A new metal-organic framework based on ethyl 1H-tetrazole-5-acetate （Hetza）, [Ag4（etza）4] （1）, has been synthesized and characterized by elemental analysis, IR, thermal gravimetric and X-ray structural analysis....A new metal-organic framework based on ethyl 1H-tetrazole-5-acetate （Hetza）, [Ag4（etza）4] （1）, has been synthesized and characterized by elemental analysis, IR, thermal gravimetric and X-ray structural analysis. Crystal data for the title complex are as follows： triclinic system, space group P1 with a = 11.0771（6）, b = 11.6636（6）, c = 13.2925（8）, a = 102.3710（10）, β =103.3810（10）, γ = 90.0890（10）°, V = 1629.60（16） A3, Mr = 1052.06, Z = 2, F（000） = 1024, Dc = 2.144 g/cm3, μ（MoKa） = 2.438 mm^-1, the final R = 0.0538 and wR = 0.1475 （I 〉 2σ（I））. Complex 1 adopts the （4.82） topological network and the alternately hydrophilic-hydrophilic and hydropho- bic-hydrophobic arrangements. The luminescent properties of complex 1 and the free Hetza ligand have been studied in the solid states.展开更多
Room temperature ionic liquids have been currently used in liquid/liquid extraction processes in order to substitute conventional organic solvents. In this paper, a series of chlorinated solvents and 1-alkyl-3-me- thy...Room temperature ionic liquids have been currently used in liquid/liquid extraction processes in order to substitute conventional organic solvents. In this paper, a series of chlorinated solvents and 1-alkyl-3-me- thylimidazolium-based ionic liquids were selected to study the extraction efficiency of a lipophilic polya- mine 1,1,7,7-tetraethyl-4-tetradecyldiethylenetriamine (TE14DT) towards the model ion Cu(II) in such dif-ferent media. The effect of temperature on the extraction efficiency was also investigated. The metal ion par-tition was found to be strongly dependent on both the nature of the solvent and on the working temperature. The viscosity of ionic liquids and the water content in ionic liquid were found to affect the extraction effi-ciency of TE14DT. The chemical nature of the cation of ionic liquids, and in particular the alkyl chain length on imidazolium ring, also seemed to be important in determining the efficiency of the extraction process. Finally, preliminary experiments on back-extraction of Cu(II) ions from ionic liquid also revealed interesting hints to the development of a continuous transport process.展开更多
Various surfactants have been used in upstream petroleum processes like chemical flooding. Ultimately, the performance of these surfactants depends on their ability to reduce the interfacial tension between oil and wa...Various surfactants have been used in upstream petroleum processes like chemical flooding. Ultimately, the performance of these surfactants depends on their ability to reduce the interfacial tension between oil and water. The surfactant concentration in the aqueous solution decreases owing to the loss of the surfactant on the rock surface in the injection process. The main objective of this paper is to inhibit the surfactant loss by means of adding nanoparticles. Sodium dodecyl sulfate and silica nanoparticles were used as ionic surfactant and nanoparticles in our experiments, respectively. AEROSIL~？ 816 and AEROSIL~？200 are hydrophobic and hydrophilic nanoparticles. To determine the adsorption loss of the surfactant onto rock samples, a conductivity approach was used. Real carbonate rock samples were used as the solid phase in adsorption experiments. It should be noted that the rock samples were water wet. This paper describes how equilibrium adsorption was investigated by examining adsorption behavior in a system of carbonate sample（solid phase） and surfactant solution（aqueous phase）. The initial surfactant and nanoparticle concentrations were 500–5000 and 500–2000 ppm, respectively. The rate of surfactant losses was extremely dependent on the concentration of the surfactant in the system, and the adsorption of the surfactant decreased with an increase in the nanoparticle concentration. Also, the hydrophilic nanoparticles are more effective than the hydrophobic nanoparticles.展开更多
RTIL consisting of 1-methyl-3-butyl-imidazolium（BMIm） cation and bis（trifluoromethane sulfone） imide（TFSI） anion was mixed with 1-methyl-3-n-butyl-imidazolium hexafluorophosphate(BMImPF6) at different ratios.The...RTIL consisting of 1-methyl-3-butyl-imidazolium（BMIm） cation and bis（trifluoromethane sulfone） imide（TFSI） anion was mixed with 1-methyl-3-n-butyl-imidazolium hexafluorophosphate(BMImPF6) at different ratios.Their room temperature conductivity,MS,LV were measured and the effect on association phenomenon by mixing is analyzed.The results demonstrate that the mixtures of ionic liquids can reduce the association degree of single ionic liquid with the better effect of properties,which mesans that the properties of the mixtures are not the average of single RTIL,but have a synergism effect.展开更多
为改善纤维素原料的亲水性,提高纤维素的可及度,将具有强亲水性的聚醚引入离子液体合成出系列聚醚功能化双核咪唑类离子液体,并将其应用于纤维素的预处理和糖化研究。相对于在咪唑类离子液体中引入烯丙基、烷基、羧酸以及乙酸乙酯等阳...为改善纤维素原料的亲水性,提高纤维素的可及度,将具有强亲水性的聚醚引入离子液体合成出系列聚醚功能化双核咪唑类离子液体,并将其应用于纤维素的预处理和糖化研究。相对于在咪唑类离子液体中引入烯丙基、烷基、羧酸以及乙酸乙酯等阳离子功能化基团,聚醚基团的烷氧基(CH2—CH2—O)可增大离子液体与纤维素的有效接触,并作为氢键受体促进纤维素中原有氢键的破坏;分子质量为400的聚乙二醇(PEG400)可提供足够数量和极化强度的氢原子改善亲水性;相对于单核咪唑类,双核咪唑类离子液体醚基上的次甲基氢原子的极性增强(E_T(30),61.33 kcal/mol),形成更高的氢键酸度(α,2.792);聚醚功能化双核咪唑类离子液体([PEG400-(Et-Im)_2][Cl]_2)对纤维素溶解度高达13.26%质量分数。相对于HCOO^-、Cl^-和Br^-阴离子功能化,OAc^-功能化的[PEG400-(Et-Im)_2][OAc]_2具有更大的氢键碱度(β,1.04),增加了对纤维素羟基上氢键的接受能力;聚醚的烷氧基会带来较低的黏度(63 c P,120℃),黏度表观活化能(E_η)为30.11 k J/mol,促进了离子液体与纤维素的接触与物质传输,由此获得[PEG400-(Et-Im)2][OAc]_2对纤维素的高溶解度(14.76%质量分数)。纤维素在[PEG400-(Et-Im)_2][OAc]_2溶解过程中没有发生衍生化反应,纤维素的结晶度由85.4%降至31.6%,实现了高结晶有序结构向无定型的转化。得到的再生纤维素膜具有各向同性和均一致密的性能,热力学稳定性稍有下降。酸性聚醚功能化离子液体[PEG400-(Et-Im)_2][HSO4]_2催化纤维素水解中葡萄糖得率为55.8%。展开更多
A new approach to the problem of cold denaturation is presented. It is based on solvent-induced effects operating on hydrophilic groups along the protein. These effects are stronger than the corresponding hydrophobic ...A new approach to the problem of cold denaturation is presented. It is based on solvent-induced effects operating on hydrophilic groups along the protein. These effects are stronger than the corresponding hydrophobic effects, and they operate on the hydrophilic groups which are plentiful than hydrophobic groups. It is shown that both heat and cold denaturation can be explained by these hydrophilic effects.展开更多
It is challenging to recognize neutral hydrophilic molecules in water.Effective use of hydrogen bonds in water is generally accepted to be the key to success.In contrast,hydrophobic cavity is usually considered to pla...It is challenging to recognize neutral hydrophilic molecules in water.Effective use of hydrogen bonds in water is generally accepted to be the key to success.In contrast,hydrophobic cavity is usually considered to play an insignificant role or only to provide a nonpolar microenvironment for hydrogen bonds.Herein,we report that hydrophobic cavity alone can also strongly bind neutral,highly hydrophilic molecules in water.We found that cucurbit[n]urils(n=7,8)bind 1,4-dioxane,crown ethers and monosaccharides in water with remarkable affinities.The best binding constant reaches 10^(7) M^(−1) for cucurbit[8]uril,which is higher than its binding affinities to common organic cations.Density functional theory(DFT)calculations and control experiments reveal that the hydrophobic effect is the major contributor to the binding through releasing the cavity water and/or properly occupying the weakly hydrated cavity.However,hydrophobic cavity still prefers nonpolar guests over polar guests with similar size and shape.展开更多
Crown ether is a new type coordinating agent. It has a hydrophilic internal cavity which can accommodate charged or neutral molecules, and also a hydrophobic external frame-work. It has been widely used in the making ...Crown ether is a new type coordinating agent. It has a hydrophilic internal cavity which can accommodate charged or neutral molecules, and also a hydrophobic external frame-work. It has been widely used in the making of ionic selective electrodes and as a. phase-transfer agent for organic synthesis and inorganic mimic of biological membranes.展开更多
基金supported by National Natural Science Foundation of China(21401147)Basic Research Program of Natural Science from Shaanxi Provincial Government(2015JQ2032)+2 种基金Scientific Research Program from Education Department of Shaanxi Provincial Government(2013JK0654)Opening Foundation from State Key Laboratory of Coordination Chemistry in Nanjing University(201219)and the Program for Distinguished Young Scholars of Xi’an Polythenic University(201403)
文摘A new metal-organic framework based on ethyl 1H-tetrazole-5-acetate （Hetza）, [Ag4（etza）4] （1）, has been synthesized and characterized by elemental analysis, IR, thermal gravimetric and X-ray structural analysis. Crystal data for the title complex are as follows： triclinic system, space group P1 with a = 11.0771（6）, b = 11.6636（6）, c = 13.2925（8）, a = 102.3710（10）, β =103.3810（10）, γ = 90.0890（10）°, V = 1629.60（16） A3, Mr = 1052.06, Z = 2, F（000） = 1024, Dc = 2.144 g/cm3, μ（MoKa） = 2.438 mm^-1, the final R = 0.0538 and wR = 0.1475 （I 〉 2σ（I））. Complex 1 adopts the （4.82） topological network and the alternately hydrophilic-hydrophilic and hydropho- bic-hydrophobic arrangements. The luminescent properties of complex 1 and the free Hetza ligand have been studied in the solid states.
文摘Room temperature ionic liquids have been currently used in liquid/liquid extraction processes in order to substitute conventional organic solvents. In this paper, a series of chlorinated solvents and 1-alkyl-3-me- thylimidazolium-based ionic liquids were selected to study the extraction efficiency of a lipophilic polya- mine 1,1,7,7-tetraethyl-4-tetradecyldiethylenetriamine (TE14DT) towards the model ion Cu(II) in such dif-ferent media. The effect of temperature on the extraction efficiency was also investigated. The metal ion par-tition was found to be strongly dependent on both the nature of the solvent and on the working temperature. The viscosity of ionic liquids and the water content in ionic liquid were found to affect the extraction effi-ciency of TE14DT. The chemical nature of the cation of ionic liquids, and in particular the alkyl chain length on imidazolium ring, also seemed to be important in determining the efficiency of the extraction process. Finally, preliminary experiments on back-extraction of Cu(II) ions from ionic liquid also revealed interesting hints to the development of a continuous transport process.
文摘Various surfactants have been used in upstream petroleum processes like chemical flooding. Ultimately, the performance of these surfactants depends on their ability to reduce the interfacial tension between oil and water. The surfactant concentration in the aqueous solution decreases owing to the loss of the surfactant on the rock surface in the injection process. The main objective of this paper is to inhibit the surfactant loss by means of adding nanoparticles. Sodium dodecyl sulfate and silica nanoparticles were used as ionic surfactant and nanoparticles in our experiments, respectively. AEROSIL~？ 816 and AEROSIL~？200 are hydrophobic and hydrophilic nanoparticles. To determine the adsorption loss of the surfactant onto rock samples, a conductivity approach was used. Real carbonate rock samples were used as the solid phase in adsorption experiments. It should be noted that the rock samples were water wet. This paper describes how equilibrium adsorption was investigated by examining adsorption behavior in a system of carbonate sample（solid phase） and surfactant solution（aqueous phase）. The initial surfactant and nanoparticle concentrations were 500–5000 and 500–2000 ppm, respectively. The rate of surfactant losses was extremely dependent on the concentration of the surfactant in the system, and the adsorption of the surfactant decreased with an increase in the nanoparticle concentration. Also, the hydrophilic nanoparticles are more effective than the hydrophobic nanoparticles.
文摘RTIL consisting of 1-methyl-3-butyl-imidazolium（BMIm） cation and bis（trifluoromethane sulfone） imide（TFSI） anion was mixed with 1-methyl-3-n-butyl-imidazolium hexafluorophosphate(BMImPF6) at different ratios.Their room temperature conductivity,MS,LV were measured and the effect on association phenomenon by mixing is analyzed.The results demonstrate that the mixtures of ionic liquids can reduce the association degree of single ionic liquid with the better effect of properties,which mesans that the properties of the mixtures are not the average of single RTIL,but have a synergism effect.
文摘为改善纤维素原料的亲水性,提高纤维素的可及度,将具有强亲水性的聚醚引入离子液体合成出系列聚醚功能化双核咪唑类离子液体,并将其应用于纤维素的预处理和糖化研究。相对于在咪唑类离子液体中引入烯丙基、烷基、羧酸以及乙酸乙酯等阳离子功能化基团,聚醚基团的烷氧基(CH2—CH2—O)可增大离子液体与纤维素的有效接触,并作为氢键受体促进纤维素中原有氢键的破坏;分子质量为400的聚乙二醇(PEG400)可提供足够数量和极化强度的氢原子改善亲水性;相对于单核咪唑类,双核咪唑类离子液体醚基上的次甲基氢原子的极性增强(E_T(30),61.33 kcal/mol),形成更高的氢键酸度(α,2.792);聚醚功能化双核咪唑类离子液体([PEG400-(Et-Im)_2][Cl]_2)对纤维素溶解度高达13.26%质量分数。相对于HCOO^-、Cl^-和Br^-阴离子功能化,OAc^-功能化的[PEG400-(Et-Im)_2][OAc]_2具有更大的氢键碱度(β,1.04),增加了对纤维素羟基上氢键的接受能力;聚醚的烷氧基会带来较低的黏度(63 c P,120℃),黏度表观活化能(E_η)为30.11 k J/mol,促进了离子液体与纤维素的接触与物质传输,由此获得[PEG400-(Et-Im)2][OAc]_2对纤维素的高溶解度(14.76%质量分数)。纤维素在[PEG400-(Et-Im)_2][OAc]_2溶解过程中没有发生衍生化反应,纤维素的结晶度由85.4%降至31.6%,实现了高结晶有序结构向无定型的转化。得到的再生纤维素膜具有各向同性和均一致密的性能,热力学稳定性稍有下降。酸性聚醚功能化离子液体[PEG400-(Et-Im)_2][HSO4]_2催化纤维素水解中葡萄糖得率为55.8%。
文摘A new approach to the problem of cold denaturation is presented. It is based on solvent-induced effects operating on hydrophilic groups along the protein. These effects are stronger than the corresponding hydrophobic effects, and they operate on the hydrophilic groups which are plentiful than hydrophobic groups. It is shown that both heat and cold denaturation can be explained by these hydrophilic effects.
基金supported by the National Natural Science Foundation of China(22101125)Shenzhen Science and Technology Innovation Committee(JCYJ20180504165810828)+2 种基金Shenzhen“Pengcheng Scholar”Guangdong High-Level Personnel of Special Support Program(2019TX05C157)Guangdong Provincial Key Laboratory of Catalysis(2020B121201002)。
文摘It is challenging to recognize neutral hydrophilic molecules in water.Effective use of hydrogen bonds in water is generally accepted to be the key to success.In contrast,hydrophobic cavity is usually considered to play an insignificant role or only to provide a nonpolar microenvironment for hydrogen bonds.Herein,we report that hydrophobic cavity alone can also strongly bind neutral,highly hydrophilic molecules in water.We found that cucurbit[n]urils(n=7,8)bind 1,4-dioxane,crown ethers and monosaccharides in water with remarkable affinities.The best binding constant reaches 10^(7) M^(−1) for cucurbit[8]uril,which is higher than its binding affinities to common organic cations.Density functional theory(DFT)calculations and control experiments reveal that the hydrophobic effect is the major contributor to the binding through releasing the cavity water and/or properly occupying the weakly hydrated cavity.However,hydrophobic cavity still prefers nonpolar guests over polar guests with similar size and shape.
文摘Crown ether is a new type coordinating agent. It has a hydrophilic internal cavity which can accommodate charged or neutral molecules, and also a hydrophobic external frame-work. It has been widely used in the making of ionic selective electrodes and as a. phase-transfer agent for organic synthesis and inorganic mimic of biological membranes.
