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2017 Volume 80 Issue 7
2017, 80(7): 603-610
Abstract:
Graphene has attracted great attention due to its excellent properties which is originated from its unique structure. In this paper, recent works on graphene thermal conduction have been summarized, and it seems that the defect, substrate used and the edge of graphene are the main factors which influence the thermal conduction property of graphene. In addition, the thermal conductivity modes simulated by molecular dynamics and non-equilibrium Green's function have also been included. Based on these theory modes, experimental methodology of the thermal conduction measurement of layered graphene were involved, and the results were provided.
Graphene has attracted great attention due to its excellent properties which is originated from its unique structure. In this paper, recent works on graphene thermal conduction have been summarized, and it seems that the defect, substrate used and the edge of graphene are the main factors which influence the thermal conduction property of graphene. In addition, the thermal conductivity modes simulated by molecular dynamics and non-equilibrium Green's function have also been included. Based on these theory modes, experimental methodology of the thermal conduction measurement of layered graphene were involved, and the results were provided.
2017, 80(7): 611-620
Abstract:
Porous metal oxides are used widely in catalysis, lithium ion battery, solar cell and gas sensor due to their high surface areas, large pore size, special morphology and structure characteristics. As a novel class of porous crystalline materials with periodic network structure, metal-organic frameworks (MOFs) are widely applied in gas storage, gas separation and catalysis. In recent years, the preparation of porous carbon and porous metal oxide using MOFs as precursors has become a new research hotspot in MOFs applications. This work reviews that porous metal oxides and metal oxides/carbon composites derived from MOFs are used as the catalysts for CO oxidation, hydrogen production, dehydrogenation of isobutane, oxidation of cyclohexene, direct oxidation of alcohols to esters, oxidative amidation of aldehydes, degradation of organic compounds and oxygen reduction.
Porous metal oxides are used widely in catalysis, lithium ion battery, solar cell and gas sensor due to their high surface areas, large pore size, special morphology and structure characteristics. As a novel class of porous crystalline materials with periodic network structure, metal-organic frameworks (MOFs) are widely applied in gas storage, gas separation and catalysis. In recent years, the preparation of porous carbon and porous metal oxide using MOFs as precursors has become a new research hotspot in MOFs applications. This work reviews that porous metal oxides and metal oxides/carbon composites derived from MOFs are used as the catalysts for CO oxidation, hydrogen production, dehydrogenation of isobutane, oxidation of cyclohexene, direct oxidation of alcohols to esters, oxidative amidation of aldehydes, degradation of organic compounds and oxygen reduction.
2017, 80(7): 621-630
Abstract:
Nowadays, liquid hydrogen storage, high pressure gaseous hydrogen storage, organic compounds hydrogen storage, metal hydride hydrogen storage, adsorption hydrogen storage and liquid phase chemical hydrogen storage materials are widely used for storage of hydrogen. Among these methods, the liquid phase chemical hydrogen storage materials attracted considerable attention due to their high hydrogen content, easy control of the hydrogen generation rate and hydrogen purity. The study on synthesis and catalytic activities of various kinds of catalyst for hydrogen production from liquid hydrogen storage materials has become a hot research topic. Owing to their low cost, abundance in earth and good catalytic performance, Co or Ni containing bi-or tri-metallic nanoparticles (NPs) have become the promising catalysts for hydrogen generation. In this review, the preparations and catalytic performances for hydrogen production of Co and Ni containing bi-or tri-metallic NPs are summarized in detail, the disadvantages and potential development directions of Co and Ni based bi-or tri-metallic NPs are also proposed.
Nowadays, liquid hydrogen storage, high pressure gaseous hydrogen storage, organic compounds hydrogen storage, metal hydride hydrogen storage, adsorption hydrogen storage and liquid phase chemical hydrogen storage materials are widely used for storage of hydrogen. Among these methods, the liquid phase chemical hydrogen storage materials attracted considerable attention due to their high hydrogen content, easy control of the hydrogen generation rate and hydrogen purity. The study on synthesis and catalytic activities of various kinds of catalyst for hydrogen production from liquid hydrogen storage materials has become a hot research topic. Owing to their low cost, abundance in earth and good catalytic performance, Co or Ni containing bi-or tri-metallic nanoparticles (NPs) have become the promising catalysts for hydrogen generation. In this review, the preparations and catalytic performances for hydrogen production of Co and Ni containing bi-or tri-metallic NPs are summarized in detail, the disadvantages and potential development directions of Co and Ni based bi-or tri-metallic NPs are also proposed.
2017, 80(7): 631-636, 620
Abstract:
Capacitive deionization (CDI) is currently widely applicable one of the desalination technologies owing to its advantages, such as energy efficiency, environmental protection and high practicability, etc. Electrode materials, as core of this technology, should have high specific surface area, better conductivity, good hydrophilicity, proper porous structure, excellent stability and so on. These properties would efficiently not only enhance desalination efficiency of CDI devices, but also keep excellent cycling stability, even in the complex systems. In the light of difference in preparation, structure-activity relationship of electrodes, the recent advances in the application of various functional electrode materials have been reviewed, combining with our previous work.
Capacitive deionization (CDI) is currently widely applicable one of the desalination technologies owing to its advantages, such as energy efficiency, environmental protection and high practicability, etc. Electrode materials, as core of this technology, should have high specific surface area, better conductivity, good hydrophilicity, proper porous structure, excellent stability and so on. These properties would efficiently not only enhance desalination efficiency of CDI devices, but also keep excellent cycling stability, even in the complex systems. In the light of difference in preparation, structure-activity relationship of electrodes, the recent advances in the application of various functional electrode materials have been reviewed, combining with our previous work.
2017, 80(7): 637-641, 683
Abstract:
Hollow carbon sphere (HCS) exhibits excellent physical and chemical properties such as high specific surface area and conductivity, good chemical stability and thermal conductivity, which makes it widely applied in electrochemical energy storage, electrochemical catalyze, electrochemical sensors, etc. Based on this, the synthesis methods of HCS and its recent applications in electrochemistry were summarized, and some critical challenges and prospects in this field were also discussed.
Hollow carbon sphere (HCS) exhibits excellent physical and chemical properties such as high specific surface area and conductivity, good chemical stability and thermal conductivity, which makes it widely applied in electrochemical energy storage, electrochemical catalyze, electrochemical sensors, etc. Based on this, the synthesis methods of HCS and its recent applications in electrochemistry were summarized, and some critical challenges and prospects in this field were also discussed.
2017, 80(7): 642-650
Abstract:
Owning to its good stability, easy preparation, high environmental tolerance, artificial enzymes had been used widely to improve the activity and the yield of natural enzymes. In this paper, according to the classification of artificial enzymes, the present progresses in the study of traditional mimic enzymes and nanomaterials mimic enzymes had been reviewed. The advantages and disadvantages of the artificial enzymes were discussed in detail, and its prospects were also described.
Owning to its good stability, easy preparation, high environmental tolerance, artificial enzymes had been used widely to improve the activity and the yield of natural enzymes. In this paper, according to the classification of artificial enzymes, the present progresses in the study of traditional mimic enzymes and nanomaterials mimic enzymes had been reviewed. The advantages and disadvantages of the artificial enzymes were discussed in detail, and its prospects were also described.
2017, 80(7): 651-655
Abstract:
A polyoxometalate compound [n-C5H10Ph3P]2[Mo6O19] was synthesized by the reaction of n-C5H10Ph3PI and (NH4)6Mo7O24·7H2O at ambient condition. This compound was characterized by single crystal X-ray diffraction, UV-Vis spectrum, IR spectrum, TGA and electrochemistry analysis. The polyoxometalate compound contains two n-C5H10Ph3P+ cations. There were hydrogen bonding interactions between terminal oxygen atoms of [Mo6O19]2- anions and phosphonium cations, and consequently one dimensional chain was formed. Three dimensional structures were constructed by the π-π stacking between the phenyl rings of the cationic phosphonium. Additionally, its photocatalytic property for the degradation of methylene blue (MB) was also investigated.
A polyoxometalate compound [n-C5H10Ph3P]2[Mo6O19] was synthesized by the reaction of n-C5H10Ph3PI and (NH4)6Mo7O24·7H2O at ambient condition. This compound was characterized by single crystal X-ray diffraction, UV-Vis spectrum, IR spectrum, TGA and electrochemistry analysis. The polyoxometalate compound contains two n-C5H10Ph3P+ cations. There were hydrogen bonding interactions between terminal oxygen atoms of [Mo6O19]2- anions and phosphonium cations, and consequently one dimensional chain was formed. Three dimensional structures were constructed by the π-π stacking between the phenyl rings of the cationic phosphonium. Additionally, its photocatalytic property for the degradation of methylene blue (MB) was also investigated.
2017, 80(7): 656-660, 678
Abstract:
The photocatalysts for C and Nd doped or codoped TiO2 were prepared by sol-gel method using tetrabutyl titanate, neodymium nitrate hexahydrate and glucose as a source of titanium, source of neodymium, and source of carbon, respectively. Its structure and properties were characterized by means of XRD, XPS, diffuse reflectance, SEM and physical adsorption. The results showed that the major crystalline form of C and Nd codoped titanium was the anatase, the surface was smooth, pore size distribution was in the range of 20~34 nm, crystalline size was dispersed uniformly. Compared to the other three catalysts, the surface area of codoped catalyst was larger. The formation of new energy bands EC2p and ENd3+4f by doping C and Nd reduced the electron transition energy, and it was beneficial to enhance the photocatalytic activity of codoped TiO2. Codope can significantly improve the absorption of visible light, its degradation effect on methyl orange was significantly increased, the decolorization rate was 61.24%.
The photocatalysts for C and Nd doped or codoped TiO2 were prepared by sol-gel method using tetrabutyl titanate, neodymium nitrate hexahydrate and glucose as a source of titanium, source of neodymium, and source of carbon, respectively. Its structure and properties were characterized by means of XRD, XPS, diffuse reflectance, SEM and physical adsorption. The results showed that the major crystalline form of C and Nd codoped titanium was the anatase, the surface was smooth, pore size distribution was in the range of 20~34 nm, crystalline size was dispersed uniformly. Compared to the other three catalysts, the surface area of codoped catalyst was larger. The formation of new energy bands EC2p and ENd3+4f by doping C and Nd reduced the electron transition energy, and it was beneficial to enhance the photocatalytic activity of codoped TiO2. Codope can significantly improve the absorption of visible light, its degradation effect on methyl orange was significantly increased, the decolorization rate was 61.24%.
2017, 80(7): 661-666, 687
Abstract:
By using hypoglycemic drugs dapagliflozin, canagliflozin and 1-deoxynojirimycin as reference, the target compound N-[(3-(4-ethoxybenzyl)-4-chlorophenyl]-1-deoxynojirimycin(A) was firstly designed and synthesized. Herein, the intermediate 2-chloro-5-amino-4'-ethoxy diphenyl methane was prepared from 2-chloro-5-nitro benzoic acid through a synthetic route including chlorination of carboxylic acid, Friedel-Crafts acylation, reduction of carbonyl and reduction of nitro. On the other hand, 5-keto-D-glucose was gotten from 1, 2-O-isopropylidene-D-glucofuranose by selective oxidation and hydrolysis. The crude A was obtained by the double reductive amination of 2-chloro-5-amino-4'-ethoxy diphenyl methane and 5-keto-D-glucose. The crude A was treated with acetic anhydride to yield tetraacetyl N-[(3-(4-ethoxybenzyl)-4-chlorophenyl]-1-deoxynojirinmycin(B). B was purified by column chromatography. Then the hydrolyzation of B gave the pure compound A. It was found that the compound A can effectively decrease the SD rats' blood glucose, increase urine volume and the excretion of urine glucose after dosing orally the compound A to SD rats.
By using hypoglycemic drugs dapagliflozin, canagliflozin and 1-deoxynojirimycin as reference, the target compound N-[(3-(4-ethoxybenzyl)-4-chlorophenyl]-1-deoxynojirimycin(A) was firstly designed and synthesized. Herein, the intermediate 2-chloro-5-amino-4'-ethoxy diphenyl methane was prepared from 2-chloro-5-nitro benzoic acid through a synthetic route including chlorination of carboxylic acid, Friedel-Crafts acylation, reduction of carbonyl and reduction of nitro. On the other hand, 5-keto-D-glucose was gotten from 1, 2-O-isopropylidene-D-glucofuranose by selective oxidation and hydrolysis. The crude A was obtained by the double reductive amination of 2-chloro-5-amino-4'-ethoxy diphenyl methane and 5-keto-D-glucose. The crude A was treated with acetic anhydride to yield tetraacetyl N-[(3-(4-ethoxybenzyl)-4-chlorophenyl]-1-deoxynojirinmycin(B). B was purified by column chromatography. Then the hydrolyzation of B gave the pure compound A. It was found that the compound A can effectively decrease the SD rats' blood glucose, increase urine volume and the excretion of urine glucose after dosing orally the compound A to SD rats.
2017, 80(7): 667-671
Abstract:
A novel 4-amino-7-nitrobenzo-2-oxa-1, 3-oxadiazole derivative (NBD-OEt) were synthesized via two steps by using 4-chloro-7-nitrobenzo-2-oxa-1, 3-diazole(NBD-Cl), ethylenediamine and ethyl bromoacetate as raw materials. The structure of NBD-OEt was confirmed by 1H NMR, 13C NMR and ESI-MS. The response to Hg2+ in HEPES aqueous buffer system containing 40% ethanol at pH 7.40, and the binding mode of NBD-OEt with Hg2+ were investigated. The results showed that the addition of Hg2+ could induce the red-shift of absorption band from 476 nm to 514 nm. Two clear isoabestic point were observed at 347 nm and 482 nm. With increasing the concentration of Hg2+, the weak fluorescence emission peak at 536 nm of NBD-OEt was intensified and red shifted to 559 nm with a obvious isoemission at 525 nm. Job's test showed that receptor NBD-OEt coordinate to Hg2+ in a 1:1 stoichiometry.
A novel 4-amino-7-nitrobenzo-2-oxa-1, 3-oxadiazole derivative (NBD-OEt) were synthesized via two steps by using 4-chloro-7-nitrobenzo-2-oxa-1, 3-diazole(NBD-Cl), ethylenediamine and ethyl bromoacetate as raw materials. The structure of NBD-OEt was confirmed by 1H NMR, 13C NMR and ESI-MS. The response to Hg2+ in HEPES aqueous buffer system containing 40% ethanol at pH 7.40, and the binding mode of NBD-OEt with Hg2+ were investigated. The results showed that the addition of Hg2+ could induce the red-shift of absorption band from 476 nm to 514 nm. Two clear isoabestic point were observed at 347 nm and 482 nm. With increasing the concentration of Hg2+, the weak fluorescence emission peak at 536 nm of NBD-OEt was intensified and red shifted to 559 nm with a obvious isoemission at 525 nm. Job's test showed that receptor NBD-OEt coordinate to Hg2+ in a 1:1 stoichiometry.
2017, 80(7): 672-678
Abstract:
Halogen-free alkyl sulfate-based surface active ionic liquids (SAILs), 1-butyl-3-methylimidazolium alkyl sulfate {[C4mim] [CnH2n+1SO4] (n=8, 12, 16)}, were synthesized through ion exchange reaction. The aggregation behaviors of synthesized SAILs in aqueous solution were investigated by surface tension, static fluorescence and static fluorescence quenching measurements. The results showed that the ionic liquid surfactants with organic imidazole cation ([C4mim]+) as counter ions have higher surface activity compared to that surfactants with traditional inorganic counter ions. The effect of inhibiting molecular ordered arrangement derived from the existence of hydrogen bonding produced by [C4mim]+ is less than the hydrophobic effect that can promote molecular ordered arrangement. The anions with long alkyl chains are the major components of interfacial film and micelles. The increase of anionic alkyl chain length promotes the formation of micelles but inhibits the participation of [C4mim]+ to the formation of interface or micelles in some degree. The longer the anionic alkyl chain, the more unfavorable for the [C4mim]+ to participate in the formation of interfacial film or micelles, which leads to the looser arrangement of surfactants in interfacial film or micelles. Correspondingly, the interfacial tension is higher and the micellar aggregation number is smaller.
Halogen-free alkyl sulfate-based surface active ionic liquids (SAILs), 1-butyl-3-methylimidazolium alkyl sulfate {[C4mim] [CnH2n+1SO4] (n=8, 12, 16)}, were synthesized through ion exchange reaction. The aggregation behaviors of synthesized SAILs in aqueous solution were investigated by surface tension, static fluorescence and static fluorescence quenching measurements. The results showed that the ionic liquid surfactants with organic imidazole cation ([C4mim]+) as counter ions have higher surface activity compared to that surfactants with traditional inorganic counter ions. The effect of inhibiting molecular ordered arrangement derived from the existence of hydrogen bonding produced by [C4mim]+ is less than the hydrophobic effect that can promote molecular ordered arrangement. The anions with long alkyl chains are the major components of interfacial film and micelles. The increase of anionic alkyl chain length promotes the formation of micelles but inhibits the participation of [C4mim]+ to the formation of interface or micelles in some degree. The longer the anionic alkyl chain, the more unfavorable for the [C4mim]+ to participate in the formation of interfacial film or micelles, which leads to the looser arrangement of surfactants in interfacial film or micelles. Correspondingly, the interfacial tension is higher and the micellar aggregation number is smaller.
2017, 80(7): 679-683
Abstract:
In this paper, Bufalin loaded nanostructure lipid carrier (BUF-NLC) was successfully prepared by high pressure homogenization. The physicochemical properties, in vitro release and cytotoxicity (MTT) were characterized. The results indicated that BUF-NLC has small particle size, good dispersibility and stability. The MTT test suggested that the cytotoxicity of BUF-NLC on tumor cells was lower than free BUF in the initial stage, but after prolonged the action time, the cytotoxicity of BUF-NLC was consistent with that of BUF, indicating that NLC package does not reduce the cytotoxicity of BUF, but gradually release it, which was very important to overcome the side-effects caused by the high toxicity of BUF.
In this paper, Bufalin loaded nanostructure lipid carrier (BUF-NLC) was successfully prepared by high pressure homogenization. The physicochemical properties, in vitro release and cytotoxicity (MTT) were characterized. The results indicated that BUF-NLC has small particle size, good dispersibility and stability. The MTT test suggested that the cytotoxicity of BUF-NLC on tumor cells was lower than free BUF in the initial stage, but after prolonged the action time, the cytotoxicity of BUF-NLC was consistent with that of BUF, indicating that NLC package does not reduce the cytotoxicity of BUF, but gradually release it, which was very important to overcome the side-effects caused by the high toxicity of BUF.
2017, 80(7): 684-687
Abstract:
Novel clusters CuNn+, ZnNn+ and ScN n+ are generated by laser ablation of Cu/BN, Zn/BN, and Sc/BN discs with N2 as carrier gas. According to the mass spectral analysis, the most stable nitrogen-doped clusters for each metal are CuN4+, ZnN6+, and ScN12+, respectively.
Novel clusters CuNn+, ZnNn+ and ScN n+ are generated by laser ablation of Cu/BN, Zn/BN, and Sc/BN discs with N2 as carrier gas. According to the mass spectral analysis, the most stable nitrogen-doped clusters for each metal are CuN4+, ZnN6+, and ScN12+, respectively.
2017, 80(7): 688-691
Abstract:
The carboxyl betaine zwitterionic polymer (PCBMA) was synthesized by free radical polymerization, the biocompatible zwitterionic carboxybetaine methacrylate (CBMA) as monomer, ammonium persulfate as initiator and sodium sulfite as a reductant. The results of 1H NMR and GPC indicated that the polymer has expected structure. As a model enzyme, the glucose oxidase (GOD) was prepared with and without PCBMA to investigate the relationship between the activity of GOD and time under different temperatures. The results showed that the activity concentration of GOD with PCBMA at 65℃ after 12h was 103% of that without PCBMA for 1h, whereas the GOD activity of control after 12h was only 35% of that without PCBMA for 1h. The carboxyl betaine zwitterionic polymer could effectively maintain the enzyme activity, and this effect was more evident as the temperature increases.
The carboxyl betaine zwitterionic polymer (PCBMA) was synthesized by free radical polymerization, the biocompatible zwitterionic carboxybetaine methacrylate (CBMA) as monomer, ammonium persulfate as initiator and sodium sulfite as a reductant. The results of 1H NMR and GPC indicated that the polymer has expected structure. As a model enzyme, the glucose oxidase (GOD) was prepared with and without PCBMA to investigate the relationship between the activity of GOD and time under different temperatures. The results showed that the activity concentration of GOD with PCBMA at 65℃ after 12h was 103% of that without PCBMA for 1h, whereas the GOD activity of control after 12h was only 35% of that without PCBMA for 1h. The carboxyl betaine zwitterionic polymer could effectively maintain the enzyme activity, and this effect was more evident as the temperature increases.
2017, 80(7): 692-695
Abstract:
A series of MAPO molecular sieves has been synthesized ionothermally in[BMIM]Br ionic liquid at 280℃ using H3PO4, Al[OCH(CH3)2]3, n-dipropylamine, magnesium acetate and HF as raw materilas. The structure transformation process (MAPO-5 to MAPO-11, finally MAPO-25) obeys the Ostwald's rule of successive crystallization, along with the increase in framework density and the change in morphology and state of the templates.
A series of MAPO molecular sieves has been synthesized ionothermally in[BMIM]Br ionic liquid at 280℃ using H3PO4, Al[OCH(CH3)2]3, n-dipropylamine, magnesium acetate and HF as raw materilas. The structure transformation process (MAPO-5 to MAPO-11, finally MAPO-25) obeys the Ostwald's rule of successive crystallization, along with the increase in framework density and the change in morphology and state of the templates.
