The hydrolysis process of Ru（III） complex （HL）[trans-RuC14L（dmso-S）] （L=l-methyl-l,2,4- triazole and dmso-S=S-dimethyl sulfoxide） （1）, a potential antitumor complex similar to the well-known antitumor agent ...The hydrolysis process of Ru（III） complex （HL）[trans-RuC14L（dmso-S）] （L=l-methyl-l,2,4- triazole and dmso-S=S-dimethyl sulfoxide） （1）, a potential antitumor complex similar to the well-known antitumor agent （Him）[trans-RuC14 （dmso-S）（im）] （NAMI-A, im=imidazole）, was investigated using density functional theory combined with the conductor-like polarizable continuum model approach. Tile structural characteristics and the detailed energy profiles for the hydrolysis processes of this complex were obtained. For the first hydrolysis step, complex 1 has slightly higher barrier energies than the reported anticancer drug NAMI-A, and the result is in accordance with the experimental evidence indicating larger half-life for complex 1. For the second hydrolysis step, the formation of cis-diaqua species is thermodynamic preferred to that of trans isomers. In addition, on the basis of the analysis of electronic characteristics of species in the hydrolysis process, the trend in nucleophilic attack abilities of hydrolysis products by pertinent biomolecules is revealed and predicted.展开更多
Liquid-liquid extraction(LLE)using ionic liquids(ILs)-based methods to remove perfluoroalkyl chemicals(PFACs),such as perfluorooctanoic acid(PFOA)and perfluorooctane sulfonic acid(PFOS),from wastewater,is an important...Liquid-liquid extraction(LLE)using ionic liquids(ILs)-based methods to remove perfluoroalkyl chemicals(PFACs),such as perfluorooctanoic acid(PFOA)and perfluorooctane sulfonic acid(PFOS),from wastewater,is an important strategy.However,the lack of physicochemical and LLE data limits the selection of the most suitable ILs for the extraction of PFACs.In this work,1763 ILs for PFACs extraction from water were systematically screened using COSMOtherm to estimate the infinite dilution activity coefficient(lnγ^(∞))of PFOA and PFOS in water and ILs.To evaluate the accuracy of COSMOtherm,8 ILs with various lnγ^(∞)values were selected,and their extraction efficiency(E)and distribution coefficient(D_(exp))were measured experimentally.The results showed that the predicted lnγ^(∞)decreased as the increase of experimental extraction efficiency of PFOA or PFOS,while the tendency of predicted distribution coefficient(D_(pre))was consistent with the experimental(D_(exp))results.This work provides an efficient basis for selecting ILs for the extraction of PFACs from wastewater.展开更多
水飞蓟素是水飞蓟种子提取出的黄酮类生物活性成分,具有保肝利胆等多种药理功能,其中水飞蓟宾活性及含量最高,本研究利用天然低共熔溶剂(Natural Deep Eutectic Solvent,NADES),对水飞蓟宾的高效提取工艺与机理进行研究。以粉碎脱脂后...水飞蓟素是水飞蓟种子提取出的黄酮类生物活性成分,具有保肝利胆等多种药理功能,其中水飞蓟宾活性及含量最高,本研究利用天然低共熔溶剂(Natural Deep Eutectic Solvent,NADES),对水飞蓟宾的高效提取工艺与机理进行研究。以粉碎脱脂后的水飞蓟种壳粉为原料,用初步筛选所得较优NADES,即:氯化胆碱+1,4-丁二醇进行提取,HPLC法测定水飞蓟宾含量,在单因素实验基础上,采用响应面法对该NADES提取水飞蓟宾工艺进行优化。结果表明:料液比1:20 g/mL,提取温度77.0℃、时间5.6 h,模型预测水飞蓟宾得率可达4.29%,与实验值4.30%基本一致。基于片段活度系数类导体屏蔽模型(Conductor-like Screening Model for Segment Activity Coefficient,COSMO-SAC),分别对水飞蓟宾和溶剂分子(NADES与传统溶剂乙醇)进行结构与能量优化,通过量子化学计算,得到水飞蓟宾在两种溶剂中的无限稀释活度系数的对数分别为-6.922和-6.043,分子间相互作用能分别为-51.62和-25.47 kJ/mol,以探讨不同溶剂提取水飞蓟宾效果差异机理。展开更多
Rare earth mineral fast ion conductors of Li 1+2 x+3y Al x Sc y Zn y Ti 2- x-2y Si x P 3- x O 12 system based on LiTi 2(PO 4) 3 were prepared by solid phase reaction at hig...Rare earth mineral fast ion conductors of Li 1+2 x+3y Al x Sc y Zn y Ti 2- x-2y Si x P 3- x O 12 system based on LiTi 2(PO 4) 3 were prepared by solid phase reaction at high temperature (1000～1300 ℃) for about 30 h using refined natural kaolinite and Sc 2O 3. The X ray diffraction analysis shows that a Nasicon like structure with R3c space group can be found in the composition range of x =0.1, 0.2, y ≤0.2. The maximum lithium ion conductivity is 1.19×10 -4 S·cm -1 for the composition with x =0.1, y =0.08 at room temperature, and its activation energy is 30.6 kJ·mol -1 in the temperature range of 150～300 ℃. The systems with these compositions have high conductivity of about 10 -2 S·cm -1 at 300 ℃.展开更多
基金This work was supported by the National Natural Science Foundation of China （No.20903027）, the Natural Science Foundation of Guangdong Province （No.9452402301001941）, and the Doctor Startup Fund of Guangdong Medical College （No.XB0802 and No.XB0804）.
文摘The hydrolysis process of Ru（III） complex （HL）[trans-RuC14L（dmso-S）] （L=l-methyl-l,2,4- triazole and dmso-S=S-dimethyl sulfoxide） （1）, a potential antitumor complex similar to the well-known antitumor agent （Him）[trans-RuC14 （dmso-S）（im）] （NAMI-A, im=imidazole）, was investigated using density functional theory combined with the conductor-like polarizable continuum model approach. Tile structural characteristics and the detailed energy profiles for the hydrolysis processes of this complex were obtained. For the first hydrolysis step, complex 1 has slightly higher barrier energies than the reported anticancer drug NAMI-A, and the result is in accordance with the experimental evidence indicating larger half-life for complex 1. For the second hydrolysis step, the formation of cis-diaqua species is thermodynamic preferred to that of trans isomers. In addition, on the basis of the analysis of electronic characteristics of species in the hydrolysis process, the trend in nucleophilic attack abilities of hydrolysis products by pertinent biomolecules is revealed and predicted.
基金support from the Brook Byers Institute for Sustainable Systems,Hightower Chair,and Georgia Research Alliance at the Georgia Institute of Technology.
文摘Liquid-liquid extraction(LLE)using ionic liquids(ILs)-based methods to remove perfluoroalkyl chemicals(PFACs),such as perfluorooctanoic acid(PFOA)and perfluorooctane sulfonic acid(PFOS),from wastewater,is an important strategy.However,the lack of physicochemical and LLE data limits the selection of the most suitable ILs for the extraction of PFACs.In this work,1763 ILs for PFACs extraction from water were systematically screened using COSMOtherm to estimate the infinite dilution activity coefficient(lnγ^(∞))of PFOA and PFOS in water and ILs.To evaluate the accuracy of COSMOtherm,8 ILs with various lnγ^(∞)values were selected,and their extraction efficiency(E)and distribution coefficient(D_(exp))were measured experimentally.The results showed that the predicted lnγ^(∞)decreased as the increase of experimental extraction efficiency of PFOA or PFOS,while the tendency of predicted distribution coefficient(D_(pre))was consistent with the experimental(D_(exp))results.This work provides an efficient basis for selecting ILs for the extraction of PFACs from wastewater.
文摘水飞蓟素是水飞蓟种子提取出的黄酮类生物活性成分,具有保肝利胆等多种药理功能,其中水飞蓟宾活性及含量最高,本研究利用天然低共熔溶剂(Natural Deep Eutectic Solvent,NADES),对水飞蓟宾的高效提取工艺与机理进行研究。以粉碎脱脂后的水飞蓟种壳粉为原料,用初步筛选所得较优NADES,即:氯化胆碱+1,4-丁二醇进行提取,HPLC法测定水飞蓟宾含量,在单因素实验基础上,采用响应面法对该NADES提取水飞蓟宾工艺进行优化。结果表明:料液比1:20 g/mL,提取温度77.0℃、时间5.6 h,模型预测水飞蓟宾得率可达4.29%,与实验值4.30%基本一致。基于片段活度系数类导体屏蔽模型(Conductor-like Screening Model for Segment Activity Coefficient,COSMO-SAC),分别对水飞蓟宾和溶剂分子(NADES与传统溶剂乙醇)进行结构与能量优化,通过量子化学计算,得到水飞蓟宾在两种溶剂中的无限稀释活度系数的对数分别为-6.922和-6.043,分子间相互作用能分别为-51.62和-25.47 kJ/mol,以探讨不同溶剂提取水飞蓟宾效果差异机理。
文摘Rare earth mineral fast ion conductors of Li 1+2 x+3y Al x Sc y Zn y Ti 2- x-2y Si x P 3- x O 12 system based on LiTi 2(PO 4) 3 were prepared by solid phase reaction at high temperature (1000～1300 ℃) for about 30 h using refined natural kaolinite and Sc 2O 3. The X ray diffraction analysis shows that a Nasicon like structure with R3c space group can be found in the composition range of x =0.1, 0.2, y ≤0.2. The maximum lithium ion conductivity is 1.19×10 -4 S·cm -1 for the composition with x =0.1, y =0.08 at room temperature, and its activation energy is 30.6 kJ·mol -1 in the temperature range of 150～300 ℃. The systems with these compositions have high conductivity of about 10 -2 S·cm -1 at 300 ℃.
