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2018 Volume 81 Issue 2
2018, 81(2): 99-108, 181
Abstract:
The rapid development of electric vehicle industries gradually increase the demand for secondary battery capacity, so it is urgent to develop new high-capacity lithium batteries. The Li-S battery has a high theoretical specific capacity (1675mAh/g) and a high theoretical specific energy (2600Wh/kg) that enables it to achieve an 3 to 5 times energy density of the lithium ion battery. However, many factors such as the capacity decay and the short cycle life caused by the dissolution and shuttling of the long-chain polysulfides limit practical applications of the lithium-sulfur battery. In this paper, the main strategies and relative progress to solve the "shuttle effect" are reviewed and analyzed from the aspects of surface coating, surface adsorption, and surface catalysis. At last, the developing tendencies of Li-S battery in future are also discussed.
The rapid development of electric vehicle industries gradually increase the demand for secondary battery capacity, so it is urgent to develop new high-capacity lithium batteries. The Li-S battery has a high theoretical specific capacity (1675mAh/g) and a high theoretical specific energy (2600Wh/kg) that enables it to achieve an 3 to 5 times energy density of the lithium ion battery. However, many factors such as the capacity decay and the short cycle life caused by the dissolution and shuttling of the long-chain polysulfides limit practical applications of the lithium-sulfur battery. In this paper, the main strategies and relative progress to solve the "shuttle effect" are reviewed and analyzed from the aspects of surface coating, surface adsorption, and surface catalysis. At last, the developing tendencies of Li-S battery in future are also discussed.
2018, 81(2): 109-115
Abstract:
Antibacterial polymers have rich molecular structures and unique antibacterial mechanisms. However their microbe resistances are rather low, which make the emergent polymer materials in the field of anti-bacteria obtain more and more attention. In this paper, the causes of bacteria resistance and the collateral medical and social problems were analyzed. Then the structural characteristics of the antibacterial macromolecules (such as block copolymers, chitosan and so on) and their antibacterial mechanism were discussed. At last, the future development of the new functional polymers in anti-bacteria was prospected.
Antibacterial polymers have rich molecular structures and unique antibacterial mechanisms. However their microbe resistances are rather low, which make the emergent polymer materials in the field of anti-bacteria obtain more and more attention. In this paper, the causes of bacteria resistance and the collateral medical and social problems were analyzed. Then the structural characteristics of the antibacterial macromolecules (such as block copolymers, chitosan and so on) and their antibacterial mechanism were discussed. At last, the future development of the new functional polymers in anti-bacteria was prospected.
2018, 81(2): 116-121
Abstract:
Venetoclax, the first selective inhibitor of B-cell lymphoma-2, was approved by FDA for treating relapsed or refractory chronic lymphocytic leukemia patients with 17p deletion who have received at least one prior therapy. In this paper, four reported synthesis routes of Venetoclax are reviewed. The comparison and analysis of these synthesis routes showed that convergent strategies are often applied in the synthesis of Venetoclax, and it includes the synthesis of four kinds of key intermediates. The synthesis routes of Venetoclax are continuously improved in these respects of using cheap and readily available raw materials, raw materials or synthesis approaches with higher reaction selectivity, milder reaction conditions and enhancing gross yields. In view of the fact that all of the four synthesis routes involve precious metal (palladium) and ligands as catalysts, investigation of polymer-supported palladium and ligands as catalysts will simplify the recovery of catalysts and separation process, and further decrease the preparation cost. This also helps to the development of sustainable industrial production of Venetoclax. If this improvement is accomplished, the fourth synthesis route of Venetoclax has the greatest potential for industrialization.
Venetoclax, the first selective inhibitor of B-cell lymphoma-2, was approved by FDA for treating relapsed or refractory chronic lymphocytic leukemia patients with 17p deletion who have received at least one prior therapy. In this paper, four reported synthesis routes of Venetoclax are reviewed. The comparison and analysis of these synthesis routes showed that convergent strategies are often applied in the synthesis of Venetoclax, and it includes the synthesis of four kinds of key intermediates. The synthesis routes of Venetoclax are continuously improved in these respects of using cheap and readily available raw materials, raw materials or synthesis approaches with higher reaction selectivity, milder reaction conditions and enhancing gross yields. In view of the fact that all of the four synthesis routes involve precious metal (palladium) and ligands as catalysts, investigation of polymer-supported palladium and ligands as catalysts will simplify the recovery of catalysts and separation process, and further decrease the preparation cost. This also helps to the development of sustainable industrial production of Venetoclax. If this improvement is accomplished, the fourth synthesis route of Venetoclax has the greatest potential for industrialization.
2018, 81(2): 122-128
Abstract:
Dehydroabietic acid is a kind of resin acid with tricyclic diterpene structure that separated from rosin. It has a wide range of biological activity and has important applications in the fields of medicine, industry and agriculture. In this paper the activities of dehydroabietic acid and its derivatives in antibacterial, antiviral, BK channel-opening activity, antitumor and other bioactivities are summarized. The research and application prospects of dehydroabietic acid and its derivatives are also previewed.
Dehydroabietic acid is a kind of resin acid with tricyclic diterpene structure that separated from rosin. It has a wide range of biological activity and has important applications in the fields of medicine, industry and agriculture. In this paper the activities of dehydroabietic acid and its derivatives in antibacterial, antiviral, BK channel-opening activity, antitumor and other bioactivities are summarized. The research and application prospects of dehydroabietic acid and its derivatives are also previewed.
2018, 81(2): 129-133
Abstract:
Quartz crystal microbalance (QCM) is a significant analytical tool which has the advantages of high sensitivity, label-free and real-time detection. In the field of biological detection, QCM combining with signal amplification methods is widely used in ultrasensitive detection of biomolecules. The novel QCM with dissipation (QCM-D) is mainly used to investigate the microscopic processes such as adsorption/desorption and configuration change of biomolecules by studying the thickness and viscoelasticity of the thin film. This paper reviewed the construction of QCM and QCM-D biosensors as well as their research progress in the detection of DNA, protein, cell and microorganism.
Quartz crystal microbalance (QCM) is a significant analytical tool which has the advantages of high sensitivity, label-free and real-time detection. In the field of biological detection, QCM combining with signal amplification methods is widely used in ultrasensitive detection of biomolecules. The novel QCM with dissipation (QCM-D) is mainly used to investigate the microscopic processes such as adsorption/desorption and configuration change of biomolecules by studying the thickness and viscoelasticity of the thin film. This paper reviewed the construction of QCM and QCM-D biosensors as well as their research progress in the detection of DNA, protein, cell and microorganism.
2018, 81(2): 134-138
Abstract:
Biofilm is referred to the bacteria forming the special microbial aggregations in order to adapt to the change of external environment. The biofilm process is an important branch of water biochemical treatment technology, which is becoming more and more attentive in the field of environmental engineering. This article summarized studies on the role of extracellular DNA in the process of biofilm forming. Firstly, the classification of extracellular polymeric substance(EPS) and eDNA distribution in EPS were described. Further, it illuminated that QS(quorum sensing)-mechanism mediated the release of eDNA in the bacterial cells. In order to provide more detailed information about the role of eDNA in the process of biofilm forming, the eDNA-mediated performance in the adhesion and aggregation of bacterial was revealed according to XDLVO theory. Moreover, the combinative behavior of eDNA with proteins and polysaccharides were also discussed. Lastly, the future trends in the influence of eDNA on the process of biofilm forming in the coming years were addressed.
Biofilm is referred to the bacteria forming the special microbial aggregations in order to adapt to the change of external environment. The biofilm process is an important branch of water biochemical treatment technology, which is becoming more and more attentive in the field of environmental engineering. This article summarized studies on the role of extracellular DNA in the process of biofilm forming. Firstly, the classification of extracellular polymeric substance(EPS) and eDNA distribution in EPS were described. Further, it illuminated that QS(quorum sensing)-mechanism mediated the release of eDNA in the bacterial cells. In order to provide more detailed information about the role of eDNA in the process of biofilm forming, the eDNA-mediated performance in the adhesion and aggregation of bacterial was revealed according to XDLVO theory. Moreover, the combinative behavior of eDNA with proteins and polysaccharides were also discussed. Lastly, the future trends in the influence of eDNA on the process of biofilm forming in the coming years were addressed.
2018, 81(2): 139-147
Abstract:
The interaction mechanisms and nanostructure between the cation and anion in 1-alkyl-3-methyl-imidazolium tetrafluroborate ionic liquids[Cnmim]2[BF4]2 were investigated at the B3LYP/6-311+G(d, p) level. Through the theoretical calculation of the energy of the interaction of the dimer, it is found that there is a strong hydrogen bond between[Cnmim]+ (n=1~6) and[BF4]-, and the interaction energy increases with the augmenting of imidazolium alkyl chain length. This consequence indicated that imidazolium alkyl chain length affects the strength of the hydrogen bonds. When the number of carbon on the imidazolium alkyl side chains is greater than four, The polymerization of alkyl tail is happen to form a kind of miecllar nanostructure. Through the analysis and calculation of NPA, NBO and weak interaction, it was also proved that there is a strong hydrogen bond in the dimer, and the number of carbon in the alkyl side chain affects the ionic liquid microstructure.
The interaction mechanisms and nanostructure between the cation and anion in 1-alkyl-3-methyl-imidazolium tetrafluroborate ionic liquids[Cnmim]2[BF4]2 were investigated at the B3LYP/6-311+G(d, p) level. Through the theoretical calculation of the energy of the interaction of the dimer, it is found that there is a strong hydrogen bond between[Cnmim]+ (n=1~6) and[BF4]-, and the interaction energy increases with the augmenting of imidazolium alkyl chain length. This consequence indicated that imidazolium alkyl chain length affects the strength of the hydrogen bonds. When the number of carbon on the imidazolium alkyl side chains is greater than four, The polymerization of alkyl tail is happen to form a kind of miecllar nanostructure. Through the analysis and calculation of NPA, NBO and weak interaction, it was also proved that there is a strong hydrogen bond in the dimer, and the number of carbon in the alkyl side chain affects the ionic liquid microstructure.
2018, 81(2): 148-157
Abstract:
Phosphoinositide 3-kinase delta (PI3Kδ) is involved in inflammatory process of chronic obstructive pulmonary disease (COPD) and has been identified as a new potential therapeutic target. In this paper, three-dimensional quantitative structure-activity relationship (3D-QSAR), molecular docking and molecular dynamics were used to study the interaction between 47 indazole derivatives and P13Kδ, and corresponding models were established. The comparative molecular field analysis (CoMFA) model q2=0.719, r2=0.972, comparative molecular similarity index analysis (CoMSIA) model q2=0.649, r2=0.983, indicating that constructed QSAR models have stable and reliable predictive ability. CoMFA and CoMSIA contour maps could graphically describe the effect of different fields on activity. The steric, hydrophobic and hydrogen bond acceptor fields have greater contribution to the activity. Then, the binding mode of small molecule and P13Kδ was explored by molecular docking. The results showed that indazole compounds were mainly bound to P13Kδ by hydrogen bonding and hydrophobic interaction, and the results of docking were further verified by molecular dynamics simulation. Finally, eight compounds were designed based on the information obtained from the contour maps, docking mode and molecular dynamics simulation, they can combine well with PI3Kδ.
Phosphoinositide 3-kinase delta (PI3Kδ) is involved in inflammatory process of chronic obstructive pulmonary disease (COPD) and has been identified as a new potential therapeutic target. In this paper, three-dimensional quantitative structure-activity relationship (3D-QSAR), molecular docking and molecular dynamics were used to study the interaction between 47 indazole derivatives and P13Kδ, and corresponding models were established. The comparative molecular field analysis (CoMFA) model q2=0.719, r2=0.972, comparative molecular similarity index analysis (CoMSIA) model q2=0.649, r2=0.983, indicating that constructed QSAR models have stable and reliable predictive ability. CoMFA and CoMSIA contour maps could graphically describe the effect of different fields on activity. The steric, hydrophobic and hydrogen bond acceptor fields have greater contribution to the activity. Then, the binding mode of small molecule and P13Kδ was explored by molecular docking. The results showed that indazole compounds were mainly bound to P13Kδ by hydrogen bonding and hydrophobic interaction, and the results of docking were further verified by molecular dynamics simulation. Finally, eight compounds were designed based on the information obtained from the contour maps, docking mode and molecular dynamics simulation, they can combine well with PI3Kδ.
2018, 81(2): 165-169
Abstract:
Four palladium(Ⅱ) complexes of organic bidentate phosphine ferrocene, [(dppf)PdCl2], [(dtbpf)PdCl2], [(dppf)PdBr2], [(dtbpf)PdBr2], were prepared via a direct reaction in an inert atmosphere using Na2PdX4 (X=Cl, Br) as the palladium precursor and the corresponding phosphine ferrocene as the ligand (dppf=1, 1'-bis(dipheny-phosphino)ferrocene, dtbpf=1, 1'-bis(di-tert-butylphosphino) ferrocene). The complexes were characterized by 1H NMR. The catalytic performance of the complexes was evaluated not only in three well-kunown coupling reactions (Suzuki, Sonogashira and Heck coupling reaction) but also in the coupling reaction between 2-hydroxypyridine and boronic acid reagent. The results showed that the complexes are stable and can efficiently catalyze a series of coupling reactions in a non-protective atmosphere. The catalyst not only has high catalytic activity in unilateral Sonogashira coupling reaction, but also has good selectivity, showing a good application prospect.
Four palladium(Ⅱ) complexes of organic bidentate phosphine ferrocene, [(dppf)PdCl2], [(dtbpf)PdCl2], [(dppf)PdBr2], [(dtbpf)PdBr2], were prepared via a direct reaction in an inert atmosphere using Na2PdX4 (X=Cl, Br) as the palladium precursor and the corresponding phosphine ferrocene as the ligand (dppf=1, 1'-bis(dipheny-phosphino)ferrocene, dtbpf=1, 1'-bis(di-tert-butylphosphino) ferrocene). The complexes were characterized by 1H NMR. The catalytic performance of the complexes was evaluated not only in three well-kunown coupling reactions (Suzuki, Sonogashira and Heck coupling reaction) but also in the coupling reaction between 2-hydroxypyridine and boronic acid reagent. The results showed that the complexes are stable and can efficiently catalyze a series of coupling reactions in a non-protective atmosphere. The catalyst not only has high catalytic activity in unilateral Sonogashira coupling reaction, but also has good selectivity, showing a good application prospect.
2018, 81(2): 170-174
Abstract:
Since platinum complexes have been found to have anti-cancer effects, the research of small molecule and metal ion coordination has become an important way to discover anti-cancer drugs. In this paper, the complex of syringic acid and copper ion was studied by UV, IR and MS, and its composition is confirmed to be (C9H8O5)Cu·H2O. Then, the effects of syringic acid-copper complex and DNA were studied by UV spectroscopy, fluorescence spectroscopy, and viscosity measurement. It was proved that the combination of syringic acid-copper complex and DNA is the insertion mode.
Since platinum complexes have been found to have anti-cancer effects, the research of small molecule and metal ion coordination has become an important way to discover anti-cancer drugs. In this paper, the complex of syringic acid and copper ion was studied by UV, IR and MS, and its composition is confirmed to be (C9H8O5)Cu·H2O. Then, the effects of syringic acid-copper complex and DNA were studied by UV spectroscopy, fluorescence spectroscopy, and viscosity measurement. It was proved that the combination of syringic acid-copper complex and DNA is the insertion mode.
2018, 81(2): 175-181
Abstract:
Mg-Al hydrotalcite-like compound (HTlc) and Fe3O4@HTlc were prepared by coprecipitation method. The phase identification and morphology of the HTlc and Fe3O4@HTlc were characterized by TEM, XRD, FTIR, VSM, N2 adsorption-desorption, and microiontophoresis apparatus. The adsorption performance of Fe3O4@HTlc and HTlc toward methyl orange(MO) was compared. The results showed that Fe3O4@HTlc particles were near spherical particles with paramagnetism, core-shell structures, larger specific surface areas and positive charges. The adsorption kinetics and adsorption isotherms of Fe3O4@HTlc and HTlc can be well described by the pseudo-first order kinetic and Langmuir isotherm. The saturated adsorption quantity of Fe3O4@HTlc and HTlc toward MO were 138.89 mg/g and 147.06 mg/g, respectively, and Fe3O4@HTlc had a strong driving force toward MO and a shorter adsorption equilibrium time. The adsorption amounts of MO on both Fe3O4@HTlc and HTlc decreased gradually with increasing temperature and increasing initial pH in the range of 5~11.
Mg-Al hydrotalcite-like compound (HTlc) and Fe3O4@HTlc were prepared by coprecipitation method. The phase identification and morphology of the HTlc and Fe3O4@HTlc were characterized by TEM, XRD, FTIR, VSM, N2 adsorption-desorption, and microiontophoresis apparatus. The adsorption performance of Fe3O4@HTlc and HTlc toward methyl orange(MO) was compared. The results showed that Fe3O4@HTlc particles were near spherical particles with paramagnetism, core-shell structures, larger specific surface areas and positive charges. The adsorption kinetics and adsorption isotherms of Fe3O4@HTlc and HTlc can be well described by the pseudo-first order kinetic and Langmuir isotherm. The saturated adsorption quantity of Fe3O4@HTlc and HTlc toward MO were 138.89 mg/g and 147.06 mg/g, respectively, and Fe3O4@HTlc had a strong driving force toward MO and a shorter adsorption equilibrium time. The adsorption amounts of MO on both Fe3O4@HTlc and HTlc decreased gradually with increasing temperature and increasing initial pH in the range of 5~11.
2018, 81(2): 158-164
Abstract:
In this paper, a cascade reaction of ethyl acetoacetate and its derivatives with aromatic aldehydes catalyzed by morpholine leads to a series of highly substituted cyclohexanones in up to 90% yields, presumably via a Knoevenagel/Michael/Aldol reaction sequence. Morpholine, acting as an organocatalyst, is proved to play an important role through iminium and enamine activations in this cascade transformation. The resulted cyclohexanones are further converted into 2-cyclohexenones by a readily available method. This method provides a simple, practical and green route to prepare cyclohexanones from readily available materials.
In this paper, a cascade reaction of ethyl acetoacetate and its derivatives with aromatic aldehydes catalyzed by morpholine leads to a series of highly substituted cyclohexanones in up to 90% yields, presumably via a Knoevenagel/Michael/Aldol reaction sequence. Morpholine, acting as an organocatalyst, is proved to play an important role through iminium and enamine activations in this cascade transformation. The resulted cyclohexanones are further converted into 2-cyclohexenones by a readily available method. This method provides a simple, practical and green route to prepare cyclohexanones from readily available materials.
2018, 81(2): 182-184
Abstract:
Using 2, 3-dihydroxybenzoic acid as the starting material, gymnothecaoxazoles A was synthesized through esterification, Williams etherification, hydrolysis, amidation, Robinson-Gabriel cyclization and deprotection with 20.0% overall yield. The structure was characterized by 1H NMR, 13C NMR and HRMS. This method has the advantages of easily available and cheap starting materials, mildly reaction conditions and simply conducted procedures, which provides reference for the preparation of gymnothecaoxazoles A rapidly.
Using 2, 3-dihydroxybenzoic acid as the starting material, gymnothecaoxazoles A was synthesized through esterification, Williams etherification, hydrolysis, amidation, Robinson-Gabriel cyclization and deprotection with 20.0% overall yield. The structure was characterized by 1H NMR, 13C NMR and HRMS. This method has the advantages of easily available and cheap starting materials, mildly reaction conditions and simply conducted procedures, which provides reference for the preparation of gymnothecaoxazoles A rapidly.
2018, 81(2): 185-191
Abstract:
In the teaching of inorganic chemistry, the occurrence of elements in nature, not only is an important property, but also determines the method for preparation and synthesis of the elements and their compounds. The occurrence of the elements in nature can be deduced from the knowledge of electronic structure of the ions and general chemical principles. By practicing with the deducing program, the understanding of electronic structure of ions and general chemical principles can be reinforced and a logic chain of element properties can be established, which reducing the burden of memorization for students. In this paper, a method of deducing the occurrence of the elements in nature based on the hard-soft acid-base concepts and the environments of the earth's crust, surface and atmosphere was proposed, which is believed to be a simple and instructive method.
In the teaching of inorganic chemistry, the occurrence of elements in nature, not only is an important property, but also determines the method for preparation and synthesis of the elements and their compounds. The occurrence of the elements in nature can be deduced from the knowledge of electronic structure of the ions and general chemical principles. By practicing with the deducing program, the understanding of electronic structure of ions and general chemical principles can be reinforced and a logic chain of element properties can be established, which reducing the burden of memorization for students. In this paper, a method of deducing the occurrence of the elements in nature based on the hard-soft acid-base concepts and the environments of the earth's crust, surface and atmosphere was proposed, which is believed to be a simple and instructive method.
