A molecular electronegativity distance vector(M)based on 13 atomic types has been used to describe the structures of 19 conjugates(LHCc)of levofloxacin-thiadiazole HDAC inhibitor(HDACi)and related inhibitory activitie...A molecular electronegativity distance vector(M)based on 13 atomic types has been used to describe the structures of 19 conjugates(LHCc)of levofloxacin-thiadiazole HDAC inhibitor(HDACi)and related inhibitory activities(pH,i=1,2,6)of LHCc against histone deacetylases(HDACs,such as HDAC1,HDAC2 and HDAC6).The quantitative structure-activity relationships(QSAR)were established by using leaps-and-bounds regression analysis for the inhibitory activities(pH)of 19 above compounds to HDAC1,HDAC2 and HDAC6 along with M.The correlation coefficients(R~2)and the leave-one-out(LOO)cross validation Rfor the pH,pHand pHmodels were 0.976 and 0.949;0.985 and 0.977;0.976 and 0.932,respectively.The QSAR models had favorable correlations,as well as robustness and good prediction capability by R~2,F,R~2,A,Fand Vtests.Validated by using 3876 training sets,the models have good external prediction ability.The results indicate that the molecular structural units:–CH–(g=1,2),–NH,–OH,=O,–O–and–S–are the main factors which can affect the inhibitory activity of pH,pHas well as pHbioactivities of these compounds directly.Accordingly,the main interactions between HDACs inhibitor and HDACs are hydrophobic interaction,hydrogen bond,and coordination with Znto form compounds,which is consistent with the results in reports.展开更多
With the ever-pressing issues of global energy demand and environmental pollution,molecular hydrogen has been receiving increasing attention as a clean alternative energy carrier.For hydrogen production,the design and...With the ever-pressing issues of global energy demand and environmental pollution,molecular hydrogen has been receiving increasing attention as a clean alternative energy carrier.For hydrogen production,the design and development of high-performance catalysts remains rather challenging.As the compositions and structures of catalyst interfaces have paramount influences on the catalytic performances,the central topic here has always been to design and engineer the interface structures via rational routes so as to boost the activities and stabilities of electrocatalysts on hydrogen evolution reaction(HER).Here in this review,we focus on the design and preparation of multi-scale catalysts specifically catering to HER applications.We start from the design and structure-activity relationship of catalytic nanostructures,summarize the research progresses related to HER nanocatalysts,and interpret their high activities from the atomistic perspective;then,we review the studies regarding the design,preparation,HER applications and structure-activity relationship of single-atom site catalysts(SASCs),and thereupon discuss the future directions in designing HER-oriented SASCs.At the end of this review,we present an outlook on the development trends and faced challenges of catalysts for electrochemical HER.展开更多
Density functional theory（DFT）-B3LYP level with the 6-311G＊＊（d,p） basis set was used to calculate a set of molecular quantum chemical descriptors of 12 chloroanilines. Quantitative structure-activity relationshi...Density functional theory（DFT）-B3LYP level with the 6-311G＊＊（d,p） basis set was used to calculate a set of molecular quantum chemical descriptors of 12 chloroanilines. Quantitative structure-activity relationship（QSAR） models of the bioconcentration factors（BCF） of the anilines in fish were established using some of the following calculated descriptors： EHOMO, ENHOMO, ELUMO, ENLUMO, ΔE1（= ELUMO- EHOMO）, ΔE2（= ENLUMO- ENHOMO）, dipole moment（μ）, molecular volume（V）, vibrational energy of 0 K（Ev）, thermodynamic energy（E）, heat capacity（Cv）, entropy（Sm） and the charge of benzene ring（Qph）. Using the variable selection and leaps-and-bounds regression, the quantum chemical descriptors derived directly from the molecular structures were employed to develop a linear QSAR model between the bioconcentration factors（BCF） and two descriptors（Sm, ENHOMO） of 12 chloroanilines. Statistically, the most significant one is a two-parameter linear equation with the correlation coefficient（R^2） of 0.981 and cross-validated correlation coefficient（Rcv^2） of 0.967. The established QSAR model has good stability and predictability based on the results from Rcv2 of leave-one-out cross-validation, AIC, FIT and tα/2. The quantum chemical analyses were performed from two aspects of frontier molecular orbital and entropy. The results show that two structural describers are crucial to the bioconcentration activity of chloroanilines.展开更多
In an attempt to find leading thiazole carboxanilides exhibiting fungicidal activities, we designed and synthesized a new series of 2-sulfursubstituted thiazole carboxanilides via the reaction between 2-sulfur substit...In an attempt to find leading thiazole carboxanilides exhibiting fungicidal activities, we designed and synthesized a new series of 2-sulfursubstituted thiazole carboxanilides via the reaction between 2-sulfur substituted thiazole carboxylic acid chlorides and substituted aniline. The fungicidal activities of the title compounds against Rhizoctonia solani were screened and the results were remarkable. The most potent compound 8i, N-[2~6-dich~~r^-4-（tri^u~r^methy~）pheny~]-2-methy^thi^-4-（tri^u~r^methy~）thiaz~~e-5-~arb^xamide~ was identified. The fungicidal ECs0 of compound 8i against Rhizoctonia solani was 1.28 mg/L, being comparable to that of Thiflu- zamide. The results indicate that compound 8i can be considered as a lead compound for further research.展开更多
Using density functional methods,some properties were studied such as the energies and compositions of frontier molecular orbitals and the atomic charges,which are related to the reactive behavior of thioureas contain...Using density functional methods,some properties were studied such as the energies and compositions of frontier molecular orbitals and the atomic charges,which are related to the reactive behavior of thioureas containing different N-substituent groupings.The calculation results indicate that the N-substituent groupings have significant effect on the flotation performance of thiourea collectors.The order of electron-donating ability is N-propyl-N'-benzyl-thiourea(PBZYTU)>N-propyl-N'-ethyl-thiourea (PETU)>N-propyl-N'-allyl-thiourea(PALTU)>>N-propyl-N'-acetyl-thiourea(PACTU)>N-propyl-N'-ethoxycarbonyl-thiourea (PECTU)>N-propyl-N'-benzoyl-thiourea(PBZOYTU),and the order of feedback-electron-accepting ability is PBZOYTU> PACTU>PECTU>>PALTU>PETU>PBZYTU.This implies that PBZOYTU,PACTU or PECTU can react with copper atoms having(t2g) 6 (eg) 3Cu(II)or t 6e 4Cu(I)configuration on the surfaces of copper sulfide minerals through normal covalent bond and back donation covalent bond,and exhibit excellently collecting performance for copper sulfide minerals.These are consistent with the experimental data reported in the literatures.展开更多
Based on Hall et al. electrotopological state indices（EK） of atom types, two quantitative structure-activity relationship（QSAR） models were developed to estimate and predict the action strength（W） of D（OM）（di...Based on Hall et al. electrotopological state indices（EK） of atom types, two quantitative structure-activity relationship（QSAR） models were developed to estimate and predict the action strength（W） of D（OM）（dimethoxy-methyl-amphetamine） for 18 phenyl-isopropyl-amine dopes（PPAD） through linear method（multiple linear regression, MLR） and non-linear method（Back propagation artificial neural network, BP-ANN）. On the basis of EK, the optimal three-parameter（E14, E9, E7） QSAR model of W for 18 PPAD was constructed. The traditional correlation coefficient（R^2） and cross-validation correlation coefficient（Rcv^2） are 0.878 and 0.815, respectively. The result demonstrates that the model is highly reliable（from the point of view of statistics） and has good predictive ability by using R^2, Rcv^2, VIF, FIT, AIC and F tests. Form the three parameters of the model, it is known that the dominant influence factors of inhibited activity are the molecular structure fragments： =CH–（secondary carbon）, =C〈（tertiary carbon atom） in aromatic ring and –O–（phenol ether bond）. The results showed that the structure parameters E14, E9 and E7 have good rationality and efficiency for the W of phenyl-isopropyl-amine dope（PPAD） analogues. A BP-ANN with 3-3-1 architecture was generated by using three electrotopological state index descriptors（E14, E9, E7） appearing in the MLR model, the above descriptors were inputs and its output was action strength（W）. The nonlinear BP-ANN model has better predictive ability compared to the linear MLR model with R^2 and Rcv^2 of leave-one-out（LOO） to be 0.995 and 0.994, respectively. The regression method gave support to the neural network with physical explanation, which offers a more accurate model for QSAR. Those models can be used in the rational design of higher stimulating extent PPAD, which provide meaningful reference information to improve the detection methods of PPAD.展开更多
Structure-activity relationship (SAR) is the key problem of nanoscience,thus to fabricate novel and well-defined nanostructure will provide a new insight on catalyst preparation method.Highly active and low cost elect...Structure-activity relationship (SAR) is the key problem of nanoscience,thus to fabricate novel and well-defined nanostructure will provide a new insight on catalyst preparation method.Highly active and low cost electrocatalysts for oxygen evolution reaction (OER) are of great importance for future renewable energy conversion and storage.Herein,NiFe-based layered double hydroxides with laminar structure (NFLS) were successfully fabricated via a one-step hydrothermal approach by using sodium dodecyl sulfate as surfactant.The as-fabricated NFLS showed a well-defined periodic layered-stacking geometry with a scale down to 1-nm.Benefitting from the unique structure,NFLS exhibited an excellent catalytic activity towards OER with current densities of 10 mA·cm^-2 at overpotential of 197 mV.The synergistic effect of Ni and Fe plays a key role in electrode reactions.The present work provides a new insight to improve the OER performance by rational design of electrocatalysts with unique structures.展开更多
Tuberculosis（TB） is one of the most common and even fatal infectious diseases known to mankind.Millions of new cases are reported every year over the world,and one-third of the world＇s population is potentially inf...Tuberculosis（TB） is one of the most common and even fatal infectious diseases known to mankind.Millions of new cases are reported every year over the world,and one-third of the world＇s population is potentially infected with mycobacteria tuberculosis（MTB）.Research to develop novel anti-TB drugs led to the identification of several isatin-based antimycobacterial agents,among which a number of potential candidates displayed excellent antimycobacterial activity and were found to be free of cytotoxicity.This review outlines the advances in the application of isatin hybrids as antimycobacterial agents and the critical aspects of design and structure-activity relationship of these derivatives.展开更多
基金supported by the National Natural Science Foundation of China(21473081,21075138)special fund of State Key Laboratory of Structure Chemistry(20160028)
文摘A molecular electronegativity distance vector(M)based on 13 atomic types has been used to describe the structures of 19 conjugates(LHCc)of levofloxacin-thiadiazole HDAC inhibitor(HDACi)and related inhibitory activities(pH,i=1,2,6)of LHCc against histone deacetylases(HDACs,such as HDAC1,HDAC2 and HDAC6).The quantitative structure-activity relationships(QSAR)were established by using leaps-and-bounds regression analysis for the inhibitory activities(pH)of 19 above compounds to HDAC1,HDAC2 and HDAC6 along with M.The correlation coefficients(R~2)and the leave-one-out(LOO)cross validation Rfor the pH,pHand pHmodels were 0.976 and 0.949;0.985 and 0.977;0.976 and 0.932,respectively.The QSAR models had favorable correlations,as well as robustness and good prediction capability by R~2,F,R~2,A,Fand Vtests.Validated by using 3876 training sets,the models have good external prediction ability.The results indicate that the molecular structural units:–CH–(g=1,2),–NH,–OH,=O,–O–and–S–are the main factors which can affect the inhibitory activity of pH,pHas well as pHbioactivities of these compounds directly.Accordingly,the main interactions between HDACs inhibitor and HDACs are hydrophobic interaction,hydrogen bond,and coordination with Znto form compounds,which is consistent with the results in reports.
基金Acknowledgements This work was supported by the National Key R&D Program of China(2016YFA0202801,2017YFA0700101 and 2018YFA0702003)the National Natural Science Foundation of China(21925202,21872076 and 21890383)+4 种基金Beijing Natural Science Foundation(JQ18007)the Fundamental Research Funds for the Central Universities(19CX02008A)the Petro China Innovation Foundation(2019D-5007-0401)Taishan Scholars Program of Shandong Province(tsqn201909065)Tsinghua University Initiative Scientific Research Program.
文摘With the ever-pressing issues of global energy demand and environmental pollution,molecular hydrogen has been receiving increasing attention as a clean alternative energy carrier.For hydrogen production,the design and development of high-performance catalysts remains rather challenging.As the compositions and structures of catalyst interfaces have paramount influences on the catalytic performances,the central topic here has always been to design and engineer the interface structures via rational routes so as to boost the activities and stabilities of electrocatalysts on hydrogen evolution reaction(HER).Here in this review,we focus on the design and preparation of multi-scale catalysts specifically catering to HER applications.We start from the design and structure-activity relationship of catalytic nanostructures,summarize the research progresses related to HER nanocatalysts,and interpret their high activities from the atomistic perspective;then,we review the studies regarding the design,preparation,HER applications and structure-activity relationship of single-atom site catalysts(SASCs),and thereupon discuss the future directions in designing HER-oriented SASCs.At the end of this review,we present an outlook on the development trends and faced challenges of catalysts for electrochemical HER.
基金co-financed by the National Natural Science Foundation of China(21075138)special fund of State Key Joint Laboratory of Environment Simulation and Pollution Control(13K02ESPCT)
文摘Density functional theory（DFT）-B3LYP level with the 6-311G＊＊（d,p） basis set was used to calculate a set of molecular quantum chemical descriptors of 12 chloroanilines. Quantitative structure-activity relationship（QSAR） models of the bioconcentration factors（BCF） of the anilines in fish were established using some of the following calculated descriptors： EHOMO, ENHOMO, ELUMO, ENLUMO, ΔE1（= ELUMO- EHOMO）, ΔE2（= ENLUMO- ENHOMO）, dipole moment（μ）, molecular volume（V）, vibrational energy of 0 K（Ev）, thermodynamic energy（E）, heat capacity（Cv）, entropy（Sm） and the charge of benzene ring（Qph）. Using the variable selection and leaps-and-bounds regression, the quantum chemical descriptors derived directly from the molecular structures were employed to develop a linear QSAR model between the bioconcentration factors（BCF） and two descriptors（Sm, ENHOMO） of 12 chloroanilines. Statistically, the most significant one is a two-parameter linear equation with the correlation coefficient（R^2） of 0.981 and cross-validated correlation coefficient（Rcv^2） of 0.967. The established QSAR model has good stability and predictability based on the results from Rcv2 of leave-one-out cross-validation, AIC, FIT and tα/2. The quantum chemical analyses were performed from two aspects of frontier molecular orbital and entropy. The results show that two structural describers are crucial to the bioconcentration activity of chloroanilines.
基金Supported by the National Natural Science Foundation of China（Nos.21272062, 21572050）.
文摘In an attempt to find leading thiazole carboxanilides exhibiting fungicidal activities, we designed and synthesized a new series of 2-sulfursubstituted thiazole carboxanilides via the reaction between 2-sulfur substituted thiazole carboxylic acid chlorides and substituted aniline. The fungicidal activities of the title compounds against Rhizoctonia solani were screened and the results were remarkable. The most potent compound 8i, N-[2~6-dich~~r^-4-（tri^u~r^methy~）pheny~]-2-methy^thi^-4-（tri^u~r^methy~）thiaz~~e-5-~arb^xamide~ was identified. The fungicidal ECs0 of compound 8i against Rhizoctonia solani was 1.28 mg/L, being comparable to that of Thiflu- zamide. The results indicate that compound 8i can be considered as a lead compound for further research.
基金Project(50604016)supported by the National Natural Science Foundation of ChinaProject(2007B52)supported by the Foundation for the Author of National Excellent Doctoral Dissertation of China+3 种基金Project(NCET-08-0568)supported by the Program for New Century Excellent Talents in Chinese UniversityProject(2007CB613602)supported by the National Basic Research Program of ChinaProject(2007AA06Z122)supported by the National High-tech Research and Development Program of ChinaProject(2007BAB22B01)supported by the National Science and Technology Support Project of China
文摘Using density functional methods,some properties were studied such as the energies and compositions of frontier molecular orbitals and the atomic charges,which are related to the reactive behavior of thioureas containing different N-substituent groupings.The calculation results indicate that the N-substituent groupings have significant effect on the flotation performance of thiourea collectors.The order of electron-donating ability is N-propyl-N'-benzyl-thiourea(PBZYTU)>N-propyl-N'-ethyl-thiourea (PETU)>N-propyl-N'-allyl-thiourea(PALTU)>>N-propyl-N'-acetyl-thiourea(PACTU)>N-propyl-N'-ethoxycarbonyl-thiourea (PECTU)>N-propyl-N'-benzoyl-thiourea(PBZOYTU),and the order of feedback-electron-accepting ability is PBZOYTU> PACTU>PECTU>>PALTU>PETU>PBZYTU.This implies that PBZOYTU,PACTU or PECTU can react with copper atoms having(t2g) 6 (eg) 3Cu(II)or t 6e 4Cu(I)configuration on the surfaces of copper sulfide minerals through normal covalent bond and back donation covalent bond,and exhibit excellently collecting performance for copper sulfide minerals.These are consistent with the experimental data reported in the literatures.
基金supported by the National Natural Science Foundation of China(21075138)special fund of State Key Laboratory of Structural Chemistry(20160003)
文摘Based on Hall et al. electrotopological state indices（EK） of atom types, two quantitative structure-activity relationship（QSAR） models were developed to estimate and predict the action strength（W） of D（OM）（dimethoxy-methyl-amphetamine） for 18 phenyl-isopropyl-amine dopes（PPAD） through linear method（multiple linear regression, MLR） and non-linear method（Back propagation artificial neural network, BP-ANN）. On the basis of EK, the optimal three-parameter（E14, E9, E7） QSAR model of W for 18 PPAD was constructed. The traditional correlation coefficient（R^2） and cross-validation correlation coefficient（Rcv^2） are 0.878 and 0.815, respectively. The result demonstrates that the model is highly reliable（from the point of view of statistics） and has good predictive ability by using R^2, Rcv^2, VIF, FIT, AIC and F tests. Form the three parameters of the model, it is known that the dominant influence factors of inhibited activity are the molecular structure fragments： =CH–（secondary carbon）, =C〈（tertiary carbon atom） in aromatic ring and –O–（phenol ether bond）. The results showed that the structure parameters E14, E9 and E7 have good rationality and efficiency for the W of phenyl-isopropyl-amine dope（PPAD） analogues. A BP-ANN with 3-3-1 architecture was generated by using three electrotopological state index descriptors（E14, E9, E7） appearing in the MLR model, the above descriptors were inputs and its output was action strength（W）. The nonlinear BP-ANN model has better predictive ability compared to the linear MLR model with R^2 and Rcv^2 of leave-one-out（LOO） to be 0.995 and 0.994, respectively. The regression method gave support to the neural network with physical explanation, which offers a more accurate model for QSAR. Those models can be used in the rational design of higher stimulating extent PPAD, which provide meaningful reference information to improve the detection methods of PPAD.
基金the National Natural Science Foundation of China (Nos.21431003 and 21521091)the National Key Technology R&D Program of China (No.2016YFA0202801).
文摘Structure-activity relationship (SAR) is the key problem of nanoscience,thus to fabricate novel and well-defined nanostructure will provide a new insight on catalyst preparation method.Highly active and low cost electrocatalysts for oxygen evolution reaction (OER) are of great importance for future renewable energy conversion and storage.Herein,NiFe-based layered double hydroxides with laminar structure (NFLS) were successfully fabricated via a one-step hydrothermal approach by using sodium dodecyl sulfate as surfactant.The as-fabricated NFLS showed a well-defined periodic layered-stacking geometry with a scale down to 1-nm.Benefitting from the unique structure,NFLS exhibited an excellent catalytic activity towards OER with current densities of 10 mA·cm^-2 at overpotential of 197 mV.The synergistic effect of Ni and Fe plays a key role in electrode reactions.The present work provides a new insight to improve the OER performance by rational design of electrocatalysts with unique structures.
文摘Tuberculosis（TB） is one of the most common and even fatal infectious diseases known to mankind.Millions of new cases are reported every year over the world,and one-third of the world＇s population is potentially infected with mycobacteria tuberculosis（MTB）.Research to develop novel anti-TB drugs led to the identification of several isatin-based antimycobacterial agents,among which a number of potential candidates displayed excellent antimycobacterial activity and were found to be free of cytotoxicity.This review outlines the advances in the application of isatin hybrids as antimycobacterial agents and the critical aspects of design and structure-activity relationship of these derivatives.
