2015 Volume 26 Issue 7

Conjugated radical cation dimerization-driven generation of supramolecular architectures
Lan Chen , Yun-Chang Zhang , Wei-Kun Wang , Jia Tian , Liang Zhang , Hui Wang , Dan-Wei Zhang , Zhan-Ting Li
2015, 26(7): 811-816  doi: 10.1016/j.cclet.2015.01.036
[Abstract](237) [FullText HTML] [PDF 1345KB](0)
This paper summarizes the recent advance in utilizing conjugated radical cation dimerization (CRCD) for constructing new unimolecular, such as foldamers, and supramolecular ordered structures, such as three-dimensional supramolecular polymers and two-dimensional supramolecular organic framework. Particularly, the stacking or dimerization of tetrathiafulvalene and 4,4'-dipyridium subunits has been highlighted, and the approaches for enhancing the stability of their radical cation dimers have been discussed.
Recent advance of photochromic diarylethenes-containing supramolecular systems
Chao Xiao , Wei-Ye Zhao , Da-Yang Zhou , Yan Huang , Ye Tao , Wan-Hua Wua , Cheng Yang
2015, 26(7): 817-824  doi: 10.1016/j.cclet.2015.05.013
[Abstract](211) [FullText HTML] [PDF 6398KB](0)
Photochromic diarylethenes were deemed to be one of themost promising molecular building blocks for photoresponsive materials. This review gives a brief summary to the recent progress of studies of diarylethenes in supramolecular systems, focusing on their applications in biological systems, photoresponsive mechanical materials and photoresponsive chemosensors.
Controlled drug delivery systems based on calixarenes
Yue Zhou , Hui Li , Ying-Wei Yang
2015, 26(7): 825-828  doi: 10.1016/j.cclet.2015.01.038
[Abstract](309) [FullText HTML] [PDF 1817KB](0)
In recent years, cancer has become the number two cause of death around the world, and scientists have exploited various treatment maps. Calixarenes, with diversified features, have been widely applied into drug delivery systems, which can respond to multi-stimuli and exhibit excellent performance. In this mini-review, we summarize the recent advances on controlled drug delivery systems based on calixarenes, in the form of inclusion complexes, amphiphilic self-assembly nanocarriers including micelles, hydrogels, vesicles and liposomes, and supramolecular nanovalves on mesoporous silica nanomaterials.
Comparative studies on molecular induced aggregation of hepta-imidazoliumyl-β-cyclodextrin towards anionic surfactants
Di Zhao , Yong Chen , Yu Liu
2015, 26(7): 829-833  doi: 10.1016/j.cclet.2014.11.028
[Abstract](199) [FullText HTML] [PDF 1448KB](0)
A b-cyclodextrin derivative bearing seven cationic arms and its singly charged analogue, i.e., per-6- deoxy-6-(1-methylimidazol-3-ium-3-yl)-β-cyclodextrin (3) and mono-6-deoxy-6-(1-methylimidazol-3-ium-3-yl)-β-cyclodextrin (4) were synthesized and fully characterized. Their induced aggregation behaviours towards two anionic surfactant, that is, sodium dodecyl sulfonate (SDS) and dioctyl sodium sulfosuccinate (Aerosol OT, AOT), were investigated by UV-vis, NMR, Zeta-potential, dynamic light scattering (DLS), and transmission electron microscopy. The results revealed that host 3 can induce the molecular aggregation of anionic surfactant at concentration far lower than its original CAC, leading to the larger diameter, the narrower size distribution and the higher thermal stability of the induced aggregate towards the anionic surfactant possessing more hydrophobic tails.
Synthesis and application of Vis/NIR dialkylaminophenylbuta-1, 3-dienyl borondipyrromethene dyes
Peng-Cheng Shi , Xin-Dong Jiang , Rui-Na Gao , Yuan-Yuan Dou , Wei-Li Zhao
2015, 26(7): 834-838  doi: 10.1016/j.cclet.2014.11.010
[Abstract](206) [FullText HTML] [PDF 1307KB](0)
Mono- and bis-dialkylaminophenylbuta-1,3-dienyl boron-dipyrromethenes (BODIPYs) 1-12 were synthesized in 36%-42% yields by a Knoevenagel-type condensation. The absorption and emission maxima (λlabs = 614-739 nm; (λlem = 655-776 nm in CHCl3) of 1-12 covered from the visuble to the nearinfrared region. Probe 1 was ratiometric Vis pH probes. Such probe was almost non-fluorescent. Upon the protonation of the tertiary amine function of 1, the strong fluorescence (φf = 0.97) was released and the florescence intensity was dramatically increased by one thousand folds. The sharp isosbestic points were discovered at 590 nm, which was a ratiometric pH probe.
Synthesis and structures of triptycene-derived Tröger's base molecular clips
Peng-Fei Li , Ying Han , Chuan-Feng Chen
2015, 26(7): 839-842  doi: 10.1016/j.cclet.2015.01.031
[Abstract](215) [FullText HTML] [PDF 1200KB](0)
A series of triptycene-derived Tröger's bases with molecular clip shaped structures have been conveniently and efficiently synthesized by one-pot condensation of corresponding amino-substituted triptycenes with paraformaldehyde in the presence of trifluoroacetic acid, and their structures have been characterized by NMR, MALDI-TOF MS spectra, elemental analyses and single-crystal X-ray diffraction.
Monofunctionalized pillar[5]arene-based stable [1]pseudorotaxane
Cai-Li Sun , Jiang-Fei Xu , Yu-Zhe Chen , Li-Ya Niu , Li-Zhu Wua , Chen-Ho Tung , Qing-Zheng Yang
2015, 26(7): 843-846  doi: 10.1016/j.cclet.2015.05.030
[Abstract](235) [FullText HTML] [PDF 1584KB](0)
We reported a new monofunctionalized pillar[5]arene bearing imidazolium moiety that formed stable [1]pseudorotaxane even at high concentration (100 mmol/L) in chloroform. The self-assembly was detailed investigated by multiple methods, including varying concentration 1H NMR, 2D COSY NMR, 2D NOESY NMR, viscosity measurements, 2D DOSY NMR, and HR-ESI-MS analysis. [1]Rotaxane was obtained efficiently through photo thiol-ene reaction which further confirmed the formation of [1]pseudorotaxane.
A facile approach to prepare hybrid nanoparticles with morphology controlled by the thickness of glyco-shell
Wei-Yi Zhang , Guo-Song Chen
2015, 26(7): 847-850  doi: 10.1016/j.cclet.2015.05.022
[Abstract](201) [FullText HTML] [PDF 2264KB](0)
Herein, we designed a novel amphiphilic triblock glycopolymer poly(oligo(ethyleneglycol) methacrylate)- block-poly(maltopyranoside methacrylate)-block-polystyrene (POMA-b-PMal-b-PS) via the combination of reversuble addition-fragmentation chain transfer (RAFT) polymerization and postpolymerization modification. The micelles with core-shell-corona structures were prepared by direct self-assembly of this glycopolymer in water. We found that these micelles can be used in in situ formation and stabilization of AuNPs. By controlling the thickness of glyco-shell, we successfully obtained Janus particles and raspberry-like particles with AuNPs in the sugar shell.
A light-regulated synthetic ion channel constructed by an azobenzene modified hydraphile
Rong-Yan Yang , Chun-Yan Bao , Qiu-Ning Lin , Lin-Yong Zhu
2015, 26(7): 851-856  doi: 10.1016/j.cclet.2015.05.010
[Abstract](230) [FullText HTML] [PDF 1128KB](0)
Biological ion channels are key molecules for cellular regulation and communication. To mimic the structure and functions of nature ion channels, a new class of light-regulated transmembrane ion channels was reported based on tri(macrocycle) hydraphile and azobenzene photoswitch (hydraphile 1). The liposome-based proton transport assays showed that hydraphile 1 exhibited excellent transmembrane activity (Y), and Ymax arrived 0.7 at 40 mmol/L. The successful isomerization of azobenzene moiety was confirmed and qualified by UV and NMR spectra. Upon alternative irradiation of 365 nm UV light and 450 nm visuble light, the transmembrane activity of hydraphile 1 was regulated between 0.35 and 0.5, reversubly. All the obtained results have demonstrated the promise of developing excellent synthetic ion channels with ion gating properties based on simple molecular design.
Synthesis, self-assembly and photo-responsive behavior of AB2 shaped amphiphilic azo block copolymer
Ren-Bo Wei , Xiao-Gong Wang , Ya-Ning He
2015, 26(7): 857-861  doi: 10.1016/j.cclet.2015.04.019
[Abstract](246) [FullText HTML] [PDF 3306KB](0)
In this work, we report the synthesis of AB2 shaped amphiphilic azo block copolymer by macromolecular azo coupling reaction. The product and intermediates were characterized by various methods. The selfassembly in selected solvents and photo-responsive behavior of the copolymer were studied bymeans of UV-vis spectrophotometry and TEM. Spherical aggregates can be obtained by gradually adding water into the solution of this amphiphilic azo block copolymer. Upon irradiation with polarized UV (365 nm) light, the aggregates can be elongated in the polarized direction.
Redox-responsive supramolecular nanoparticles based on amphiphilic sulfonatocalixarene and selenocystamine dihydrochloride
Xin-Yue Hu , Yong Chen , Yu Liu
2015, 26(7): 862-866  doi: 10.1016/j.cclet.2015.01.003
[Abstract](221) [FullText HTML] [PDF 1540KB](0)
A supramolecular nanoparticle was fabricated based on the aggregation of amphiphilic p-sulfonatocalixarene induced by selenocystamine dihydrochloride (Se-Cys). The application of Se-Cys remarkably decreases the critical aggregation concentration of sulfonatocalixarene, and the resultant spherical nanoparticle was investigated by fluorescence spectroscopy, dynamic laser scattering, and transmission electron microscopy. Owing to the property of Se-Cys, the nanoparticles showed the redoxresponsive disassembly behaviors with the addition of H2O2 and GSH.
A cucurbit[8]uril recognized rigid supramolecular polymer with photo-stimulated responsiveness
Tian-Tian Cao , Xu-Yang Yao , Jing Zhang , Qiao-Chun Wang , Xiang Ma
2015, 26(7): 867-871  doi: 10.1016/j.cclet.2015.01.032
[Abstract](218) [FullText HTML] [PDF 2170KB](0)
A rigid supramolecular polymer was constructed in aqueous solution via cucurbit[8]uril (CB[8]) host recognition with a rigid monomer containing an azobenzene unit and two 4,40-bipyridin-1-ium (BP) moieties in the two ends, which also exhibited photo-responsiveness owing to the photoinduced transcis isomerization of azobenzene group.
Synthesis and self-assembly behavior of 2,5-diphenylethynyl thiophene based bolaamphiphiles
Shou-Bing Yi , Hong-Fei Gao , Quan Li , Ya-Fei Ye , Na Wu , Xiao-Hong Cheng
2015, 26(7): 872-876  doi: 10.1016/j.cclet.2015.05.031
[Abstract](257) [FullText HTML] [PDF 2870KB](0)
Novel T-shaped bolaamphiphiles consisting of a bent 2,5-diphenylethynyl thiophene rigid core with two terminal glycerol units and a lateral n-alkyl chain have been synthesized via Kumuda and Sonogashira coupling reactions as key steps. Their liquid crystalline behavior was investigated by polarizing optical microscopy (POM), differential scanning calorimetry (DSC), and X-ray diffraction (XRD). All such bolaamphiphiles can self-organize into square honeycomb LC phases with p4mm symmetries in the presence of water. UV and PL measurements indicate fluorescent properties making them potential candidates for application in fluorescence sensor devices.
Tetraphenylethene based zinc complexes as fluorescent chemosensors for pyrophosphate sensing
Hao-Ran Xu , Kun Li , Shu-Yan Jiao , Ling-Ling Li , Sheng-Lin Pan , Xiao-Qi Yu
2015, 26(7): 877-880  doi: 10.1016/j.cclet.2015.05.037
[Abstract](211) [FullText HTML] [PDF 1664KB](0)
We described a serious of zinc complexes that exhibit characteristic fluorescence responses toward pyrophosphate (PPi) and adenosine triphosphate (ATP) in aqueous media. These novel probes exploited tetraphenylethene (TPE) as fluorophore and macrocycle-polyamine (including 1,4,7,10-tetraazacyclododecane and 1,4,7-triazacyclononane) Zn(II) complexes as binding group. These “OFF-ON” type probes exhibited promising selectivity and sensitivity to PPi and ATP via a restriction of intramolecular rotation (RIR) mechanism. The detection limit for PPi was found within nmol/L range.
Direct one-pot synthesis of zolimidine pharmaceutical drug and imidazo[1,2-a]pyridine derivatives via I2/CuO-promoted tandem strategy
Qun Cai , Mei-Cai Liu , Bi-Ming Mao , Xuan Xie , Feng-Cheng Jia , Yan-Ping Zhu , An-Xin Wu
2015, 26(7): 881-884  doi: 10.1016/j.cclet.2014.12.016
[Abstract](204) [FullText HTML] [PDF 1977KB](0)
An efficient one-pot synthetic protocol was developed for the synthesis of imidazo[1,2-a]pyridines from easily available starting materials: Aromatic ketones, α,β-unsaturated ketones, β-keto esters and 2- aminopyridines. The present reaction proceeded well in MeOH under the media of I2/CuO. By using this method, themarketed drug zolimidine could be prepared easily with 95% yield. All these target products were characterized by NMR, HRMS and IR spectra. Furthermore, the target compound 3fa was determined by X-ray crystallographic analysis.
A switchable bistable [2]rotaxane based on phosphine oxide functional group
Shuang-Jin Zhang , Qi Wang , Ming Cheng , Xiao-Hong Qian , Yang Yang , Ju-Li Jiang , Le-Yong Wang
2015, 26(7): 885-888  doi: 10.1016/j.cclet.2015.05.015
[Abstract](209) [FullText HTML] [PDF 1853KB](0)
A switchable bistable rotaxane based phosphine oxide functional group-containingmacrocycle has been constructed successfully, in which the macrocycle can be easily switched between dibenzylammonium and triazole recognition sites by using the simple base/acid stimuli.
Convenient synthesis of spiro[indoline-3,4'-pyrano[2,3-c]pyrazole] and spiro[acenaphthyl-3,4'-pyrano[2,3-c]pyrazoles] via fourcomponent reaction
Chao Wang , Yan-Hong Jiang , Chao-Guo Yan
2015, 26(7): 889-893  doi: 10.1016/j.cclet.2015.05.018
[Abstract](204) [FullText HTML] [PDF 747KB](0)
The domino four-component reaction of hydrated hydrazine, dimethyl acetylenedicarboxylate, isatin and malononitrile or ethyl cycanoacetate in ethanol in the presence of triethylamine afforded the polysubstituted spiro[indoline-3,4'-pyrano[2,3-c]pyrazole] derivatives in satisfactory yields. Under similar conditions, the four-component reaction containing acenaphthenequinone also resulted in the spiro[acenaphthyl-3,4'-pyrano[2,3-c]pyrazole] in good yields.
[12]aneN3-based BODIPY as a selective and sensitive off–on sensor for the sequential recognition of Cu2+ ions and ADP
Ying Zhang , Yong-Guang Gao , You-Di Shi , Lian-Qian Tan , Jessica S. Yue , Zhong-Lin Lu
2015, 26(7): 894-898  doi: 10.1016/j.cclet.2015.05.032
[Abstract](233) [FullText HTML] [PDF 1993KB](0)
A new [12]aneN3-based BODIPY sensor 1 showed highly selective and sensitive recognition of Cu2+ ions through fluorescence quenching effect in aqueous solution. The above copper complex solution can further be used as a turn-on fluorescent probe for detecting ADP with high selectivity, and also applied in imaging of living cells.
Modulation of photovoltaic behavior of dye-sensitized solar cells by electron donors of porphyrin dyes and cosensitization
Bin Chen , Lu Sun , Yong-Shu Xie
2015, 26(7): 899-904  doi: 10.1016/j.cclet.2015.04.021
[Abstract](246) [FullText HTML] [PDF 902KB](0)
Porphyrin dyes have received great attention due to their excellent photovoltaic performance in dyesensitized solar cells (DSSCs). In this work, dyes XC1-XC3 were synthesized by introducing various numbers of bis(4-methoxyphenyl)amino and p-hexyloxyphenyl groups to porphyrin meso-positions. The XC1 molecule contains two p-hexyloxyphenyl groups, and its DSSCs showed the power conversion efficiency of 4.81%. For XC2 and XC3, the replacement of p-hexyloxyphenyl with diphenylamino groups can effectively enhance the light harvesting around 500 nm. However, the highest occupied molecular orbitals (HOMOs) were elevated too much, which suppressed the dye regeneration processes, leading to low cell efficiencies of 2.51% and 1.27% for XC2, and XC3, respectively. To further improve the cell performance, an anthracene derivative C1 was used as the cosensitizer for XC1, which increased both the Jsc and Voc values, with an improved efficiency of 5.75%.
Dielectric relaxation behavior of SDS/β-CD organized self-assembly in dilute aqueous solution
Ya-Wen Zhou , Meng-Yuan Wang , Wei Zhou , Fu Han , Bao-Cai Xu
2015, 26(7): 905-908  doi: 10.1016/j.cclet.2015.05.014
[Abstract](196) [FullText HTML] [PDF 2200KB](0)
Dielectric relaxation behavior of SDS/β-CD self-organized with mass concentrations from 1% to 7% was investigated. The phase microstructure of SDS/β-CD aqueous solution was confirmed by analyzing the dielectric parameters. The dielectric relaxation behavior was attributed to the interfacial polarization between vesicle and medium, and the relaxation distribution parameter can indicate the shape transition from vesicles to microtubules with increasing concentration. Dielectric relaxation provided a new method to study surfactant organized self-assembly.
Novel nanoparticles composed of chitosan and β-cyclodextrin derivatives as potential insoluble drug carrier
Yan-Zuo Chen , Yu-Kun Huang , Yuan Chen , Ya-Jing Ye , Kai-Yan Lou , Feng Gao
2015, 26(7): 909-913  doi: 10.1016/j.cclet.2015.05.044
[Abstract](197) [FullText HTML] [PDF 1224KB](0)
This research was aim to develop novel cyclodextrin/chitosan (CD/CS) nanocarriers for insoluble drug delivery through themild ionic gelation method previously developed by our lab. A series of different bcyclodextrin (β-CD) derivatives were incorporated into CS nanoparticles including hydroxypropyl-bcyclodextrin (HP-β-CD), sulphobutylether-β-cyclodextrin (SB-β-CD), and 2,6-di-O-methy-β-cyclodextrin (DM-β-CD). Various process parameters for nanoparticle preparation and their effects on physicochemical properties of CD/CS nanoparticles were investigated, such as the type of CD derivatives, CD and CS concentrations, the mass ratio of CS to TPP (CS/TPP), and pH values. In the optimal condition, CD/CS nanoparticles were obtained in the size range of 215-276 nm and with the zeta potential from 30.22 mV to 35.79 mV. Moreover, the stability study showed that the incorporation of CD rendered the CD/CS nanocarriers more stable than CS nanoparticles in PBS buffer at pH 6.8. For their easy preparation and adjustable parameters in nanoparticle formation as well as the diversified hydrophobic core of CD derivatives, the novel CD/CS nanoparticles developed herein might represent an interesting and versatile drug delivery platform for a variety of poorly water-soluble drugs with different physicochemical properties.
Synthesis and structures of malonate derivative-calix[4]arene conjugates
Wen-Jing Hu , Ming-Liang Ma , Yahu A. Liu , Jiu-Sheng Li , Biao Jiang , Ke Wen
2015, 26(7): 914-917  doi: 10.1016/j.cclet.2015.05.017
[Abstract](219) [FullText HTML] [PDF 618KB](0)
A series of malonate derivatives-calix[4]arene conjugates were synthesized through Knoevenagel condensation reaction between formyl-tetrapropoxycalix[4]arene and malonate derivatives. The structures of the resulting malonate derivative functionalized calix[4]arenes were characterized by NMR spectroscopy, mass spectrometry and even single crystal X-ray diffraction analysis.
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