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2016 Volume 79 Issue 3
2016, 79(3): 196-204
Abstract:
In face of the academic disputes such as various ways to improve the Hammett equation in physical organic chemistry, the history of searching scientific truth of three topics are analyzed, i.e. the equation of state of real gas, the electronegativity and the principle of hard and soft acids and bases. The conclusion is that in order to approach the truth, the phenomenological theory can not be improved further by fitting more experimental data solely, and there exists no one successful example in the history. The way successful in the sense of statistics is nothing to the correctness in the physical meaning.
In face of the academic disputes such as various ways to improve the Hammett equation in physical organic chemistry, the history of searching scientific truth of three topics are analyzed, i.e. the equation of state of real gas, the electronegativity and the principle of hard and soft acids and bases. The conclusion is that in order to approach the truth, the phenomenological theory can not be improved further by fitting more experimental data solely, and there exists no one successful example in the history. The way successful in the sense of statistics is nothing to the correctness in the physical meaning.
2016, 79(3): 205-212
Abstract:
Biomass-based activated carbons have the advantages including renewable and abundant raw materials, low cost, large specific surface area, developed porous structure as well as good thermal and chemical stability, and they are widely used in agriculture, environmental remediation, chemical industry, energy storage and other fields. This paper reviews the preparation strategies of biomass-based activated carbons, factors influencing the properties, surface modification methods and the applications. Their application in adsorption, catalysis, gas storage, electrode and supercapacitor are also summarized.
Biomass-based activated carbons have the advantages including renewable and abundant raw materials, low cost, large specific surface area, developed porous structure as well as good thermal and chemical stability, and they are widely used in agriculture, environmental remediation, chemical industry, energy storage and other fields. This paper reviews the preparation strategies of biomass-based activated carbons, factors influencing the properties, surface modification methods and the applications. Their application in adsorption, catalysis, gas storage, electrode and supercapacitor are also summarized.
2016, 79(3): 213-219
Abstract:
Antibiotics as a type of medicine which kills bacterium or inhibits bacterial growth are widely applied to food, clinical practice, veterinary medicine and agriculture. However, its residue may penetrate surface water and thus portable water source which can not be cleared by standard water treatment method and harmful to human health and will cause disease (e.g. allergy, fever, drug resistance and aplastic anemia). Therefore, study on detection of antibiotic residues in drinking water attracts increasing attention recently. Here the progress in analysis methods (high-performance liquid chromatography, terahertz time-domain spectroscopy, immunoassays and surface-enhanced Raman spectroscopy) of antibiotic residues in drinking water are reviewed, and development in future as well as the problems of the present situation are also commented.
Antibiotics as a type of medicine which kills bacterium or inhibits bacterial growth are widely applied to food, clinical practice, veterinary medicine and agriculture. However, its residue may penetrate surface water and thus portable water source which can not be cleared by standard water treatment method and harmful to human health and will cause disease (e.g. allergy, fever, drug resistance and aplastic anemia). Therefore, study on detection of antibiotic residues in drinking water attracts increasing attention recently. Here the progress in analysis methods (high-performance liquid chromatography, terahertz time-domain spectroscopy, immunoassays and surface-enhanced Raman spectroscopy) of antibiotic residues in drinking water are reviewed, and development in future as well as the problems of the present situation are also commented.
2016, 79(3): 220-225
Abstract:
As phosphorus analogues of amino acids, α-aminophosphonic acids and their esters have great important applications not only in chemistry and pesticide but also in medicine. Therefore, people have done a lot of work on their synthetic methods. In this paper, recent works on green synthesis of α-aminophosphonic acids and their esters are reviewed and its developing trend is also discussed.
As phosphorus analogues of amino acids, α-aminophosphonic acids and their esters have great important applications not only in chemistry and pesticide but also in medicine. Therefore, people have done a lot of work on their synthetic methods. In this paper, recent works on green synthesis of α-aminophosphonic acids and their esters are reviewed and its developing trend is also discussed.
2016, 79(3): 226-231
Abstract:
Hydrogenated rosin is one of the important natural deep-processing products of renewable resources rosin. It has important applications in the field of electronics, food, medicine and other fields. The mainly composition, the history of the industrial production at home and abroad and the preparation process using the precious metal palladium and non-precious metal nickel catalyst of hydrogenated rosin were introduced in this paper. The preparation of derivatives of hydrogenated rosin and abietenoic acid, especially derivatives of hydrogenated rosin as a whole were reviewed, and the research foreground of hydrogenated rosin and their derivatives were forecasted.
Hydrogenated rosin is one of the important natural deep-processing products of renewable resources rosin. It has important applications in the field of electronics, food, medicine and other fields. The mainly composition, the history of the industrial production at home and abroad and the preparation process using the precious metal palladium and non-precious metal nickel catalyst of hydrogenated rosin were introduced in this paper. The preparation of derivatives of hydrogenated rosin and abietenoic acid, especially derivatives of hydrogenated rosin as a whole were reviewed, and the research foreground of hydrogenated rosin and their derivatives were forecasted.
2016, 79(3): 232-237
Abstract:
Significant progress has been made in biotechnological production of flavoring materials in recent years, especially in 2014, due to the quest for sustainability and cost reduction in flavor and fragrance industry. A number of important flavoring ingredients have been manufactured successfully. The development of monosodium glutamate, γ-glutamyl-valyl-glycine, patchouli oil, vanillin, sclareol, and β-santalol by means of enzymology and fermentation techniques in the industry was herein reviewed.
Significant progress has been made in biotechnological production of flavoring materials in recent years, especially in 2014, due to the quest for sustainability and cost reduction in flavor and fragrance industry. A number of important flavoring ingredients have been manufactured successfully. The development of monosodium glutamate, γ-glutamyl-valyl-glycine, patchouli oil, vanillin, sclareol, and β-santalol by means of enzymology and fermentation techniques in the industry was herein reviewed.
2016, 79(3): 238-242
Abstract:
Three pyrimidine-contained π-conjugated macrocycles 1 (18mer, 110mer and 112mer) were synthesized by Pd(PPh3)4-catalyzed one-step Suzuki cross-coupling reaction between (3,5-di(5-bromopyrimidine-2-yl)-1-tert-butylbenzene) (2) and (3,5-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-1-tert-butylbenzene) (3). The structures of macrocycles 1 were characterized by 1H NMR and MALDI-TOF MS, and their optical properties were investigated by UV-Vis absorption and fluorescence spectrometry. The results showed that the one-step method could be efficient in preparing conjugated macrocycles with expended ring size, which provide a new synthetic strategy for the preparation of similar conjugated macrocycles.
Three pyrimidine-contained π-conjugated macrocycles 1 (18mer, 110mer and 112mer) were synthesized by Pd(PPh3)4-catalyzed one-step Suzuki cross-coupling reaction between (3,5-di(5-bromopyrimidine-2-yl)-1-tert-butylbenzene) (2) and (3,5-di(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)-1-tert-butylbenzene) (3). The structures of macrocycles 1 were characterized by 1H NMR and MALDI-TOF MS, and their optical properties were investigated by UV-Vis absorption and fluorescence spectrometry. The results showed that the one-step method could be efficient in preparing conjugated macrocycles with expended ring size, which provide a new synthetic strategy for the preparation of similar conjugated macrocycles.
2016, 79(3): 243-247
Abstract:
A simple commercial ligand 4-benzoyl-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one has been applied to the palladium-catalyzed Suzuki-Miyaura cross-coupling in this paper. The effect of reaction condition, such as temperature, time, solvents and bases on the yield of product has been evaluated. Under the optimized conditions, a variety of aryl bromides and phenylboronic acid were successfully cross-coupled in high yield at a low catalytic loading of 0.1 (mol)%. Furthermore, the less reactive reactants such as aryl chlorides was explored to enlarge the scope of this cross-coupling, and it was found that the catalytic system employing the ligand in DMF/H2O provided a general and convenient method to prepare biaryls from activated aryl chlorides. Besides, the optimal experiments revealed that the improvement of reaction time/temperature as well as the polarity of the proton solvent turned out to be the effective method for the coupling reaction.
A simple commercial ligand 4-benzoyl-3-methyl-1-phenyl-1H-pyrazol-5(4H)-one has been applied to the palladium-catalyzed Suzuki-Miyaura cross-coupling in this paper. The effect of reaction condition, such as temperature, time, solvents and bases on the yield of product has been evaluated. Under the optimized conditions, a variety of aryl bromides and phenylboronic acid were successfully cross-coupled in high yield at a low catalytic loading of 0.1 (mol)%. Furthermore, the less reactive reactants such as aryl chlorides was explored to enlarge the scope of this cross-coupling, and it was found that the catalytic system employing the ligand in DMF/H2O provided a general and convenient method to prepare biaryls from activated aryl chlorides. Besides, the optimal experiments revealed that the improvement of reaction time/temperature as well as the polarity of the proton solvent turned out to be the effective method for the coupling reaction.
2016, 79(3): 248-253
Abstract:
A novel methionine derivative corrosion inhibitor was synthesized by amidation of methionine. The performance of methionine and its derivative as corrosion inhibitors of N80 steel were investigated in the aggressive condition of 3(wt)% sodium chloride solution with potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and SEM. The mechanism of corrosion inhibitor on carbon steel surface in molecular structure level was explored, too. The results showed that the methionine and its derivative act as the anodic type inhibitor, and the corrosion rate was increased with the increase of inhibitor concentrations. The inhibition efficiency reached approximately 86.94% with methionine derivative dosage of 250mg/L in the aggressive condition of 3(wt)% NaCl solution for N80 carbon steel. At the same concentration, the inhibition efficiency of methionine derivative is better than that of methionine, which origins from the increase of the adsorption sites and hydrophobic long chain in molecular structure of methionine derivative.
A novel methionine derivative corrosion inhibitor was synthesized by amidation of methionine. The performance of methionine and its derivative as corrosion inhibitors of N80 steel were investigated in the aggressive condition of 3(wt)% sodium chloride solution with potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and SEM. The mechanism of corrosion inhibitor on carbon steel surface in molecular structure level was explored, too. The results showed that the methionine and its derivative act as the anodic type inhibitor, and the corrosion rate was increased with the increase of inhibitor concentrations. The inhibition efficiency reached approximately 86.94% with methionine derivative dosage of 250mg/L in the aggressive condition of 3(wt)% NaCl solution for N80 carbon steel. At the same concentration, the inhibition efficiency of methionine derivative is better than that of methionine, which origins from the increase of the adsorption sites and hydrophobic long chain in molecular structure of methionine derivative.
2016, 79(3): 254-258
Abstract:
Three kinds of new polymeric solid-solid phase change meterials (SSPCMs) with different crosslinking structures were synthesized and characterized for thermal energy storage. In the SSPCMs, the hexahydroxy compounds sorbitol, dipentaerythritol and inositol were individually employed as the molecular skeleton and polyethylene glycol (PEG) was used as the phase change functional chain. The molecular structure, crystalline properties, phase change behaviors, thermal reliability and stability of the synthesized SSPCMs were investigated by FT IR, XRD, POM, DSC and TG, respectively. The results showed that the synthesized SSPCMs have high thermal energy storage density and an applicable temperature range of 30~70℃, and the maximum phase change enthalpy in the heating and cooling process for them is 107.5J·g-1 and 102.9J·g-1, respectively. They have good reusability, excellent thermal reliability and stability from the heating-cooling thermal cycle test and TG curves. So they have potential application in the areas of thermal energy storage and temperature-control.
Three kinds of new polymeric solid-solid phase change meterials (SSPCMs) with different crosslinking structures were synthesized and characterized for thermal energy storage. In the SSPCMs, the hexahydroxy compounds sorbitol, dipentaerythritol and inositol were individually employed as the molecular skeleton and polyethylene glycol (PEG) was used as the phase change functional chain. The molecular structure, crystalline properties, phase change behaviors, thermal reliability and stability of the synthesized SSPCMs were investigated by FT IR, XRD, POM, DSC and TG, respectively. The results showed that the synthesized SSPCMs have high thermal energy storage density and an applicable temperature range of 30~70℃, and the maximum phase change enthalpy in the heating and cooling process for them is 107.5J·g-1 and 102.9J·g-1, respectively. They have good reusability, excellent thermal reliability and stability from the heating-cooling thermal cycle test and TG curves. So they have potential application in the areas of thermal energy storage and temperature-control.
2016, 79(3): 259-263,237
Abstract:
The effects of different refluxing and water removal time on the synthesis of bisphenol S are studied when one water distributor or two water distributors are installed. The water removal efficiency can be significantly improved with two water distributors. The refluxing time can be reduced and the crude yield can also be increased. The preferred conditions are as follows: 492.5g phenol, 500g mesitylene and 25g 2,6-naphthalene disulfonic acid are mixed, then 256g concentrated sulfuric acid is dropped, after which refluxing is kept for 6.5h. The crude yield is more than 99% and the mass fraction of bisphenol S is 96.69%. In the purification of bisphenol S, a single alcohol-mesitylene and mixed alcohol-mesitylene system are compared. Taking the cost, yield, color and other aspects into accounts, the mixed alcohol including isopropanol and isoamyl alcohol is better than a single isopropanol. In the selection of the decolorants, the activated carbon for sugar is much better. The preferred conditions of a single alcohol-mesitylene system are as follows: 11.1g crude wet product is dissolved in 44.4g isopropanol, after 66.6g mesitylene and 1.11g activated carbon for sugar are added, the whole system is stirred and decolored under 60℃ for 1h. The yield is 97.0% and the mass fraction of bisphenol S is 99.89%. The preferred conditions of mixed alcohol-mesitylene system are as follows：10g crude product is dissolved in 40g mixed alcohol(isopropanol:isoamyl alcohol=1:1), after 60g mesitylene and 1g activated carbon are added, the whole system is stirred and decolored under 60℃ for 1h. The final yield is 90.6% and the mass fraction of bisphenol S is 99.87%.
The effects of different refluxing and water removal time on the synthesis of bisphenol S are studied when one water distributor or two water distributors are installed. The water removal efficiency can be significantly improved with two water distributors. The refluxing time can be reduced and the crude yield can also be increased. The preferred conditions are as follows: 492.5g phenol, 500g mesitylene and 25g 2,6-naphthalene disulfonic acid are mixed, then 256g concentrated sulfuric acid is dropped, after which refluxing is kept for 6.5h. The crude yield is more than 99% and the mass fraction of bisphenol S is 96.69%. In the purification of bisphenol S, a single alcohol-mesitylene and mixed alcohol-mesitylene system are compared. Taking the cost, yield, color and other aspects into accounts, the mixed alcohol including isopropanol and isoamyl alcohol is better than a single isopropanol. In the selection of the decolorants, the activated carbon for sugar is much better. The preferred conditions of a single alcohol-mesitylene system are as follows: 11.1g crude wet product is dissolved in 44.4g isopropanol, after 66.6g mesitylene and 1.11g activated carbon for sugar are added, the whole system is stirred and decolored under 60℃ for 1h. The yield is 97.0% and the mass fraction of bisphenol S is 99.89%. The preferred conditions of mixed alcohol-mesitylene system are as follows：10g crude product is dissolved in 40g mixed alcohol(isopropanol:isoamyl alcohol=1:1), after 60g mesitylene and 1g activated carbon are added, the whole system is stirred and decolored under 60℃ for 1h. The final yield is 90.6% and the mass fraction of bisphenol S is 99.87%.
2016, 79(3): 264-267,242
Abstract:
In this work, AlPO4-42 molecular sieves was rapidly synthesized by ionothermal synthesis with phosphoric acid as phosphorus sources and isopropanol aluminum as aluminum sources in ionic liquid [BMIM]Br at 280℃, and some other type aluminophosphate molecular sieves were synthesized by this way. XRD, SEM, BET and solid-state mas NMR were used to investigate the influence of the ratio of materials, template agent and different crystallization time on synthesis. The specific surface area, size of the entrance and filler in the pore for as-prepared AlPO4-42 molecular sieves were characterized as well. The results indicated that the structure of AlPO4-42 molecular sieves has been already formed after 4 min. The synthesized AlPO4-42 molecular sieves had a tetrakaidecahedron morphology, which is obviously different with the AlPO4-42 molecular sieves of cube morphology obtained by conventional approach, and the specific surface area and pore volume of AlPO4-42 molecular sieves were changed too. In the process of synthesis AlPO4-42 molecular sieves, the coordinated action of ionic liquid and template led to form the products.
In this work, AlPO4-42 molecular sieves was rapidly synthesized by ionothermal synthesis with phosphoric acid as phosphorus sources and isopropanol aluminum as aluminum sources in ionic liquid [BMIM]Br at 280℃, and some other type aluminophosphate molecular sieves were synthesized by this way. XRD, SEM, BET and solid-state mas NMR were used to investigate the influence of the ratio of materials, template agent and different crystallization time on synthesis. The specific surface area, size of the entrance and filler in the pore for as-prepared AlPO4-42 molecular sieves were characterized as well. The results indicated that the structure of AlPO4-42 molecular sieves has been already formed after 4 min. The synthesized AlPO4-42 molecular sieves had a tetrakaidecahedron morphology, which is obviously different with the AlPO4-42 molecular sieves of cube morphology obtained by conventional approach, and the specific surface area and pore volume of AlPO4-42 molecular sieves were changed too. In the process of synthesis AlPO4-42 molecular sieves, the coordinated action of ionic liquid and template led to form the products.
2016, 79(3): 268-271
Abstract:
The equilibrium molecular dynamic simulation was carried out to study the diffusion behavior of pure component and the binary components in zeolite ITQ-3. For pure Ar, the diffusion coefficient along the z direction is an increasing function as the loading increase and reaches a maximum value at some intermediate loading level, and then it decreases at higher loading level. But in the y direction, the diffusion coefficient decreases monotonically as increasing of the loading. For SF6 and CF4, the diffusion coefficients along the y direction were same as the function of Ar in the z direction. Then the diffusion coefficients of binary components SF6/CF4 in zeolite ITQ-3 had been studied using molecular dynamic simulation methods. It was noted that the diffusion coefficients of binary components retains the trend of their pure component, however CF4 diffused much more slowly in the mixture than as a pure species. Compared to the pure SF6, the diffusion coefficient of SF6 in the mixture was increased. It appears to be due to the influence of coupling effect between diffusing species.
The equilibrium molecular dynamic simulation was carried out to study the diffusion behavior of pure component and the binary components in zeolite ITQ-3. For pure Ar, the diffusion coefficient along the z direction is an increasing function as the loading increase and reaches a maximum value at some intermediate loading level, and then it decreases at higher loading level. But in the y direction, the diffusion coefficient decreases monotonically as increasing of the loading. For SF6 and CF4, the diffusion coefficients along the y direction were same as the function of Ar in the z direction. Then the diffusion coefficients of binary components SF6/CF4 in zeolite ITQ-3 had been studied using molecular dynamic simulation methods. It was noted that the diffusion coefficients of binary components retains the trend of their pure component, however CF4 diffused much more slowly in the mixture than as a pure species. Compared to the pure SF6, the diffusion coefficient of SF6 in the mixture was increased. It appears to be due to the influence of coupling effect between diffusing species.
2016, 79(3): 272-275
Abstract:
Two tetrathiafulvalenes substituted with a phenyl (Ph) (TTF-A) [A=Ph-COOCH3 (7) and A=Ph-COOH (8)] have been synthesized to clear the nature of the donor-acceptor interaction between the TTF unit and the acceptor group. Their structures were characterized by 1H NMR, 13C NMR and mass spectra. The synthesized compounds both display two reversible redox peaks corresponding to the TTF/TTF+· and TTF+·/TTF2+ and show the similar redox potentials comparable to other Ph-substituted TTF derivatives. And the results indicated that compound 7 and 8 are good donor molecules. We also got the crystal of the key intermediate 5 for the synthesis of compound 7 and 8. Compound 5 belongs to monoclinic space group Pc with cell parameters of a=0.3890 (1) nm, b=1.065 (1) nm, c=1.318 (1) nm, Z=2, V=534.5 (2) nm3, Dc=1.542 g·cm-3,F(000)=260,R=0.0467, ωR=0.0739 (I>2σ(I)).
Two tetrathiafulvalenes substituted with a phenyl (Ph) (TTF-A) [A=Ph-COOCH3 (7) and A=Ph-COOH (8)] have been synthesized to clear the nature of the donor-acceptor interaction between the TTF unit and the acceptor group. Their structures were characterized by 1H NMR, 13C NMR and mass spectra. The synthesized compounds both display two reversible redox peaks corresponding to the TTF/TTF+· and TTF+·/TTF2+ and show the similar redox potentials comparable to other Ph-substituted TTF derivatives. And the results indicated that compound 7 and 8 are good donor molecules. We also got the crystal of the key intermediate 5 for the synthesis of compound 7 and 8. Compound 5 belongs to monoclinic space group Pc with cell parameters of a=0.3890 (1) nm, b=1.065 (1) nm, c=1.318 (1) nm, Z=2, V=534.5 (2) nm3, Dc=1.542 g·cm-3,F(000)=260,R=0.0467, ωR=0.0739 (I>2σ(I)).
2016, 79(3): 276-278
Abstract:
Betrixaban was synthesized from 5-methoxy-2-nitrobenzoic acid through hydrogenation, acylation and nucleophilic addition reaction with dimethylamine in an overall yield of 61%. The synthetic route has the advatages of easy to operate, mild conditions and high yield, it has a good prospect in industrial application.
Betrixaban was synthesized from 5-methoxy-2-nitrobenzoic acid through hydrogenation, acylation and nucleophilic addition reaction with dimethylamine in an overall yield of 61%. The synthetic route has the advatages of easy to operate, mild conditions and high yield, it has a good prospect in industrial application.
2016, 79(3): 279-282,231
Abstract:
Ag nanoparticles (Ag NPs) were synthesized by the chemical reduction method and the morphology of them was observed by using SEM and TEM. Interaction of the Ag NPs with human serum albumin (HSA) in aqueous solution had been investigated by UV-Vis absorption spectroscopy, fluorescence (FL) spectroscopy and SEM. The absorbance of the mixture solution was progressively increased, but the fluorescence intensity was decreased with increasing concentration of Ag NPs. The results showed that there were interaction between the Ag NPs and HSA. Furthermore, the morphology change of the Ag NPs in the mixed solution investigated by SEM was in coinciding with that by UV-Vis and FL experiments. The association equilibrium constant (K), the number of binding sites (n) and the standard free energy change (ΔG°) were calculated by using the Stern-Volmer method. These thermodynamic data indicated that the binding processes of Ag NPs and HSA are spontaneous, and the association complex can be formed in the solution.
Ag nanoparticles (Ag NPs) were synthesized by the chemical reduction method and the morphology of them was observed by using SEM and TEM. Interaction of the Ag NPs with human serum albumin (HSA) in aqueous solution had been investigated by UV-Vis absorption spectroscopy, fluorescence (FL) spectroscopy and SEM. The absorbance of the mixture solution was progressively increased, but the fluorescence intensity was decreased with increasing concentration of Ag NPs. The results showed that there were interaction between the Ag NPs and HSA. Furthermore, the morphology change of the Ag NPs in the mixed solution investigated by SEM was in coinciding with that by UV-Vis and FL experiments. The association equilibrium constant (K), the number of binding sites (n) and the standard free energy change (ΔG°) were calculated by using the Stern-Volmer method. These thermodynamic data indicated that the binding processes of Ag NPs and HSA are spontaneous, and the association complex can be formed in the solution.
2016, 79(3): 283-287,253
Abstract:
Michael Polanyi (1891-1976) is remembered today as both physical chemists and philosopher of science. He is best-known among chemists and physicists for his theoretical and experimental work in chemical kinetics and dynamics, especially his development of the theory of the "transition state". Indeed Polanyi has been called one of the founders of the field of modern chemical dynamics. This paper introduced his life and achievements, especially his contributions to physical chemistry.
Michael Polanyi (1891-1976) is remembered today as both physical chemists and philosopher of science. He is best-known among chemists and physicists for his theoretical and experimental work in chemical kinetics and dynamics, especially his development of the theory of the "transition state". Indeed Polanyi has been called one of the founders of the field of modern chemical dynamics. This paper introduced his life and achievements, especially his contributions to physical chemistry.
