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2018 Volume 81 Issue 4
2018, 81(4): 291-296
Abstract:
The micro/nanomotors are nanometer or micrometer-sized devices which can be activated by chemical reactions or external physical energy sources (light energy, sound energy, electric energy, magnetic energy etc.). The activated micro/nanomotors display rotation, rolling, shuttling, delivery, contraction, or collective behavior. The device has the advantages of small volume, good controllability, simple preparation and so on, and has shown good application prospects in many fields such as self-assembly of nano-particles, degradation of polymers, drug transport and water pollution control. The aggregation and dispersion of micro-nanomotors is a very important group behavior of motor. When aggregated, the efficiency of motors can be greatly improved. In dispersed state, they can also become independent individuals, and exercise their own missions. This article will outline the important research progress and the latest research results of micro-nano motors in gathering and dispersing behavior in recent years, and give a detailed description of the conversion process and its mechanism under different stimuli, which can provide some reference for the in-depth study of micro-nano motor dynamic behavior.
The micro/nanomotors are nanometer or micrometer-sized devices which can be activated by chemical reactions or external physical energy sources (light energy, sound energy, electric energy, magnetic energy etc.). The activated micro/nanomotors display rotation, rolling, shuttling, delivery, contraction, or collective behavior. The device has the advantages of small volume, good controllability, simple preparation and so on, and has shown good application prospects in many fields such as self-assembly of nano-particles, degradation of polymers, drug transport and water pollution control. The aggregation and dispersion of micro-nanomotors is a very important group behavior of motor. When aggregated, the efficiency of motors can be greatly improved. In dispersed state, they can also become independent individuals, and exercise their own missions. This article will outline the important research progress and the latest research results of micro-nano motors in gathering and dispersing behavior in recent years, and give a detailed description of the conversion process and its mechanism under different stimuli, which can provide some reference for the in-depth study of micro-nano motor dynamic behavior.
2018, 81(4): 297-302, 348
Abstract:
Compared with traditional metal-organic frameworks (MOFs), the amino functionalized MOFs are very attractive materials. They have both the advantages of MOFs and amino functional groups, such as high specific surface area, adjustable pore size, and easy post-modification. Novel functionalized MOFs, which have potential applications in gas storage, drug carriers, selective adsorption of gas molecules and catalysis, can be obtained through some simple chemical reactions. This paper summarizes the recent research progress of amino functionalized MOFs in catalysis and adsorption fields, including their preparation methods, influencing factors, environmental applications. Finally, the future development of amino functionalized MOFs is also prospected.
Compared with traditional metal-organic frameworks (MOFs), the amino functionalized MOFs are very attractive materials. They have both the advantages of MOFs and amino functional groups, such as high specific surface area, adjustable pore size, and easy post-modification. Novel functionalized MOFs, which have potential applications in gas storage, drug carriers, selective adsorption of gas molecules and catalysis, can be obtained through some simple chemical reactions. This paper summarizes the recent research progress of amino functionalized MOFs in catalysis and adsorption fields, including their preparation methods, influencing factors, environmental applications. Finally, the future development of amino functionalized MOFs is also prospected.
2018, 81(4): 303-311
Abstract:
Arylnaphthalene lignan lactones, widely distributed in plants, are a class of natural products containing the phenyl-naphthyl skeleton. These compounds have attracted considerable attention of many scientists for decades because of their wide biological activities. This article reviews the recent progress in chemical synthesis of α-arylnaphthalene lignan lactones since 1980, aiming to provide references for the syntheses and clinical development of α-arylnaphthalene lignan lactones.
Arylnaphthalene lignan lactones, widely distributed in plants, are a class of natural products containing the phenyl-naphthyl skeleton. These compounds have attracted considerable attention of many scientists for decades because of their wide biological activities. This article reviews the recent progress in chemical synthesis of α-arylnaphthalene lignan lactones since 1980, aiming to provide references for the syntheses and clinical development of α-arylnaphthalene lignan lactones.
2018, 81(4): 312-318, 379
Abstract:
The chemical conversion of carbon dioxide, a non-toxic, non-flammable, abundant and cheap renewable C1 resource, into high value-added organic compounds has become an important strategy for sustainable development. Among various transformations, CO2 as the carboxylating agent for the synthesis of carboxylic acids and derivatives has attracted much attention in the field of activation and conversion of CO2. This review summarizes the progress in carboxylation of unsaturated hydrocarbons with CO2 catalyzed by transition-metal catalysis in recent years.
The chemical conversion of carbon dioxide, a non-toxic, non-flammable, abundant and cheap renewable C1 resource, into high value-added organic compounds has become an important strategy for sustainable development. Among various transformations, CO2 as the carboxylating agent for the synthesis of carboxylic acids and derivatives has attracted much attention in the field of activation and conversion of CO2. This review summarizes the progress in carboxylation of unsaturated hydrocarbons with CO2 catalyzed by transition-metal catalysis in recent years.
2018, 81(4): 319-325
Abstract:
As a low-temperature eutectic mixture, deep eutectic solvent (DES) with some remarkable properties such as low cost, negligible vapor pressure, non-toxicity, non-flammablility, biodegradablity, adjustablility and recyclability, which makes DES gradually become a new type of green solvent or catalyst. In this paper, the composition and classification of DES were introduced, and the applications of DES as a solvent or catalyst in some organic reactions, including addition, substitution, coupling, condensation, cyclization, esterification, multi-component and depolymerization reactions, were reviewed. Finally, the prospect of DES in organic reactions is forecasted.
As a low-temperature eutectic mixture, deep eutectic solvent (DES) with some remarkable properties such as low cost, negligible vapor pressure, non-toxicity, non-flammablility, biodegradablity, adjustablility and recyclability, which makes DES gradually become a new type of green solvent or catalyst. In this paper, the composition and classification of DES were introduced, and the applications of DES as a solvent or catalyst in some organic reactions, including addition, substitution, coupling, condensation, cyclization, esterification, multi-component and depolymerization reactions, were reviewed. Finally, the prospect of DES in organic reactions is forecasted.
2018, 81(4): 326-331, 383
Abstract:
Noncovalent interactions are utilized as the driving force to construct supramolecular polymers (SPs). Due to the dynamic and reversible natures, SPs have drawn increasing attention in the field of stimuli-responsive polymeric materials. As one of host molecules, cyclodextrin can form complexes with ferrocene, azobenzene, adamantine or benzene molecules which possess the proper size through host-guest inclusion interaction. The obtained SPs display fascinating property such as stimuli-responsive property, low cytotoxicity and good biocompatibility, which may further applied in the field of drug/gene delivery. Based on the biomedical application of cyclodextrin-based SPs, the main contents are summarized including three aspects as following, cyclodextrin-based SPs used in the drug controlled release, cyclodextrin-based SPs used in the gene transfection, cyclodextrin-based SPs used in the drug/gene co-delivery. Furthermore, new research trends are also expected on the progress of this kind of SPs.
Noncovalent interactions are utilized as the driving force to construct supramolecular polymers (SPs). Due to the dynamic and reversible natures, SPs have drawn increasing attention in the field of stimuli-responsive polymeric materials. As one of host molecules, cyclodextrin can form complexes with ferrocene, azobenzene, adamantine or benzene molecules which possess the proper size through host-guest inclusion interaction. The obtained SPs display fascinating property such as stimuli-responsive property, low cytotoxicity and good biocompatibility, which may further applied in the field of drug/gene delivery. Based on the biomedical application of cyclodextrin-based SPs, the main contents are summarized including three aspects as following, cyclodextrin-based SPs used in the drug controlled release, cyclodextrin-based SPs used in the gene transfection, cyclodextrin-based SPs used in the drug/gene co-delivery. Furthermore, new research trends are also expected on the progress of this kind of SPs.
2018, 81(4): 332-338
Abstract:
A facile method was developed for reductive loading of well-dispersed noble metal (Pd, Ag, Ru and Au) nanoparticles on layered double hydroxide (LDH). It involves the preparation of formate-LDH by coprecipitation and the subsequent in situ reduction of noble metal precursors by interlayer formate anion. Nanoparticles from both anionic (Au) and cationic (Pd, Ag, Ru) precursors could be loaded successfully, demonstrating the feasibility of this method. In addition, as an example, the obtained Pd/LDH shows a good activity for Suzuki cross-coupling reaction, suggesting potential catalytical application of prepared composites.
A facile method was developed for reductive loading of well-dispersed noble metal (Pd, Ag, Ru and Au) nanoparticles on layered double hydroxide (LDH). It involves the preparation of formate-LDH by coprecipitation and the subsequent in situ reduction of noble metal precursors by interlayer formate anion. Nanoparticles from both anionic (Au) and cationic (Pd, Ag, Ru) precursors could be loaded successfully, demonstrating the feasibility of this method. In addition, as an example, the obtained Pd/LDH shows a good activity for Suzuki cross-coupling reaction, suggesting potential catalytical application of prepared composites.
2018, 81(4): 339-343
Abstract:
A novel one-dimensional Ag(Ⅰ) coordination polymer, [Ag(C10H9N6Cl)(NO3)]n (1), was synthesized by the reaction of 4-chloro-6-[2-(pyrazin-2-ylmethylene) hydrazinyl] pyrimidine (HL) with silver nitrate. In complex 1, the HL ligands are arranged alternately to link the Ag(Ⅰ) ion through N5 atom from the pyrazine ring and N1, N4, N6 atoms from another ligand, leading to an extended zigzag chain coordination structure. Furthermore, the zigzag one-dimensional chains are extended into a supramolecular architecture via N-H…O and N-H…N hydrogen-bond interactions and π-π stacking interactions. The complex 1 was found to have superior radical scavenging potency against superoxide anion and hydroxyl than free HL. The antibacterial effects of complex 1 against different bacteria were also better than that of free HL.
A novel one-dimensional Ag(Ⅰ) coordination polymer, [Ag(C10H9N6Cl)(NO3)]n (1), was synthesized by the reaction of 4-chloro-6-[2-(pyrazin-2-ylmethylene) hydrazinyl] pyrimidine (HL) with silver nitrate. In complex 1, the HL ligands are arranged alternately to link the Ag(Ⅰ) ion through N5 atom from the pyrazine ring and N1, N4, N6 atoms from another ligand, leading to an extended zigzag chain coordination structure. Furthermore, the zigzag one-dimensional chains are extended into a supramolecular architecture via N-H…O and N-H…N hydrogen-bond interactions and π-π stacking interactions. The complex 1 was found to have superior radical scavenging potency against superoxide anion and hydroxyl than free HL. The antibacterial effects of complex 1 against different bacteria were also better than that of free HL.
2018, 81(4): 344-348
Abstract:
As it is well known that the performance of electrode materials are highly related to particle size, morphology and configuration, it is essential to build controllable synthesis strategies for the electrode materials. In this work, valuable explorations have been carried out on the size and morphology control of LiFePO4 nano-materials in ethylene glycol solution, and their electrochemical performances were carefully characterized. By changing the concentration of the reagents, the sizes of obtained LiFePO4 nano-materials were altered. When the concentration of FeSO4 reagent reached 0.15mol/L, the obtained LiFePO4 nano-materials showed the minimum size and highest specific capability. By adding different amount of glucose, the morphology of the obtained LiFePO4 nano-materials were changed, but the electrochemical performance of these materials were not obviously influenced.
As it is well known that the performance of electrode materials are highly related to particle size, morphology and configuration, it is essential to build controllable synthesis strategies for the electrode materials. In this work, valuable explorations have been carried out on the size and morphology control of LiFePO4 nano-materials in ethylene glycol solution, and their electrochemical performances were carefully characterized. By changing the concentration of the reagents, the sizes of obtained LiFePO4 nano-materials were altered. When the concentration of FeSO4 reagent reached 0.15mol/L, the obtained LiFePO4 nano-materials showed the minimum size and highest specific capability. By adding different amount of glucose, the morphology of the obtained LiFePO4 nano-materials were changed, but the electrochemical performance of these materials were not obviously influenced.
2018, 81(4): 349-354
Abstract:
The titled hybrid solid solutions with different thickness and size were successfully synthesized by changing the atomic ratio of S/(Zn+Cd) in the hydrothermal reaction. The results showed that the content of thiourea amount in solvent has an important effect on the composition and structure, photoelectric property and hydrophilic property of the prepared solid solutions. With the increase of thiourea amount in the reaction system, the nanosheet solid solutions were gradually formed. Fluorescence emission spectra (photoluminescence spectra) and photocatalytic activity tests showed that the proper S/(Zn+Cd) atomic ratio can improve the separation efficiency of photogenerated electrons and holes, resulting in the superior photocatalytic activity. Under visible light irradiation, the titled solid solution exhibites the highest hydrogen yield of 12100μmol·h-1·g-1 at S/(Zn+Cd) of 4.75. The improved photocatalytic activity is mainly related to the less surface defects, suitable morphology, and high separation efficiency of photo-generated electrons and holes.
The titled hybrid solid solutions with different thickness and size were successfully synthesized by changing the atomic ratio of S/(Zn+Cd) in the hydrothermal reaction. The results showed that the content of thiourea amount in solvent has an important effect on the composition and structure, photoelectric property and hydrophilic property of the prepared solid solutions. With the increase of thiourea amount in the reaction system, the nanosheet solid solutions were gradually formed. Fluorescence emission spectra (photoluminescence spectra) and photocatalytic activity tests showed that the proper S/(Zn+Cd) atomic ratio can improve the separation efficiency of photogenerated electrons and holes, resulting in the superior photocatalytic activity. Under visible light irradiation, the titled solid solution exhibites the highest hydrogen yield of 12100μmol·h-1·g-1 at S/(Zn+Cd) of 4.75. The improved photocatalytic activity is mainly related to the less surface defects, suitable morphology, and high separation efficiency of photo-generated electrons and holes.
2018, 81(4): 355-360
Abstract:
Based on the diversity of the structures of cantharidin derivatives and their excellent anti-hepatoma activity, thirty-five cantharidin derivatives have been synthesized starting from furan and maleic anhydride. The anti-hepatoma activities in vitro of the synthesized compounds were evaluated against HepG2 cell by the MTT assay. The biological results demonstrated that compounds 6d, 6f, 6g, 6h and 6i were commensurate with cisplatin in anti-hepatoma activity. The cantharidin imides showed good anti-hepatoma activity on the whole. When the substituent are electron withdrawing groups or nitrogen containing heterocycles, the compounds showed higher anti-hepatoma activity, so they may have potential application in anti-hepatoma drug discovery.
Based on the diversity of the structures of cantharidin derivatives and their excellent anti-hepatoma activity, thirty-five cantharidin derivatives have been synthesized starting from furan and maleic anhydride. The anti-hepatoma activities in vitro of the synthesized compounds were evaluated against HepG2 cell by the MTT assay. The biological results demonstrated that compounds 6d, 6f, 6g, 6h and 6i were commensurate with cisplatin in anti-hepatoma activity. The cantharidin imides showed good anti-hepatoma activity on the whole. When the substituent are electron withdrawing groups or nitrogen containing heterocycles, the compounds showed higher anti-hepatoma activity, so they may have potential application in anti-hepatoma drug discovery.
2018, 81(4): 361-365, 383
Abstract:
Artificial polymers of amino acids, polypeptides, show the advantages of biocompatibility and biodegradability. In this study, the oligo-L-phenylalanine was prepared by the polymerization reaction of bromelain from L-phenylalanine methyl ester in the non-aqueous media under mild conditions. The structure and polymerization degree of the oligo-L-phenylalanine were elucidated by FT-IR, 1H-NMR, MS and MALDI-TOF. The optimum polymerization conditions were evaluated through single-factor approach. The highest value of yield, 35.67%, could be achieved when 0.43g L-phenylalanine methyl ester hydrochloride in 15% DMSO phosphate buffer (pH=8.0) was polymerized by 2.44U bromelain at 40℃ for 3 hours.
Artificial polymers of amino acids, polypeptides, show the advantages of biocompatibility and biodegradability. In this study, the oligo-L-phenylalanine was prepared by the polymerization reaction of bromelain from L-phenylalanine methyl ester in the non-aqueous media under mild conditions. The structure and polymerization degree of the oligo-L-phenylalanine were elucidated by FT-IR, 1H-NMR, MS and MALDI-TOF. The optimum polymerization conditions were evaluated through single-factor approach. The highest value of yield, 35.67%, could be achieved when 0.43g L-phenylalanine methyl ester hydrochloride in 15% DMSO phosphate buffer (pH=8.0) was polymerized by 2.44U bromelain at 40℃ for 3 hours.
2018, 81(4): 366-371
Abstract:
Gemini surfactants can be used as surface stabilizers for preparing gold nanoparticles (AuNPs) due to their special structures. The particle size and stability of AuNPs were affected by different spacers in the structure of gemini surfactants significantly. Gold nanoparticle colloids were prepared with the gemini surfactants (16-n-16, n=2, 3, 4 and 6). The effect of pH value on the stability of AuNPs in the dispersion systems was investigated. The catalytic property of the AuNPs on hydrogenation of 4-nitrophenol was studied. 16-4-16 and 16-3-16 have good effect on stabilizing AuNPs. 16-3-16-AuNPs showed the best stability in different pH environment. The catalytic activity of 16-4-16-AuNPs in 4-nitrophenol hydrogen reduction reaction was better than others.
Gemini surfactants can be used as surface stabilizers for preparing gold nanoparticles (AuNPs) due to their special structures. The particle size and stability of AuNPs were affected by different spacers in the structure of gemini surfactants significantly. Gold nanoparticle colloids were prepared with the gemini surfactants (16-n-16, n=2, 3, 4 and 6). The effect of pH value on the stability of AuNPs in the dispersion systems was investigated. The catalytic property of the AuNPs on hydrogenation of 4-nitrophenol was studied. 16-4-16 and 16-3-16 have good effect on stabilizing AuNPs. 16-3-16-AuNPs showed the best stability in different pH environment. The catalytic activity of 16-4-16-AuNPs in 4-nitrophenol hydrogen reduction reaction was better than others.
2018, 81(4): 372-375
Abstract:
Bamboo charcoal modified by polyaspartic acid (PAsp) was used for the removal of cadmium from shellfish enzymatic hydrolysates. The effects of pH, adsorption time, bamboo charcoal dosage and temperature on the cadmium removal rate were investigated, and the conditions of cadmium removal were optimized by response surface method. The cadmium removal rate was up to 96.59% when pH is 5.0, adsorption time is 25 min, and the bamboo charcoal dosage is 0.26g in 10mL enzymatic hydrolysate. Therefore, PAsp modified bamboo charcoal can significantly improve the efficiency and ability of adsorbing cadmium, and can be used for the removal of cadmium from shellfish enzymatic hydrolysates.
Bamboo charcoal modified by polyaspartic acid (PAsp) was used for the removal of cadmium from shellfish enzymatic hydrolysates. The effects of pH, adsorption time, bamboo charcoal dosage and temperature on the cadmium removal rate were investigated, and the conditions of cadmium removal were optimized by response surface method. The cadmium removal rate was up to 96.59% when pH is 5.0, adsorption time is 25 min, and the bamboo charcoal dosage is 0.26g in 10mL enzymatic hydrolysate. Therefore, PAsp modified bamboo charcoal can significantly improve the efficiency and ability of adsorbing cadmium, and can be used for the removal of cadmium from shellfish enzymatic hydrolysates.
2018, 81(4): 376-379
Abstract:
Based on the reported synthesis of perhydroxycucurbi[6]turil with cucurbituril-potassium persulfate system, the effect of adding KOH to the original system has been studied. Under the optimized reaction conditions, the desired product can be obtained in satisfactory yield (27%). The product was further identified by the 1H NMR, 13C NMR and HR-ESI-MS.
Based on the reported synthesis of perhydroxycucurbi[6]turil with cucurbituril-potassium persulfate system, the effect of adding KOH to the original system has been studied. Under the optimized reaction conditions, the desired product can be obtained in satisfactory yield (27%). The product was further identified by the 1H NMR, 13C NMR and HR-ESI-MS.
2018, 81(4): 380-383
Abstract:
Using methyl 4-bromophenylacetate as the starting material, Macitentan was synthesized by a 6-step reaction of nucleophilic substitution of carbon anion, ring-closing reaction, chlorination, nucleophilic substitution of nitrogen anion, nucleophilic substitution of oxygen anion, and the synthetic process was also optimized. The structures of the intermediates and products were confirmed by 1H-NMR and ESI-MS. The optimized process improves the purity of the intermediate, the operation is more simple and more conducive to industrial production.
Using methyl 4-bromophenylacetate as the starting material, Macitentan was synthesized by a 6-step reaction of nucleophilic substitution of carbon anion, ring-closing reaction, chlorination, nucleophilic substitution of nitrogen anion, nucleophilic substitution of oxygen anion, and the synthetic process was also optimized. The structures of the intermediates and products were confirmed by 1H-NMR and ESI-MS. The optimized process improves the purity of the intermediate, the operation is more simple and more conducive to industrial production.
