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2020 Volume 83 Issue 8
2020, 83(8): 674-689
Abstract:
Coronaviruses are a kind of widely exist pathogens that could cause serious health hazard to human and multiple species of animals, among them, Severe Acute Respiratory Syndrome virus (SARS-CoV)and Middle East respiratory syndrome (MERS-CoV)were broken out in 2003 and 2012 respectively, both of them cause serious health risk to human and considerable loss to global economy. Especially, the Novel Coronavirus(SARS-CoV-2)which was broken out at the end of 2019 has caused millions of infections and tens of thousands death. It is obviously that coronaviruses are highly contagious infectious virus with high mortality rate, which seriously threaten people's health and safety. However, there is no effective drug approved for treatment of them and no vaccine for protect people at present. In this review, we introduced the drugs-like target in coronaviruses and the design and synthesis of representative inhibitors of them, hoping to provide some references for the development of effective therapeutic drugs.
Coronaviruses are a kind of widely exist pathogens that could cause serious health hazard to human and multiple species of animals, among them, Severe Acute Respiratory Syndrome virus (SARS-CoV)and Middle East respiratory syndrome (MERS-CoV)were broken out in 2003 and 2012 respectively, both of them cause serious health risk to human and considerable loss to global economy. Especially, the Novel Coronavirus(SARS-CoV-2)which was broken out at the end of 2019 has caused millions of infections and tens of thousands death. It is obviously that coronaviruses are highly contagious infectious virus with high mortality rate, which seriously threaten people's health and safety. However, there is no effective drug approved for treatment of them and no vaccine for protect people at present. In this review, we introduced the drugs-like target in coronaviruses and the design and synthesis of representative inhibitors of them, hoping to provide some references for the development of effective therapeutic drugs.
2020, 83(8): 690-697
Abstract:
Carbon dioxide (CO2) is a kind of abundant renewable resources, and researchers have been working to develop a catalytic system that can efficiently convert it. N-heterocyclic carbene is a very important type of catalyst in organic chemistry. The efficient conversion of CO2 by the use of N-heterocyclic carbene-transition metal complexes has attracted extensive attention. In this paper, based on the classification of N-heterocyclic carben-transition metal complexes, the progress in N-heterocyclic carben-transition metal complexes catalyzed carboxylation reaction of CO2 in recent years is summarized.
Carbon dioxide (CO2) is a kind of abundant renewable resources, and researchers have been working to develop a catalytic system that can efficiently convert it. N-heterocyclic carbene is a very important type of catalyst in organic chemistry. The efficient conversion of CO2 by the use of N-heterocyclic carbene-transition metal complexes has attracted extensive attention. In this paper, based on the classification of N-heterocyclic carben-transition metal complexes, the progress in N-heterocyclic carben-transition metal complexes catalyzed carboxylation reaction of CO2 in recent years is summarized.
2020, 83(8): 698-703
Abstract:
Perovskite solar cells (PSCs) have attracted considerable research attention because of their ease of fabrication, low-production cost and excellent power conversion efficiencies. PEDOT:PSS has become a research hotspot of hole transport layer in PSCs due to its low temperature processing, high transmittance and suitable hole mobility. This paper briefly describes the structure and working principle of inverted PSCs, and focuses on the research status of doped PEDOT:PSS hole transport layer in the field of PSCs. The effects of doped PEDOT:PSS hole transport layer on the performance of PSCs are summarized in terms of organic compound dopants, inorganic compound dopants and surfactant dopants. Finally, potential measures are proposed to improve the application of doped PEDOT:PSS layer in PSCs.
Perovskite solar cells (PSCs) have attracted considerable research attention because of their ease of fabrication, low-production cost and excellent power conversion efficiencies. PEDOT:PSS has become a research hotspot of hole transport layer in PSCs due to its low temperature processing, high transmittance and suitable hole mobility. This paper briefly describes the structure and working principle of inverted PSCs, and focuses on the research status of doped PEDOT:PSS hole transport layer in the field of PSCs. The effects of doped PEDOT:PSS hole transport layer on the performance of PSCs are summarized in terms of organic compound dopants, inorganic compound dopants and surfactant dopants. Finally, potential measures are proposed to improve the application of doped PEDOT:PSS layer in PSCs.
2020, 83(8): 704-710
Abstract:
Aquaporins (AQPs) are transmembrane proteins with high selectivity and permeability to water molecules. Biomimetic water channel is self-assembled from various inorganic or organic materials, such as carbon nanomaterial, organic compounds and peptides, aiming to mimic natural aquaporins. In this paper, the structure of AQPs and specific water permeability functions are described. On this basis, the research progress in biomimetic water channel based on carbon nanomaterial, organic and peptide pore are reviewed. This review focus on the material properties of three kinds of biomimetic water channel and their effects on the structure and function of biomimetic water channel. Finally, in view of the shortcomings of the existing biomimetic water channel, the challenge and prospect of developing novel biomimetic water channel are proposed.
Aquaporins (AQPs) are transmembrane proteins with high selectivity and permeability to water molecules. Biomimetic water channel is self-assembled from various inorganic or organic materials, such as carbon nanomaterial, organic compounds and peptides, aiming to mimic natural aquaporins. In this paper, the structure of AQPs and specific water permeability functions are described. On this basis, the research progress in biomimetic water channel based on carbon nanomaterial, organic and peptide pore are reviewed. This review focus on the material properties of three kinds of biomimetic water channel and their effects on the structure and function of biomimetic water channel. Finally, in view of the shortcomings of the existing biomimetic water channel, the challenge and prospect of developing novel biomimetic water channel are proposed.
2020, 83(8): 711-717
Abstract:
In this paper, the syntheses of two 1, 4-diketopyrrolopyrrole (DPP) based conjugated polymers, PDPP4T-1 and PDPP4T-2, in which the molar ratios of the 2, 2, 6, 6-tetramethyl-1-piperidinyloxyl (TEMPO) unit-contianing alkyl chains vs. branching alkyl chains are 1:5 and 1:10 and their semiconductor properties were reported. The test results indicated that introduction of TEMPO units in the alkyl side chains has almost no effect on their electronic configuration of polymer conjugated backbones. The thin films of PDPP4T-1 and PDPP4T-2 exhibit p-type semiconducting properties with hole mobilities up to 2.12 cm2·V-1·s-1, though lower than that of PDPP4T without TEMPO units in the alkyl side chains. Furthermore, their thin films were characterized with AFM and GIXRD to explore the possibilities for their performance variation.
In this paper, the syntheses of two 1, 4-diketopyrrolopyrrole (DPP) based conjugated polymers, PDPP4T-1 and PDPP4T-2, in which the molar ratios of the 2, 2, 6, 6-tetramethyl-1-piperidinyloxyl (TEMPO) unit-contianing alkyl chains vs. branching alkyl chains are 1:5 and 1:10 and their semiconductor properties were reported. The test results indicated that introduction of TEMPO units in the alkyl side chains has almost no effect on their electronic configuration of polymer conjugated backbones. The thin films of PDPP4T-1 and PDPP4T-2 exhibit p-type semiconducting properties with hole mobilities up to 2.12 cm2·V-1·s-1, though lower than that of PDPP4T without TEMPO units in the alkyl side chains. Furthermore, their thin films were characterized with AFM and GIXRD to explore the possibilities for their performance variation.
2020, 83(8): 718-723
Abstract:
Two new dihydrothiazole zinc porphyrin(2+2 type and A4 type) based Mn (Ⅱ) ion coordination polymers (CPsx, x=1, 2) have been synthesized and well-characterized. Two as-synthesized coordination polymers and anchored porphyrins (ZnPA) self-assembled into dye-sensitized solar cells through axial coordination of metal-ligands. The assemby modes of the assemblies immobilized on TiO2 electrode surfaces were also verified by TEM. The photovoltaic performance tests showed that the self-assembly polymer has better photoelectric conversion efficiency than the monomer, especially the A4 type CPs2 based solar cell showed higher short circuit current and conversion efficiency. Their optical performance and EIS were also investigated to further understand the photoelectrochemical results.
Two new dihydrothiazole zinc porphyrin(2+2 type and A4 type) based Mn (Ⅱ) ion coordination polymers (CPsx, x=1, 2) have been synthesized and well-characterized. Two as-synthesized coordination polymers and anchored porphyrins (ZnPA) self-assembled into dye-sensitized solar cells through axial coordination of metal-ligands. The assemby modes of the assemblies immobilized on TiO2 electrode surfaces were also verified by TEM. The photovoltaic performance tests showed that the self-assembly polymer has better photoelectric conversion efficiency than the monomer, especially the A4 type CPs2 based solar cell showed higher short circuit current and conversion efficiency. Their optical performance and EIS were also investigated to further understand the photoelectrochemical results.
2020, 83(8): 724-729
Abstract:
Three arylene cyclopentanone visible light initiators containing benzene ring (BDMA), thiophene ring (BDTA) and furan ring (BDFA) were synthesized respectively. Their photophysical and photochemical properties were studied by UV-Vis absorption spectra, fluorescence emission spectra, laser flash photolysis and electron paramagnetic resonance. In contrast with BDMA, the absorption spectra of BDTA and BDFA exhibited a redshift due to the introduction of heterocycles, which can match the emitting spectrum of commercial 532 nm diode lasers. The photopolymerization kinetics showed that all of as-synthesized inititators could induce polymerization of acrylate monomer PEGDA400 directly under visible light irradiation. Among them, BDTA has the best initiation efficiency, suggesting it has potential application prospect in visible light polymerization.
Three arylene cyclopentanone visible light initiators containing benzene ring (BDMA), thiophene ring (BDTA) and furan ring (BDFA) were synthesized respectively. Their photophysical and photochemical properties were studied by UV-Vis absorption spectra, fluorescence emission spectra, laser flash photolysis and electron paramagnetic resonance. In contrast with BDMA, the absorption spectra of BDTA and BDFA exhibited a redshift due to the introduction of heterocycles, which can match the emitting spectrum of commercial 532 nm diode lasers. The photopolymerization kinetics showed that all of as-synthesized inititators could induce polymerization of acrylate monomer PEGDA400 directly under visible light irradiation. Among them, BDTA has the best initiation efficiency, suggesting it has potential application prospect in visible light polymerization.
2020, 83(8): 730-734
Abstract:
To expand an efficient strategy for the conversion of antibacterial activity of fluoroquinolones into an antitumor activity, utilizing pharmacophore bioelectronics isosteric and its flattening and skeleton migration medicinal molecule construction method, a series of fluoroquinolone-3-N-amide compounds were synthesized by using amide group as the bioisostere of the fluoroquinolone C-3 carboxyl group and fluoroquinolone skeleton as a functional modification group, and their structures are confirmed by elemental analysis and spectral data. The results of in vitro antitumor activity showed that the anti-proliferative activity of the target compounds against the two experimental tumor cells (Hep-3B、Capan-1) was significantly stronger than that of the raw material ciprofloxacin, suggesting that replacing the C-3 carboxyl group with an amide group is beneficial to improve the antitumor activity of the quinolones, which provides a new structural modification pathway for transforming antibacterial activity of fluoroquinolone to antitumor activity.
To expand an efficient strategy for the conversion of antibacterial activity of fluoroquinolones into an antitumor activity, utilizing pharmacophore bioelectronics isosteric and its flattening and skeleton migration medicinal molecule construction method, a series of fluoroquinolone-3-N-amide compounds were synthesized by using amide group as the bioisostere of the fluoroquinolone C-3 carboxyl group and fluoroquinolone skeleton as a functional modification group, and their structures are confirmed by elemental analysis and spectral data. The results of in vitro antitumor activity showed that the anti-proliferative activity of the target compounds against the two experimental tumor cells (Hep-3B、Capan-1) was significantly stronger than that of the raw material ciprofloxacin, suggesting that replacing the C-3 carboxyl group with an amide group is beneficial to improve the antitumor activity of the quinolones, which provides a new structural modification pathway for transforming antibacterial activity of fluoroquinolone to antitumor activity.
2020, 83(8): 735-740
Abstract:
1, 4-dihydropyridine compounds have a variety of biological activities and are widely used in the treatment of various cardiovascular and cerebrovascular diseases. The intermediate salts were synthesized from 3-cyanopyridine and benzyl bromide containing different substituents under the condition of reflux for 15 hours. Potassium borohydride (KBH4) was used for the reduction of the intermediate salts in an ice-water bath, 15 relatively novel 1, 4-dihydrogen pyridine derivatives (a~o) were synthesized with the yield of 85%~90%. Their structures were characterized by 1H NMR, 13C NMR and MS. The method has the characteristics of low cost, environmently friendly, easy operation and high yield.
1, 4-dihydropyridine compounds have a variety of biological activities and are widely used in the treatment of various cardiovascular and cerebrovascular diseases. The intermediate salts were synthesized from 3-cyanopyridine and benzyl bromide containing different substituents under the condition of reflux for 15 hours. Potassium borohydride (KBH4) was used for the reduction of the intermediate salts in an ice-water bath, 15 relatively novel 1, 4-dihydrogen pyridine derivatives (a~o) were synthesized with the yield of 85%~90%. Their structures were characterized by 1H NMR, 13C NMR and MS. The method has the characteristics of low cost, environmently friendly, easy operation and high yield.
2020, 83(8): 741-746
Abstract:
This paper studies the relationship between the chemical structure and biological activity of STAT3 inhibitors. The methods of comparative molecular field analysis (CoMFA) and comparative molecular similarity index analysis (CoMSIA) in 3D-QSAR were used to establish a 3D-QSAR model for 52 kinds of STAT3 inhibitors, which clarified the relationship between chemical structure of the inhibitor and its biological activity. The cross validation coefficient of the constructed CoMFA model is 0.548, the non-cross validation coefficient is 0.754, the standard deviation is 0.278, and the significant coefficient is 58.297. The cross validation coefficient of the constructed CoMSIA model is 0.892, the non-cross validation coefficient is 0.597, the standard deviation is 0.192, and the significant coefficient is 57.794. The results showed that the CoMFA and CoMSIA models have good stability and predictive ability, the relevant field information provided by the potential maps such as the 3D-QSAR model has guiding significance for the design of new STAT3 inhibitors.
This paper studies the relationship between the chemical structure and biological activity of STAT3 inhibitors. The methods of comparative molecular field analysis (CoMFA) and comparative molecular similarity index analysis (CoMSIA) in 3D-QSAR were used to establish a 3D-QSAR model for 52 kinds of STAT3 inhibitors, which clarified the relationship between chemical structure of the inhibitor and its biological activity. The cross validation coefficient of the constructed CoMFA model is 0.548, the non-cross validation coefficient is 0.754, the standard deviation is 0.278, and the significant coefficient is 58.297. The cross validation coefficient of the constructed CoMSIA model is 0.892, the non-cross validation coefficient is 0.597, the standard deviation is 0.192, and the significant coefficient is 57.794. The results showed that the CoMFA and CoMSIA models have good stability and predictive ability, the relevant field information provided by the potential maps such as the 3D-QSAR model has guiding significance for the design of new STAT3 inhibitors.
2020, 83(8): 747-754
Abstract:
Pinacol rearrangement of 1, 2-diols is a classical chemical rearrangement. Including acyclic and cyclic 1, 2-diols, under the action of protonic acid or Lewis acid, the 1, 2-transfer of substituents occurs, and the products are often generated with the migration of different groups. However, the main product depends on the spatial structure and properties of the substituents on the dihydroxy linked carbon atoms. In this paper, the mechanism of pinacol rearrangement of 1, 2-diols is quantitatively described by using the net electrophilic index (Multiphilic index), Wiberg bond index and other quantum chemical reactivity indexes, which can be used as the basis for predicting the main products of pinacol rearrangement.
Pinacol rearrangement of 1, 2-diols is a classical chemical rearrangement. Including acyclic and cyclic 1, 2-diols, under the action of protonic acid or Lewis acid, the 1, 2-transfer of substituents occurs, and the products are often generated with the migration of different groups. However, the main product depends on the spatial structure and properties of the substituents on the dihydroxy linked carbon atoms. In this paper, the mechanism of pinacol rearrangement of 1, 2-diols is quantitatively described by using the net electrophilic index (Multiphilic index), Wiberg bond index and other quantum chemical reactivity indexes, which can be used as the basis for predicting the main products of pinacol rearrangement.
2020, 83(8): 755-760
Abstract:
In order to understand the molecular mechanism of biological effects for hydrogen, M06-2X/6-311+G(d, p) and CCSD(t)/aug-cc-pVTZ methods were used to simulate the reaction of hydrogen molecules with superoxide anion free radicals under the conditions of human body (310 K, liquid phase). It was found that the variation value of Gibbs free energy and the barrier of activation free energy for the reaction were 117.2 kJ·mol-1 and 156.2 kJ·mol-1, respectively, indicating that the reaction is not easy to proceed either from a thermodynamic or kinetic perspective. Besides, the microscopic mechanism of the reaction was discussed from the level of electronic structure and orbital interaction. The results showed that both the orbital composition and the orbital energy level of the complex changed significantly during the transition from reactant to transition state (especially the energy level of the eighth orbital increased the most, reaching to 2.73 eV). The number of electron transfer from the fragment O2- to the fragment H2 increased by 0.1760, and the transferred electrons were mainly concentrated in the eighth orbital, which weakened the chemical bond between the two H atoms of the fragment H2 and was also the main source of activation energy for the reaction.
In order to understand the molecular mechanism of biological effects for hydrogen, M06-2X/6-311+G(d, p) and CCSD(t)/aug-cc-pVTZ methods were used to simulate the reaction of hydrogen molecules with superoxide anion free radicals under the conditions of human body (310 K, liquid phase). It was found that the variation value of Gibbs free energy and the barrier of activation free energy for the reaction were 117.2 kJ·mol-1 and 156.2 kJ·mol-1, respectively, indicating that the reaction is not easy to proceed either from a thermodynamic or kinetic perspective. Besides, the microscopic mechanism of the reaction was discussed from the level of electronic structure and orbital interaction. The results showed that both the orbital composition and the orbital energy level of the complex changed significantly during the transition from reactant to transition state (especially the energy level of the eighth orbital increased the most, reaching to 2.73 eV). The number of electron transfer from the fragment O2- to the fragment H2 increased by 0.1760, and the transferred electrons were mainly concentrated in the eighth orbital, which weakened the chemical bond between the two H atoms of the fragment H2 and was also the main source of activation energy for the reaction.
2020, 83(8): 761-767
Abstract:
The adsorption and hydrophobic behavior of 1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane (PFOTMS), 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane (PFOTES), (heptadecafluoro-1, 1, 2, 2-tetradecyl) trimethoxysilane (HFTMS) on the (111) and (110) crystal surfaces of α-iron were studied by molecular dynamics. The parameters such as radial distribution function, binding energy and relative concentration were analyzed. The interaction mechanism between three fluorosilane coupling agents and metal iron was discussed, and the surface modification of iron was analyzed. The results showed that the adsorption of three fluorosilane coupling agents on (111) crystal surface was stronger than that on (110) surface, and the adsorption of PFOTMS on (111) crystal surface was the strongest. The radial distribution function showed that all three fluorosilane coupling agents are easy to form hydrogen bonds with hydroxyl iron, covering the surface of the iron to form a stable bond, which greatly improves the hydrophobicity of the iron surface. The hydrophobicity of PFOTMS was the best on (111) surface. However, on the (110) surface, the three fluorosilane coupling agents have little difference in hydrophobic properties.
The adsorption and hydrophobic behavior of 1H, 1H, 2H, 2H-perfluorooctyltrimethoxysilane (PFOTMS), 1H, 1H, 2H, 2H-perfluorooctyltriethoxysilane (PFOTES), (heptadecafluoro-1, 1, 2, 2-tetradecyl) trimethoxysilane (HFTMS) on the (111) and (110) crystal surfaces of α-iron were studied by molecular dynamics. The parameters such as radial distribution function, binding energy and relative concentration were analyzed. The interaction mechanism between three fluorosilane coupling agents and metal iron was discussed, and the surface modification of iron was analyzed. The results showed that the adsorption of three fluorosilane coupling agents on (111) crystal surface was stronger than that on (110) surface, and the adsorption of PFOTMS on (111) crystal surface was the strongest. The radial distribution function showed that all three fluorosilane coupling agents are easy to form hydrogen bonds with hydroxyl iron, covering the surface of the iron to form a stable bond, which greatly improves the hydrophobicity of the iron surface. The hydrophobicity of PFOTMS was the best on (111) surface. However, on the (110) surface, the three fluorosilane coupling agents have little difference in hydrophobic properties.
