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2020 Volume 83 Issue 1
2020, 83(1): 3-9
Abstract:
Anion photoelectron spectroscopy (aPES) has become one of the most important techniques for exploring the fundamental problems of spectroscopy and chemical dynamics. In this paper, the development history of aPES and its applications in the study of electronic structures and bonding characteristics of actinide elements and compounds, beryllium-containing compounds are briefly reviewed. Several major techniques in the development of aPES including zero electron kinetic energy (ZEKE) and slow electron velocity-map imaging (SEVI) techniques to improve resolution are reviewed. Subsequently, the combination of electrospray ionization (ESI) source and aPES to study the electronic properties of multiply charged anions and their corresponding neutral molecules under gas phase conditions are introduced. The progress made in the study of the electronic structure and bonding properties of actinides and their compounds, beryllium-containing compounds by aPES are then discussed.
Anion photoelectron spectroscopy (aPES) has become one of the most important techniques for exploring the fundamental problems of spectroscopy and chemical dynamics. In this paper, the development history of aPES and its applications in the study of electronic structures and bonding characteristics of actinide elements and compounds, beryllium-containing compounds are briefly reviewed. Several major techniques in the development of aPES including zero electron kinetic energy (ZEKE) and slow electron velocity-map imaging (SEVI) techniques to improve resolution are reviewed. Subsequently, the combination of electrospray ionization (ESI) source and aPES to study the electronic properties of multiply charged anions and their corresponding neutral molecules under gas phase conditions are introduced. The progress made in the study of the electronic structure and bonding properties of actinides and their compounds, beryllium-containing compounds by aPES are then discussed.
2020, 83(1): 10-16
Abstract:
Thermo-sensitive hydrogels are a class of intelligent polymer gels that undergo a phase change by sensing temperature changes. Preparation of antibacterial hydrogels by loading antibacterial agents or by antibacterial monomers is a hot spot in the fields of drug controlled release, tissue engineering and biological immunity in recent years. In this paper, the research progress in physical crosslinking and chemical crosslinking preparation technology of temperature-sensitive antibacterial hydrogels are reviewed. The control technology, such as the pore diameter, the preparation material and drug loading mode regulation is described. And the application of thermo-sensitive antibacterial hydrogel in controlled release technology, and especially the application prospect in the field of biomass materials are prospected.
Thermo-sensitive hydrogels are a class of intelligent polymer gels that undergo a phase change by sensing temperature changes. Preparation of antibacterial hydrogels by loading antibacterial agents or by antibacterial monomers is a hot spot in the fields of drug controlled release, tissue engineering and biological immunity in recent years. In this paper, the research progress in physical crosslinking and chemical crosslinking preparation technology of temperature-sensitive antibacterial hydrogels are reviewed. The control technology, such as the pore diameter, the preparation material and drug loading mode regulation is described. And the application of thermo-sensitive antibacterial hydrogel in controlled release technology, and especially the application prospect in the field of biomass materials are prospected.
2020, 83(1): 17-22
Abstract:
Formic acid is the simplest carboxylic acid. It is colorless, low toxicity, and easy to transport and store at room temperature. Recently, formic acid is one of the most promising hydrogen storage materials, and the use of heterogeneous catalysts to decompose formic acid to produce hydrogen at room temperature has attracted wide attention of researchers. Compared to the other catalysts, Pd-based catalysts exhibit excellent performance for the decomposition of formic acid to yield hydrogen under mild condition. The properties and preparation methods of Pd-based catalysts and the applications in the fields of the production of hydrogen from formic acid decomposition are reviewed. The future research directions of Pd-based catalysts are also discussed.
Formic acid is the simplest carboxylic acid. It is colorless, low toxicity, and easy to transport and store at room temperature. Recently, formic acid is one of the most promising hydrogen storage materials, and the use of heterogeneous catalysts to decompose formic acid to produce hydrogen at room temperature has attracted wide attention of researchers. Compared to the other catalysts, Pd-based catalysts exhibit excellent performance for the decomposition of formic acid to yield hydrogen under mild condition. The properties and preparation methods of Pd-based catalysts and the applications in the fields of the production of hydrogen from formic acid decomposition are reviewed. The future research directions of Pd-based catalysts are also discussed.
2020, 83(1): 23-29
Abstract:
High arsenic pollution in groundwater is a global environmental issue. Under specific geological, geomorphological, climatic and hydrological and hydrochemical conditions, arsenic-containing minerals undergo adsorption and desorption reactions. Therefore the arsenic was released into groundwater and caused the formation of high arsenic groundwater. Based on the previous researches, the mechanism of adsorption-desorption during arsenic migration and intention in groundwater was analyzed and summarized. Effects of competitive adsorption, redox, pH and organic matter on arsenic adsorption-desorption were discussed from the aspects of adsorbate and adsorbent. Three mechanisms on arsenic adsorption-desorption, i.e. electrostatic attraction mechanism, ion exchange mechanism and complexation species mechanism, were summarized. This paper can provide useful help for revealing the mechanism of high arsenic groundwater and conducting arsenic pollution control and treatment.
High arsenic pollution in groundwater is a global environmental issue. Under specific geological, geomorphological, climatic and hydrological and hydrochemical conditions, arsenic-containing minerals undergo adsorption and desorption reactions. Therefore the arsenic was released into groundwater and caused the formation of high arsenic groundwater. Based on the previous researches, the mechanism of adsorption-desorption during arsenic migration and intention in groundwater was analyzed and summarized. Effects of competitive adsorption, redox, pH and organic matter on arsenic adsorption-desorption were discussed from the aspects of adsorbate and adsorbent. Three mechanisms on arsenic adsorption-desorption, i.e. electrostatic attraction mechanism, ion exchange mechanism and complexation species mechanism, were summarized. This paper can provide useful help for revealing the mechanism of high arsenic groundwater and conducting arsenic pollution control and treatment.
2020, 83(1): 30-34
Abstract:
The anaerobic ammonium oxidation process has become a hot topic in current research because of its low energy consumption, no external organic carbon source addition, low sludge yield and so on. Howerer, the growth rate of anammox bacteria (AnAOB) was especially slow, so the rapid enrichment and the effective retention of AnAOB has become the biggest obstacle in its application in engineering. The granulation of anammox sludge could effectively control the loss of sludge and became the main form of anammox application. Based on the rapid start-up control strategy of anammox granular sludge, the micro-structure and physicochemical properties of anammox granular sludge are analyzed, and the organic matter, salinity, temperature metal ions, antibiotics, signal molecules (AHLs), nitrogen load and other factors in the process of granular sludge are discussed. It is expected that this paper can provide useful reference for the basic research and engineering application of anammox granular sludge.
The anaerobic ammonium oxidation process has become a hot topic in current research because of its low energy consumption, no external organic carbon source addition, low sludge yield and so on. Howerer, the growth rate of anammox bacteria (AnAOB) was especially slow, so the rapid enrichment and the effective retention of AnAOB has become the biggest obstacle in its application in engineering. The granulation of anammox sludge could effectively control the loss of sludge and became the main form of anammox application. Based on the rapid start-up control strategy of anammox granular sludge, the micro-structure and physicochemical properties of anammox granular sludge are analyzed, and the organic matter, salinity, temperature metal ions, antibiotics, signal molecules (AHLs), nitrogen load and other factors in the process of granular sludge are discussed. It is expected that this paper can provide useful reference for the basic research and engineering application of anammox granular sludge.
2020, 83(1): 35-41
Abstract:
The high value-added comprehensive utilization of fly ash has become one of the most important issues in the field of circular economy and environmental protection. The use of fly ash for water treatment is an active attempt to turn waste into treasure and turn harm into profit. Fly ash has significant application value in membrane filtration, Fenton treatment, photocatalysis and adsorption due to its morphological characteristics, specific surface area, porosity and chemical composition. This paper focuses on the application of fly ash in these aspects, and prospects its application in wastewater treatment.
The high value-added comprehensive utilization of fly ash has become one of the most important issues in the field of circular economy and environmental protection. The use of fly ash for water treatment is an active attempt to turn waste into treasure and turn harm into profit. Fly ash has significant application value in membrane filtration, Fenton treatment, photocatalysis and adsorption due to its morphological characteristics, specific surface area, porosity and chemical composition. This paper focuses on the application of fly ash in these aspects, and prospects its application in wastewater treatment.
2020, 83(1): 42-49
Abstract:
LiNi1/3Mn1/3Co1/3O2 has high theoretical specific capacity, but the surface structure of the cathode material greatly decays at high charging voltage, which leads to the deterioration of cycle performance and rate performance for batteries. In this paper it was reported that LiNi1/3Mn1/3Co1/3O2 coated with lithium-rich spinel Li4Mn5O12 can effectively improve the electrochemical performance. XRD, SEM, XPS and TEM were used to analyze the cathode material. It was confirmed that Li4Mn5O12uniformly formed a coating layer of 10 nm thick on the surface of LiNi1/3Mn1/3Co1/3O2. LiNi1/3Mn1/3Co1/3O2@Li4Mn5O12 has a high discharge capacity of 179.5 mAh/g, and the capacity retention rate is 88.6% after 100 cycles, which is significantly higher than that of LiNi1/3Mn1/3Co1/3O2(78.3%). Therefore, the coating of LiNi1/3Mn1/3Co1/3O2 with lithium-rich spinel Li4Mn5O12 provides a new way to achieve a high energy density of lithium-ion batteries.
LiNi1/3Mn1/3Co1/3O2 has high theoretical specific capacity, but the surface structure of the cathode material greatly decays at high charging voltage, which leads to the deterioration of cycle performance and rate performance for batteries. In this paper it was reported that LiNi1/3Mn1/3Co1/3O2 coated with lithium-rich spinel Li4Mn5O12 can effectively improve the electrochemical performance. XRD, SEM, XPS and TEM were used to analyze the cathode material. It was confirmed that Li4Mn5O12uniformly formed a coating layer of 10 nm thick on the surface of LiNi1/3Mn1/3Co1/3O2. LiNi1/3Mn1/3Co1/3O2@Li4Mn5O12 has a high discharge capacity of 179.5 mAh/g, and the capacity retention rate is 88.6% after 100 cycles, which is significantly higher than that of LiNi1/3Mn1/3Co1/3O2(78.3%). Therefore, the coating of LiNi1/3Mn1/3Co1/3O2 with lithium-rich spinel Li4Mn5O12 provides a new way to achieve a high energy density of lithium-ion batteries.
2020, 83(1): 50-57
Abstract:
The application of lithium-ion batteries involves key materials such as cathode and anode, electrolytes. The diffusion of lithium ions in materials is the core microscopic process. Through experimental measurements and theoretical calculations, we can find excellent materials with low lithium-ion diffusion activation energy, but with a good activation energy parameter, we cannot clarify what the influencing factors are, nor can we optimize existing materials and discover new lithium batteries material. In this paper, using MGI research ideas, using the first-principles calculation of the activation energy parameters of more than 40 typical systems, combined with the calculation results of the energy band structure characteristics, and through data analysis, we have identified the influence of lithium-ion diffusion in the lattice structure. The role of activation energy influenced by gene parameters such as valence band width and d orbital proportion in valence band was determined. These results reflect the necessity of the study of the overall characteristics of the lithium ion material band, and also reflect the advantages and characteristics of the MGI research method.
The application of lithium-ion batteries involves key materials such as cathode and anode, electrolytes. The diffusion of lithium ions in materials is the core microscopic process. Through experimental measurements and theoretical calculations, we can find excellent materials with low lithium-ion diffusion activation energy, but with a good activation energy parameter, we cannot clarify what the influencing factors are, nor can we optimize existing materials and discover new lithium batteries material. In this paper, using MGI research ideas, using the first-principles calculation of the activation energy parameters of more than 40 typical systems, combined with the calculation results of the energy band structure characteristics, and through data analysis, we have identified the influence of lithium-ion diffusion in the lattice structure. The role of activation energy influenced by gene parameters such as valence band width and d orbital proportion in valence band was determined. These results reflect the necessity of the study of the overall characteristics of the lithium ion material band, and also reflect the advantages and characteristics of the MGI research method.
2020, 83(1): 64-69
Abstract:
The naphthalene benzimidazole (NBI) with 1 and 4 monosubstituted derivatives 1~4 were synthesized and purified. The structure of compound 1 was analyzed in detail by using UV-Vis, IR, MS, 1H NMR, 13C NMR, DEPT, 1H-13C HSQC, 1H-13C HMBC techniques, and the positions of 1H and 13C NMR peaks of the derivatives were assigned. Quantum calculations were also applied by GIAO and CSGT methods to calculate the NMR shifts of NBI derivatives. The structure of the compounds were confirmed by various spectral techniques.
The naphthalene benzimidazole (NBI) with 1 and 4 monosubstituted derivatives 1~4 were synthesized and purified. The structure of compound 1 was analyzed in detail by using UV-Vis, IR, MS, 1H NMR, 13C NMR, DEPT, 1H-13C HSQC, 1H-13C HMBC techniques, and the positions of 1H and 13C NMR peaks of the derivatives were assigned. Quantum calculations were also applied by GIAO and CSGT methods to calculate the NMR shifts of NBI derivatives. The structure of the compounds were confirmed by various spectral techniques.
2020, 83(1): 70-74
Abstract:
Imidazo[1, 5-a] pyridinium salts were synthesized via a facile three-component coupling reaction. Their structures were confirmed by 1H NMR, 13C NMR, MS and X-ray crystal diffraction analysis. Unexpected structures were obtained using diethylenetriamine and triethylenetetramine as raw materials. The antibacterial properties of the as-synthesized salts were studied by minimal inhibitory concentration (MIC) method using penicillin as a control. The results showed that all the compounds have antibacterial effect on Micrococcus lysococcus and Streptococcus B, and the antibacterial effect of compound 2 was the best. Compound 3 containing heteroatom O has stronger antibacterial activity against Maltophilia maltophilia and Klebsiella pneumoniae than that of penicillin. The biphenyl bridged bidentate imidazole[1, 5-a]pyridinium salt (compound 5) has a better antibacterial effect than the ethyl bridged bidentate imidazole[1, 5-a]pyridinium salt (compound 4). Compound 6 having a monodentate large π system aromatic ring has better antibacterial effect than that of compounds 7 and 8 containing a bidentate large π system aromatic ring.
Imidazo[1, 5-a] pyridinium salts were synthesized via a facile three-component coupling reaction. Their structures were confirmed by 1H NMR, 13C NMR, MS and X-ray crystal diffraction analysis. Unexpected structures were obtained using diethylenetriamine and triethylenetetramine as raw materials. The antibacterial properties of the as-synthesized salts were studied by minimal inhibitory concentration (MIC) method using penicillin as a control. The results showed that all the compounds have antibacterial effect on Micrococcus lysococcus and Streptococcus B, and the antibacterial effect of compound 2 was the best. Compound 3 containing heteroatom O has stronger antibacterial activity against Maltophilia maltophilia and Klebsiella pneumoniae than that of penicillin. The biphenyl bridged bidentate imidazole[1, 5-a]pyridinium salt (compound 5) has a better antibacterial effect than the ethyl bridged bidentate imidazole[1, 5-a]pyridinium salt (compound 4). Compound 6 having a monodentate large π system aromatic ring has better antibacterial effect than that of compounds 7 and 8 containing a bidentate large π system aromatic ring.
2020, 83(1): 75-79
Abstract:
Three novel urea-based Gemini surfactants (LY-12, LY-14, LY-16) were synthesized using N, N-dimethyl-1, 3-propanediamine, triphosgene and bromoalkanes as raw materials. The structure was characterized by 1H NMR, ESI-MS and FT-IR, and the Krafft point, emulsifying properties and foaming properties were measured. The surface activity parameters (Γmax, Amin, pc20) and the thermodynamics parameters (ΔGmθ, ΔHmθ, ΔSmθ) were calculated by measuring the surface tension (γcmc) and the critical micelle concentration (CMC) at different temperatures. The results showed that the Krafft points of LY-12 and LY-14 were all below 0℃, and the Krafft point of LY-16 is lower than 10℃; the emulsification time of LY-12, LY-14 and LY-16 were 173, 275 and 338 s, respectively. The foaming ability of LY-12 was significantly higher than those of LY-14 and LY-16. The surface tension(γcmc) were 38.77, 37.42 and 36.59 mN/m, and the CMC value were 0.19, 0.15, 0.13 mmol/L at 298.15 K, respectively. All the three surfactants had high surface activity, and the formation of micelles was an entropy-driven self-heating process.
Three novel urea-based Gemini surfactants (LY-12, LY-14, LY-16) were synthesized using N, N-dimethyl-1, 3-propanediamine, triphosgene and bromoalkanes as raw materials. The structure was characterized by 1H NMR, ESI-MS and FT-IR, and the Krafft point, emulsifying properties and foaming properties were measured. The surface activity parameters (Γmax, Amin, pc20) and the thermodynamics parameters (ΔGmθ, ΔHmθ, ΔSmθ) were calculated by measuring the surface tension (γcmc) and the critical micelle concentration (CMC) at different temperatures. The results showed that the Krafft points of LY-12 and LY-14 were all below 0℃, and the Krafft point of LY-16 is lower than 10℃; the emulsification time of LY-12, LY-14 and LY-16 were 173, 275 and 338 s, respectively. The foaming ability of LY-12 was significantly higher than those of LY-14 and LY-16. The surface tension(γcmc) were 38.77, 37.42 and 36.59 mN/m, and the CMC value were 0.19, 0.15, 0.13 mmol/L at 298.15 K, respectively. All the three surfactants had high surface activity, and the formation of micelles was an entropy-driven self-heating process.
2020, 83(1): 80-87
Abstract:
A novel electromagnetic material 4, 4'-oxydianiline molecular imprinted polymer composite poly 4, 4'-oxydianiline (4, 4'-ODL-MIP/P-4, 4'-ODL) was prepared on the surface of graphene modified pencil electrode (G-PEC) by means of the secondary electrochemical polymerization. The effects of the effective conductive length, the concentration of graphene, pH of buffer, the concentration ratio of 4, 4'-oxydianiline to functional monomer acrylamide, the range of scanning potential, the number of scanning cycles, scanning rate and elution time on the charge of composite materials were investigated. The testing results of the vector network analyzers showed that as-synthesized composite material exhibited a reflection loss of -10.57dB at 12.56MHz, and the effective electromagnetic wave absorption rate reached 90%. However, the reflection loss of a single 4, 4'-ODL-MIP and graphene were both higher than -10 dB, the effective electromagnetic wave absorption rates were only about 68% and 60%, respectively. Therefore, the composite material exhibited good wave absorbing properties.
A novel electromagnetic material 4, 4'-oxydianiline molecular imprinted polymer composite poly 4, 4'-oxydianiline (4, 4'-ODL-MIP/P-4, 4'-ODL) was prepared on the surface of graphene modified pencil electrode (G-PEC) by means of the secondary electrochemical polymerization. The effects of the effective conductive length, the concentration of graphene, pH of buffer, the concentration ratio of 4, 4'-oxydianiline to functional monomer acrylamide, the range of scanning potential, the number of scanning cycles, scanning rate and elution time on the charge of composite materials were investigated. The testing results of the vector network analyzers showed that as-synthesized composite material exhibited a reflection loss of -10.57dB at 12.56MHz, and the effective electromagnetic wave absorption rate reached 90%. However, the reflection loss of a single 4, 4'-ODL-MIP and graphene were both higher than -10 dB, the effective electromagnetic wave absorption rates were only about 68% and 60%, respectively. Therefore, the composite material exhibited good wave absorbing properties.
2020, 83(1): 58-63
Abstract:
Three kinds of novel N-coumarin derivatives with thiophene as π bridge, named 7-N, N-diethylamino-3-(5-pyren-1-yl-thiophen-2-yl)-coumarin (Py-Th-NC), 7-(N, N-diethylamino)-3-(4-(5-(7-(N, N-diethylamino)-coumarin-3-yl) thiophen-2-yl)phenyl)-coumarin (NC-Th-Ph-NC) and 3-(4-(5-(7-(N, N-diethylamino)-coumarin-3-yl) thiophen-2-yl)phenyl)-coumarin (NC-Th-Ph-C), were successfully synthesized. Their structures were confirmed by HRMS, 1H NMR and IR. The luminescence properties, electrochemical properties and thermal stabilities of these compounds were investigated. The results revealed that they exhibit good thermal stabilities and show strong blue-green or green photoluminescence in dichloromethane solution.
Three kinds of novel N-coumarin derivatives with thiophene as π bridge, named 7-N, N-diethylamino-3-(5-pyren-1-yl-thiophen-2-yl)-coumarin (Py-Th-NC), 7-(N, N-diethylamino)-3-(4-(5-(7-(N, N-diethylamino)-coumarin-3-yl) thiophen-2-yl)phenyl)-coumarin (NC-Th-Ph-NC) and 3-(4-(5-(7-(N, N-diethylamino)-coumarin-3-yl) thiophen-2-yl)phenyl)-coumarin (NC-Th-Ph-C), were successfully synthesized. Their structures were confirmed by HRMS, 1H NMR and IR. The luminescence properties, electrochemical properties and thermal stabilities of these compounds were investigated. The results revealed that they exhibit good thermal stabilities and show strong blue-green or green photoluminescence in dichloromethane solution.
2020, 83(1): 88-91
Abstract:
Fiacitabine (FIAC) is a pyrimidine nucleoside analog with activity against various herpesviruses. In this paper, ((2R, 3S, 4S)-3-(benzoyloxy)-5-bromo-4-fluorotetrahydrofuran-2-yl)methyl benzoate (4) is afforded in high yields through brominiation, starting with (2R, 3S, 4R, 5R)-5-(benzoyloxymethyl)-3-fluorotetrahydrofuran-2, 4-dily dibenzoate at room temperature; and simultaneously N-(5-iodo-1, 2-dihydropyrimidin-4-yl)benzamind (5) was effectively synthesized through two steps including iodobenzene, Bz-protection, starting with cytosine, which can be obtained cheaply and conveniently. Then FIAC is obtained by substitution reaction with intermediate 4 and 5 followed by deprotection reaction. This synthetic route has the advantages of brief reaction steps, convenient manipulation and high product selectivity for FIAC. The overall yield is 43%.
Fiacitabine (FIAC) is a pyrimidine nucleoside analog with activity against various herpesviruses. In this paper, ((2R, 3S, 4S)-3-(benzoyloxy)-5-bromo-4-fluorotetrahydrofuran-2-yl)methyl benzoate (4) is afforded in high yields through brominiation, starting with (2R, 3S, 4R, 5R)-5-(benzoyloxymethyl)-3-fluorotetrahydrofuran-2, 4-dily dibenzoate at room temperature; and simultaneously N-(5-iodo-1, 2-dihydropyrimidin-4-yl)benzamind (5) was effectively synthesized through two steps including iodobenzene, Bz-protection, starting with cytosine, which can be obtained cheaply and conveniently. Then FIAC is obtained by substitution reaction with intermediate 4 and 5 followed by deprotection reaction. This synthetic route has the advantages of brief reaction steps, convenient manipulation and high product selectivity for FIAC. The overall yield is 43%.
2020, 83(1): 92-95
Abstract:
Thirteen 7-N, Ndiethylaminocoumarin-based hydrazone/acylhydrazone derivatives were synthesized from 7-N, Ndiethylamino-4-methylcoumarin via oxidation with SeO2, and then reacting with substituted hydrazine and acylhydrazine by using the impregnation method. Their structures were confirmed by melting point, 1H NMR and MS. Preliminary bioassay results showed that compounds 4a and 4c had potential inhibitory activity against acetylcholinesterase, and their IC50 values were 42.89 and 90.32 μmol/L, respectively. The preliminary study on the structure-activity relationships indicated that acylhydrazone derivatives have better inhibitory activity against acetylcholinesterase than those of the hydrazone derivatives.
Thirteen 7-N, Ndiethylaminocoumarin-based hydrazone/acylhydrazone derivatives were synthesized from 7-N, Ndiethylamino-4-methylcoumarin via oxidation with SeO2, and then reacting with substituted hydrazine and acylhydrazine by using the impregnation method. Their structures were confirmed by melting point, 1H NMR and MS. Preliminary bioassay results showed that compounds 4a and 4c had potential inhibitory activity against acetylcholinesterase, and their IC50 values were 42.89 and 90.32 μmol/L, respectively. The preliminary study on the structure-activity relationships indicated that acylhydrazone derivatives have better inhibitory activity against acetylcholinesterase than those of the hydrazone derivatives.
