogenous indole metabolites of tryptophan in rat feces samples with functional dyspepsia intervention by acupuncture. The developed method offers a useful tool for studying tryptophan metabolism-related diseases.
Self-powered anti-interference photoelectrochemical immunosensor based on Au/ZIS/CIS heterojunction photocathode with zwitterionic peptide anchoring
Ze Hu, Yaqun Xu, Hao Wang, Gao-Chao Fan, Xiliang Luo
2022, 33(11): 4750-4755  doi: 10.1016/j.cclet.2021.12.088
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Accurate detection of important biomarkers with ultra-low levels in complex biological matrix is one of the frontier scientific issues because of possible signal interference of potential reductive agents and protein molecules. Herein, a self-powered anti-interference photoelectrochemical (PEC) immunosensor was explored for sensitive and specific detection of model target of cardiac troponin I (cTnI). Specifically, a novel ternary heterojunction served as the photocathode to offer a remarkable current output and a zwitterionic peptide was introduced to build a robust antifouling biointerface. CuInS2 (CIS) film with porous network nanostructure was first prepared and then modified in order with ZnIn2S4 (ZIS) nanocrystals and Au nanoparticles to fabricate the Au/ZIS/CIS heterojunction photocathode. After capture cTnI antibody (Ab) was immobilized, the zwitterionic peptide KAEAKAEAPPPPC was then anchored to compete the immunosensor. The elaborated PEC immunosensor exhibited high sensitivity for target cTnI antigen (Ag) detection, with good anti-interference against reductive agents and nonspecific proteins. This integration strategy of heterojunction photocathode with zwitterionic peptide provides a new sight to develop advanced PEC immunosensors applying in practical biosamples.
The role of Cs dopants for improved activation of molecular oxygen and degradation of tetracycline over carbon nitride
Qian Liu, Hui Li, Hao Zhang, Zhurui Shen, Huiming Ji
2022, 33(11): 4756-4760  doi: 10.1016/j.cclet.2021.12.089
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Molecular oxygen (O2) is activated to reactive oxygen species (ROS) by transferring energy and carriers in the photocatalytic process, which plays an important role in environmental remediation. Herein, Cs-doped carbon nitride (CN-xCs, x = 0.2, 0.8, 1) was prepared by CsCl directly inducing the structural reconstruction of carbon nitride (CN), which had obvious molecular oxygen activation ability to promote tetracycline (TC) degradation. Besides, we explored the influence of Cs doping concentration. As a consequence, the doping concentration of Cs was an important factor affecting the activation of O2, which could cause changes in the physical and chemical structure of CN, make O enter the CN structure, form N vacancy defects and cyano groups. In addition, a proper amount of Cs doping could reduce the band gap value, increase the light absorption range, have better charge separation and transfer performance, which could remarkably promote the activation of O2. Benefiting from these advantages, CN-0.8Cs could generate a higher concentration of superoxide radicals (O2, 179.30 µmol/L), which was much higher than CN (6.22 µmol/L). Therefore, it exhibited excellent TC degradation photocatalytic performance, and the rate constant k of TC degradation was 0.020 min−1, which was 6.7 times the degradation rate of CN (k = 0.0030 min−1). Furthermore, the possible degradation pathways of TC were proposed based on the results of HPLC-MS.
Heterostructures of NiFe LDH hierarchically assembled on MoS2 nanosheets as high-efficiency electrocatalysts for overall water splitting
Xiao-Peng Li, Li-Rong Zheng, Si-Jie Liu, Ting Ouyang, Siyu Ye, Zhao-Qing Liu
2022, 33(11): 4761-4765  doi: 10.1016/j.cclet.2021.12.095
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Typically, rational interfacial engineering can effectively modify the adsorption energy of active hydrogen molecules to improve water splitting efficiency. NiFe layered double hydroxide (NiFe LDH) composite, an efficient oxygen evolution reaction (OER) catalyst, suffers from slow hydrogen evolution reaction (HER) kinetics, restricting its application for overall water splitting. Herein, we construct the hierarchical MoS2/NiFe LDH nanosheets with a heterogeneous interface used for HER and OER. Benefiting the hierarchical heterogeneous interface optimized hydrogen Gibbs free energy, tens of exposed active sites, rapid mass- and charge-transfer processes, the MoS2/NiFe LDH displays a highly efficient synergistic electrocatalytic effect. The MoS2/NiFe LDH electrode in 1 mol/L KOH exhibits excellent HER activity, only 98 mV overpotential at 10 mA/cm2. Significantly, when it assembled as anode and cathode for overall water splitting, only 1.61 V cell voltage was required to achieve 10 mA/cm2 with excellent durability (50 h).
Activation of sulfite by ferric ion for the degradation of 2,4,6-tribromophenol with the addition of sulfite in batches
Zongping Wang, Fan Bai, Lisan Cao, Siyang Yue, Jingwen Wang, Songlin Wang, Jun Ma, Pengchao Xie
2022, 33(11): 4766-4770  doi: 10.1016/j.cclet.2022.01.003
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In this work, the removal of 2,4,6-tribromophenol (TBP) by ferric ion-activated sulfite [Fe(III)/S(IV)] process was systematically investigated with determining the intermediate products and evaluating the influences of some operational conditions and water matrices. Our results show that batching addition of S(IV) benefits the S(IV) utilization efficiency and TBP removal, with SO4•‒ being the primary reactive radical accounting for TBA degradation. The maximum TBP removal in the Fe(III)/S(IV) process was observed at pH 4.0 and oxygen is essential in this process. With increasing Fe(III) and S(IV) dosages from 0.05 and 0.1 mmol/L to 0.2 and 2.0 mmol/L, respectively, TBP removal followed trends of first increase then decrease. As the acute toxicity of the TBP solution was significantly reduced, the Fe(III)/S(IV) process was believed to be a good choice in the treatment of TBP.
Graphene enhanced α-MnO2 for photothermal catalytic decomposition of carcinogen formaldehyde
Xiaoshan Zeng, Chuanjia Shan, Mingdi Sun, Danni Ding, Shaopeng Rong
2022, 33(11): 4771-4775  doi: 10.1016/j.cclet.2021.12.085
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Formaldehyde (HCHO) causes increasing concerns due to its ubiquitously found in indoor air and being irritative and carcinogenic to humans. Photothermal-catalysis developed in recent years has been considered as a significant strategy for enhancing catalytic activity. Manganese oxides, compared with its strong thermocatalytic activity, generally suffer from much lower photocatalytic activity make its photochemical properties less concerned. Herein, α-MnO2 nanowires were composited with the graphene oxide (GO) via mechanical grinding and co-precipitating method, respectively. α-MnO2/GO nanohybrids prepared by co-precipitating method exhibits excellent activity, achieving 100% decomposition of HCHO with the solar-light irradiation at ambient temperature. It is found that, besides the photo-driven thermocatalysis, the photocatalysis mechanism made a major contribution to the decomposition of HCHO. The incorporation of GO, on the one hand, is beneficial to improve the optical absorption capacity and photothermal conversion efficiency; on the other hand, is conductive to electron transfer and effective separation of electrons and holes. These synergistic effects significantly improve the catalytic activity of α-MnO2/GO nanohybrids. This work proposes a new approach for the utilization of solar energy by combining manganese oxides, and also develops an efficient photothermal-catalyst to control HCHO pollution in indoor air.
Electrochemical reaction mechanism of porous Zn2Ti3O8 as a high-performance pseudocapacitive anode for Li-ion batteries
Weijie Cheng, Qi Feng, Zhanglin Guo, Guanjun Chen, Yong Wang, Lixiong Yin, Jiayin Li, Xingang Kong
2022, 33(11): 4776-4780  doi: 10.1016/j.cclet.2022.01.002
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Zn2Ti3O8, as a new type of anode material for lithium-ion batteries, is attracting enormous attention because of its low cost and excellent safety. Though decent capacities have been reported, the electrochemical reaction mechanism of Zn2Ti3O8 has rarely been studied. In this work, a porous Zn2Ti3O8 anode with considerably high capacity (421 mAh/g at 100 mA/g and 209 mAh/g at 5000 mA/g after 1500 cycles) was reported, which is even higher than ever reported titanium-based anodes materials including Li4Ti5O12, TiO2 and Li2ZnTi3O8. Here, for the first time, the accurate theoretical capacity of Zn2Ti3O8 was confirmed to be 266.4 mAh/g. It was also found that both intercalation reaction and pseudocapacitance contribute to the actual capacity of Zn2Ti3O8, making it possibly higher than the theoretical value. Most importantly, the porous structure of Zn2Ti3O8 not only promotes the intercalation reaction, but also induces high pseudocapacitance capacity (225.4 mAh/g), which boosts the reversible capacity. Therefore, it is the outstanding pseudocapacitance capacity of porous Zn2Ti3O8 that accounts for high actual capacity exceeding the theoretical one. This work elucidates the superiorities of porous structure and provides an example in designing high-performance electrodes for lithium-ion batteries.
Dual modulation of morphology and electronic structures of VN@C electrocatalyst by W doping for boosting hydrogen evolution reaction
Danyang He, Liyun Cao, Liangliang Feng, Shuainan Li, Yongqiang Feng, Guodong Li, Yifei Zhang, Jinhan Li, Jianfeng Huang
2022, 33(11): 4781-4785  doi: 10.1016/j.cclet.2022.01.006
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Developing high-efficiency and robust durability electrocatalyst for hydrogen evolution reaction (HER) in water electrolysis functions as a crucial role for the construction of green hydrogen economy, herein, ultrafine W-doped vanadium nitride nanoparticles anchored on N-doped graphitic carbon framework (WVN@NGC) are synthesized through a one-step simple pyrolysis protocol. Owing to the enlarged catalytically active sites, enhanced electrical conductivity and optimized electronic structure, the resultant VN/WN@NGC delivered the prominent HER performance with overpotentials of 143 mV and 158 mV at 10 mA/cm2 in acid and alkaline media, respectively, accompanied by the long-term stability for at least 50 h. This work highlights a novel strategy for a metal-triggered modulation of nitride-based HER electrocatalyst for sustainable energy conversion device.
Bromate formation during oxidation of bromide-containing water by the CuO catalyzed peroxymonosulfate process
Jingxin Yang, Hongrui Ma, Chuan Wang, Hong Liu
2022, 33(11): 4786-4791  doi: 10.1016/j.cclet.2022.01.008
[摘要]  (42) [HTML全文] (42) [PDF 951KB] (0)
Bromate formation has been found in the SO4•−-based oxidation processes, but previous studies primarily focused on the bromate formation in the homogeneous SO4•−-based oxidation processes. The kinetics and mechanisms of bromate formation are poorly understood in the heterogeneous SO4•−-based oxidation processes, although which have been widely studied in the eliminations of micropollutants. In this work, we found that the presence of CuO, a common heterogeneous catalyst of peroxymonosulfate (PMS), appreciably enhanced the bromate formation from the oxidation of bromide by PMS. The conversion ratio of bromide to bromate achieved over 85% within 10 min in this process. CuO was demonstrated to play a multiple role in the bromate formation: (1) catalyzed PMS to generate SO4•−, which then oxidizes bromide to bromate; (2) catalyzed the formed free bromine to disproportionate to bromate; (3) catalyzed the formed free bromine to decomposed back into bromide. In the CuO-PMS-Br system, bromate formation increases with increasing CuO dosages, initial CuO and bromide concentrations, but decreases with increasing bicarbonate concentrations. The presence of NOM (natural organic matter) resulted in a lower formed bromate accompanied with organic bromine formation. Notably, CuO catalyzes PMS to transform more than 70% of initial bromide to bromate even after recycled used for six times. The formation of bromate in the PMS catalysis by CuO system was also confirmed in real water.
A natural manganese ore as a heterogeneous catalyst to effectively activate peroxymonosulfate to oxidize organic pollutants
Jinchuan Gu, Ping Yin, Yi Chen, Honglin Zhu, Rui Wang
2022, 33(11): 4792-4797  doi: 10.1016/j.cclet.2022.01.029
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Heterogeneous transition metal catalysts are indispensable in improving environmental pollution. However, their fabrication is often costly and cumbersome, and they can easily pollute the environment. This study proposed using a natural Gabonese ore (GBO) containing MnxOy and FexOy as catalysts to degrade orange Ⅱ (OII) via peroxymonosulfate (PMS) activation. The GBO + PMS system exhibited extraordinarily high stability and catalytic activity towards OII elimination (92.2%, 0.0453 min−1). The reactive oxygen species (ROS) generated in the system were identified using radical scavenging tests and electron spin-resonance (ESR) analysis. Singlet oxygen (1O2) represented the dominant reactive species for OII degradation, while the system presented a lower reaction energy barrier and was effective in a broad pH range (2–10). This work also proposed the activation mechanism for the GBO + PMS system and OII degradation pathways. This study revealed a new approach for exploring inexpensive, eco-friendly, efficient, and stable heterogeneous transition metal catalysts.
High sensitivity ratiometric fluorescence temperature sensing using the microencapsulation of CsPbBr3 and K2SiF6: Mn4+ phosphor
Jingwen Jin, Jie Lin, Yipeng Huang, Linchun Zhang, Yaqi Jiang, Dongjie Tian, Fangyuan Lin, Yiru Wang, Xi Chen
2022, 33(11): 4798-4802  doi: 10.1016/j.cclet.2022.01.017
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A dual emission sensing film has been prepared for colorimetric temperature sensing using CsPbBr3 perovskite nanocrystals (CsPbBr3 NCs) and manganese doped potassium fluorosilicate (K2SiF6: Mn4+, KSF) encapsulated in polystyrene by a microencapsulation strategy. The CsPbBr3-KSF-PS film shows good temperature sensing response from 30 ℃ to 70 ℃, with a relative temperature sensitivity (Sr) up to 10.31% ℃−1 at 45 ℃. Meanwhile, the film maintains more than 95% intensity after 6 heating-cooling cycles and keeps its fluorescence characteristics after 3 months. The film can be used to monitor temperature change by naked eye under a UV lamp. In particular, the temperature discoloration point of the sensing film can be controlled by the ratio change of CsPbBr3: KSF to expand its applications. The study of the CsPbBr3-KSF-PS sensing mechanism in this work is helpful to provide effective strategies for the design of reliable, high sensitivity and stable temperature sensing system using CsPbBr3 NCs.
CDs assembled metal-organic framework: Exogenous coreactant-free biosensing platform with pore confinement-enhanced electrochemiluminescence
Xiu-Li Tao, Mei-Chen Pan, Xia Yang, Ruo Yuan, Ying Zhuo
2022, 33(11): 4803-4807  doi: 10.1016/j.cclet.2022.01.010
[摘要]  (38) [HTML全文] (38) [PDF 4120KB] (0)
Despite the various synthesis approachs to obtain luminous carbon dots (CDs), it is still quite challenging to construct the efficient electrochemiluminescence (ECL) owing to their low ECL reactivity and easy agglomeration. Herein, an efficient and concise ECL system was skillfully constructed by taking advantage of the nitrogen and sulfur co-doped CDs (N, S-CDs) with surfaces rich in hydrazide groups as luminophors to emit intense ECL, and metal-organic framework (MOF) as the matrix to confine CDs in its nanospace. Surprisingly, the proposed CDs assembled MOF (CDs/ZIF-8) enhanced anodic ECL signal up to 250% of pure CDs under the exogenous coreactant-free condition. As a proof of concept, the highly sensitive detection of uric acid (UA) was realized by the constructed ECL platform with a low detection limit of 3.52 nmol/L ranging from 10 nmol/L to 50 µmol/L. This work expanded ideas for the application of pore confinement effect, and provided references for the detection of disease biomarkers of gout and hyperuricemia.
Rapid differentiation of simple saccharides based on cluster ions by paper spray tandem mass spectrometry
Wangmin Hu, Tianyi Li, Yulei Yang, Shanshan Jia, Mei Zhang
2022, 33(11): 4808-4816  doi: 10.1016/j.cclet.2022.01.026
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Simple saccharides have a variety of biological functions, but their structural diversity and inherent structural features pose a major challenge for rapid analysis. In this work, we developed a derivative-free and ion mobility-free method for the rapid analysis of monosaccharides and disaccharides using paper spray tandem mass spectrometry. Trimeric cluster ions consisting of saccharide analytes, ligands and transition metal ions are used as precursor ions. We defined the R-value as the ratio of the intensity of the product ion that loses one molecule of ligand over the intensity of the product ion that loses one molecule of saccharide via collision induced dissociation (CID). The species and conformation of simple saccharides can be easily differentiated by calculating this R-value. With the capability of directly analyzing clinical samples using paper spray ionization, our method can be used to rapidly quantify the molar ratio of galactose to glucose in dried plasma samples to aid in the diagnosis of galactosemia. The analytical strategy provided herein has good potential to be applied to a wide range of saccharide analysis applications in the future.
A bench-stable reagent for C-4 selective deuteriodifluoromethylation of azines
Junqing Liang, Lefeng Dong, Feng Qian, Yijin Kong, Mingxia Wang, Xiaoyong Xu, Xusheng Shao, Zhong Li
2022, 33(11): 4817-4821  doi: 10.1016/j.cclet.2022.01.085
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Deuteriodifluoromethyl (CF2D) is a challenging and important functional group due to difficult deuterium incorporation and lack of effective precursor reagents. Herein, we report a bench-stable reagent, deuteriodifluoromethyl phosphine (DDFP) from cheap deuterium source for selectivity deuteriodifluoromethylation of azines with a high deuterium incorporation yield. The late-stage modification of complex molecules further confirmed the potential of this reagent for practical applications. We expect that our reagent to find applications in synthesis of isotope-labelled molecules of interests for drug-discovery and related ilucidation of mechanism of action.
Promotion effect of Au single-atom support graphene for CO oxidation
Ping Yan, Song Shu, Xian Shi, Jianjun Li
2022, 33(11): 4822-4827  doi: 10.1016/j.cclet.2022.01.032
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CO oxidation is a vital catalytic reaction for environmental purification, facing challenges due to the catalysts applied to oxidize CO are mainly rare and expensive noble catalysts. Since the high atomic availability, catalytic efficiency, and selectivity of single-atom catalysis, it has been widely studied and proven to be brilliant in CO oxidation. Au single-atom catalysts are regarded as excellent single-atom catalysts in oxidizing CO, whose progress is limited by the indistinct understanding of the reaction mechanism and role of the active atom. Hence, DFT calculation was used to investigate CO oxidation processes, active mechanisms, and the role of Au single-atom. Graphene involving prominent physical and chemical properties was selected as a model supporter. The single-atom support graphene materials exhibit better CO oxidation activities than pristine graphene, among which CO oxidation property on Au/GP is the highest with a 0.38 eV rate-determining barrier following ER mechanism. The outstanding performances including excellent electronic structures, adsorption properties, and strong activation of intermediate products contribute to the high CO oxidation activity of Au/GP, and the Au single-atom is the active center. Our work provides a novel guide for single-atom catalytic CO oxidation, accelerating the development of single-atom catalysis.
Effective norfloxacin elimination via photo-Fenton process over the MIL-101(Fe)-NH2 immobilized on α-Al2O3 sheet
Qian Zhao, Chong-Chen Wang, Peng Wang
2022, 33(11): 4828-4833  doi: 10.1016/j.cclet.2022.01.033
[摘要]  (51) [HTML全文] (51) [PDF 1900KB] (0)
MIL-101(Fe)-NH2@Al2O3 (MA) catalysts were successfully synthesized by reactive seeding (RS) method on α-Al2O3 substrate, which demonstrated excellent photo-Fenton degradation performance toward fluoroquinolone antibiotics (i.e., norfloxacin, ciprofloxacin, and enrofloxacin). The structure and morphology of the obtained MA were characterized by transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), atomic force microscope (AFM). The as-prepared MA could accomplish > 90% of norfloxacin degradation efficiency for 10 cycles' photo-Fenton processes, owing to its excellent chemical and water stability. In addition, the effects of operational factors including H2O2 concentration, foreign ions, and pH on the photo-Fenton degradation of norfloxacin over MA were clarified. The ESR spectra further document that O2, 1O2 and OH radicals are prominent in the decomposition process of antibiotic molecules. Finally, the plausible photo-Fenton norfloxacin degradation mechanisms were proposed and verified.
A general method for one-step synthesis of monofluoroiodane(Ⅲ) reagents using silver difluoride
Jing Ren, Meng-Cheng Jia, Feng-Huan Du, Chi Zhang
2022, 33(11): 4834-4837  doi: 10.1016/j.cclet.2022.01.070
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Herein we report a new general method for one-step synthesis of four kinds of fluoroiodane(Ⅲ) reagents by treating the corresponding aryl iodides with silver difluoride (AgF2). This is the first method applicable for the synthesis of all four fluoroiodane(Ⅲ) reagents including p-iodotoluene difluoride (1), fluoro-benziodoxole (2), fluoro-benziodoxolone (3), and fluoro-N-acetylbenziodazole (4). AgF2 was firstly employed in the direct oxidative fluorination of iodobenzene and thus has shown its outstanding oxidation and fluorine-transfer ability. The use of AgF2 has improved the synthesis of fluoroiodane(Ⅲ) reagents by shortening the reaction steps, avoiding the use of hazardous reagents, and simplifying the experimental operations. It was worth noting that we have developed the first one-step direct synthetic method for 3, while 3 can only be synthesized through Cl→F ligand exchange reaction previously.
A cationic amphiphilic tetraphenylethylene derivative with hydrochromic sensitive property: Applications in anti-counterfeiting ink and rewritable paper
Qian Xu, Ziyu Qin, Yiling Bei, Shengyu Feng, Xing-Dong Xu
2022, 33(11): 4838-4841  doi: 10.1016/j.cclet.2022.01.079
[摘要]  (41) [HTML全文] (41) [PDF 4808KB] (1)
Since the discovery of aggregation induced emission (AIE) phenomenon, various stimuli-responsive materials have been rapidly developed, but there are still great challenges in the application of ink printing due to the bad water solubility. In this research, a new cationic amphiphilic TPE-functionalized pyridine salt (TPE-OTs) was designed, which shows good water solubility and hydrochromic properties. The optical properties of the compound have been studied, which is equipped with the typical AIEE characteristics and TICT effect. The compound can self-assemble to form aggregates with a particle size of about 30 nm in water. What is more, the compound is responsive to the environmental humidity, whose fluorescent color changes from green to yellow as the humidity gradually increased. Based on this characteristic, we applied it to the fluorescent anti-counterfeiting ink, realizing the protection and encryption of information.
Iron-catalyzed hydroaminocarbonylation of alkynes: Selective and efficient synthesis of primary α, β-unsaturated amides
Zijun Huang, Jia Tang, Xiongwei Jiang, Tianle Xie, Minmin Zhang, Donghui Lan, Shaofeng Pi, Zhengde Tan, Bing Yi, Yuehui Li
2022, 33(11): 4842-4845  doi: 10.1016/j.cclet.2022.01.080
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α, β-Unsaturated primary amides are important intermediates and building blocks in organic synthesis. Herein, we report a ligand-free iron-catalyzed hydroaminocarbonylation of alkynes using NH4HCO3 as the ammonia source, enabling the highly efficient and regioselective synthesis of linear α, β-unsaturated primary amides. Various aromatic and aliphatic alkynes are transformed into the desired linear α, β-unsaturated primary amides in good to excellent yields. Further studies show that using NH4HCO3 as the ammonia source is key to obtain good yields and selectivity. The utility of this route is demonstrated with the synthesis of linear α, β-unsaturated amides including vanilloid receptor-1 antagonist TRPV-1.
Polymerization of pyrrole induced by pillar[5]arene functionalized graphene for supercapacitor electrode
Fang Guo, Junqiang Guo, Zhiqiang Zheng, Tao Xia, Aadil Nabi Chishti, Liwei Lin, Wang Zhang, Guowang Diao
2022, 33(11): 4846-4849  doi: 10.1016/j.cclet.2022.01.088
[摘要]  (42) [HTML全文] (42) [PDF 2178KB] (0)
Conducting polymer is an important electrode material for supercapacitors because of its high initial specific capacitance. Herein, a novel nanocomposite composed of polypyrrole (PPy) film homogeneously immobilized on the pillar[5]arene functionalized reduced graphene oxide nanosheets (RGO-HP5A-PPy) was successfully prepared. RGO-HP5A induced pyrrole to polymerize on the graphene surface and the specific capacitance loss caused by PPy agglomeration was avoided. Noticeably, the specific capacitance of RGO-HP5A-PPy was up to 495 F/g at 1 A/g. Compared with pure PPy (319 F/g), the specific capacitance was increased by 55%. The specific capacitance retention of the assembled symmetric supercapacitor reached 76% after 10,000 cycles at 5 A/g. This study gave full play to the advantages of pillar[5]arene, graphene and PPy, and was expected to promote the development of supramolecular functionalized composites in energy storage.
Palladium-catalyzed base- and solvent-controlled chemoselective allylation of amino acids with allylic carbonates
Yang Zhou, Hang Chen, Panpan Lei, Chunming Gui, Haifeng Wang, Qiongjiao Yan, Wei Wang, Fener Chen
2022, 33(11): 4850-4855  doi: 10.1016/j.cclet.2022.02.029
[摘要]  (49) [HTML全文] (49) [PDF 3627KB] (0)
The utilization of readily available amino acids, which is not only an oxygen nucleophile but also a nitrogen nucleophile, in palladium-catalyzed allylic substitution is realized under mild conditions. The chemoselectivity and multiple allylation are controlled by adjusting the reaction conditions. This represents the first example of this convenient access to valuable N,O-diallylated amino acids. Under the title conditions, a range of amino acids (α-, β-, γ-) and dipeptides can be readily converted in to the corresponding allylic products with excellent yields (67 examples, up to 99% yield) as well as good functional group tolerance.
Dimensionally confined nanosheets self-assembled through self-shielding multiple hydrogen bonding interactions in aqueous media
Jing Zhang, Shuaiwei Qi, Hao Yu, Ze Lin, Bao Li, Ming Wang, Zeyuan Dong
2022, 33(11): 4856-4859  doi: 10.1016/j.cclet.2022.02.023
[摘要]  (39) [HTML全文] (39) [PDF 3085KB] (0)
Herein, we adopt a simple supramolecular strategy to effectively control the tautomerism of ureidopyrimidinone (UPy) moiety and ultimately realize the complete arrangement of enol configuration. The obtained UPy derivatives containing self-complementary quadruple hydrogen bonding interactions can spontaneously self-assemble towards the formation of well-controlled, self-organized supramolecular nanostructure morphologies in both chloroform and water. The resulting aggregates had been fully characterized by various spectroscopy (absorption, emission) and microscopy (TEM, SEM and AFM) studies. It is anticipated that this study can provide an exact and excellent monomeric unit for controllable and precise supramolecular polymerization. The results achieved here also demonstrate the utility and feasibility of multiple hydrogen bonds to direct the self-assembly of small-molecule building blocks in aqueous media, which provides a strategy for the construction of well-defined and stable supramolecular architectures with chemical functionalities and physical properties as advanced materials for biological applications.
Generation of sulfonylureas under photoredox catalysis and their biological evaluations
Xuefeng Wang, Jun Zhang, Qi Chen, Wei Zhou, Jie Wu
2022, 33(11): 4860-4864  doi: 10.1016/j.cclet.2022.02.025
[摘要]  (45) [HTML全文] (45) [PDF 4111KB] (0)
Traditional synthesis of sulfonylureas largely depends on nucleophilic addition of arylsulfonamides to pre-synthesized isocyanates. Now we report a new access to alkylsulfonylureas with good yields and broad substrate scope. With the insertion of commercialized chlorosulfonyl isocyanate under photoredox catalysis, alkylsulfonylureas are synthesized in one-pot from the corresponding anilines and silyl enolates. A reaction mechanism is proposed showing the transformation undergoes a radical process, and the practicality of this methodology is proven via application to bioactive molecules. Additionally, the anti-cancer and anti-virus screening of these compounds is evaluated.
Iridium(Ⅰ)-catalyzed deoxgenation of fluoroalkylsulfoxides with dimethyl diazomalonate to access fluoroalkylthioethers
Wenqing Lu, Wenlin Li, Yicheng Zhou, Yongbin Xie, Wenbo Chen
2022, 33(11): 4865-4869  doi: 10.1016/j.cclet.2022.02.061
[摘要]  (55) [HTML全文] (55) [PDF 1709KB] (0)
A new method for the preparation of fluoroalkylthioethers including trifluoromethylthioether and difluoromethylthioether by iridium(Ⅰ)-catalyzed deoxgenation of fluoroalkylsulfoxides with dimethyl diazomalonate was developed. In the reaction system, dimethyl diazomalonate was used as reducing reagent and the corresponding fluoroalkylthioethers were produced through oxygen atom transfer from fluoroalkylsulfoxides to diazomalonate. The protocol featuring effective oxygen atom transfer, mild reaction conditions and good functional groups tolerance offers an alternative strategy for the synthesis of fluoroalkylthioethers.
Palladium-catalyzed cyclization of 1-alkynyl-8-iodonaphthalene and double isocyanides for the synthesis of acenaphtho[1,2-b]pyrroles
Shangfeng Ren, Keke Huang, Jin-Biao Liu, Lianpeng Zhang, Min Hou, Guanyinsheng Qiu
2022, 33(11): 4870-4873  doi: 10.1016/j.cclet.2022.02.028
[摘要]  (43) [HTML全文] (43) [PDF 990KB] (0)
A palladium-catalyzed formal [2 + 2 + 1] cyclization of 1-alkynyl-8-iodonaphthalene with double isocyanides is developed herein. The transformation worked well to produce a series of 7H-acenaphtho[1,2-b]pyrrole with a broad reaction scope. Isocyanides play a dual role in the reaction. One is a C1 building block, and another is used as C1N1 component. In the process, the [2 + 2 + 1] cyclization involves imidoylation, regioselective addition of imidoylpalladium species into alkyne, double imidoylation, and another addition of the resulting imidoylpalladium species into imine bonds.
Cross-coupling of 2-methylquinolines and in-situ activated isoquinolines: Construction of 1,2-disubstituted isoquinolinones
Jianyi Shi, Zheng Zeng, Shengting Xu, Zechun Cai, Yuehua Luo, Yongbo Fan, Zhongzhi Zhu, Tingting Wen, Xiuwen Chen
2022, 33(11): 4874-4877  doi: 10.1016/j.cclet.2022.02.032
[摘要]  (40) [HTML全文] (40) [PDF 4153KB] (0)
In this study, a method was developed to form C(sp3)–C(sp2) bonds via copper catalyst-promoted cross coupling of 2-methylquinoline and in-situ-activated 3-haloisoquinoline under mild conditions. The multi-component tandem reaction was used to construct new C–N, C=O and C–C bonds in one pot via sequential functionalization of the N1, C3 and C1 positions of 3-haloisoquinoline. This method can be used to efficiently access 1,2-disubstituted isoquinolinones by the three-component reaction of 3-halogen isoquinoline, alkyl halide, and 2-methylquinoline.
Catalytic and highly stereoselective β-mannopyranosylation using a 2,6-lactone-bridged mannopyranosyl ortho-hexynylbenzoate as donor
Yingle Feng, Jie Yang, Chenglin Cai, Taotao Sun, Qi Zhang, Yonghai Chai
2022, 33(11): 4878-4881  doi: 10.1016/j.cclet.2022.02.071
[摘要]  (36) [HTML全文] (36) [PDF 3173KB] (0)
An efficient and catalytic protocol for highly stereoselective construction of β-mannopyranosylation has been developed. Glycosylation of 2,6-lactone-bridged mannopyranosyl ortho-hexynylbenzoate with various acceptors proceeded smoothly in the presence of 5% Hg(Ⅱ) at room temperature, resulting in the corresponding β-mannosides in high yield and exclusive β-stereoselectivity.
MUC1 vaccines using β-cyclodextrin grafted chitosan (CS-g-CD) as carrier via host-guest interaction elicit robust immune responses
Hangyan Yu, Han Lin, Yuntian Xie, Mengyuan Qu, Min Jiang, Jie Shi, Haofei Hong, Hongrui Xu, Ling Li, Guochao Liao, Zhimeng Wu, Zhifang Zhou
2022, 33(11): 4882-4885  doi: 10.1016/j.cclet.2022.02.072
[摘要]  (38) [HTML全文] (38) [PDF 1925KB] (0)
We construct MUC1 vaccines using β-cyclodextrin grafted chitosan (CS-g-CD) as carrier via host-guest interaction. These vaccines based on non-covalent assembling can provoke robust immune responses, including high level of specific antibodies and cytokines. The induced antibodies can specifically recognize tumor cells and mediate cytotoxicity against tumor cells. These results indicate that CS-g-CD with strong immunostimulatory activities can be a straightforward platform for peptide-based vaccine construction.
Visible-light-irradiated tandem sulfonylation/cyclization of indole tethered alkenes for the synthesis of tetrahydrocarbazoles
Yingjie Yu, Aiyao Liu, Jingrui He, Chengting Wang, Haibo Mei, Jianlin Han
2022, 33(11): 4886-4890  doi: 10.1016/j.cclet.2022.03.038
[摘要]  (40) [HTML全文] (40) [PDF 1262KB] (2)
A visible-light-mediated reaction of indole derivatives employing arylsulfonyl chlorides as sulfonyl surrogates has been developed, which proceeds via the sequence of reduction of sulfonyl chloride, sulfonylation, and intramolecular cyclization. This mild protocol transforms a diverse array of indole tethered alkenes and simple sulfonyl chlorides into highly valuable functionalized tetrahydrocarbazoles in good yields. This reaction is also suitable for gram-scale synthesis, which provides an efficient and green access to multi-substituted tetrahydrocarbazoles.
CuBr-promoted domino Biginelli reaction for the diastereoselective synthesis of bridged polyheterocycles: Mechanism studies and in vitro anti-tumor activities
Mengting Zeng, Ying Xue, Yunan Qin, Fen Peng, Quan Li, Ming-Hua Zeng
2022, 33(11): 4891-4895  doi: 10.1016/j.cclet.2022.02.075
[摘要]  (45) [HTML全文] (45) [PDF 2391KB] (0)
The low-cost CuBr-promoted domino Biginelli reaction among readily available ketones, salicylaldehyde derivatives and 3-amino-1, 2, 4-triazole was studied under solvothermal conditions, giving the novel bridged polyheterocycles bearing two or three stereocenters depending on the starting ketones. This multicomponent reaction proceeded with high diastereoselectivity (dr > 20:1) based on a combined 1H NMR, crystallographic and supercritical fluid chromatographic (SFC) analysis of the product. Time-dependent high-resolution mass spectrometry (HRMS) was performed to track the reaction process, and several key intermediates were identified, leading to the drawing of a plausible reaction mechanism. Density functional theory (DFT) calculation was supplemented, and two reaction pathways were differentiated. Moreover, in vitro antitumor activity was evaluated using HeLa and HepG2 cell lines, and two of these polyheterocycles demonstrated promising activities against HepG2 cells with EC50 down to 10 µmol/L. Additionally, ESI-MS/MS studies on all the polyheterocycles suggest a common fragmentation pathway (loss of one molecule of amino-triazole) they shared, providing the first-hand fragmentation rules for future rapid structural identification of them. The multicomponent domino reaction presented here may offer prospects for future design of more efficient strategies to access medicinally important bridged polyheterocycles.
Selective recognition of methyl viologen by an endo-functionalized naphthobox
Weier Liu, Linghui Kong, Mao Quan, Huan Yao, Liupan Yang, Ho Yu Au-Yeung, Wei Jiang
2022, 33(11): 4896-4899  doi: 10.1016/j.cclet.2022.02.076
[摘要]  (39) [HTML全文] (39) [PDF 2682KB] (1)
Highly selective binding of structurally similar substrates is common for biomolecular recognition, but is often challenging to realize in synthetic hosts. Herein, we report highly selective binding of methyl viologen over other analogues by an endo-functionalized naphthobox. X-ray single crystal structure and Density Functional Theory (DFT) calculations revealed that the endo-functionalized groups in the cavity of the naphthobox is important for the high binding selectivity through the formation of multiple C–H…N, C–H…π, and ππ interactions with methyl viologen.
Simultaneous enhancement of phosphorescence and chirality by host–guest recognition of molecular tweezers
Diankun Jia, Hua Zhong, Sixun Jiang, Risheng Yao, Feng Wang
2022, 33(11): 4900-4903  doi: 10.1016/j.cclet.2022.02.081
[摘要]  (42) [HTML全文] (42) [PDF 2167KB] (0)
A novel type of host–guest recognition systems have been developed on the basis of a Au(Ⅲ) molecular tweezer receptor and chiral Pt(Ⅱ) guests. The complementary host–guest motifs display high non-covalent binding affinity (Ka: ~104 L/mol) due to the participation of two-fold intermolecular π–π stacking interactions. Both phosphorescence and chirality signals of the Pt(Ⅱ) guests strengthen in the resulting host–guest complexes, because of the cooperative rigidifying and shielding effects rendered by the tweezer receptor. Their intensities can be reversibly switched toward pH changes, by taking advantage of the electronic repulsion effect between the protonated form of tweezer receptor and the positive-charged guests in acidic environments. Overall, the current study demonstrates the feasibility to enhance and modulate phosphorescence and chirality signals simultaneously via molecular tweezer-based host–guest recognition.
Optically probing molecular shuttling motion of [2]rotaxane by a conformation-adaptive fluorophore
Chengyuan Yu, Xiaodong Wang, Cai-Xin Zhao, Shun Yang, Jiaan Gan, Zhuo Wang, Zhanqi Cao, Da-Hui Qu
2022, 33(11): 4904-4907  doi: 10.1016/j.cclet.2022.03.004
[摘要]  (43) [HTML全文] (43) [PDF 2288KB] (2)
A bistable [2]rotaxane with a conformation-adaptive macrocycle bearing a 9, 14-diphenyl-9, 14-dihydrodibenzo[a, c]phenazine (DPAC) unit was synthesized, which could be utilized to optical probe the molecular shuttling motion of the functionalized rotaxane system. The UV–vis, 1H NMR and PL spectroscopic data clearly demonstrated that the DPAC ring was interlocked onto the thread and the fluorescence intensity of the DPAC unit in the macrocycle was effectively regulated by the location change of the macrocycle along the thread under acid/base stimulation, which was attributed to the modulation of the intramolecular photo-induced electron transfer between the DPAC unit and the methyltriazole (MTA) unit. This bistable rotaxane system containing a conformation-adaptive fluorophore unit in the macrocycle moiety opens an alternative way to design functional bistable mechanically interlocked molecules.
Metal coordination to a deep cavitand promotes binding selectivities in water
Yong-Qing Chen, Hua-Wei Guan, Kuppusamy Kanagaraj, Julius Rebek, Yang Yu
2022, 33(11): 4908-4911  doi: 10.1016/j.cclet.2022.03.039
[摘要]  (45) [HTML全文] (45) [PDF 2258KB] (1)
One goal of supramolecular chemistry is the creation of synthetic receptors that have a high affinity for hydrophilic molecules in water. We found that cavitands with upper rims extended by pyridyl groups coax hydrophilic guests into the cavity where they are shielded from the aqueous environment. The ability of Pd(Ⅱ) to coordinate adjacent pyridyl groups leads to increased selectivity for highly hydrophilic solvent molecules such as acetone, 1, 4-dioxane and tetrahydrofuran in water. Analysis of the binding behavior indicated that metal-coordination restricts the container entrance, shrinks the effective cavity volume and increases the energetic barrier to guest exchange.
A bio-based epoxy resin derived from p-hydroxycinnamic acid with high mechanical properties and flame retardancy
Xin Song, Ze-Peng Deng, Chun-Bo Li, Fei Song, Xiu-Li Wang, Li Chen, De-Ming Guo, Yu-Zhong Wang
2022, 33(11): 4912-4917  doi: 10.1016/j.cclet.2021.12.067
[摘要]  (41) [HTML全文] (41) [PDF 6091KB] (1)
Recent advances in epoxy resins have been forward to achieving high mechanical performance, thermal stability, and flame retardancy. However, seeking sustainable bio-based epoxy precursors and avoiding introduction of additional flame-retardant agents are still of increasing demand. Here we report the synthesis of p-hydroxycinnamic acid-derived epoxy monomer (HCA-EP) via a simple one-step reaction, and the HCA-EP can be cured with 4, 4′-diaminodiphenylmethane (DDM) to prepare epoxy resins. Compared with the typical petroleum-based epoxy resin, bisphenol A epoxy resin, the HCA-EP-DDM shows a relatively high glass transition temperature (192.9 ℃) and impressive mechanical properties (tensile strength of 98.3 MPa and flexural strength of 158.9 MPa). Furthermore, the HCA-EP-DDM passes the V-1 flammability rating in UL-94 test and presents the limiting oxygen index of 32.6%. Notably, its char yield is as high as 31.6% under N2, and the peak heat rate release is 60% lower than that of bisphenol A epoxy resin. Such findings provide a simple way of using p-hydroxycinnamic acid instead of bisphenol A to construct high-performance bio-based thermosets.
Fmoc-protected amino acids as luminescent and circularly polarized luminescence materials based on charge transfer interaction
Yiran Xia, Aiyou Hao, Pengyao Xing
2022, 33(11): 4918-4923  doi: 10.1016/j.cclet.2022.02.077
[摘要]  (47) [HTML全文] (47) [PDF 6524KB] (0)
Fluorenylmethyloxycarbonyl (Fmoc)-protected amino acids are effective building blocks in self-assembled architectures at hierarchical levels, which however show limited luminescent properties and chiroptical activities. Here we introduce a charge-transfer strategy to build two-component luminescent materials with emerged circularly polarized luminescence properties. A library of Fmoc-amino acids was built, which selectively form charge-transfer complexes with the electron-deficient acceptor. Embedding in amorphous polymer matrix or physical grinding could trigger the charge-transfer luminescence with adjusted wavelengths in a general manner. X-ray diffraction results suggest the multiple binding modes between donor and acceptor. And, the solution-processed coassembly could selectively exhibit circularly polarized luminescence with high dissymmetry g-factors. This work illustrates a noncovalent charge-transfer strategy to construct luminescent and chiroptical organic composites based on the easy-accessible and economic chiral N-terminal aromatic amino acids.
Oral colon-targeted mucoadhesive micelles with enzyme-responsive controlled release of curcumin for ulcerative colitis therapy
Chen Zhang, Jiaxin Li, Meng Xiao, Di Wang, Yan Qu, Liang Zou, Chuan Zheng, Jinming Zhang
2022, 33(11): 4924-4929  doi: 10.1016/j.cclet.2022.03.110
[摘要]  (48) [HTML全文] (48) [PDF 6137KB] (0)
Although multitudinous nanoscale drug-delivery systems (DDSs) have been recommended to improve anti-ulcerative colitis (UC) outcomes, to enhance the mucoadhesion of nanosystems on the colon and specifically release the loaded drugs in response to the colon micro-environment would be critical factors. The application of curcumin (Cur), an acknowledged anti-UC phytochemical compound, for UC therapy requires more efficient nano-carriers to improve its therapeutic outcome. Herein, we developed the colon-targeted nano-micelles with mucoadhesive effect and Azo reductase-triggered drug release profiles for Cur delivery in UC treatment. Specifically, the amphiphilic block polymer containing the Azo-reductase sensitive linkage (PEG-Azo-PLGA), and catechol-modified TPGS (Cat-TPGS) were synthesized respectively. Based on the self-assembly of the mixed polymers, Cur-micelles (142.7 ± 1.7 nm of average size, 72.36% ± 1.54% of DEE) were obtained. Interestingly, the Cur-micelles exhibited the Azo-reductase sensitive particle dissociation and drug release, the enhanced cellular uptake and the prolonged retention on colonic mucosa, mediated by the strong mucoadhesion of catechol structure. Ultimately, Cur-micelles significantly mitigated colitis symptoms and accelerated colitis repair in DSS-treated mice by regulating the intestinal flora and the levels of pro-inflammatory factors (MPO, IL-6, IL-1β, and TNF-α) related to TLR4/MyD88/NF-κB signaling pathway. This work provides an effective drug delivery strategy for anti-UC drugs by oral administration.
Ruthenium-modified porous NiCo2O4 nanosheets boost overall water splitting in alkaline solution
Rui Yang, Xuezhao Shi, Yanyan Wang, Jing Jin, Hanwen Liu, Jie Yin, Yong-Qing Zhao, Pinxian Xi
2022, 33(11): 4930-4935  doi: 10.1016/j.cclet.2021.12.058
[摘要]  (44) [HTML全文] (44) [PDF 4924KB] (0)
Exploring efficient oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) electrocatalysts is crucial for developing water splitting devices. The composition and structure of catalysts are of great importance for catalytic performance. In this work, a heterogeneous Ru modified strategy is engineered to improve the catalytic performance of porous NiCo2O4 nanosheets (NSs). Profiting from favorable elements composition and optimized structure property of decreased charge transfer barrier, more accessible active sites and increased oxygen vacancy concentration, the Ru-NiCo2O4 NSs exhibits excellent OER activity with a low overpotential of 230 mV to reach the current density of 10 mA/cm2 and decent durability. Furthermore, Ru-NiCo2O4 NSs show superior HER activity than the pristine NiCo2O4 NSs, as well. When assembling Ru-NiCo2O4 NSs couple as an alkaline water electrolyzer, a cell voltage of 1.60 V can deliver the current density of 10 mA/cm2. This work provides feasible guidance for improving the catalytic performance of spinel-based oxides.
Toward accurate and efficient dynamic computational strategy for heterogeneous catalysis: Temperature-dependent thermodynamics and kinetics for the chemisorbed on-surface CO
Jun Chen, Tan Jin, Yihuang Jiang, Tonghao Shen, Mingjun Yang, Zhe-Ning Chen
2022, 33(11): 4936-4942  doi: 10.1016/j.cclet.2022.03.080
[摘要]  (41) [HTML全文] (41) [PDF 2353KB] (2)
Computational tools on top of first principle calculations have played an indispensable role in revealing the molecular details, thermodynamics, and kinetics in catalytic reactions. Here we proposed a highly efficient dynamic strategy for the calculation of thermodynamic and kinetic properties in heterogeneous catalysis on the basis of efficient potential energy surface (PES) and MD simulations. Taking CO adsorbate on Ru(0001) surface as the illustrative model system, we demonstrated the PES-based MD can efficiently generate reliable two-dimensional potential-of-mean-force (PMF) surfaces in a wide range of temperatures, and thus temperature-dependent thermodynamic properties can be obtained in a comprehensive investigation on the whole PMF surface. Moreover, MD offers an effective way to describe the surface kinetics such as adsorbate on-surface movement, which goes beyond the most popular static approach based on free energy barrier and transition state theory (TST). We further revealed that the dynamic strategy significantly improves the predictions of both thermodynamic and kinetic properties as compared to the popular ideal statistic mechanics approaches such as harmonic analysis and TST. It is expected that this accurate yet efficient dynamic strategy can be powerful in understanding mechanisms and reactivity of a catalytic surface system, and further guides the rational design of heterogeneous catalysts.
A TICS-fluorophore based probe for dual-color GSH imaging
Wenjuan Liu, Jie Chen, Qinglong Qiao, Xiaogang Liu, Zhaochao Xu
2022, 33(11): 4943-4947  doi: 10.1016/j.cclet.2022.03.121
[摘要]  (46) [HTML全文] (46) [PDF 4267KB] (2)
Cascading reactions in fluorophores accompanied by the replacement of different fluorescence wavelengths can be used to develop luminescent materials and reactive fluorescent probes. Based on multiple signal channels, the selectivity of probes can be improved and the range of response to guest molecule recognition can be expanded. By regulating the position, number, and activity of active sites in fluorophores, fluorescent probes that successively react with thiol and amino groups in cysteine (Cys), homocysteine (Hcy) have been developed, which can only react with the thiol group of GSH. In this paper, we report the first probe capable of cascading nucleophilic substitution reaction with the thiol group and amino group of GSH at a single reaction site, and showed the dual-color recognition of GSH, which improved the selectivity of GSH also was an extension of GSH probes. The probe Rho-DEA was based on a TICS fluorophore, and the intramolecular cascade nucleophilic substitution reaction occurs with Cys/Hcy. The thiol substitution of the first step reaction with Cys/Hcy was quenched due to intersystem crossing to triplet state, so GSH can be selectively recognized from the fluorescence signal. Rho-DEA has the ability of mitochondrial localization, and finally realized in situ dual-color fluorescence recognition of GSH in mitochondria.
Insight into the in vivo fate of intravenous herpetrione amorphous nanosuspensions by aggregation-caused quenching probes
Lingyu Hang, Chengying Shen, Baode Shen, Hailong Yuan
2022, 33(11): 4948-4951  doi: 10.1016/j.cclet.2022.03.108
[摘要]  (37) [HTML全文] (37) [PDF 3162KB] (0)
Intravenous nanosuspensions are attracted growing attention as a viable strategy for development of intravenous formulations of poorly water-soluble drugs. However, only few information about the biological fate of intravenous nanosuspensions is currently known, especially amorphous nanosuspensions are not reported yet. In this study, the in vivo fate of herpetrione (HPE) amorphous nanosuspensions following intravenous administration was explored by using an aggregation-caused quenching (ACQ) probe and HPLC methods. The ACQ probe is physically embedded into HPE nanoparticles via anti-solvent method to form HPE hybrid nanosuspensions (HPE-HNSs) for bioimaging. HPE-HNSs emit strong and stable fluorescence, but fluorescence quenches immediately upon the dissolution of HPE-HNSs, confirming the self-discrimination of HPE-HNSs. Following intravenous administration of HPE-HNSs, integral HPE-HNSs and HPE show similar degradation and biodistribution, with rapid clearance from blood circulation and obvious accumulation in liver and lung. Due to the slower dissolution and enhanced recognition by reticulo-endothelial system, 450 nm HPE-HNSs accumulate more in liver, lung and spleen than that of 200 nm HPE-HNSs. These results demonstrate that integral HPE-HNSs determine the in vivo performance of HPE-HNSs. This study provides insight into the in vivo fate of intravenous amorphous nanosuspensions.
Distinct structural characteristics define a new subfamily of Mycoplasma ferritin
Wenming Wang, Xiaojia Liu, Yajie Wang, Yuan Wang, Dan Fu, Hongfang Xi, Yi Zhao, Hongfei Wang
2022, 33(11): 4952-4955  doi: 10.1016/j.cclet.2022.03.119
[摘要]  (48) [HTML全文] (48) [PDF 2815KB] (1)
Ferritins can generally be divided into four subfamilies based on their structural characteristics, namely, the classic ferritins (Ftns), bacterioferritins (Bfrs), DNA-binding proteins from starved cells (Dps'), and encapsulated ferritins (EncFtns). However, the ferritin from Mycoplasma penetrans (Mpef) possesses a particular ferroxidase center with an extreme low activity and exhibits unusual characteristics, indicating that it could be a member of a quite different subfamily of ferritins. Hereby, the crystal structure of the ferritin from Ureaplasma urealyticum (Uurf) is presented, Mpef and Uurf have very similar properties, though they display very low sequence similarity. Thus, ferritins from Mycoplasma with these unique properties do not belong to any known subfamily, but they should rather be placed in a novel ferritin subfamily, which we term Mycoplasma Ferritin (Mfr).

Direct catalytic nitrogen oxide removal using thermal, electrical or solar energy
Xiaohu Zhang, Lixiao Han, Hao Chen, Shengyao Wang
2022, 33(3): 1117-1130  doi: 10.1016/j.cclet.2021.07.034
[摘要]  (65) [HTML全文] (65) [PDF 1624KB] (65)
Considering the significant importance in both ecological and environmental fields, converting nitrogen oxide (NOx, especially NO) into value-added NH3 or harmless N2 lies in the core of research over the past decades. Exploring catalyst for related gas molecular activation and highly efficient reaction systems operated under low temperature or even mild conditions are the key issues. Enormous efforts have been devoted to NO removal by utilizing various driving forces, such as thermal, electrical or solar energy, which shine light on the way to achieve satisfying conversion efficiency. Herein, we will review the state-of-the-art catalysts for NO removal driven by the above-mentioned energies, including a comprehensive introduction and discussion on the pathway and mechanism of each reaction, and the recent achievements of catalysts on each aspect. Particularly, the progress of NO removal by environmentally friendly photocatalysis and electrocatalysis methods will be highlighted. The challenges and opportunities in the future research on the current topic will be discussed as well.
Construction and applications of DNA-based nanomaterials in cancer therapy
Hedong Qi, Yuwei Xu, Pin Hu, Chi Yao, Dayong Yang
2022, 33(3): 1131-1140  doi: 10.1016/j.cclet.2021.09.026
[摘要]  (97) [HTML全文] (97) [PDF 1122KB] (97)
As a biologically active macromolecule, deoxyribonucleic acid (DNA) has the advantages of sequence programmability and structure controllability and can accurately transmit sequence information to specific biological functions. Facing the complex internal microenvironment and heterogeneity in tumor treatment, the construction and applications of DNA-based nanomaterials have become a focus point of research. In particular, the hybridization of DNA molecules with other materials endows DNA-based nanomaterials with multiple functions such as targeting, stimulus responsiveness and regulations of biological activities, making DNA nanostructures great potential in the treatment of major human diseases. In this review, the construction and characteristics of DNA-based nanomaterials are introduced. Then, the functions and applications of DNA-based nanomaterials in the delivery of chemotherapy drugs and gene drugs, stimulus-responsive release and regulation of cell homeostasis are reviewed. Finally, the future development and challenges of DNA-based nanomaterials are prospected. We envision that DNA-based nanomaterials can enrich the nanomaterial system by rational design and synthesis and address the growing demands on biological and biomedical applications in the real world.
Recent research progress of bimetallic phosphides-based nanomaterials as cocatalyst for photocatalytic hydrogen evolution
Chunmei Li, Daqiang Zhu, Shasha Cheng, Yan Zuo, Yun Wang, Changchang Ma, Hongjun Dong
2022, 33(3): 1141-1153  doi: 10.1016/j.cclet.2021.07.057
[摘要]  (66) [HTML全文] (66) [PDF 1473KB] (66)
Hydrogen energy (H2) has been considered as the most possible consummate candidates for replacing the traditional fossil fuels because of its higher combustion heat value and lower environmental pollution. Photocatalytic hydrogen evolution (PHE) from water splitting based on semiconductors is a promising technology towards converting solar energy into sustainable H2 fuel evolution. Developing high-activity and abundant source semiconductor materials is particularly important to realize highly efficient hydrogen evolution as for photocatalysis technology. However, unmodified pristine photocatalysts are often unable to overcome the weakness of low performance due to their limitations. In recent years, transition metal phosphides (TMPs) were used as valid co-catalysts to replace the classic precious metal materials in the process of photocatalytic reaction owing to their lower cost and higher combustion heat value. What is more, bimetallic phosphides have been also caused widespread concern in H2 evolution reaction owing to its much lower overpotential, more superior conductivity, and weaker charge carriers transfer impedance in comparison to those of single metal phosphides. In this minireview, we concluded the latest developments of bimetallic phosphides for a series of photocatalytic reactions. Firstly, we briefly summarize the present loading methods of bimetallic phosphides (BMPs) anchored on the photocatalyst. After that, the H2 evolution efficiency based on BMPs as cocatalyst is also studied in detail. Besides, the application of BMPs-based host photocatalyst for H2 evolution under dye sensitization effect has also been discussed. At last, the current development prospects and prospective challenges in many ways of BMPs are proposed. We sincerely hope this minireview has certain reference value for great developments of BMPs in the future research.
Nanostructured materials with localized surface plasmon resonance for photocatalysis
Juan Li, Zaizhu Lou, Baojun Li
2022, 33(3): 1154-1168  doi: 10.1016/j.cclet.2021.07.059
[摘要]  (105) [HTML全文] (105) [PDF 1625KB] (105)
Localized surface plasmon resonance (LSPR) enhanced photocatalysis has fascinated much interest and considerable efforts have been devoted toward the development of plasmonic photocatalysts. In the past decades, noble metal nanoparticles (Au and Ag) with LSPR feature have found wide applications in solar energy conversion. Numerous metal-based photocatalysts have been proposed including metal/semiconductor heterostructures and plasmonic bimetallic or multimetallic nanostructures. However, high cost and scarce reserve of noble metals largely limit their further practical use, which drives the focus gradually shift to low-cost and abundant nonmetallic nanostructures. Recently, various heavily doped semiconductors (such as WO3-x, MoO3-x, Cu2-xS, TiN) have emerged as potential alternatives to costly noble metals for efficient photocatalysis due to their strong LSPR property in visible-near infrared region. This review starts with a brief introduction to LSPR property and LSPR-enhanced photocatalysis, the following highlights recent advances of plasmonic photocatalysts from noble metal to semiconductor-based plasmonic nanostructures. Their synthesis methods and promising applicability in plasmon-driven photocatalytic reactions such as water splitting, CO2 reduction and pollution decomposition are also summarized in details. This review is expected to give guidelines for exploring more efficient plasmonic systems and provide a perspective on development of plasmonic photocatalysis.
Recent progress of Pd/zeolite as passive NOx adsorber: Adsorption chemistry, structure-performance relationships, challenges and prospects
Ce Bian, Dan Li, Qian Liu, Shoute Zhang, Lei Pang, Zhu Luo, Yanbing Guo, Zhen Chen, Tao Li
2022, 33(3): 1169-1179  doi: 10.1016/j.cclet.2021.07.066
[摘要]  (80) [HTML全文] (80) [PDF 665KB] (80)
Due to the technology limitation and inferior deNOx efficiency of urea selective catalytic reduction (SCR) catalysts at low temperatures, passive NOx adsorber (PNA) for decrease of NOx, CO and hydrocarbons (HCs) during "cold start" of vehicles was proposed to meet the further tighten NOx emission regulations in future. Among them, Pd modified zeolite PNA materials have received more attention because of their excellent NOx storage capacity, anti-poisoning and hydrothermal stability and since Pd/zeolite PNA was proposed, a variety of advanced characterization methods have been applied to investigate its adsorption behavior and structure-performance relationship. The comprehension of the active sites and adsorption chemistry of Pd/zeolite PNA was also significantly improved. However, there are few reviews that systematically summarize the recent progress and application challenges in atomic-level understanding of this material. In this review, we summarized the latest research progress of Pd/zeolite PNA, including active adsorption sites, adsorption mechanism, material physicochemical properties, preparation methods, storage and release performance and structure-performance relationships. In addition, the deactivation challenges faced by Pd/zeolite PNA in practical applications, such as chemical poisoning, high temperature hydrothermal aging deactivation, etc., were also discussed at the micro-level, and some possible effective countermeasures are given. Besides, some possible improvements and research hotspots were put forward, which could be helpful for designing and constructing more efficient PNA materials for meeting the ultra-low NOx emission regulation in the future.
Microfluidic methods for cell separation and subsequent analysis
Tianyou Chen, Chunxia Huang, Yanran Wang, Jing Wu
2022, 33(3): 1180-1192  doi: 10.1016/j.cclet.2021.07.067
[摘要]  (64) [HTML全文] (64) [PDF 1142KB] (64)
Cell is the most basic unit of the morphological structure and life activity of an organism. Learning the composition, structure and function of cells, exploring the life activities of cells and studying the interaction between cells are of great significance for human cognition and control of the life activities of organisms. Therefore, rapid, convenient, inexpensive, high-precision and reliable methods of cell separation and analysis are being developed to obtain accurate information for the study of cytology and pathology. Microfluidic chip is a new emerging technology in recent years. It has a micromanufacturing structure, which can not only realize the precise space-time control of fluid and cells, but also reproduces the three-dimensional dynamic microenvironment of cell growth in the body. In addition, the microfluidic chip has unique microphysical properties and facilitates the integration of microdevices, which provides the possibility of real-time monitoring, continuous culture, separation and enrichment, and even in situ analysis of cells. In this review, we summarized recent advances in the development of different techniques for cell isolation and analysis on microfluidic platforms. Focus was put on biochemical and physical methods for cell separation on microfluidic chips. Subsequent cell analysis depending on fluorescence, Raman, cytomicroscopic imaging, mass spectrometry and electrochemical methods also was remarked. Through analyzing and learning the advantages and disadvantages of different technologies, we hope that microfluidic chips will continue to be improved and expanded for medical and clinical applications.
C–F bond functionalizations of trifluoromethyl groups via radical intermediates
Tesfaye Tebeka Simur, Tian Ye, You-Jie Yu, Feng-Lian Zhang, Yi-Feng Wang
2022, 33(3): 1193-1198  doi: 10.1016/j.cclet.2021.08.043
[摘要]  (59) [HTML全文] (59) [PDF 839KB] (59)
Selective functionalization of C–F bonds in trifluoromethyl groups has recently received a growing interest, as it offers atom- and step-economic pathways to access highly valuable mono- and difluoroalkyl-substituted organic molecules using simple and inexpensive trifluoromethyl sources as the starting materials. In this regard, impressive progress has been made on the defluorinative functionalization reactions that proceed via radical intermediates. Nevertheless, it is still a great challenge to precisely control the defluorination process, due to the continuous decrease of the C–F bond strength after the replacement of one or two fluorine atoms with various functionalities. This review article is aimed to provide a brief overview of recently reported methods used to functionalize C–F bonds of CF3 groups via radical intermediates. An emphasis is placed on the discussion of mechanistic aspects and synthetic applications
C(sp3)−H bond functionalization of oximes derivatives via 1, 5−hydrogen atom transfer induced by iminyl radical
Dao-Qing Dong, Jing-Cheng Song, Shao-Hui Yang, Qi-Xue Qin, Zu-Li Wang, En-Xuan Zhang, Yuan-Yuan Sun, Qing-Qing Han, Shan Yue
2022, 33(3): 1199-1206  doi: 10.1016/j.cclet.2021.08.067
[摘要]  (74) [HTML全文] (74) [PDF 1164KB] (74)
Oximes derivatives have been vastly used in organic synthesis. In this review, C(sp3)−H bond functionalization of oximes derivatives via iminyl radical induced 1, 5−hydrogen atom transfer was discussed. According to the different type of products, this review was divided into three parts: (1) C(sp3)−H bond functionalization for C−C bond formation. (2) C(sp3)−H bond functionalization for C−N bond formation. (3) C(sp3)−H bond functionalization for C−S, C−F bond formation.
Transition metal-catalyzed conversion of aldehydes to ketones
Zijuan Yan, Pan-Lin Shao, Qing Qiang, Feipeng Liu, Xuchao Wang, Yongjie Li, Zi-Qiang Rong
2022, 33(3): 1207-1226  doi: 10.1016/j.cclet.2021.08.112
[摘要]  (85) [HTML全文] (85) [PDF 1628KB] (85)
Ketones are one of the most important classes of organic compounds, and widely present in various pharmacological compounds, biologically active molecules and functional materials. Over the past few decades, transition metal-catalyzed conversion of aldehydes has been found to be a powerful method. With the continuous development in recent years, it has become an efficient and uncomplicated strategy for constructing ketones. There are four major mechanisms for transition metal-catalyzed ketone synthesis from aldehyde: (1) carbonyl-Heck reaction, that is 1, 2-insertion of organometal species to aldehydic C=O double bond, (2) direct insertion of transition metal catalysts to aldehydic C-H bond, (3) aldehyde as acyl radical, (4) aldehyde as carbon radical acceptor. This article summarizes related reports on the transformations of aldehydes to generate corresponding ketones under different reaction conditions.
Application of Langlois' reagent (NaSO2CF3) in C–H functionalisation
Jiabin Shen, Jun Xu, Lei He, Chenfeng Liang, Wanmei Li
2022, 33(3): 1227-1235  doi: 10.1016/j.cclet.2021.09.005
[摘要]  (124) [HTML全文] (124) [PDF 1169KB] (124)
The process of selectively introducing a CF3 group into an organic molecule using inexpensive, stable, and solid sodium trifluoromethanesulfinate has rapidly advanced in recent years to become an eco-friendly method used by organic chemists to synthesize various natural and bioactive molecules. This review focuses on advances made within the last five years regarding C–H functionalisation, namely thermochemical C(sp2)–H (thio)trifluoromethylations, photochemical C(sp2)–H trifluoromethylations, and electrochemical C(sp2)–H trifluoromethylations, using Langlois' reagent (NaSO2CF3).
Strategies for constructing manganese-based oxide electrode materials for aqueous rechargeable zinc-ion batteries
Ying Liu, Xiang Wu
2022, 33(3): 1236-1244  doi: 10.1016/j.cclet.2021.08.081
[摘要]  (77) [HTML全文] (77) [PDF 1080KB] (77)
Commercial lithium-ion batteries (LIBs) have been widely used in various energy storage systems. However, many unfavorable factors of LIBs have prompted researchers to turn their attention to the development of emerging secondary batteries. Aqueous zinc ion batteries (AZIBs) present some prominent advantages with environmental friendliness, low cost and convenient operation feature. MnO2 electrode is the first to be discovered as promising cathode material. So far, manganese-based oxides have made significant progresses in improving the inherent capacity and energy density. Herein, we summarize comprehensively recent advances of Mn-based compounds as electrode materials for ZIBs. Especially, this review focuses on the design strategies of electrode structures, optimization of the electrochemical performance and the clarification of energy storage mechanisms. Finally, their future research directions and perspective are also proposed.
Quantum dots-hydrogel composites for biomedical applications
Wenjie Zhou, Zhe Hu, Jinxin Wei, Hanqing Dai, Yuanyuan Chen, Siyu Liu, Zhongtao Duan, Fengxian Xie, Wanlu Zhang, Ruiqian Guo
2022, 33(3): 1245-1253  doi: 10.1016/j.cclet.2021.09.027
[摘要]  (78) [HTML全文] (78) [PDF 855KB] (78)
Quantum dots-hydrogel composites are promising new materials that have attracted extensive attention due to their incomparable biocompatibility and acceptable biodegradability, leading to enormous potential applications for various fields. This review summarizes the recent advances in quantum dots-hydrogel composites with a focus on synthesis methods, including hydrogel gelation in quantum dots (QDs) solution, embedding prepared QDs into hydrogels after gelation, forming QDs in situ within the preformed gel and cross-linking via QDs to form hydrogels. In particularly, biomedical applications as bioimaging, biosensing and drug delivery are also reviewed, followed by a discussion on the inherent challenges of design optimization, biocompatibility and bimodal applications and the prospect of the future development. These results will guide the development of quantum dots-hydrogel composites and provide critical insights to inspire researchers in future.
Four-step spin-crossover in an oxamide-decorated metal-organic framework
Siguo Wu, Sukhen Bala, Zeyu Ruan, Guozhang Huang, Zhaoping Ni, Mingliang Tong
2022, 33(3): 1381-1384  doi: 10.1016/j.cclet.2021.08.012
[摘要]  (65) [HTML全文] (65) [PDF 300KB] (65)
Spin-crossover (SCO) complexes with multiple spin states are promising candidates for high-order magnetic storage and multiple switches. Here, by employing the N, Nʹ-4-dipyridyloxalamide (dpo) ligand, we synthesize two Hofmann-type metal-organic frameworks (MOFs) [Fe(dpo){Ag(CN)2}2]3DMF (1) and [Fe(dpo){Ag(CN)2}2]0.5MeCN2DEF (2), which exhibit guest dependent four-step SCO behaviors with the sequences of LS → ~LS2/3HS1/3 → LS1/2HS1/2 → ~LS3/10HS7/10 → HS and LS → ~LS2/3HS1/3 → LS1/2HS1/2 → ~LS1/4HS3/4 → HS, respectively. Therefore, the incorporation of hydrogen-donating/hydrogen-accepting groups into the Hofmann-type MOFs may effectively explore the multi-step SCO materials by tuning hydrogen-bonding interactions.
Tuning band structure of graphitic carbon nitride for efficient degradation of sulfamethazine: Atmospheric condition and theoretical calculation
Yue Liu, Long Chen, Xiaona Liu, Tianwei Qian, Meng Yao, Wen Liu, Haodong Ji
2022, 33(3): 1385-1389  doi: 10.1016/j.cclet.2021.08.061
[摘要]  (70) [HTML全文] (70) [PDF 355KB] (70)
Numerous approaches have been used to modify graphitic carbon nitride (g-C3N4) for improving its photocatalytic activity. In this study, we demonstrated a facial post-calcination method for modified graphitic carbon nitride (g-C3N4-Ar/Air) to direct tuning band structure, i.e., bandgap and positions of conduction band (CB)/valence band (VB), through the control of atmospheric condition without involving any additional elements or metals or semiconductors. The synthesized g-C3N4-Ar/Air could efficiently degrade sulfamethazine (SMT) under simulated solar light, i.e., 99.0% removal of SMT with rate constant k1 = 2.696 h−1 within 1.5 h (4.9 times than pristine g-C3N4). Material characterizations indicated that the damaged/partial-collapsed structure and decreased nanosheet-interlayer distance for g-C3N4-Ar/Air resulted in the shift of band structure due to the denser stacking of pristine g-C3N4 through oxidative exfoliation and planarization by air calcination. In addition, the bandgap of g-C3N4-Ar/Air was slightly shrunk from 2.82 eV (pristine g-C3N4) to 2.79 eV, and the CB was significantly upshifted from −0.44 eV (pristine g-C3N4) to −0.81 eV, suggesting the powerful ability for donating the electrons for O2 to form O2. Fukui index (f ) based on theoretical calculation indicated that the sites of SMT molecule with high values, i.e., N9, C4 and C6, preferred to be attacked by O2 and OH, which is confirmed by the intermediates' analysis. The tuning method for graphitic carbon nitride provides a simple approach to regulate the charge carrier lifetime then facilitate the utilization efficiency of solar light, which exhibits great potential in efficient removal of emerging organic contaminants from wastewater.
H2S-assisted growth of 2D MS2 (M = Ti, Zr, Nb)
Yiwei Zhang, Peng Zhang, Tengfei Xu, Xingguo Wang, Huaning Jiang, Yongji Gong
2022, 33(3): 1390-1394  doi: 10.1016/j.cclet.2021.07.036
[摘要]  (65) [HTML全文] (65) [PDF 538KB] (65)
2D transition metal dichalcogenides (TMDCs) have drawn an enormous amount of attention due to their fascinating properties and application potential in next-generation information process and storage. However, the lack of proper synthesis approach limits their application. Here, we report a controllable synthesis method to grow ultrathin MS2 (M = Ti, Nb, Zr) nanosheets with H2S-assisted chemical vapor deposition (CVD). We found that the presence of H2S plays an important role to control the morphology of nanosheets including the lateral size and the nucleation density. With the assistance of H2S, the growth of MS2 shows much thinner thickness with largely decreased nucleation density, beneficial for the device application, which can be attributed to the kinetics dominated growth. Our method hence opens a new avenue for the CVD growth of 2D TMDCs and the corresponding heterojunction, and paves the way for exploring their intriguing properties and applications.
Synthesis of Co4S3/Co9S8 nanosheets and comparison study toward the OER properties induced by different metal ion doping
Fenghua Chen, Zhaoqian Zhang, Weiwei Liang, Xiaoyun Qin, Zhen Zhang, Liying Jiang
2022, 33(3): 1395-1402  doi: 10.1016/j.cclet.2021.08.019
[摘要]  (84) [HTML全文] (84) [PDF 1100KB] (84)
Regulation of chemical composition and nanostructure, such as the introduction of dopant into two-dimensional nanomaterials, is a general and valid strategy for the efficient electrocatalyst design. In this work, Co4S3/Co9S8 nanosheets, with an ultrathin layer structure, were successfully synthesized via an efficient solvothermal process combined with ultrasonic exfoliation. Different metal ions (M = Fe3+, Cr3+, Mn2+ and Ni2+) were then doped by a simple cation exchange method and the effects of different dopants on the OER activities of Co4S3/Co9S8 NS were further investigated in alkaline media. The corresponding results implied that M-doped Co4S3/Co9S8 NS (M = Fe3+, Cr3+, Mn2+ and Ni2+) exhibited different electrocatalytic properties. Evidenced by XPS spectra, the different OER activities were mainly aroused by the redistribution of charge at the interface due to an electronic interaction between the doped metal ions and Co4S3/Co9S8 NS.
Robust hydrogen production from HCOOH over amino-modified KIT-6-confined PdIr alloy nanoparticles
Wenfang Peng, Shiwen Liu, Xiugang Li, Gang Feng, Jianhui Xia, Zhang-Hui Lu
2022, 33(3): 1403-1406  doi: 10.1016/j.cclet.2021.08.033
[摘要]  (73) [HTML全文] (73) [PDF 510KB] (73)
Formic acid (FA), which can be produced via CO2 reduction and biomass conversion, has received extensive interest as a convenient and safe hydrogen carrier due to its wide range of sources, renewable, high hydrogen content (4.4 wt%), and convenient storage/transportation. Designing highly efficient catalysts is the main challenge to realize the hydrogen production from FA. In this work, well-dispersed and electron-rich PdIr alloy nanoparticles with a size of 1.8 nm are confined in amino-modified 3D mesoporous silica KIT-6 and applied as a highly efficient catalyst for robust hydrogen production from FA at ambient temperature. Small PdIr alloy nanoparticles confined by amino-modified KIT-6 (PdIr/KIT-6-NH2) lead to better catalytic activity compared to that of Pd/KIT-6-NH2 and PdIr confined by bare KIT-6, achieving a high turnover frequency (TOF) value of 3533 h−1 at ambient temperature (303 K), 100% H2 selectivity and conversion toward the dehydrogenation of FA, which is comparable to the best heterogeneous catalysts ever reported. The high catalytic activity of PdIr/KIT-6-NH2 can be attributed to the synergistic effect between Pd and Ir, strong interaction between PdIr and KIT-6-NH2, as well as the amino-groups of KIT-6-NH2 which can act as a proton scavenger to promote the breaking of O-H bond of formic acid.
"Series and parallel" design of ether linkage and imidazolium cation synergistically regulated four-armed polymerized ionic liquid for all-solid-state polymer electrolyte
Zehui Xie, Yang Zhou, Canhui Ling, Xinlin Zhu, Zhao Fang, Xiaolong Fu, Wuwei Yan, Yong Yang
2022, 33(3): 1407-1411  doi: 10.1016/j.cclet.2021.08.031
[摘要]  (79) [HTML全文] (79) [PDF 403KB] (79)
Developing all-solid-state polymer electrolytes (SPEs) with high electrochemical performances and stability is of great importance for exploiting of high energy density and safe batteries. Herein, ether linkage and imidazolium ionic liquid (ILs) are incorporated into the multi-armed polymer backbone though the series and parallel way. The parallel polymeric ionic liquid (P-P (PEGMA-IM)) maximizes the synergistic effect of ILs and ether linkage, which endowed the material with low crystallinity and high flame retardancy. The P-P (PEGMA-IM) based P-SPE presents a high ionic conductivity of 0.489 mS/cm at 60 ℃, an excellent lithium-ion transference number of 0.46 and a wide electrochemical window of 4.87 V. The assembled lithium metal battery using P-SPE can deliver a capacity of 151 mAh/g at 0.2 C, and the capacity retention ratio reaches 82% with a columbic efficiency beyond 99%. The overpotential of P-SPE based symmetric battery is 0.08 V, and there is no apparent magnifying even after 130 h cycling. This new design provides a new avenue for exploitation of advanced SPEs for the next-generation batteries.
Self-assembly of single metal sites embedded covalent organic frameworks into multi-dimensional nanostructures for efficient CO2 electroreduction
Yi-Lu Yang, Yi-Rong Wang, Guang-Kuo Gao, Ming Liu, Chang Miao, Le-Yan Li, Wei Cheng, Zi-Yue Zhao, Yifa Chen, Zhifeng Xin, Shun-Li Li, Dong-Sheng Li, Ya-Qian Lan
2022, 33(3): 1439-1444  doi: 10.1016/j.cclet.2021.08.063
[摘要]  (78) [HTML全文] (78) [PDF 499KB] (78)
Morphology-controlled electrocatalysts with the ability of CO2 adsorption/activation, mass transfer, high stability and porosity are much desired in electrochemical CO2 reduction reaction (CO2RR). Here, three kinds of multi-dimensional nanostructures (i.e., hollow sphere, nanosheets and nanofibers) have been successfully produced through the modulation of porphyrin-based covalent organic frameworks (COFs) with various modulators. The obtained nanostructures with high-stability, large surface-area, and single metal sites enable efficient CO2RR into CH4. Notably, they all exhibit higher FE (hollow sphere, 68.2%; nanosheet, 64.2% and nanofiber, 71.0%, −0.9 V) than COF-366-Cu (43.0%, −0.9 V) after morphology control. Noteworthy, the FE of COF-366-Cu (HS) keeps higher than 52.4% over a wide potential range from −0.9 V to −1.1 V and the achieved FECH4+C2H4 (82.8%, −0.9 V) is superior to most of reported COFs and copper-based electrocatalysts. This work paves a new way in the exploration of COF-based multi-dimensional nanostructures applicable in efficient CO2RR to CH4.
Light-mediated CO2-responsiveness of metallopolymer microgels
Xiaofei Wang, Xuezhen Lin, Huijuan Qiu, Jianda Xie, Zhengyu Lu, Yusong Wang, Weitai Wu
2022, 33(3): 1445-1449  doi: 10.1016/j.cclet.2021.08.051
[摘要]  (74) [HTML全文] (74) [PDF 381KB] (74)
Here, we report a finding on light-mediated CO2-responsiveness. It is found on the microgels that are made of side-chain type metallopolymers containing metalla-aromatics. Turbidity and laser light scattering studies on dilute aqueous dispersion of these microgels in dark indicate high CO2-responsivity, but poor reversibility upon N2 purge, which can be improved by exposing to light. This light-mediated CO2-responsiveness can be elucidated by the loss of aromaticity from initial photoexcitation and concurrent formation of a less reactive, antiaromatic excited state of relatively low CO2 binding affinity, and by subsequent relief of antiaromaticity that can enhance the CO2 removal. The finding is also checked by CO2 uptake-release experiments on the microgels, which enables both CO2 capture of high capacity and CO2 removal of good reversibility under a mild condition, allowing effective and reversible response to dilute CO2.
Strain tuned efficient heterostructure photoelectrodes
Haihong Zheng, Mingyang Li, Jinsong Chen, Anchang Quan, Kaihang Ye, Hang Ren, Sheng Hu, Yang Cao
2022, 33(3): 1450-1454  doi: 10.1016/j.cclet.2021.08.062
[摘要]  (81) [HTML全文] (81) [PDF 427KB] (81)
van der Waals (vdWs) heterostructures based on two-dimensional (2D) materials have become a promising candidate for photoelectrochemical (PEC) catalyst not only because of the freedom in materials design that enable the band-offset construction and facilitate the charge separation. They also provide a platform for the study of various of interface effect in PEC. Here, we report a new kind of mixed-dimensional vdWs heterostructure photoelectrode and investigate the strain enhanced PEC performance at vdWs interfaces. Our heterostructures are composed of 2D n-type MoS2 nanosheets and three-dimensional (3D) p-type Cu2O nanorod arrays (NRAs), where Cu2O NRAs introduce periodically strain in the p-n junction interface. We find a promotion of the HER catalytic activities in heterostructure based PEC photoelectrodes using in-situ measurement techniques including the scanning electrochemical cell microscopy and various local spectrum probe measurements. This is attributed to the efficient charge separation at the strained heterointerface. Our results demonstrate an interesting venue for understanding the local interface effects with high spatial resolution, and shed light on design and developing high-efficiency photoelectrodes. 1L MoS2/Cu2O vdWs heterostructure photocathodes were prepared by nanoindentation technology. The effects of strain on promoting charge separation at the heterointerface were verified by the enhanced performances in PEC hydrogen evolution reaction of vdWs heterostructure through scanning electrochemical cell microscopy technique and various local spectrum probe measurements.
Modulation effect in adjacent dual metal single atom catalysts for electrochemical nitrogen reduction reaction
Xiaonan Zheng, Yang Liu, Yu Yan, Xiaoxiao Li, Yuan Yao
2022, 33(3): 1455-1458  doi: 10.1016/j.cclet.2021.08.102
[摘要]  (65) [HTML全文] (65) [PDF 328KB] (65)
Nitrogen reduction reaction (NRR) is a clean mode of energy conversion and the development of highly efficient NRR electrocatalysts under ambient conditions for industrial application is still a big challenge. Metal-nitrogen-carbon (M-N-C) has emerged as a class of single atom catalyst due to the unique geometric structure, high catalytic activity, and clear selectivity. Herein, we designed a series of dual metal single atom catalysts containing adjacent M-N-C dual active centers (MN4/M'N4-C) as NRR electrocatalysts to uncover the structure-activity relationship. By evaluating structural stability, catalytic activity, and selectivity using density functional theory (DFT) calculations, 5 catalysts, such as CrN4/M'N4-C (M' = Cr, Mn, Fe, Cu and Zn), were determined to exhibit the best NRR catalytic performance with the limiting potential ranging from −0.64 V to −0.62 V. The CrN4 center acted as the main catalytic site and the adjacent M'N4 center could enhance the NRR catalytic activity by modulation effect based on the analysis of the electronic properties including the charge density difference, partial density of states (PDOS), and Bader charge variation. This study offers useful insights on understanding the structure-activity relationship of dual metal single atom catalysts for electrochemical NRR.
Molecular self-induced configuration for improving dissymmetry factors in tetradentate platinum(II) enantiomers cycloaddition
Li Yuan, Qian-Jun Ding, Zhen-Long Tu, Xiang-Ji Liao, Xu-Feng Luo, Zhi-Ping Yan, Zheng-Guang Wu, You-Xuan Zheng
2022, 33(3): 1459-1462  doi: 10.1016/j.cclet.2021.08.104
[摘要]  (76) [HTML全文] (76) [PDF 394KB] (76)
Two pairs of Pt(II) enantiomers ((RR)/(SS)-PyPt, ((RR)/(SS)-Py: N, N'-(1, 2-diphenylethane-1, 2-diyl)dipicolinamide; (RR)-P/M-QPt, ((RR)/(SS)-Q: N, N'-((1R, 2R)-1, 2-diphenylethane-1, 2-diyl)bis(quinoline-2-carboxamide)) were synthesized, respectively, with good circularly polarized luminescence (CPL) and tunable dissymmetry factors (g) by molecular self-induction with (RR)/(SS)-1, 2-diphenylethane-1, 2-diamine as carbon chiral sources. In the (RR)-P-QPt and (SS)-M-QPt, specific P- and M-configurations were effectively induced from intrinsic chiral carbon centres (R or S), ingeniously avoiding the racemic mixture formation and chiral separation. Furthermore, the chirality originating from both chiral carbon centres and helicene-like structure improves the g factor significantly, which provides a new molecular design strategy for chiral Pt(II) enantiomers with good CPL properties.
Scalable synthesis of macroscopic porous carbon sheet anode for potassium-ion capacitor
Yuying Qin, Yuhao Xie, Han Zhao, Chunyan Zhu, Tong Li, Shuxian Zhang, Rutao Wang, Yuanchang Shi, Longwei Yin
2022, 33(3): 1463-1467  doi: 10.1016/j.cclet.2021.08.101
[摘要]  (82) [HTML全文] (82) [PDF 462KB] (82)
Carbon materials hold the great promise for application in energy storage devices owing to their low cost, high thermal/chemical stability, and high electrical conductivity. However, it remains challenging to synthesize high-performance carbon electrodes in a simple, scalable and sustainable way. Here, we report a facile method for scalable synthesis of porous carbon anode by using cheap and easily accessible zeolitic imidazolate framework-8 as a template and polyvinylpyrrolidone as an additional carbon source. The obtained porous carbon shows the macroscopic sheet-like morphology, which has the highly disordered structure, expanded interlayer spacing, abundant pore structure, and nitrogen doping properties. This porous carbon anode is demonstrated to have the excellent K+ charge storage properties in specific capacity, rate capability, and cycling stability. A potassium-ion capacitor assembled by using this porous carbon as the anode, delivers a maximum energy density of 85.12 Wh/kg and power density of 11860 W/kg as well as long cycle life exceeding 3000 cycles. This represents a critical advance in the design of low cost and scalable carbon material for applications in energy storage devices.
Bicyclic stapled peptides based on p53 as dual inhibitors for the interactions of p53 with MDM2 and MDMX
Hongjin Li, Xiangyan Chen, Minghao Wu, Panpan Song, Xia Zhao
2022, 33(3): 1254-1258  doi: 10.1016/j.cclet.2021.08.130
[摘要]  (75) [HTML全文] (75) [PDF 506KB] (75)
In recent years, the strategy of inhibiting the interactions of p53 with murine double minute 2 (MDM2) and murine double minute X (MDMX) has been proved to be a promising approach for tumor therapy. However, the poor proteolytical stability and low intracellular delivery efficiency of peptide inhibitors limit their clinical application. Here, we designed and synthesized the bicyclic stapled peptides based on p53 by combining all-hydrocarbon stapling and lactam stapling strategies. We demonstrated that bicyclic stapled peptide p53-16 significantly improved α-helicity and proteolytic stability. Especially, p53-16 showed nanomolar binding affinity for MDM2 and MDMX. In addition, p53-16 could penetrate the cell membrane, and selectively inhibited the activity of tumor cells via activating p53 pathway in vitro. Our data suggest that p53-16 is a potential dual inhibitor of MDM2 and MDMX interactions. The bicyclic stapling strategy is a promising drug design strategy for protein–protein interactions inhibitors.
Highly efficient photocatalytic NO removal and in situ DRIFTS investigation on SrSn(OH)6
Wendong Zhang, Yun Wang, Yi Wang, Yi Liang, Fan Dong
2022, 33(3): 1259-1262  doi: 10.1016/j.cclet.2021.07.065
[摘要]  (48) [HTML全文] (48) [PDF 786KB] (48)
A novel SrSn(OH)6 photocatalyst with large plate and particle size were synthesized via a facile chemical precipitation method. The photocatalytic activity of the SrSn(OH)6 was evaluated by the removal of NO at ppb level under UV light irradiation. Based on the ESR measurements, SrSn(OH)6 photocatalyst was found to have the ability to generate the main active species of O2•−, OH and 1O2 during the photocatalytic process. Moreover, SrSn(OH)6 photocatalyst not only exhibits high photocatalytic activity for NO removal (79.6%), but also has good stability after five cycles. The in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) was used to investigate the NOx transfer pathway and the intermediate products distribution during the adsorption and photocatalytic NO oxidation process. The present work not only provides an efficient material for air pollutants purification at room temperature but also in-depth understanding of the mechanism involved in the photocatalytic NO removal process.
Crystallinity engineering of Au nanoparticles on graphene for in situ SERS monitoring of Fenton-like reaction
Danni Guo, Lixia Zhao, Hui Zhang
2022, 33(3): 1263-1266  doi: 10.1016/j.cclet.2021.07.051
[摘要]  (71) [HTML全文] (71) [PDF 382KB] (71)
Fabrication of multifunctional nanoplatform to in situ monitor Fenton reaction is of vital importance to probe the underlying reaction process and design high-performance catalyst. Herein, a hybrid catalyst comprising of single-crystalline Au nanoparticles (SC Au NPs) on reduced graphene oxide (RGO) sheet was prepared, which not only exhibited an excellent 1O2 mediated Fenton-like catalytic activity in promoting rhodamine 6G (R6G) degradation by activating H2O2, but also displayed a sensitive surface-enhanced Raman spectroscopy (SERS) detection performance to R6G with a linear response range from 1.0 × 10-8 mol/L to 1.0 × 10-5 mol/L thus providing a powerful and versatile nanoplatform for in situ SERS monitoring Fenton-like catalytic reaction. The integration of catalytic and SERS activities into a single nanostructure are expected to provide great potentials for practical applications in environmental catalysis.
Old commercialized magnetic particles new trick: Intrinsic internal standard
Chaoqun Wang, Ziqiang Deng, Hu Zhang, Rui Liu, Yi Lv
2022, 33(3): 1267-1270  doi: 10.1016/j.cclet.2021.07.049
[摘要]  (62) [HTML全文] (62) [PDF 258KB] (62)
Magnetic particles (MPs) are the most widely used commercialized engineering particles, which gained great success in various biological applications. Inspired by their intrinsic Fe isotope composition, we discovered a commercialized MPs-internal standard's novel function to realize the accurate quantification of biomolecules. The bioassay of carcinoembryonic antigen (CEA) was chosen as a modal system. The Fe isotope in MPs and Au isotope in report probes were simultaneously and sensitively detected by the elemental mass spectrometry. 197Au/57Fe isotopic ratios and CEA concentrations showed good linearity in the range of 0.6–300 ng/mL, with a detection limit of 0.09 ng/mL (3σ). The accuracy and precision of the proposed MPs-based immunoassay were greatly improved, by eliminating potential MPs loss during magnetic separation and absolute intensity fluctuations. Considering the exceptional availability and universality of commercialized MPs, the proposed method might open a new avenue for MPs' biological applications.
Nanoplasmonic zirconium nitride photocatalyst for direct overall water splitting
Yu Liu, Xiaowei Zhang, Lisha Lu, Jun Ye, Jianlin Wang, Xiaomin Li, Xuedong Bai, Wenlong Wang
2022, 33(3): 1271-1274  doi: 10.1016/j.cclet.2021.07.054
[摘要]  (81) [HTML全文] (81) [PDF 465KB] (81)
The ability of plasmonic nanostructures to efficiently harvest light energy and generate energetic hot carriers makes them promising materials for utilization in photocatalytic water spitting. Apart from the traditional Au and Ag based plasmonic photocatalysts, more recently the noble–metal–free alternative plasmonic materials have attracted ever–increasing interest. Here we report the first use of plasmonic zirconium nitride (ZrN) nanoparticles as a promising photocatalyst for water splitting. Highly crystalline ZrN nanoparticles with sizes dominating at 30–50 nm were synthesized that exhibit intense visible and near–infrared absorption due to localized surface plasmon resonance (LSPR). Without utilizing any noble metal cocatalysts such as Pt, the plasmonic ZrN nanoparticles alone showed stable photocatalytic activity for H2 evolution in aqueous solution with methanol as sacrificial electron donor. The addition of a cobalt oxide (CoOx) cocatalyst can facilitate the separation of photogenerated charge carriers and further improve the photocatalytic activity. The optimized CoOx modified ZrN photocatalyst was observed not only to activate the O2 evolution reaction with presence of electron acceptor, but also to drive overall water splitting for the simultaneous H2 and O2 evolution in the absence of any sacrificial agents.
Amplification effects of magnetic field on hydroxylamine-promoted ZVI/H2O2 near-neutral Fenton like system
Wei Xiang, Mingjie Huang, Xiaohui Wu, Fugang Zhang, Dan Li, Tao Zhou
2022, 33(3): 1275-1278  doi: 10.1016/j.cclet.2021.07.072
[摘要]  (62) [HTML全文] (62) [PDF 376KB] (62)
This study has demonstrated an interesting amplification effect of magnetic field (MF) on the hydroxylamine (HA)-promoted zero valent iron (ZVI)/H2O2 Fenton-like system. Sulfamethoxazole (SMX) could be efficiently degraded at near neutral pH. Conditional parameters affecting the SMX degradation in the ZVI/H2O2/HA/MF system, e.g., pH and the dosages of ZVI, HA and H2O2, were investigated. Unlike the acid-favorable ZVI/H2O2 and ZVI/H2O2/HA systems, the MF-assisted system exhibited good performances even at pH up to 6.0 and highest degradation rate at pH of 5.0. OH was still identified as the responsible oxidant. A mechanism involving the MF-enhanced heterogeneous-homogeneous iron cycle was proposed in the near-neutral ZVI/H2O2/HA system. Without MF, HA-induced reductive dissolution of the surface iron oxides occurred and thus leaded to homogeneous Fenton reactions. After the introduction of MF, the gradient magnetic field formed on the ZVI particles would induce the generation of concentration cells of Fe(Ⅱ) and local corrosion of iron. Large amounts of aqueous and bounded Fe(Ⅱ) catalyzed H2O2 to efficiently produce OH, while HA maintained the surface and bulk cycles of Fe(Ⅱ)/Fe(Ⅲ). The result of study is expected to provide a green, energy-free method in improving the effectiveness of ZVI-based Fenton-like technologies at weak-acidic circumstances.
High temperature H2S selective oxidation on a copper-substituted hexaaluminate catalyst: A facile process for treating low concentration acid gas
Xin Xu, Ganggang Li, Fenglian Zhang, Guoxia Jiang, Zhengping Hao
2022, 33(3): 1279-1282  doi: 10.1016/j.cclet.2021.07.053
[摘要]  (69) [HTML全文] (69) [PDF 986KB] (69)
H2S selective catalytic oxidation technology is a prospective way for the treatment of low concentration acid gas with simple process operation and low investment. However, undesirable results such as large formation of SO2 and catalyst deactivation inevitably occur, due to the temperature rise of fixed reaction bed caused by the exothermic reaction. Catalyst with high activity in wide operating temperature window, especially in high temperature range, is urgently needed. In this paper, a series of copper-substituted hexaaluminate catalysts (LaCux, x = 0, 0.5, 1, 1.5, 2, 2.5) were prepared and investigated for the H2S selective oxidation reaction at high temperature conditions (300-550℃). The LaCu1 catalyst exhibited excellent catalytic performance and great stability, which was attributed to the best reductive properties and proper pore structure. Besides, two facile deep processing paths were proposed to eliminate the remaining H2S and SO2 in the tail gas.
Constructing a novel Ag nanowire@CeVO4 heterostructure photocatalyst for promoting charge separation and sunlight driven photodegradation of organic pollutants
Yan Song, Ran Wang, Xiuyuan Li, Baiqi Shao, Hongpeng You, Chaozheng He
2022, 33(3): 1283-1287  doi: 10.1016/j.cclet.2021.07.060
[摘要]  (60) [HTML全文] (60) [PDF 425KB] (60)
Exploiting efficient and recyclable photocatalysts is a vital matter for environmental purification. Herein, cerium vanadate (CeVO4) sub-microspheres and silver nanowire (AgNW)@CeVO4 with core-shell architecture as photocatalysts are rationally constructed by hydrothermal approach. The AgNW@CeVO4 photocatalyst obtained by depositing CeVO4 on the surface of Ag NWs possess one dimensional continuous structure, which expand the optical absorption range and reduce the band gap of CeVO4 photocatalyst. Moreover, the resultant AgNW@CeVO4 photocatalyst demonstrates superior photocatalytic performance in the degradation of rhodamine B, methylene blue, and 4-nitrophenol pollutants upon solar light irradiation, compared with pure CeVO4. The excellent photocatalytic activity can be ascribed to the introduction of Ag NWs, which afford rapid charge transport channels and reservoir for the electrons in the AgNW@CeVO4 heterostructure to promote separation of electron–hole pairs. The first-principles investigations reveal increase of adsorption energy of oxygen molecules on the CeVO4 surface with the presence of Ag. Meanwhile, Ag NWs can further improve the photocatalytic efficiency of the AgNW@CeVO4 based on the plasmonic effect. More importantly, the good structural stability and recyclability of AgNW@CeVO4 are observed due to the strong synergistic effect, which ensures long-term usability of photocatalyst and great promise in water purification. This work can offer valuable reference into designs and construction of Ce-based heterojunction photocatalysts for environmental remediation.
Embedding wasted hairs in Ti/PbO2 anode for efficient and sustainable electrochemical oxidation of organic wastewater
Dan Shao, Zekang Wang, Cuiping Zhang, Weijia Li, Hao Xu, Guoqiang Tan, Wei Yan
2022, 33(3): 1288-1292  doi: 10.1016/j.cclet.2021.07.061
[摘要]  (69) [HTML全文] (69) [PDF 502KB] (69)
Despite of the hazardous risk of Pb2+ leakage, lead dioxide has been attributed as a quasi-ideal anode material with high oxygen evolution potential, excellent conductivity, good stability and low cost in electrochemical oxidation wastewater treatment technique. In this study, a novel Ti/PbO2 anode was fabricated by embedding raw materials that are readily and cheaply available, i.e., hairs. The structure-activity relationship of the new electrode was firstly revealed by material and electrochemical characterizations. Then different levels of pollutants (azo dye, phenol and maleic acid) were used to investigate the electrochemical oxidation performance of the new electrode. Finally, the accelerated electrode lifetime and Pb2+ leakage tests were carried out. Results showed that the embedded hairs changed the preferential crystallographic orientation of PbO2 and decreased the grain size. Hairs introduced additional roughness and active sites, and decreased the electrode impedance, especially under 5 mg/cm2 of embedding amount. The removal efficiencies of different target pollutants were enhanced more or less by embedding appropriate amount of hairs, depending on the current density, but loading excessive hairs had a negative effect. The accumulation of intermediate products during phenol degradation was also changed by the hairs. The new electrode could undergo ~550 h of harsh electrolysis. It is also relieved that the Pb2+ leakage was found to be suppressed during this long-term electrolysis process.
Compared effects of "solid-based" hydrogen peroxide pretreatment on disintegration and properties of waste activated sludge
Hai-Chao Luo, Wan-Qian Guo, Qi Zhao, Hua-Zhe Wang, Nan-Qi Ren
2022, 33(3): 1293-1297  doi: 10.1016/j.cclet.2021.08.002
[摘要]  (92) [HTML全文] (92) [PDF 292KB] (92)
The effects of two solid-based hydrogen peroxides sodium percarbonate (SPC) and calcium peroxide (CP) on waste activated sludge (WAS) disintegration were investigated. Both oxidants achieved efficient WAS disintegration for the synergistic effect of alkaline and oxidation. The strong alkaline condition led to the leakage of ammonia and the existence of abundant calcium ions accelerated the fixation of phosphorus via precipitation in CP WAS disintegration process. However, the spongy-like layer and low pH condition retarded the release of gaseous ammonia in SPC group. Hydroxyl radical was the main oxygen reactive species in SPC approaches which were more intense than CP by electron spin resonance (ESR) analysis. CP treated WAS contented more small particle size matter and total suspended solids (TSS) increased dramatically. In conclusion, CP pretreated sludge was more suitable for fertilization, while SPC was in favor of anaerobic digestion. This study clarified the differences between these two oxidants and their intermediates on nutrients release in sludge disintegration.
In-situ synthesis of N, S co-doped hollow carbon microspheres for efficient catalytic oxidation of organic contaminants
Yongbing Xie, Ya Liu, Yujie Yao, Yanchun Shi, Binran Zhao, Yuxian Wang
2022, 33(3): 1298-1302  doi: 10.1016/j.cclet.2021.07.055
[摘要]  (60) [HTML全文] (60) [PDF 377KB] (60)
Metal-free heteroatom doped nanocarbons are promising alternatives to the metal-based materials in catalytic ozonation for destruction of aqueous organic contaminants. In this study, N, S co-doped hollow carbon microspheres (NSCs) were synthesized from the polymerization products during persulfate wet air oxidation of benzothiazole. The contents of doped N and S as well as the structural stability were maneuvered by adjusting the subsequent N2-annealing temperature. Compared with the prevailing single-walled carbon nanotubes, the N2-annealed NSCs demonstrated a higher catalytic ozonation activity for benzimidazole degradation. According to the quantitative structure-activity relationship (QSAR) analysis, the synergistic effect between the graphitic N and the thiophene-S which redistributed the charge distribution of the carbon basal plane contributed to the activity enhancement of the N2-annealed NSCs. Additionally, the hollow structure within the microspheres served as the microreactor to boost the mass transfer and reaction kinetics via the nanoconfinement effects. Quenching and electron paramagnetic resonance (EPR) tests revealed that benzimidazole degradation was dominated by the produced singlet oxygen (1O2) species, while hydroxyl radicals (·OH) were also generated and participated. This study puts forward a novel strategy for synthesis of heteroatom-doped nanocarbons and sheds a light on the relationship between the active sites on the doped nanocarbons and the catalytic performance.
Enhanced photocatalytic hydrogen production under visible light of an organic-inorganic hybrid material based on enzo[1, 2-b: 4, 5-b']dithiophene polymer and TiO2
Fang Jing, Yanmeng Guo, Bo Li, Yi-Fan Chen, Chunman Jia, Jianwei Li
2022, 33(3): 1303-1307  doi: 10.1016/j.cclet.2021.07.056
[摘要]  (70) [HTML全文] (70) [PDF 408KB] (70)
Titanium dioxide (TiO2) has been limited in photocatalysis due to its wide band gap (3.2 eV) and limited absorption in the ultraviolet range. Therefore, organic components have been introduced to hybrid with TiO2 for enhanced photocatalytic efficiency under visible light. Here, we report that benzo[1, 2-b: 4, 5-b']dithiophene polymer was an ideal organic material for the preparation of a hybrid material with TiO2. The energy band gap of the resulting hybrid material decreased to 2.9 eV and the photocatalytic hydrogen production performance reached 745.0 µmol g−1 h−1 under visible light irradiation. Meanwhile, the material still maintained the stability of hydrogen production performance after 40 h of photocatalytic cycles. The analysis of the transient current response and electrochemical impedance revealed that the main reasons for the enhanced water splitting of the hybrid materials were the faster separation of electron hole pairs and the lower recombination of photocarrier ions. Our findings suggest that polythiophene is a promising organic material for exploring hybrid materials with enhanced photocatalytic hydrogen production.
Microfluidics embedded with microelectrodes for electrostimulation of neural stem cells proliferation
Qian Li, Bodong Kang, Libin Wang, Tao Chen, Yu Zhao, Shilun Feng, Rongjing Li, Hongtian Zhang
2022, 33(3): 1308-1312  doi: 10.1016/j.cclet.2021.08.006
[摘要]  (89) [HTML全文] (89) [PDF 427KB] (89)
The regeneration of the injured nerve and recovery of its function have brought attention in the medical field. Electrical stimulation (ES) can enhance the cellular biological behavior and has been widely studied in the treatment of neurological diseases. Microfluidic technology can provide a cell culture platform with the well-controlled environment. Here a novel microfluidic/microelectrode composite microdevice was developed by embedding the microelectrodes to the microfluidic platform, in which microfluidics provided a controlled cell culture platform, and ES promoted the NSCs proliferation. We performed ES on rat neural stem cells (NSCs) to observe the effect on their growth, differentiation, proliferation, and preliminary explored the ES influence on cells in vitro. The results of immunofluorescence showed that ES had no significant effect on the NSCs specific expression, and the NSCs specific expression reached 98.9% ±0.4% after three days of ES. In addition, ES significantly promoted cell growth and the cell proliferation rate reached 49.41%. To conclude, the microfluidic/microelectrode composite microdevice can play a positive role in the nerve injury repair and fundamental research of neurological diseases.
Achieving simultaneous Cu particles anchoring in meso-porous TiO2 nanofabrication for enhancing photo-catalytic CO2 reduction through rapid charge separation
Jinyan Xiong, Mengmeng Zhang, Mengjie Lu, Kai Zhao, Chao Han, Gang Cheng, Zhipan Wen
2022, 33(3): 1313-1316  doi: 10.1016/j.cclet.2021.07.052
[摘要]  (67) [HTML全文] (67) [PDF 472KB] (67)
A facile solvo-thermal approach was successfully employed to prepare titanium oxide (TiO2) nano-aggregates with simultaneous copper particles anchoring. The as-synthesized composite could convert CO2 into CH4 and CO products under simulated solar irradiation. The impact of copper loading amounts on the photo-reduction capability was evaluated. It was found proper amount of Cu loading could enhance the activity of CO2 photo-reduction. As a result, the optimal composite (TiO2-Cu-5%) consisting of TiO2 supported with 5% (mole ratio) Cu exhibits 2.2 times higher CH4 yield and 3 times higher CO yield compared with pure TiO2. Conduction band calculated from the band gap and valence X-ray photoelectron spectroscopy (XPS) indicated TiO2 nano-aggregates have suitable band edge alignment with respect to the CO2/CH4 and CO2/CO redox potential. Furthermore, with involving of Cu particles, an efficient separation of photo-generated charges was achieved on the basis of photocurrent response and photoluminescence spectra results, which contributed to the improved photo-catalytic performance. The present work suggested that the Cu-decorated TiO2 could serve as an efficient photo-catalyst for solar-driven CO2 photo-reduction.
Defect-rich and ultrathin nitrogen-doped carbon nanosheets with enhanced peroxidase-like activity for the detection of urease activity and fluoride ion
Yu Zhang, Lei Jiao, Weiqing Xu, Yifeng Chen, Yu Wu, Hongye Yan, Wenling Gu, Chengzhou Zhu
2022, 33(3): 1317-1320  doi: 10.1016/j.cclet.2021.07.062
[摘要]  (76) [HTML全文] (76) [PDF 437KB] (76)
Although carbon nanozymes have attracted great interest due to their good biocompatibility, low cost, and high stability, designing high-active carbon nanozymes still faces great challenges. Herein, ultrathin nitrogen-doped carbon nanosheets with rich defects (d-NC) were prepared through a high-temperature annealing process, using potassium chloride and ammonium chloride as templates. Owing to the large specific surface area, rich defects and the high exposure of active sites, the proposed d-NC nanozymes exhibited excellent peroxidase-like activity. The d-NC nanozymes possess maximal reaction velocity and their specific activity is 9.4-fold higher than that of nitrogen-doped carbon nanozymes, indicating that the induced defects can boost the catalytic performance. Benefited from the good peroxidase-like activities of d-NC nanozymes, the colorimetric sensing platforms were constructed for the detection of urease activity and fluoride ion, exhibiting satisfactory stability and selectivity. This study not only offers a way to synthesize carbon nanozymes with improved enzyme-like activities but also broadens their applications in colorimetric biosensing.
Molybdenum phosphide (MoP) with dual active sites for the degradation of diclofenac in Fenton-like system
Xiuying Li, Shuangqiu Huang, Huaihao Xu, Yuepeng Deng, Zhu Wang, Zhao-Qing Liu
2022, 33(3): 1321-1324  doi: 10.1016/j.cclet.2021.07.058
[摘要]  (94) [HTML全文] (94) [PDF 394KB] (94)
The leaching and non-recoverability of mental ions have always limited the practical application of Fenton-like processes. For the first time, we synthesized molybdenum phosphide (MoP) with dual active sites for the degradation of diclofenac (DCF) in the Fenton-like process. The DCF degradation rate constant (k) of MoP + H2O2 process was calculated to be 0.13 min-1 within 40 min, indicating a highly efficient catalytic ability of MoP. In addition, this catalyst exhibits a stable structure and good activity, which could apply in a broad pH range, different ions solution and real wastewater condition. Accordingly, this efficient catalytic capability may be attributed to the presence of the metal sites Moδ+ and the electron-rich sites Pδ in MoP, which could induce the generation of hydroxyl radical (·OH) and superoxide radical (·O2) through electron transfer, resulting in the effective removal of DCF. This study provides an idea for the optimization of Fenton-like technologies and environmental remediation.
Silicotungstic acid-derived WO3 composited with ZrO2 supported on SBA-15 as a highly efficient mesoporous solid acid catalyst for the alkenylation of p-xylene with phenylacetylene
Xueting Bai, Yongle Guo, Zhongkui Zhao
2022, 33(3): 1325-1330  doi: 10.1016/j.cclet.2021.07.071
[摘要]  (58) [HTML全文] (58) [PDF 378KB] (58)
Highly dispersed silicotungstic acid-derived WO3 composited with ZrO2 supported on SBA-15 (WZ/SBA-15) as an ordered mesoporous solid acid catalyst was prepared via a facile incipient wetness impregnation (IWI) method that active ingredients, ZrO2 and WO3, were impregnated into the channels of SBA-15 simultaneously with a subsequent calcination process. The relationship between catalyst nature and performance was explored by high resolution transmission electron microscopy (HRTEM), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), FT-IR, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), N2 adsorption-desorption, NH3 temperature-programmed desorption (NH3-TPD), and FT-IR of pyridine adsorption (Py-IR) characterization techniques. The catalytic performance of W12Z15/SBA-15 is not only greater than that of single component solid acid catalysts, WO3/SBA-15 and ZrO2/SBA-15, but also W12/Z15/SBA-15 prepared by impregnating active ingredients, ZrO2 and WO3, into SBA-15 in sequence. The outstanding performance of W12Z15/SBA-15 is derived from the strong interaction between ZrO2 and WO3, which results in more acid sites, and relatively high specific surface area, large pore volume, and ordered mesoporous structure of SBA-15. The characterization and reaction results clearly demonstrate that the synergy of ZrO2 and WO3 has a clear boost for the alkenylation. The optimized W12Z15/SBA-15-500 achieves a 99.4% conversion of phenylacetylene and a 92.3% selectivity of main product α-arylstyrene for the alkenylation of p-xylene with phenylacetylene, with very low level of oligomers producing at the same time. Moreover, W12Z15/SBA-15-500 shows excellent catalytic stability and regeneration. Therefore, W12Z15/SBA-15-500 is a promising solid acid catalyst for the alkenylation.
In situ synthesis of red fluorescent gold nanoclusters with enzyme-like activity for oxidative stress amplification in chemodynamic therapy
Wenying Mi, Shuang Tang, Shaoshi Guo, Hejing Li, Na Shao
2022, 33(3): 1331-1336  doi: 10.1016/j.cclet.2021.07.073
[摘要]  (66) [HTML全文] (66) [PDF 595KB] (66)
Chemodynamic therapy (CDT) has attracted tremendous interest in cancer therapy because it is independent of oxygen and photoirradiation. However, the therapeutic efficacy of CDT is restricted by insufficient H2O2 levels in tumor cells. Herein, employing endogenous GSH as a template and cationic polymeric chitosan (CS) as crosslinker and stabilizer exhibiting easy cell uptake, red luminescent gold nanoclusters (denoted CS-GSH@AuNCs) were successfully synthesized in HeLa cells. The in situ synthesized CS-GSH@AuNCs exhibited both superoxidase dismutase (SOD) and peroxidase (POD)-like activity, which could promote the production of H2O2 from superoxide anion radicals (O2·−) and then ·OH. The combination of GSH elimination and H2O2 elevation boosted the generation of ·OH, which could trigger cancer cell apoptosis and death. The enzyme-like activity of CS-GSH@AuNCs could be effectively activated under acidic conditions, and showed a high killing effect on tumor cells but minimal toxicity to normal cells. The developed GSH consumption and ·OH promotion theranostic platform is an innovative route for enhanced CDT by the amplification of oxidative stress.
Degradation of tetracycline hydrochloride by ultrafine TiO2 nanoparticles modified g-C3N4 heterojunction photocatalyst: Influencing factors, products and mechanism insight
Bin Zhang, Xu He, Chengze Yu, Guocheng Liu, Dong Ma, Chunyue Cui, Qinghua Yan, Yingjie Zhang, Guangshan Zhang, Jun Ma, Yanjun Xin
2022, 33(3): 1337-1342  doi: 10.1016/j.cclet.2021.08.008
[摘要]  (98) [HTML全文] (98) [PDF 878KB] (98)
The unique heterojunction photocatalyst of graphite carbon nitride (g-C3N4) modified ultrafine TiO2 (g-C3N4/TiO2) was successfully fabricated by electrochemical etching and co-annealing method. However, the effects of various environmental factors on the degradation of TC by g-C3N4/TiO2 and the internal reaction mechanism are still unclear. In this study, the effects of initial pH, anions, and cations on the photocatalytic degradation of tetracycline hydrochloride (TC) by g-C3N4/TiO2 were systematically explored, and the scavenging experiment and intermediate detection were conducted to better reveal the mechanism on photocatalytic degradation of TC. The results showed that the removal efficiency of photocatalytic degradation of TC by g-C3N4/TiO2 could reach 99.04% under Xenon lamp irradiation within 120 min. The unique g-C3N4/TiO2 heterojunction photocatalyst showed excellent photocatalytic performance for the degradation of TC at pH 3~7, and possesses outstanding anti-interference ability to NO3, Cl, Na+, Ca2+ and Mg2+ ions in natural waters during the photocatalytic degradation TC process. Superoxide radicals (O2·−) and hydroxyl radicals (·OH) were proved as the main reactive species for TC degradation, and the possible mechanism of the unique photocatalytic system for g-C3N4/TiO2 was also proposed. The above results can provide a reliable basis and theoretical guidance for the design and application of visible photocatalyst with high activity to degrade the actual wastewater containing TC.
Fractionation-free negative enriching for in-depth C-terminome analysis
Jingtian Lu, Ting Wang, Huimin Bao, Haojie Lu
2022, 33(3): 1343-1345  doi: 10.1016/j.cclet.2021.08.022
[摘要]  (72) [HTML全文] (72) [PDF 229KB] (72)
Herein, we developed a fractionation-free negative enriching method incorporating methylamidation, site-selective dimethylation and aldehyde resin coupling (MADMAR) for in-depth C-terminome analysis. The methylamidation blocked the free carboxyl group on proteins first, followed by LysC digestion of methylamidated proteins. Then, the site-selective dimethylation blocked the N-terminal amino group of the digested peptides without affecting the amino groups of lysine. Finally, the aldehyde resin was used to capture non-C-terminal peptides containing amino groups from lysine, while leaving the C-terminal peptides without free amino group in the supernatant for its analysis. We identified 1359 database-annotated protein C-termini from 50 µg HeLa proteins, which was 74% more than our previous method based on aldehyde resin. Moreover, 279 protein neo-C-termini were identified.
Fe doped aluminoborate PKU-1 catalysts for the ketalization of glycerol to solketal: Unveiling the effects of iron composition and boron
Weilu Wang, Xiangke Zeng, Yanliu Dang, Ping Ouyang, Haidong Zhang, Guangming Jiang, Fan Dong, Tao Yang, Steven L. Suib, Yang He
2022, 33(3): 1346-1352  doi: 10.1016/j.cclet.2021.08.056
[摘要]  (63) [HTML全文] (63) [PDF 546KB] (63)
An inexpensive Fe doped aluminoborate consisted of 18% Fe in PKU-1 material that exhibits high selectivity of 4-hydroxymethy-2,2-dimethyl-1,3-dioxolane (Solketal, 98.3%), considerable activity (TOF 51.7 h-1), and recyclable ability in the ketalization of glycerol to Solketal with acetone at 318 K has been developed. Our study demonstrated that the structure of Fe (less agglomerated iron species vs. FeOx clusters) can be tuned by changing Fe loading in the PKU-1 material, which correlated well with experimental observations. Furthermore, the surface boron sites were promoted by iron loading and behaved as Lewis-acid sites to facilitate the reaction process of glycerol ketalization, while the Solketal selectivity was closely related with the structure of iron species in PKU-1, which was proved by kinetic studies, density function theory (DFT) calculations, and a series of spectroscopy studies. This investigation demonstrates that the surface B sites can play important roles in the reaction instead of being spectators.
A new Eu-MOF for ratiometrically fluorescent detection toward quinolone antibiotics and selective detection toward tetracycline antibiotics
Chao-Yang Wang, Chong-Chen Wang, Xiu-Wu Zhang, Xue-Ying Ren, Baoyi Yu, Peng Wang, Zi-Xuan Zhao, Huifen Fu
2022, 33(3): 1353-1357  doi: 10.1016/j.cclet.2021.08.095
[摘要]  (79) [HTML全文] (79) [PDF 366KB] (79)
Development of new self-calibrating fluorescent sensing methods has been a popular research field with the aim of protecting the human health and environment sustainability. In this work, a novel Eu-based metal organic framework (MOF) Eu(2,6-NDC)(COO) (BUC-88) was developed by employing 2,6-NDC (2,6-naphthalenedicarboxylic acid) as bridging ligands. BUC-88 performed different sensing process toward quinolone antibiotics and tetracyclines antibiotics in terms of fluorescence intensity and color. BUC-88 exhibited excellent selectivity and sensitivity detection property toward enrofloxacin (ENR), norfloxacin (NOR) and ciprofloxacin (CIP) over other Pharmaceutical and Personal Care Products (PPCPs), accomplishing the detection limit of 0.12 μmol/L, 0.52 μmol/L, 0.75 μmol/L, respectively. Notably, BUC-88 acted as an excellent fluorescence sensor for tetracyclines antibiotics with fast response time (less than 1 s), high selectivity and sensitivity (LODs = 0.08 μmol/L). The fluorescent detection method was successfully used for visual and ultrasensitive detection of ENR, NOR, CIP and tetracycline hydrochloride (TC) in lake water with satisfied recovery from 99.75% to 102.30%. Finally, the photoinduced electron transfer and the competitive absorption of ultraviolet light are the main mechanisms for sensitive detection toward quinolone antibiotics and tetracyclines antibiotics.
Development of environmentally friendly biological algicide and biochemical analysis of inhibitory effect of diatom Skeletonema costatum
Jie Yang, Qingzheng Zhu, Jinlong Chai, Feng Xu, Yunfei Ding, Qiang Zhu, Zhaoxin Lu, Kuan Shiong Khoo, Xiaoying Bian, Shujun Wang, Pau Loke Show
2022, 33(3): 1358-1364  doi: 10.1016/j.cclet.2021.09.053
[摘要]  (76) [HTML全文] (76) [PDF 533KB] (76)
Skeletonema costatum is a diatom widely distributed in red tide microalgae blooms and as one of the main algae causing harmful algal blooms, because of their rapid reproduction and production of toxic and harmful substances, often play a negative role in aquatic ecosystems, and human health and wellbeing. Bacillomycin D is a nonribosomal cyclic antifungal lipopeptide in the iturins family. In this study, Bacillomycin D was tested for its ability to inhibit the growth of S. costatum. The EC50 24h of Bacillomycin D on S. costatum was 24.70 μg/mL. The chlorophyll fluorescence parameters Fv/Fm, Fv/Fo, and yield of the diatoms decreased significantly with increasing concentrations of Bacillomycin D. Study of the mechanism showed that Bacillomycin D induced cell death by changing cell membrane permeability, promoting the release of cellular contents. In this study, transcriptomic analysis showed Bacillomycin D significantly inhibited the photosynthesis and metabolism of S. costatum. These findings investigated the inhibitory effect of Bacillomycin D on the growth of S. costatum and provided a theoretical foundation for the development of new environmentally friendly biological algicide.
"Small amount for multiple times" of H2O2 feeding way in MoS2-Fex heterogeneous fenton for enhancing sulfadiazine degradation
Zhuan Chen, Cheng Lian, Kai Huang, Jiahui Ji, Qingyun Yan, Jinlong Zhang, Mingyang Xing
2022, 33(3): 1365-1372  doi: 10.1016/j.cclet.2021.08.016
[摘要]  (73) [HTML全文] (73) [PDF 666KB] (73)
In recent years, MoS2 catalyzed/cocatalyzed Fenton/Fenton-like systems have attracted wide attention in the field of pollution control, but there are few studies on the effect of H2O2 feeding way on the whole Fenton process. Here, we report a new type of composite catalyst (MoS2-Fex) prepared in a simple way with highly dispersed iron to provide more active sites. MoS2-Fex was proved to possess selectivity for singlet oxygen (1O2) in effectively degrading sulfadiazine with a wide pH adaptability (4.0~10.0). Importantly, the mechanism of the interaction between H2O2 and MoS2 on the Fenton reaction activity was revealed through the combination of experiment and density functional theory (DFT) calculations. Compared to the traditional "a large amount for one time" feeding way of H2O2, the "small amount for multiple times" of H2O2 feeding way can increase the degradation rate of sulfadiazine from 36.9% to 91.1% in the MoS2-Fex heterogeneous Fenton system. It is demonstrated that the "small amount for multiple times" of H2O2 feeding way can reduce the side reaction of decomposition of H2O2 by MoS2 and effectively improve the utilization rate of H2O2 and the stability of MoS2-Fex. Compared with Fe2O3-based Fenton system, MoS2-Fex can significantly save the amount of H2O2. Compared with nano-iron powder, the formation of iron sludge in MoS2-Fex system was significantly reduced. Furthermore, long-term degradation test showed that the MoS2-Fe75/H2O2 system could maintain the effectiveness of degrading organic pollutants for 10 days (or even longer). This study has a guiding significance for the large-scale treatment of industrial wastewater by improved Fenton technology in the future.
A modular single-cell pipette microfluidic chip coupling to ETAAS and ICP-MS for single cell analysis
Xing Wei, Meng Yang, Ze Jiang, Jinhui Liu, Xuan Zhang, Mingli Chen, Jianhua Wang
2022, 33(3): 1373-1376  doi: 10.1016/j.cclet.2021.08.024
[摘要]  (96) [HTML全文] (96) [PDF 315KB] (96)
Accurate single-cell capture is a crucial step for single cell biological and chemical analysis. Conventional single-cell capturing often confront operational complexity, limited efficiency, cell damage, large scale but low accuracy, incompetence in the acquirement of nano-upgraded single-cell liquid. Flow cytometry has been widely used in large-scale single-cell detection, while precise single-cell isolation relies on both a precision operating platform and a microscope, which is not only extremely inefficient, but also not conducive to couple with modern analytical instruments. Herein, we develop a modular single-cell pipette (mSCP) microfluidic chip with high efficiency and strong applicability for accurate direct capture of single viable cell from cell suspensions into nanoliter droplets (30-1000 nL). The mSCP is used as a sampling platform for the detection of CdTe quantum dots in single cells with electrothermal atomic absorption spectrometry (ETAAS) for the first time. It also ensures precise single-cell sampling and detection by inductively coupled plasma mass spectrometry (ICP-MS).
Di-4-ANEPPDHQ probes the response of lipid packing to the membrane tension change in living cells
Nan Li, Weifei Zhang, Haifeng Lin, Jin-Ming Lin
2022, 33(3): 1377-1380  doi: 10.1016/j.cclet.2021.08.060
[摘要]  (79) [HTML全文] (79) [PDF 425KB] (79)
Membrane tension plays a significant role in many cellular processes including cell adhesion, migration and spreading. Despite the importance of membrane tension, it remains difficult to measure in vivo. Recently, the development of non-invasive fluorescent probes have made great progress, especially excited-state deplanarization in molecular rotors has been applied to image membrane tension in living cells. Nevertheless, an intrinsic limitation of such kind of probe is that they depend on the lipid packing, and how the lipid packing responds to the membrane tension change remains unclear. Therefore, in this work, we used a polarity-sensitive membrane probe to investigate the possible response mechanism of lipid packing to the change of membrane tension that was regulated by osmotic shocks. The results showed that an increase in membrane tension could stretch the lipids apart with large displacements, and this change was not homogeneous on the whole membrane, instead, increase of membrane tension induced phase separation.
Heat treatment-induced Co3+ enrichment in CoFePBA to enhance OER electrocatalytic performance
Wenhui Hu, Mingbo Zheng, Huiyu Duan, Wei Zhu, Ying Wei, Yi Zhang, Kunming Pan, Huan Pang
2022, 33(3): 1412-1416  doi: 10.1016/j.cclet.2021.08.025
[摘要]  (71) [HTML全文] (71) [PDF 466KB] (71)
Increasing active metal sites is a valid approach to improve the catalytic activity of the catalyst. Co3+ is the main active metal site of Co-based catalysts. In this research work, through the partial transformation of CoFePBA (CFP) via low-temperature heat treatment, the effective control of the Co3+/Co2+ ratio has been achieved. The partial transformation strategy of low-temperature heat treatment can not only maintain the original framework structure of CFP, but also increase more active sites. The characterization results show that the CFP-200 sample obtained via heat treatment at 200 ℃ for 2 h under N2 atmosphere has the highest Co3+/Co2+ ratio. As an oxygen evolution reaction electrocatalyst, CFP-200 shows the best electrocatalytic activity among all samples. In 1.0 mol/L KOH electrolyte, the overpotential is 312 mV at a current density of 10 mA/cm2. Therefore, low-temperature heat treatment provides an effective method for preparing low-cost and high-efficiency electrocatalysts.
Single molecule magnetic behavior and photo-enhanced proton conductivity in a series of photochromic complexes
Qian Zhang, Jixiang Hu, Qi Li, Dongxue Feng, Zhenni Gao, Guoming Wang
2022, 33(3): 1417-1421  doi: 10.1016/j.cclet.2021.08.029
[摘要]  (68) [HTML全文] (68) [PDF 377KB] (68)
Molecules with multifunctional properties are of immense interest in hybrid materials, while challenges still existed because of the limited compatibility of multiple functionalities in a single system. In this work, a series of metal-organic complexes were synthesized and characterized under the assembly of electron donor phosphonate, electron acceptor polypyridine ligand and spin carrier rare earth ions. All the compounds exhibited remarkable and reversible responses with photochromism and photomodulated fluorescence, originated from photogenerated radicals via electron transfer from phosphonates to polypyridine ligands. For the Dy analog, slow magnetic relaxation was observed at cryogenic temperature, indicating the single-molecule magnetic behavior. Furthermore, photogenerated radicals could enhance the proton conductive behavior, with about 2 times larger in magnitude after light irradiation for Dy and Y compounds. The introduction of photoluminescence, magnetism and proton conduction into metallic phosphonates can provide potential applications for photochromic materials.
Deuteration triggered downward shift of dielectric phase transition temperature in a hydrogen-bonded molecular crystal
Bei-Dou Liang, Tong Jin, Le-Ping Miao, Chao-Yang Chai, Chang-Chun Fan, Xiang-Bin Han, Wen Zhang
2022, 33(3): 1422-1424  doi: 10.1016/j.cclet.2021.08.032
[摘要]  (70) [HTML全文] (70) [PDF 317KB] (70)
Deuteration of hydrogen-bonded phase transition crystals can increase the transition temperatures due to the isotope effect. But rare examples show the opposite trend that originates from the structural changes of the hydrogen bond, known as the geometric H/D isotope effect. Herein, we report an organic crystal, diethylammonium hydrogen 1,4-terephthalate, exhibits a reversible structural phase transition and dielectric switching. Structural study shows the cations reside in channels formed by one-dimensional hydrogen-bonded anionic chains and undergo an order-disorder transition at around 206 K. The deuterated counterpart shows an elongation of the O···O hydrogen bond by about 0.005 Å. This geometric isotope effect releases the internal pressure of the anionic host on the cation guests and results in a downward shift of the phase transition temperature by 10 K.
Low temperature fabrication for high-performance semitransparent CsPbI2Br perovskite solar cells
Xiaogang Yang, Jiejia Han, Wei Ruan, Yanqiang Hu, Zhengyan He, Xiangrui Jia, Shufang Zhang, Dehua Wang
2022, 33(3): 1425-1429  doi: 10.1016/j.cclet.2021.08.039
[摘要]  (82) [HTML全文] (82) [PDF 437KB] (82)
All-inorganic CsPbI2Br perovskite with suitable bandgap and excellent thermal stability has been reported as the most promising candidate for efficient perovskite solar cells (PSCs). However, the high annealing temperature (> 250 ℃) and poor stability of α-CsPbI2Br greatly limit the future application in photovoltaic field. Herein, a facile method is reported to prepare α-CsPbI2Br perovskite film with high stability at low temperature (70 ℃) by incorporating a small amount of γ-aminobutyric acid (GABA) in the precursor solutions. The devices exhibit reproducible photovoltaic performance with a champion efficiency up to 15.16%, along with the excellent stability, maintaining more than 80% of its initial efficiency after stored in ambient condition for 600 h without any encapsulation. Most importantly, the method enables fabrication of semitransparent CsPbI2Br PSCs with a PCE of 6.76%, as well as an average visible transparency (AVT) of 25.38%. To the best of our knowledge, this is the first attempt to apply CsPbI2Br to the semitransparent solar cells.
Cascading V2O3/N-doped carbon hybrid nanosheets as high-performance cathode materials for aqueous zinc-ion batteries
Yue Niu, Denghui Wang, Yingjie Ma, Linjie Zhi
2022, 33(3): 1430-1434  doi: 10.1016/j.cclet.2021.08.058
[摘要]  (83) [HTML全文] (83) [PDF 563KB] (83)
In recent years, especially when there is increasing concern about the safety issue of lithium-ion batteries (LIBs), aqueous Zn-ion batteries (ZIBs) have been getting a lot of attention because of their cost-effectiveness, materials abundance, high safety, and ecological friendliness. Their working voltage and specific capacity are mainly determined by their cathode materials. Vanadium oxides are promising cathode materials for aqueous ZIBs owing to their low cost, abundant resources, and multivalence. However, vanadium oxide cathodes still suffer from unsatisfactory capacity, poor stability, and low electrical conductivity. In this work, cascading V2O3/nitrogen doped carbon (V2O3/NC) hybrid nanosheets are prepared for high-performance aqueous ZIBs by pyrolyzing pentyl viologen dibromide (PV) intercalated V2O5 nanosheets. The unique structure features of V2O3/NC nanosheets, including thin sheet-like morphology, small crystalline V2O3 nanoparticles, and conductive NC layers, endow V2O3/NC with superior performance compared to most of the reported vanadium oxide cathode materials for aqueous ZIBs. The V2O3/NC cathode exhibits the discharge capacity of 405 mAh/g at 0.5 A/g, excellent rate capability (159 mAh/g at 20 A/g), and outstanding cycling stability with 90% capacity retention over 4000 cycles at 20 A/g.
Copper fluoride as a low-cost sodium-ion battery cathode with high capacity
Yiming Dai, Qiujie Chen, Chenchen Hu, Yangyang Huang, Wangyan Wu, Mingliang Yu, Dan Sun, Wei Luo
2022, 33(3): 1435-1438  doi: 10.1016/j.cclet.2021.08.050
[摘要]  (68) [HTML全文] (68) [PDF 386KB] (68)
Sodium-ion batteries (SIBs) are promising alternatives to lithium-ion batteries (LIBs) for large-scale energy storage considering the abundance and low cost of Na-containing resources. However, the energy density of SIBs has been limited by the typically low specific capacities of traditional intercalation-based cathodes. Metal fluorides, in contrast, can deliver much higher capacities based on multi-electron conversion reactions. Among metal fluorides, CuF2 presents a theoretical specific capacity as high as 528 mAh/g while its Na-ion storage mechanism has been rarely reported. Here, we report CuF2 as a SIB cathode, which delivers a high capacity of 502 mAh/g but suffers from poor electrochemical reversibility. As a solution, we adjust the cell configuration by inserting a carbon-coated separator, which hinders the transportation of dissolved Cu ions and improves the reversibility of the CuF2 cathode. By using in-situ XRD measurements and theoretical calculation, we propose that a one-step conversion reaction occurs during the discharge process, and a reconversion reaction competes with the oxidization of Cu to dissolved Cu ion during the charge process.
Ingeniously designed Ni-Mo-S/ZnIn2S4 composite for multi-photocatalytic reaction systems
Jing Chen, Yumei Tang, Shihao Wang, Lingbin Xie, Cheng Chang, Xiaolei Cheng, Mingming Liu, Longlu Wang, Lianhui Wang
2022, 33(3): 1468-1474  doi: 10.1016/j.cclet.2021.08.103
[摘要]  (88) [HTML全文] (88) [PDF 645KB] (88)
Molybdenum disulfide (MoS2) with low cost, high activity and high earth abundance has been found to be a promising catalyst for the hydrogen evolution reaction (HER), but its catalytic activity is considerably limited due to its inert basal planes. Here, through the combination of theory and experiment, we propose that doping Ni in MoS2 as catalyst can make it have excellent catalytic activity in different reaction systems. In the EY/TEOA system, the maximum hydrogen production rate of EY/Ni-Mo-S is 2.72 times higher than that of pure EY, which confirms the strong hydrogen evolution activity of Ni-Mo-S nanosheets as catalysts. In the lactic acid and Na2S/Na2SO3 systems, when Ni-Mo-S is used as co-catalyst to compound with ZnIn2S4 (termed as Ni-Mo-S/ZnIn2S4), the maximum hydrogen evolution rates in the two systems are 5.28 and 2.33 times higher than those of pure ZnIn2S4, respectively. The difference in HER enhancement is because different systems lead to different sources of protons, thus affecting hydrogen evolution activity. Theoretically, we further demonstrate that the Ni-Mo-S nanosheets have a narrower band gap than MoS2, which is conducive to the rapid transfer of charge carriers and thus result in multi-photocatalytic reaction systems with excellent activity. The proposed atomic doping strategy provides a simple and promising approach for the design of photocatalysts with high activity and stability in multi-reaction systems.
Water-soluble pillar[4]arene[1]quinone: Synthesis, host-guest property and application in the fluorescence turn-on sensing of ethylenediamine in aqueous solution, organic solvent and air
Jin Wang, Moupan Cen, Jian Wang, Di Wang, Yue Ding, Guohua Zhu, Bing Lu, Xiaolei Yuan, Yang Wang, Yong Yao
2022, 33(3): 1475-1478  doi: 10.1016/j.cclet.2021.08.044
[摘要]  (78) [HTML全文] (78) [PDF 408KB] (78)
Water-soluble pillar[5]arenes are a class of typical macrocycles and have aroused tremendous attention for its easy to modify, abundant host-guest properties and extensive applications. However, up to now, all the reported water-soluble pillar[5]arenes acted as the host molecules, whereas they failed to be postsynthetically modified, which seriously impeded the development of the pillar[5]arene-based supramolecular chemistry. In this work, a new water-soluble pillar[5]arene, pillar[4]arene[1]quinone, was designed and synthsized with eight quaternary ammonium groups as well as a quinone units. Such a new water-soluble pillar[4]arene[1]quinone was capable of forming 1:1 stable complex with sodium 1-octanesulfonate in aqueous solution. Since the 1, 4-quinone unit of WP[4]Q[1] could react with ethylenediamine (EDA) to form a conjugated quinoxaline structure, so pillar[4]arene[1]quinone could apply to the facile fluorescence turn-on sensing of EDA in aqueous solution, organic solvent and air.
Visible-light-initiated 4CzIPN catalyzed multi-component tandem reactions to assemble sulfonated quinoxalin-2(1H)-ones
Zhiwei Wang, Qishun Liu, Ruisheng Liu, Zhongyin Ji, Yan Li, Xiaohui Zhao, Wei Wei
2022, 33(3): 1479-1482  doi: 10.1016/j.cclet.2021.08.036
[摘要]  (68) [HTML全文] (68) [PDF 510KB] (68)
A mild and efficient photochemical multi-component tandem reaction of quinoxalin-2(1H)-ones, alkenes and sulfinic acids is reported. This tandem reaction could be conveniently carried out at room temperature by employing 4CzIPN as the metal-free photocatalyst and dioxygen (air) as the environmentally benign oxidant. A number of sulfonated quinoxalin-2(1H)-ones were obtained in satisfactory yields with favorable functional group tolerance. Radical trapping experiment and fluorescence quenching experiments were performed to elucidate this visible-light mediated radical reaction process.
H4SiW12O40-catalyzed cyclization of epoxides/aldehydes and sulfonyl hydrazides: An efficient synthesis of 3, 4-disubstituted 1H-pyrazoles
Guoping Yang, Xuanjie Xie, Mengyuan Cheng, Xiaofei Gao, Xiaoling Lin, Ke Li, Yuanyuan Cheng, Yufeng Liu
2022, 33(3): 1483-1487  doi: 10.1016/j.cclet.2021.08.037
[摘要]  (84) [HTML全文] (84) [PDF 871KB] (84)
A simple and efficient method for the synthesis of pyrazoles through a silicotungstic acid (H4SiW12O40)-catalyzed cyclization of epoxides/aldehydes and sulfonyl hydrazides has been developed. Various epoxides/aldehydes were smoothly reacted with sulfonyl hydrazides to furnish regioselectivity 3, 4-disubstituted 1H-pyrazoles. The application of such an earth-abundant, readily accessible, and nontoxic catalyst provides a green approach for the construction of 3, 4-disubstituted 1H-pyrazoles. A plausible reaction mechanism has been proposed on the basis of control experiments, GC-MS and DFT calculations.
Chirality and chiral functional composites of bicontinuous cubic nanostructured cubosomes
Deyin Wang, Hongkai Liu, Wei Wang
2022, 33(3): 1488-1492  doi: 10.1016/j.cclet.2021.08.040
[摘要]  (78) [HTML全文] (78) [PDF 481KB] (78)
Molecular self-assembly is the most important strategy for the development of chiral aggregates and chiral functional materials. In this study, we rationally designed and synthesized chiral fluorescent heteroclusters that were self-assembled into microscale cubosomes with a three-dimensional (3D) bicontinuous cubic phase nanostructure. The cubosomes exhibited chirality, indicating that chirality is transferred from the molecules to the 3D nanostructure. Therefore, we confirmed the formation of a chiral bicontinuous cubic phase nanostructure for the first time. We also showed that this chirality originates from the continuous change in the saddle-splay distortion of the molecules within the curved bilayer. At the same time, transparent films of chiral composites were prepared by mixing the chiral cubosomes with an epoxy resin and then curing the mixture. Therefore, we demonstrated an effective method for preparing chiral composites.
Fluorescence detection of perfluorooctane sulfonate in water employing a tetraphenylethylene-derived dual macrocycle BowtieCyclophane
Sheng-Nan Lei, Huan Cong
2022, 33(3): 1493-1496  doi: 10.1016/j.cclet.2021.08.068
[摘要]  (80) [HTML全文] (80) [PDF 482KB] (80)
Because the widely used perfluorooctane sulfonate (PFOS) is harmful to both environment and human health, it is of great significance and urgency to develop sensitive and selective sensors for the detection of trace PFOS in water. In this study, a tetraphenylethylene-derived macrocycle BowtieCyclophane has been developed as a fluorescent sensor based on aggregation-induced emission enhancement and fluorochromism. Sensitive detection of PFOS has been achieved with a limit of detection (LOD) of 47.3 ± 2.0 nmol/L (25.4 ± 1.1 µg/L) accompanied by visual fluorescence color changes.
Iodine-catalyzed amination of benzothiazoles with KSeCN in water to access primary 2-aminobenzothiazoles
Yu-Shen Zhu, Linlin Shi, Lianrong Fu, Xiran Chen, Xinju Zhu, Xin-Qi Hao, Mao-Ping Song
2022, 33(3): 1497-1500  doi: 10.1016/j.cclet.2021.08.070
[摘要]  (75) [HTML全文] (75) [PDF 844KB] (75)
A facile and sustainable approach for the amination of benzothiazoles with KSeCN using iodine as the catalyst in water has been disclosed under transition-metal free conditions. The reaction proceeded smoothly to afford various primary 2-amino benzothiazoles in up to 96% yield. A series of control experiments were performed, suggesting a ring-opening mechanism was involved via a radical process. This protocol provides efficient synthesis of primary 2-aminobenzothiazoles
Electrochemical regioselective synthesis of N-substituted/unsubstituted 4-selanylisoquinolin-1(2H)-ones
Zhi-Lin Wu, Jin-Yang Chen, Xian-Zhi Tian, Wen-Tao Ouyang, Zhuo-Tao Zhang, Wei-Min He
2022, 33(3): 1501-1504  doi: 10.1016/j.cclet.2021.08.071
[摘要]  (74) [HTML全文] (74) [PDF 435KB] (74)
A novel and efficient electro-chemical initiated radical strategy was developed for the preparation of both N-substituted and N-unsubstituted 4-selanylisoquinolin-1(2H)-ones through selenylation of isoquinolin-1(2H)-ones with organodiselenides under chemical oxidant-, additive-free and ambient conditions.
Pseudo-crown ether having AIE and PET effects from a TPE-CD conjugate for highly selective detection of mercury ions
Kai-Ran Zhang, Ming Hu, Jun Luo, Fengying Ye, Ting-Ting Zhou, Ying-Xue Yuan, Miao-Li Gao, Yan-Song Zheng
2022, 33(3): 1505-1510  doi: 10.1016/j.cclet.2021.08.072
[摘要]  (70) [HTML全文] (70) [PDF 568KB] (70)
A new tetraphenylethylene-cyclodextrin (TPE-CD) conjugate with a linkage composed of long triethylene glycol chain and triazole ring on the CD rim has been designed and synthesized. The TPE-CD conjugate exists in a stretched form in DMSO and enhances its fluorescence after addition of a small amount of water due to aggregation-induced emission (AIE) effect. However, in the presence of a large amount of water, the TPE unit will enter the cyclodextrin cavity to form a folded self-inclusion compound. In the self-inclusion compound, not only nitrogen-containing pseudo-crown ether is formed but also arouses photo-induced electron transfer (PET) process from nitrogen atoms of triazole ring to TPE unit and quenches the fluorescence although more aggregation occurs in more water. This is the first finding that TPE-macrocycle conjugate can form pseudo-crown ether and has both the AIE phenomenon and the PET effect. Interestingly, only mercury ion arouses the fluorescence recover of the self-inclusion compound by entering the pseudo-crown ether cavity and blocking the PET process by binding to the nitrogen atoms, while other tested metal ions almost have no effect on the fluorescence. Therefore, the TPE-CD conjugate can be used for the highly selective fluorescence "Turn-On" detection of Hg2+.
[4 + 1] Cyclization of benzohydrazide and ClCF2COONa towards 1,3,4-oxadiazoles and 1,3,4-oxadiazoles-d5
Ya Wang, Shiqiang Mu, Xin Li, Qiuling Song
2022, 33(3): 1511-1514  doi: 10.1016/j.cclet.2021.08.089
[摘要]  (80) [HTML全文] (80) [PDF 538KB] (80)
A facile synthesis of 1,3,4-oxadiazoles and 1,3,4-oxadiazoles-d5 via [4 + 1] cyclization of ClCF2COONa with non-amine compounds containing amino groups is developed. Of note, this is the first time that halofluorinated compounds are used as C1 synthon to construct deuterated nitrogen-heterocyclic compounds. The current protocol features simple operation, readily accessible raw materials, wide substrate scope and valuable products
Theoretical and experimental investigations of the enantioselective epoxidation of olefins catalyzed by manganese complexes
Jin Lin, Fang Wang, Jing Tian, Jisheng Zhang, Yong Wang, Wei Sun
2022, 33(3): 1515-1518  doi: 10.1016/j.cclet.2021.08.092
[摘要]  (60) [HTML全文] (60) [PDF 642KB] (60)
The enantioselective epoxidation of olefin by Mn(R,R-PMCP)(OTf)2, H2O2 and H2SO4 was explored by DFT calculations and experiments. Theoretical results suggest that [Mn(O)(R,R-PMCP)(SO4)]+ species with a triplet ground spin state serves as the active species for the olefin epoxidation. It can be generated by the H2SO4 assisted O-O heterolysis of Mn(OOH) species. Mn-persulfate is also involved in this system, but it cannot promote the olefin epoxidation directly, preferring instead to transform into Mn(O). Actually, the asymmetric epoxidation reactions with H2O2/H2SO4 or Oxone provide similar enantioselectivity in the presence of manganese catalyst. These observations further support the transformation of Mn-persulfate to Mn(O) species.
Cleavage∕cross-coupling strategy for converting β-O-4 linkage lignin model compounds into high valued benzyl amines via dual C–O bond cleavage
Le Jia, Chao-Jun Li, Huiying Zeng
2022, 33(3): 1519-1523  doi: 10.1016/j.cclet.2021.08.125
[摘要]  (77) [HTML全文] (77) [PDF 1077KB] (77)
Lignin is the most recalcitrant of the three components of lignocellulosic biomass. The strength and stability of the linkages have long been a great challenge for the degradation and valorization of lignin biomass to obtain bio-fuels and commercial chemicals. Up to now, the selective cleavage of C–O linkages of lignin to afford chemicals contains only C, H and O atoms. Our group has developed a cleavage/cross-coupling strategy for converting 4-O-5 linkage lignin model compounds into high value-added compounds. Herein, we present a palladium-catalyzed cleavage/cross-coupling of the β-O-4 lignin model compounds with amines via dual C–O bond cleavage for the preparation of benzyl amine compounds and phenols.
Q[8]/SC[6]A-based framework constructed via OSIQ for metal ion capture
Li-Fei Tian, Ming Liu, Li-Xia Chen, Chao Huang, Qian-Jiang Zhu, Kai Chen, Jiang-Lin Zhao, Zhu Tao
2022, 33(3): 1524-1528  doi: 10.1016/j.cclet.2021.08.106
[摘要]  (65) [HTML全文] (65) [PDF 493KB] (65)
Since the outer surface interaction of Q[n]s (OSIQ, including self-, anion- and aromatic-induced OSIQs) was proposed in 2014, it has become the most important research area in our group to construct various Q[n]-based supramolecular frameworks via the OSIQ strategy. Herein, we report a novel supramolecular framework constructed using cucurbit[8]uril (Q[8]) and 4-sulfocalix[6]arene (SC[6]A). This Q[8]/SC[6]A-based supramolecular framework is a product via the perfect combination of self-, anion- and aromatic-induced OSIQs. This framework has the characteristics of easy preparation and high stability with the most important feature being the sequence selective capture of specific metal cations, such as common alkali- and alkaline earth metal ions, and renewability. Thus, this framework may be used in seawater desalination, potassium ion enrichment, radioactive cesium ion pollution source treatment, Gruinard's treatment or water softening and other applications.
Host-guest interaction tailored cucurbit[6]uril-based supramolecular organic frameworks (SOFs) for drug delivery
Chun Liu, Yu Xia, Zhu Tao, Xin-Long Ni
2022, 33(3): 1529-1532  doi: 10.1016/j.cclet.2021.08.108
[摘要]  (58) [HTML全文] (58) [PDF 481KB] (58)
An approach for the construction of crystalline porous supramolecular organic frameworks (SOFs) via outer-surface interactions of cucurbit[6]uril (Q[6]) with high yield is presented. This approach enables the noncovalent integration of guest molecules into ordered topologies and creates new host–guest-complex-based SOFs; i.e., the topology can be predesigned and constructed by using [ZnCl4]2− anions to induce the formation of solid Q[6]-SOFs, and the pore wall surface can be easily modified by the Q[6]-encapsulated guest molecules. In addition, one of prepared solid Q[6]-SOFs showed a high drug-loading capacity and smart potential release control for drug-delivery applications
An acid-base responsive linear-cyclic polymer rotaxane molecular shuttle with fluorescence signal output
Zhanqi Cao, Dongpu Wu, Mengzhen Li, Fan Yang, Zhikai Li, Wankai An, Song Jiang, Xin Zheng, Caoyuan Niu, Dahui Qu
2022, 33(3): 1533-1536  doi: 10.1016/j.cclet.2021.09.001
[摘要]  (56) [HTML全文] (56) [PDF 368KB] (56)
The preparation of intelligent-responsive materials with controllable topology structure has long been a significant objective for chemists in the field of materials science. In this paper, we designed and prepared a linear-cyclic reversible topological structure polymer based on the bistable [1]rotaxane molecular shuttle. A ferrocene-functionalized [1]rotaxane and naphthalimide fluorophore group are introduced into the both ends of the polymer, which exhibit distance-induced photo-electron transfer effect. The structural transformation between linear and cyclic state of polymer is demonstrated by simple acid-base stimuli, accompanying visual fluorescence changes. The transformation process was characterized by 1H NMR spectra and fluorescence spectra. This work provides a novel strategy to construct functionalized polymers with topological structure.
Electrochemical determination of paraquat using a glassy carbon electrode decorated with pillararene-coated nitrogen-doped carbon dots
Hao Zhang, Kun-Tao Huang, Ling Ding, Jie Yang, Ying-Wei Yang, Feng Liang
2022, 33(3): 1537-1540  doi: 10.1016/j.cclet.2021.09.002
[摘要]  (76) [HTML全文] (76) [PDF 395KB] (76)
An electrochemical sensor (carboxylatopillar[5]arene-coated nitrogen-doped carbon dots, namely CCDs) based on carboxylatopillar[5]arene (CP[5]) functionalized nitrogen-doped carbon dots (N-CDs) has been developed in a facile and economic manner. To improve the performance of this electrochemical sensor in pesticide detection, the optimal solution pH (pH 7) and loading amount of CCDs on the electrode (0.50 mg/mL) have been determined. By virtue of the good conductivity of N-CDs and the molecular recognition property of CP[5], CCDs modified glassy carbon electrode, namely CCDs/GCE, shows excellent anti-interference capability, selectivity, stability, and reproducibility in the sensitive detection of paraquat. The peak currents are proportional to the paraquat concentration (from 0.1 µmol/L to 10 µmol/L) with a detection limit of 6.4 nmol/L (S/N = 3), indicating a great potential in pesticide detection. In comparison with the electrochemical sensors that require expensive metal nanoparticles and complex preparation processes, CCDs/GCE exhibits excellent detection capability of paraquat with lower cost and simpler preparation processes.
The Pd-catalyzed synthesis of difluoroethyl and difluorovinyl compounds with a chlorodifluoroethyl iodonium salt (CDFI)
Yaru Niu, Chengyao Kimmy Cao, Chenxin Ge, Hongmei Qu, Chao Chen
2022, 33(3): 1541-1544  doi: 10.1016/j.cclet.2021.09.004
[摘要]  (61) [HTML全文] (61) [PDF 505KB] (61)
Herein, we report a simple and efficient method for the direct installation of chlorodifluoroethyl group onto aromatic molecules of various aromatic amides with a new 2-chloro, 2, 2-difluoroethyl(mesityl)iodonium salt (CDFI). Moreover, the chlorodifluoroethyl compounds could be smoothly converted into difluorovinyl compounds in a one-pot or discrete procedure and regarded as a steady source of difluorovinyl compounds with "HCl-mask".
Programmed co-assembly of DNA-peptide hybrid microdroplets by phase separation
Shengtao Yao, Yue Liao, Rizhao Pan, Weiping Zhu, Yufang Xu, Yangyang Yang, Xuhong Qian
2022, 33(3): 1545-1549  doi: 10.1016/j.cclet.2021.08.116
[摘要]  (83) [HTML全文] (83) [PDF 441KB] (83)
Biopolymers, including DNA and peptides have been used as excellent self-assembling building blocks for programmable single-component or hybrid materials, due to their controlled molecular interactions. However, combining two assembling principles of DNA-based programmability and peptide-based specific molecular interactions for hybrid structures to microscale has not yet been achieved. In this study, we describe a hybrid microsystem that emerges from the co-assembly of DNA origami structure and short elastin-like polypeptide conjugated oligonucleotides, and initiates liquid-liquid phase separation to generate microdroplets upon heating above the transition temperature. Moreover, the hybrid microdroplets are capable for guest molecule trapping and perform bi-/tri-enzymatic cascades with rate enhancements as open "microreactors". Our programmed assembled DNA-peptide microsystem represents a new combination of DNA nanotechnology and peptide science and opens potential application routes toward life-inspired biomaterials.
[4 + 1] Annulation of in situ generated azoalkenes with amines: A powerful approach to access 1-substituted 1, 2, 3-triazoles
Hongwei Wang, Yongquan Ning, Paramasivam Sivaguru, Giuseppe Zanoni, Xihe Bi
2022, 33(3): 1550-1554  doi: 10.1016/j.cclet.2021.09.008
[摘要]  (71) [HTML全文] (71) [PDF 1030KB] (71)
1-Substituted 1, 2, 3-triazoles represents 'privileged' structural scaffolds of many clinical pharmaceuticals. However, the traditional methods for their preparation mainly rely on thermal [3 + 2] cycloaddition of potentially dangerous acetylene and azides. Here we report a base-mediated [4 + 1] annulation of azoalkenes generated in situ from readily available difluoroacetaldehyde N-tosylhydrazones (DFHZ-Ts) with amines under relatively mild conditions. This azide- and acetylene-free strategy provides facile access to diverse 1-substituted 1, 2, 3-triazole derivatives in high yield in a regiospecific manner. This transformation has great functional group tolerance and can suit a broad substrate scope. Furthermore, the application of this novel methodology in the gram-scale synthesis of an antibiotic drug PH-027 and in the late-stage derivatization of several bioactive small molecules and clinical drugs demonstrated its generality, practicability and applicability.
Electrochemically promoted decarboxylative borylation of alkyl N-hydroxyphthalimide esters
Jian-Jun Dai, Xin-Xin Teng, Wen Fang, Jun Xu, Hua-Jian Xu
2022, 33(3): 1555-1558  doi: 10.1016/j.cclet.2021.09.011
[摘要]  (65) [HTML全文] (65) [PDF 762KB] (65)
An electrochemically promoted decarboxylative borylation reaction is reported. The reaction proceeds under mild conditions in an undivided cell without use of transition metal- or photo-catalysts. The key feature of the reaction is the compatibility of diboron reagents with the electrochemical conditions. This reaction exhibits broad substrate scope, good functional group tolerability, and easy scalability.
Electrochemical utilization of methanol and methanol-d4 as a C1 source to access (deuterated) 2, 3-dihydroquinazolin-4(1H)-one
Mingzhu Liu, Liang Xu, Yu Wei
2022, 33(3): 1559-1562  doi: 10.1016/j.cclet.2021.09.019
[摘要]  (72) [HTML全文] (72) [PDF 471KB] (72)
Herein, an electrocatalytic protocol for the synthesis of 2, 3-dihydroquinazolin-4(1H)-one has been disclosed. Methanol is activated and utilized as the C1 source to cyclize with 2-aminobenzamides. This cyclization reaction proceeds conveniently (room temperature and air atmosphere) without any homogeneous metal catalysts, external oxidants, or bases. A wide variety of N, N-disubstituted 2, 3-dihydroquinazolin-4(1H)-ones are obtained via this approach. Moreover, when methanol-d4 is used, a deuterated methylene motif is incorporated into the N-heterocycles, providing an efficient approach to the deuterated N-heterocycles.
A chemical labeling of N6-formyl adenosine (f6A) RNA
Li-Jun Xie, Cui-Lian Lin, Li Liu, Liang Cheng
2022, 33(3): 1563-1566  doi: 10.1016/j.cclet.2021.09.028
[摘要]  (75) [HTML全文] (75) [PDF 339KB] (75)
N6-methyl adenosine (m6A) is an eminent epigenetic mark in mRNAs that affects a broad range of biological functions in diverse species. However, the chemically inert methyl group prevents a direct labeling of this modification for subsequent detection and sequencing. Therefore, most current approaches for the labeling of m6A still have limitations of relying on the utilization of corresponding methyltransferases, which resulted in the lacking of efficiency. Here we present an approach which selectively alkylated the N6-formyl adenosine (f6A), the key intermediate during chemical oxidation of m6A, with an alkyne functionality that can be further labeled with click reactions. This covalent labeling approach will be able to facilitate in the affinity purification, detection and genome-wide profiling studies.
Construction of a biotin-targeting drug delivery system and its near-infrared theranostic fluorescent probe for real-time image-guided therapy of lung cancer
Xinyu Song, Rui Wang, Junfang Gao, Xiaoyue Han, Jianfeng Jin, Changjun Lv, Fabiao Yu
2022, 33(3): 1567-1571  doi: 10.1016/j.cclet.2021.08.111
[摘要]  (77) [HTML全文] (77) [PDF 597KB] (77)
The therapy of non-small lung cancer (NSCLC) is limited by wide metastasis and chemotherapy resistance, herein, we present a new cancer-targeting prodrug PBG with the integration of real-time fluorescence visualization. The potent anticancer drug Gefitinib conjugates a biotin recognition ligand yielding the prodrug PBG via a GSH-activatable disulfide bond linker. Once coupling a near-infrared azo-BODIPY fluorophore into the molecular structure of PBG, we obtain its fluorescent theranostic TBG. The prodrug PBG can sustain Gefitinib release by the high level of GSH in the pathophysiological milieu. We evaluate the drug delivery of the prodrug PBG using fluorescent TBG in PC9 cancer bearing nude mice models, which indicate that TBG can be utilized to monitor the in vivo drug release process. Prodrug PBG can be targeted to accumulate in the cancer lesion with a better and efficaciously therapeutic result compared with the single Gefitinib treatment in cells and in vivo. The fluorescence images also reveal that the targeting accumulation and longitudinal retention of anticancer drug in cancer lesions will contribute to the superior therapeutic effects. The above applications of our new prodrug PBG and its fluorescent theranostic TBG have the potential contribution to the research in biology and the clinical medicine.
Specific tracking of monoamine oxidase A in heart failure models by a far-red fluorescent probe with an ultra large Stokes shift
Xinming Li, Donglei Shi, Yihe Song, Yixiang Xu, Ying Gao, Wenjing Qiu, Xin Chen, Xiaokang Li, Yunyuan Huang, Yanjun Feng, Baoli Li, Yuan Guo, Jian Li
2022, 33(3): 1572-1576  doi: 10.1016/j.cclet.2021.08.114
[摘要]  (60) [HTML全文] (60) [PDF 402KB] (60)
Monoamine oxidase A (MAO-A) is a prominent myocardial source of reactive oxygen species (ROS), and its expression and activity are strongly increased in failing hearts. Therefore, accurate evaluation of MAO-A activity in cardiomyocytes is of great importance for understanding its biological functions and early diagnosing the progression of heart failure. However, so far, there is no report on the fluorescent diagnosis of heart failure by a specific probe for MAO-A. In this work, two far-red emissive fluorescent turn-on probes (KXS-M1 and KXS-M2) for the highly selective and sensitive detection of MAO-A were fabricated. Both probes exhibit good response to MAO-A, one of which, KXS-M2, performs better than the other one in terms of a fluorescence increment and sensitivity. Using the pioneering probe KXS-M2, specific fluorescence imaging of MAO-A in glucose-deprived H9c2 cardiac cells, zebrafish and isoprenaline-induced failing heart tissues was achieved, proving that KXS-M2 can serve as a powerful tool for the diagnosis and treatment of heart failure.
A "cluster bomb" oral drug delivery system to sequentially overcome the multiple absorption barriers
Qingling Song, Huirui Wang, Junfei Yang, Hui Gao, Ke Wang, Hao Wang, Yun Zhang, Lei Wang
2022, 33(3): 1577-1583  doi: 10.1016/j.cclet.2021.08.113
[摘要]  (78) [HTML全文] (78) [PDF 1064KB] (78)
Oral drugs have been widely used in clinical therapy, but their developments were severely limited by the side effects of drug exposure as well as the multiple biological barriers. In this study, we constructed a "cluster bomb" oral drug delivery system (DOX@PFeL@L100) with core-shell structure to overcome the complex absorption barriers. The inner core termed as "bomb" that contains a lot of ultra-small diameter Fe3O4 nanoparticles (DOX@PFeL NPs) loaded with doxorubicin (DOX) and modified with l-valine, which can efficiently penetrate the epithelial cells via PePT1 receptor mediated endocytosis. The outer shell of this "cluster bomb" is a layer of pH-sensitive polymer (Eudragit®L100) that can be served as a pH-responsive switch and effectively control the "bomb" release in the intestinal microenvironment to improve the antitumor efficiency by the Fenton like reaction of DOX and Fe2+/Fe3+. This study demonstrates that the "cluster comb" oral drug delivery system can sequentially overcome the multiple biological barriers, providing a safe and effective approach for tumor therapy.
Endogenous peroxynitrite activated fluorescent probe for revealing anti‐tuberculosis drug induced hepatotoxicity
Nannan Wang, Han Wang, Jian Zhang, Xin Ji, Huihui Su, Jinying Liu, Jiamin Wang, Weili Zhao
2022, 33(3): 1584-1588  doi: 10.1016/j.cclet.2021.09.046
[摘要]  (61) [HTML全文] (61) [PDF 503KB] (61)
Pyrazinamide (PZA), isoniazid (INH) and rifampicin (RFP) are all commonly used anti-tuberculosis drugs in clinical practice, and long-term medication may cause severe liver damage and toxicity. The level of peroxynitrite (ONOO) generated in liver has long been regarded as a biomarker for the prediction and measurement of drug-induced liver injury (DILI). In this article, we constructed a BODIPY-based fluorescent probe (BDP-Py+) that enabled quickly and sensitively detect and image ONOO in vivo. Utilizing this probe, we demonstrated the change of ONOO content in cells and mice model of DILI induced by acetaminophen (APAP), and for the first time revealed the mechanism of liver injury induced by antituberculosis drug PZA. Moreover, BDP-Py+ could be applied to screen out and evaluate the hepatotoxicity of different anti-tuberculosis drugs. Comparing with the existing serum enzymes detection and H & E staining, the probe could achieve early diagnosis of DILI before solid lesions in liver via monitoring the up-regulation of ONOO levels. Collectively, this work will promote the understanding of the pathogenesis of anti-tuberculosis drug induced liver injury (ATB-DILI), and provide a powerful tool for the early diagnosis and treatment of DILI.
A near-infrared multifunctional fluorescent probe for hypoxia monitoring and tumor-targeted therapy
Yuxun Lu, Jiajia Xu, Zongyun Jia, Siyu Kong, Yimu Qiao, Lin Li, Qiong Wu, Ying Zhou
2022, 33(3): 1589-1594  doi: 10.1016/j.cclet.2021.09.013
[摘要]  (77) [HTML全文] (77) [PDF 589KB] (77)
Hypoxia is one of the key characteristics of solid tumors. The over-expression of azoreductase resulting from hypoxia can be used as a target to visualize hypoxic levels and a trigger of the drug release system in tumor treatment. In this work, we developed a near-infrared fluorescent probe YLOD, composed of a near-infrared fluorophore, an azo bond, and an analogue of the anti-tumor drug melphalan. In the presence of azoreductase, YLOD displayed a red emission at 620 nm and released the anti-tumor drug concomitantly, thus achieving the integrated effects of hypoxic imaging and tumor treatment. Furthermore, YLOD successfully inhibited the growth of solid tumors during the tumor suppression experiments in nude mice. Considering all the results, YLOD emerges as a new fluorescence tool that can quickly determine the location and the edges of a tumor, showing concrete potential in clinical cancer treatment.
A photopatterned SERS substrate with a sandwich structure for multiplex detection
Yuan Xue, Duo Liu, Xuebin Wang, Yanxin Xiang, Shengjie Du, Kai Ye, Chunyan Bao, Linyong Zhu
2022, 33(3): 1595-1598  doi: 10.1016/j.cclet.2021.09.016
[摘要]  (64) [HTML全文] (64) [PDF 440KB] (64)
Substrate photopatterning has provided versatile applications in biomedical fields. Herein, an universal and efficient photoligation reaction has been used to prepare a patterned capture substrate for a sandwich SERS immunoassay. Photoirradiation induces mild and efficient immobilization of antibodies at the desired region of a gold surface, and the antibody-antigen interaction helps the substrate to capture the antigens in solution specifically. After exposing to SERS probes, i.e., the gold nanoparticles labelled with both antibodies and intrinsically strong Raman reporters, multiple quantitative SERS determination of antigens can be achieved with high sensitivity and specificity. The limit of detection can be as low as 10−12 mol/L for four kinds of cancer biomarkers, which provides a promising method for the construction of highly sensitive and high-throughput SERS detection chip and the application of in vitro diagnosis.
The marriage of sealant agent between structure transformable silk fibroin and traditional Chinese medicine for faster skin repair
Rongjun Zhang, Youbin Zheng, Tianqing Liu, Ning Tang, Lianzhi Mao, Lihan Lin, Jiahui Ye, Luoyijun Xie, Wenwen Hu, Weiwei Wu, Wenzhen Liao, Miaomiao Yuan
2022, 33(3): 1599-1603  doi: 10.1016/j.cclet.2021.09.018
[摘要]  (62) [HTML全文] (62) [PDF 528KB] (62)
Fast skin repair is critical for less infection, less pain and high quality of life, which is still limited with undesirable rehabilitation speed and side effects. Currently, laser-activated silk sealant agent without suture and gauze has been demonstrated promising for fast skin repair taking advantage of its structural transformation after heating. Nevertheless, more efficient healing effects and less side effects of laser-activated silk sealant agent remains challenging due to absence of suitable photo-thermal materials and robust/biomimetic protein materials. In this work, the marriage between silk protein and Rehmanniae radix preparata (a kind of the traditional Chinese herb) has been demonstrated as a novel and effective way to achieve an excellent healing effect for skin repair. The non-toxicity, high photothermal conversion efficiency and healing mechanism are systematically studied and proved. This new methodology might shed a new light for combining dark traditional Chinese medicine and silk fibroin for advanced wound healing technology.
Chemical chaperone delivered nanoscale metal–organic frameworks as inhibitor of endoplasmic reticulum for enhanced sensitization of thermo-chemo therapy
Xiaoyan Ma, Qiong Wu, Longfei Tan, Changhui Fu, Xiangling Ren, Qijun Du, Lufeng Chen, Xianwei Meng
2022, 33(3): 1604-1608  doi: 10.1016/j.cclet.2021.09.084
[摘要]  (62) [HTML全文] (62) [PDF 432KB] (62)
Thermotherapy and chemotherapy have received extensive attention to tumor treatment. However, thermal tolerance and drug resistance severely limit clinical effect of tumor therapy owing to endoplasmic reticulum (ER) stress. Reducing thermal tolerance and drug resistance of tumors is an urgent challenge to be solved. In this work, we design a nanoplatform of PBA-Dtxl@MIL-101 as an ER inhibitor. Amino functionalized Fe-metal organic framework (MIL-101) nanoparticles are synthesized as pH and microwave (MW) dual stimuli-responsive drug delivery system. Then, the chemical chaperones of 4-phenylbutyric acid (PBA) and antineoplastic drug Docetaxel (Dtxl) were successfully loaded into MIL-101 nanoparticles to form PBA-Dtxl@MIL-101 nanoparticles. Furthermore, PBA-Dtxl@MIL-101 nanoparticles exhibit inhibitor effect of ER stress through upregulating caspase 9 proteins and reduce thermal tolerance by downregulating HSP 90. It was demonstrated that the therapy sensitized by PBA-Dtxl@MIL-101 nanoparticles obviously destroyed tumor cells, showing simultaneously enhanced thermo-chemo therapy.
A multisite-binding fluorescent probe for simultaneous monitoring of mitochondrial homocysteine, cysteine and glutathione in live cells and zebrafish
Huimin Jiang, Guoxing Yin, Yabing Gan, Ting Yu, Youyu Zhang, Haitao Li, Peng Yin
2022, 33(3): 1609-1612  doi: 10.1016/j.cclet.2021.09.036
[摘要]  (58) [HTML全文] (58) [PDF 397KB] (58)
Homocysteine (Hcy), cysteine (Cys) and glutathione (GSH) play crucial roles in redox homeostasis during mitochondria functions. Simultaneous differentiation and visualization of mitochondrial biothiols dynamics are significant for understanding cell metabolism and their related diseases. Herein, a multisite-binding fluorescent probe (MCP) was developed for simultaneous sensing of mitochondrial Cys, GSH and Hcy from three fluorescence channels for the first time. This novel probe exhibited rapid fluorescence turn-on, good water-solubility, high selectivity and large spectral separation for discriminating Cys, GSH and Hcy with 131-, 96-, 748-fold fluorescence increasement at 471, 520, 567 nm through different excitation wavelengths, respectively. Importantly, this probe was successfully applied to simultaneous monitoring of mitochondrial Cys, GSH, and Hcy in live cells and zebrafish from three fluorescence channels, promoting the understanding of the functions of Hcy, Cys and GSH.
Dithienylethene metallodendrimers with high photochromic efficiency
Yuxuan Wang, Qifeng Zhou, Xiaoxiao He, Ying Zhang, Hongwei Tan, Jianhua Xu, Cuihong Wang, Wei Wang, Xiping Luo, Jinquan Chen, Lin Xu
2022, 33(3): 1613-1618  doi: 10.1016/j.cclet.2021.09.048
[摘要]  (61) [HTML全文] (61) [PDF 437KB] (61)
It has been challenging to achieve multi-photochromic systems without affecting the individual photoswitching properties of the constituent units. Herein, we present the design and synthesis of a new family of platinum-acetylide dendrimers containing up to twenty-one photochromic dithienylethene (DTE) units that exhibit both high photochromic efficiency and individual switching properties. Upon irradiation with ultraviolet (UV) and visible (vis) light, the resultant metallodendrimers display high conversion yield and good fatigue resistance. More interestingly, cyclization-cycloreversion kinetics revealed that the photochromic property of each DTE unit in these metallodendrimers is unaffected by its neighbor and the full ring-closure of up to twenty-one DTE units in one single dendrimer has been achieved.
Virus-inspired nanoparticles as versatile antibacterial carriers for antibiotic delivery against Gram-negative and Gram-positive bacteria
Kefurong Deng, Yachao Li, Xiaoyu Liang, Cheng Shen, Zenan Zeng, Xianghui Xu
2022, 33(3): 1619-1622  doi: 10.1016/j.cclet.2021.09.045
[摘要]  (71) [HTML全文] (71) [PDF 446KB] (71)
Infectious diseases become one of the leading causes of human death. Traditional treatment based on classical antibiotics could not provide enough antibacterial activity to combat bacterial infections due to low bioavailability, even leading to antibiotic resistance. In recent years, biomimetic delivery systems have been developed to improve drug therapy for various diseases, such as malignant tumor and cardiovascular disease. In this work, we designed virus-inspired nanodrugs (VNDs) through co-assembly of amphiphilic lipopeptide dendrons and poly(lactic-co-glycolic acid) polymers for high-efficiency antibiotic delivery. These VNDs had well-defined and stable nanostructures for tetracycline encapsulation and delivery. The VNDs were capable of promoting antibiotic internalization and enhancing their antibacterial effects against Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus. Additionally, no obvious cytotoxicity of VNDs was observed to human cell lines. This work successfully demonstrated the virus-mimetic nanoparticles served as promising and applicable antibiotic delivery platform for antibacterial treatment.
Metal-phenolic networks modified polyurethane as periosteum for bone regeneration
Qingyi Zhang, Kai Huang, Jie Tan, Xiongxin Lei, Liping Huang, Yuting Song, Qianjin Li, Chenyu Zou, Huiqi Xie
2022, 33(3): 1623-1626  doi: 10.1016/j.cclet.2021.09.105
[摘要]  (70) [HTML全文] (70) [PDF 590KB] (70)
Treatment of bone defects still poses a great challenge in orthopedic clinics, and the vital role of periosteum in such processes has attracted widespread attention. However, studies focusing on the oxidative stress micro-environment with an artificial periosteum at the site of defect have been scarce. The intrinsic anti-oxidative properties and therapeutic potential for bone defects of metal-phenolic networks (MPNs) have provided a potential solution to this. Herein, we have developed a protocatechualdehyde + zinc ion (PCA+Zn) MPN coating on a thermoplastic polyurethane membrane with a one-pot method to fabricate a new-type of periosteum with meritorious biocompatibility and abilities of modulating oxidative stress condition and promoting osteogenesis and mineralization for better bone regeneration, which has shown to be a promising strategy for constructing artificial periosteum with various MPNs.
Selective probes targeting c-MYC Pu22 G-quadruplex and their application in live mice imaging
Zhuo Yu, Wenbo Huang, Liqiao Shi, Shaoyong Ke, Shengzhen Xu
2022, 33(3): 1627-1631  doi: 10.1016/j.cclet.2021.09.087
[摘要]  (75) [HTML全文] (75) [PDF 443KB] (75)
Several probes containing benzothiazole-guided conjugated systems (BGCS) were designed and synthesized, and two molecules (BGCS5 and BGCS6) of which were discovered as selective probes targeting c-MYC Pu22 G-quadruplex DNA. The fluorescence intensity of BGCS5 and BGCS6 in the presence of c-MYC Pu22 far exceeds that of the typical G4 probe TO1. Especially, the fluorescence of BGCS6 increased almost 193-fold in the presence of c-MYC Pu22 G4 compared to that alone in aqueous buffer condition with almost no fluorescence and 10–30 folds than those in the presence of other DNAs, which will be useful tools for disease detection in mammals.
Carbon dot-based fluorescent and colorimetric sensor for sensitive and selective visual detection of benzoyl peroxide
Xiangcao Li, Xuejian Xing, Shaojing Zhao, Shaohua Zhu, Benhua Wang, Minhuan Lan, Xiangzhi Song
2022, 33(3): 1632-1636  doi: 10.1016/j.cclet.2021.09.086
[摘要]  (73) [HTML全文] (73) [PDF 1071KB] (73)
Benzoyl peroxide (BPO) has been added in wheat flour because of its bleaching effect. However, the abnormal used BPO has caused increasing concern due to its strong oxidization capability which may have adverse effects on living organisms. Herein, we present a carbon dot (CD)-based fluorescent and colorimetric probe for visually, sensitively and selectively sensing BPO. The addition of BPO could quench the red fluorescence of CDs peaked at 622 and 677 nm, and decrease the absorbance at 613 nm, while increase the absorbance at 450 nm, resulting in a fluorescence turn-off and colorimetric spectral response. Moreover, the CDs had short response time of 10 min and high sensitivity towards BPO with a low limit of detection of 28 nmol/L. The applicability of the CDs in detecting BPO in wheat, noodle and starch samples was further demonstrated, and good recovery results were obtained.
High-contrast and real-time visualization of membrane proteins in live cells with malachite green-based fluorogenic probes
Yefeng Chen, Chenghong Xue, Jie Wang, Minqiu Xu, Yuyao Li, Yiru Ding, Heng Song, Weipan Xu, Hexin Xie
2022, 33(3): 1637-1642  doi: 10.1016/j.cclet.2021.09.088
[摘要]  (80) [HTML全文] (80) [PDF 570KB] (80)
Imaging dynamics of membrane proteins of live cells in a wash-free and real-time manner has been a challenging task. Herein, we report unprecedented applications of malachite green (MG), an organic dye widely used in pigment industry, as a switchable fluorophore to monitor membrane enzymes or non-catalytic proteins in live cells. Conformationally flexible MG is non-fluorescent in aqueous solution, yet covalent binding with endogenous proteins of cells significantly enhances its fluorescence at 670 nm by restricting flexibility of dye. Integrating a phosphate-caged quinone methide precursor with MG yielded a covalent labeling fluorogenic probe, allowing real-time imaging of membrane alkaline phosphatase (ALP, a model catalytic protein) activity in live cells with over 100-fold enhancement of fluorescence intensity. Moreover, MG is also applicable to image non-catalytic protein by conjugation with protein-specific ligand. A fluorogenic probe consisted of c-RGDfK peptide and MG proved to be compatible with wash-free and real-time visualization of non-catalytic integrin αvβ3 in live cells with high contrast.
Design and synthesis of novel α-aminoamides derivatives as Nav1.7 inhibitors for antinociception
Dengqi Xue, Yani Liu, Yilin Zheng, Heling Niu, Liying Dong, Xiangshuo Ouyang, Siyu Song, Denggao Zhang, Qianwei Ge, Kewei Wang, Liming Shao
2022, 33(3): 1643-1646  doi: 10.1016/j.cclet.2021.08.026
[摘要]  (65) [HTML全文] (65) [PDF 359KB] (65)
Three novel series of α-aminoamides derivatives were designed and synthesized based on ralfinamide, and their Nav1.7 inhibitory activities were evaluated using manual patch clamp electrophysiology. Active compounds inhibited Nav1.7 with half maximal inhibitory concentration (IC50) values ranging from 2.9 µmol/L to 21.4 µmol/L. Among them, the most potent compound 19h exhibited about 12-fold potency better than ralfinamide. The investigation of their structure-activity relationship gives a strategy to improve the Nav1.7 inhibition of ralfinamide analogues. Compound 19h was efficacious in antinociception in the mouse spared nerve injury (SNI) model of neuropathic pain without causing sedation in the open field test.