New descriptors were constructed and structures of some oxygen-containing organic compounds were parameterized. The multiple linear regression（MLR） and partial least squares regression（PLS） methods were employed t...New descriptors were constructed and structures of some oxygen-containing organic compounds were parameterized. The multiple linear regression（MLR） and partial least squares regression（PLS） methods were employed to build two relationship models between the structures and octanol/water partition coefficients（LogP） of the compounds. The modeling correlation coefficients（R） were 0.976 and 0.922, and the ＂leave one out＂ cross validation correlation coefficients（R（CV）） were 0.973 and 0.909, respectively. The results showed that the structural descriptors could well characterize the molecular structures of the compounds; the stability and predictive power of the models were good.展开更多
The n-octanol/water partition coefficients （lgKow） of 18 substituted anilines were determined at 25 ℃ by shake-flask method. The geometrical optimization of substituted anilines has been performed at B3LYP/6-311G^...The n-octanol/water partition coefficients （lgKow） of 18 substituted anilines were determined at 25 ℃ by shake-flask method. The geometrical optimization of substituted anilines has been performed at B3LYP/6-311G^＊＊ level with Gaussian98 program, and the molecular surface areas of substituted anilines were calculated using ChemOffice 2004 program. The calculated structural parameters of substituted anilines were used as theoretical descriptors and the two-parameter （molecular surface area （MA） and the energy of the highest occupied molecular orbital （EaoMo）） quantitative structure-property relationship （QSPR） model of lgKow for substituted aniline with molecular structural parameters was developed by multi-linear regression method. The regression coefficient square （r^2） is 0.990 and the standard deviation SE 0.109. The model was validated by variance inflation factors （VIF） and t-test, and the results show that there exists small self-correlation between variables of the model with perfect stability. The model gives results in good qualitative agreement with experimental data. At last, the model was applied to predict lgKow values of five substituted anilines whose lgKow values have not been determined experimentally.展开更多
Optimized calculations of 75 PCDDs and their parent DD were carded out at the B3LYP/6-31G＊ level by density functional theory （DFT） method. The structural parameters were obtained and significant correlation betwee...Optimized calculations of 75 PCDDs and their parent DD were carded out at the B3LYP/6-31G＊ level by density functional theory （DFT） method. The structural parameters were obtained and significant correlation between the C1 substitution position and some structural parameters was found. Consequently, the number of C1 substitution positions was taken as theoretical descriptors to establish two novel QSPR models for predicting lgKow and -lgSw of all PCDD congeners. The two models achieved in this work contain two variables （Na and Nβ）, of which r = 0.9312, 0.9965 and SD = 0.27, 0.12 respectively, and t values are all large. The variation inflation factors （VIF） of variables in the two models herein are both less than 5.0, suggesting high accuracy of the lgKow and -lgSw predicting models, and the results of cross-validation test also show that the two models exhibit optimum stability and good predictive power. By comparison, the correlation and predictive ability of the present work are more advantageous than those obtained using semi-empirical AM1 and GC-RI methods.展开更多
Quantum chemistry parameters of 28 alkyl（1-phenylsulfonyl） cycloalkane-carboxy-lates were computed at the 6-31G＊ level in fully optimal manner using B3LYP method of density functional theory （DFT）. With GQSARF2.0...Quantum chemistry parameters of 28 alkyl（1-phenylsulfonyl） cycloalkane-carboxy-lates were computed at the 6-31G＊ level in fully optimal manner using B3LYP method of density functional theory （DFT）. With GQSARF2.0 program, the correlation equations that can predict n-octanol/water partition coefficient （lgKow） were developed using the structural and thermodynamic parameters of 28 alkyl（1-phenylsulfonyl） cycloalkane-carboxylates with experimental data of lgKow as theoretical descriptors; the correlation coefficient （R^2） was 0.9452 and the cross-validation squared correlation coefficient （Rcv^2） 0.9312. Furthermore, a four-variable model from MEDV was obtained, of which R2 = 0.9497 and Rov^2 =0.9388. The models were validated by variance inflation factor （VIF） and t-test. Cross-validation indicates that the correlation and predicting ability of the model based on both DFT method and MEDV are more advantageous than those obtained from semi-empirical AM1 method.展开更多
Optimized calculation of 35 dialkyl phenyl phosphate compounds （OPs） was carded out at the B3LYP/6-31G^＊ level in Gaussian 98 program. Based on the theoretical linear solvation energy relationship （TLSER） model, ...Optimized calculation of 35 dialkyl phenyl phosphate compounds （OPs） was carded out at the B3LYP/6-31G^＊ level in Gaussian 98 program. Based on the theoretical linear solvation energy relationship （TLSER） model, the obtained parameters were taken as theoretical descriptors to establish the novel QSPR model for predicting n-octanol/water partition coefficients （lgKow） of OPs. The new model achieved in this work contains three variables, i.e., molecular volume （Vm）, dipole moment of the molecules （μ） and enthalpy （H^0）. For this model, R^2 = 0.9167 and SD = 0.31 at large t values. In addition, the variation inflation factors （VIF） of variables are all close to 1.0, suggesting high accuracy of the predicting model. And the results of cross-validation test （q^2 = 0.8993） and method validation also showed the model of this study exhibited optimum stability and better predictive power than that from semi-empirical method. The model achieved can be used to predict IgKow of congeneric compounds.展开更多
Structural parameters of 24 substituted naphthalin compounds were computed at four levels using Hartree-Fock and DFT methods. Based on the experimental data of octanol/water partition coefficient （lgKow）, three-para...Structural parameters of 24 substituted naphthalin compounds were computed at four levels using Hartree-Fock and DFT methods. Based on the experimental data of octanol/water partition coefficient （lgKow）, three-parameter （energy of the highest occupied molecular orbital （EHOMO）, the most positive, atomic net charges of molecule （q^＋） and molecular average polarizability （α）） dependent equations were developed using structural parameters as theoretical descriptors. Especially, lgKow dependent equation calculated at the HF/6-311G^＊＊ level is more advantageous than others in view of their correlation and predictive abilities. This dependent equation was validated by variance inflation factors （VIF） and t-test methods and used to predict lgKow of eight designed compounds. Upon comparison, the predictive abilities of our work are all more advantageous than those calculated from molecular property calculator program.展开更多
Octanol/water partition coefficient （Kow） is a crucial property for evaluating the environmental behavior and fate of organic compound. Herein, some quantitative structure-property relationship （QSPR） studies were...Octanol/water partition coefficient （Kow） is a crucial property for evaluating the environmental behavior and fate of organic compound. Herein, some quantitative structure-property relationship （QSPR） studies were performed to estimate and predict the lgK ow of substituted anilines. 2D method （multiple linear regression, MLR） and 3D method （comparative molecular field analysis, CoMFA） were applied in this study. Successful 2D and 3D models yielded the correlation coefficient （R2） values of 0.981 and 0.966 and the Leave-One-Out （LOO） cross-validated correlation coefficient （q2） values of 0.933 and 0.820, respectively. The developed models have a highly predictive ability in both internal and external validation. In addition, the results were interpreted in terms of physical and chemical meanings of descriptors and field contribution maps. It showed that the steric and electrostatic properties are the primary factors that govern the lgK ow of substituted anilines. The information obtained from the QSPR models would be helpful to the interpretation of structural features pertinent to the lgK ow of substituted anilines, which may be helpful in estimating the organic compounds＇ potential harm to the environment.展开更多
A shake-flask method was used to determine 1-octanol/water partition coefficients of ofloxacin, norfloxacin, lomefloxacin, ciprofloxacin, pefloxacin and pipemidic acid from 293.15 K to 323.15 K. The results show that ...A shake-flask method was used to determine 1-octanol/water partition coefficients of ofloxacin, norfloxacin, lomefloxacin, ciprofloxacin, pefloxacin and pipemidic acid from 293.15 K to 323.15 K. The results show that 1-octanol/water partition coefficient of each quinolone increased with the increase of temperature. Based on the fluid phase equilibrium theory, the thermodynamic relationship of 1-octanol/water partition coefficient depending on the temperature was proposed, and the changes of enthalpy, entropy, and Gibbs free energy for quinolones partitioning in 1-octanol/water were determined, respectively. Quinolones molecules partitioning in 1-octanol/water was mainly an entropy driving process, during which the order degree of system decreased. The temperature effects of 1-octanol/water partition coefficient were investigated. The results show that its magnitude is the same as the values in the literature.展开更多
Optimized calculation of dibenzofuran （DF） and 135 polychlorinated dibenzofurans （PCDFs） was carried out at the B3LYP/6-31G＊ level in GAUSSIAN 98 program. Based on the theoretical linear solvation energy relation...Optimized calculation of dibenzofuran （DF） and 135 polychlorinated dibenzofurans （PCDFs） was carried out at the B3LYP/6-31G＊ level in GAUSSIAN 98 program. Based on the theoretical linear solvation energy relationship （TLSER） model, the obtained structural parameters were taken as theoretical descriptors to establish the novel quantitative structureproperty relationship （QSPR） model for predicting n-octanol/water partition coefficients （lgKow） of PCDFs. The new model of lgKow achieved in this work contains three variables： energy of the highest occupied molecular orbital （EHOMO）, the most negative atomic partial charge （q^-） and average molecular polarizability （a）, of which R^2= 0.9011 and SD = 0,17 with larger t values. In addition, the variation inflation factors （VIF） of variables in the present model are all less than 5.5, suggesting high accuracy of the lgKow model. And the results of cross-validation test （q^2 = 0.8688） and method validation also show this model exhibits optimum stability and better predictive power than semi-empirical method. At the same time, it is found that the aqueous solubility （-lgSw） has high relative correlation with constant volume molar heat capacity （Cv^0）, of which R^2 = 0.9777 and SD = 0.22. Moreover, lgKow and -lgSw values of all PCDF congeners were predicted respectively.展开更多
Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen e...Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen evolution reaction(HER)and the anodic oxygen evolution reaction(OER).Transition metal-based catalysts have garnered significant research interest as promising alternatives to noble-metal catalysts,owing to their low cost,tunable composition,and noble-metal-like catalytic activity.Nevertheless,systematic reviews on their application as bifunctional catalysts for overall water splitting(OWS)are still limited.This review comprehensively outlines the principal categories of bifunctional transition metal electrocatalysts derived from electrospun nanofibers(NFs),including metals,oxides,phosphides,sulfides,and carbides.Key strategies for enhancing their catalytic performance are systematically summarized,such as heterointerface engineering,heteroatom doping,metal-nonmetal-metal bridging architectures,and single-atom site design.Finally,current challenges and future research directions are discussed,aiming to provide insightful perspectives for the rational design of high-performance electrocatalysts for OWS.展开更多
Ion-solvaing membranes(ISMs)have received extensive attention in recent years as a key component in electrochemical energy conversion and storage devices.This article provides an overview of structural composition,per...Ion-solvaing membranes(ISMs)have received extensive attention in recent years as a key component in electrochemical energy conversion and storage devices.This article provides an overview of structural composition,performance advan-tages,research progress,ion conduction mechanism and existing issues of ISMs,primarily classifying them according to the matrix structure.A detailed analysis of performance enhancement methods,key performance indicators of ISMs and performance influencing factors is also presented.The article contributes to further optimizing the design and application of ion-solvation membranes,providing theoretical support for the development of fields such as hydrogen production through electrolysis of water and electrochemical energy in the future.展开更多
To maintain soil quality under long-term saline water irrigation,the influence of manure on soil physical properties was examined.Long-term saline irrigation has been conducted from 2015 to 2024 at the Nanpi Eco-Agric...To maintain soil quality under long-term saline water irrigation,the influence of manure on soil physical properties was examined.Long-term saline irrigation has been conducted from 2015 to 2024 at the Nanpi Eco-Agricultural Experimental Station of Chinese Academy Sciences in the Low Plain of the North China Plain,comprising four irrigation treatments:irrigation once at the jointing stage for winter wheat with irrigation water containing salt at fresh water,3,4 and 5 g·L^(–1),and maize irrigation at sowing using fresh water.Manure application was conducted under all irrigation treatments,with treatments without manure application used as controls.The results showed that under long-term irrigation with saline water,the application of manure increased the soil organic matter content,exchangeable potassium,available phosphorus,and total nitrogen content in the 0–20 cm soil layer by 46.8%,117.0%,75.7%,and 45.5%,respectively,compared to treatments without manure application.The application of manure reduced soil bulk density.It also increased the proportion of water-stable aggregates and the abundance of bacteria,fungi,and actinomycetes in the tillage soil layer compared to the controls.Because of the salt contained in the manure,the application of manure had dual effects on soil salt content.During the winter wheat season,manure application increased soil salt content.The salt content was significantly reduced during the summer maize season,owing to the strong salt-leaching effects under manure application,resulting in a smaller difference in salt content between the manure and non-manure treatments.During the summer rainfall season,improvements in soil structure under manure application increased the soil desalination rate for the 1 m top soil layer.The desalination rate for 0–40 cm and 40–100 cm was averagely by 39.1%and 18.9%higher,respectively,under manure application as compared with that under the nomanure treatments.The yield of winter wheat under manure application was 0.12%lower than that of the control,owing to the higher salt content during the winter wheat season.In contrast,the yield of summer maize improved by 3.9%under manure application,owing to the increased soil nutrient content and effective salt leaching.The results of this study indicated that manure application helped maintain the soil physical structure,which is important for the long-term use of saline water.In practice,using manure with a low salt content is suggested to reduce the adverse effects of saline water irrigation on soil properties and achieve sustainable saline water use.展开更多
In Bom Jesus Municipality,a cool breeze drifts in from the Kwanza River,softening the edges of a town marked by landmarks such as António Agostinho Neto International Airport.Yet beneath Luanda’s scenic faç...In Bom Jesus Municipality,a cool breeze drifts in from the Kwanza River,softening the edges of a town marked by landmarks such as António Agostinho Neto International Airport.Yet beneath Luanda’s scenic façade,daily life for many residents is defined by a persistent struggle for water.“We have to walk 5 to 15 km to access water.This perennial problem is so depressing.What’s more,the lack of clean water causes waterborne diseases in our community,”local resident Isabel Fernando told ChinAfrica.展开更多
The mining industry is frequently subjected to various disasters,one of the major concerns is water-related disasters,particularly seam floor water inrush.These disasters pose significant threats to the safety and pro...The mining industry is frequently subjected to various disasters,one of the major concerns is water-related disasters,particularly seam floor water inrush.These disasters pose significant threats to the safety and production of deep coal mines.The primary reason for this is that the fracturing of the rock mass induces the formation of a fluid(water)with both kinetic and potential energy.In this paper,a novel water inrush mechanism for deep floor failure due to water hammer effects is proposed based on the Xingdong coal mine in China.The water hammer pressure within rock pore channels has a different impact on the surrounding rock,leading to the degradation of the rock mass channel through repeated conduction and instantaneous cutoff.To further investigate this phenomenon,a progressive corrosion fracture mechanics(PCFM)model induced by a water hammer is established.The results show that the water hammer pressure caused by instantaneous channel truncation increases with increasing water flow velocity.The chemical damage factor(i.e.,stress corrosion fracture)is also incorporated into the Dugdale-Barenblatt(D-B)model to analyze the factors influencing the PCFM.These findings indicate that the greater the degree of damage is,the more likely the concealed fault is to experience water inrush.Finally,methods for controlling water inrush caused by the water hammer effects of deep floors are proposed.The failure mechanisms of the water hammer and the PCFM provide theoretical and practical guidance for controlling water inrush from the deep floor.展开更多
In permafrost regions of the QinghaiXizang Plateau,embankments of the Qinghai-Xizang Highway and Qinghai-Xizang Railway experiencing roadside water accumulation exhibit more pronounced engineering deteriorations.A wid...In permafrost regions of the QinghaiXizang Plateau,embankments of the Qinghai-Xizang Highway and Qinghai-Xizang Railway experiencing roadside water accumulation exhibit more pronounced engineering deteriorations.A widely accepted view is that the accumulated water adjacent to the embankment possesses substantial thermal energy,which accelerates the degradation-even disappearance-of the underlying permafrost.Moreover,the presence of roadside water keeps the embankment soil in a persistently high-moisture state,thereby making the frozen-soil embankment more susceptible to deformation under traffic loading.However,in the permafrost regions of the QinghaiXizang Plateau,deteriorations of embankments affected by roadside water are more commonly manifested as undulating pavement surfaces,and extensive crack networks appear on the embankment crest even where thermosyphons are installed.These manifestations are not fully consistent with the deterioration mechanisms proposed by existing viewpoints.We propose the hypothesis that temperature gradients,formed due to the freezing and thawing processes between the roadside wateraffected soil and the roadbed soil,lead to moisture migration under the influence of temperature gradients,resulting in frost heave and thaw settlement in the roadbed soil.To validate this hypothesis,we conducted the following investigations sequentially.Initially,we selected a roadbed with a thermosyphon(TPCT)system,which has a significant cooling effect,as the study object.By analyzing the temperature monitoring data of the roadbed section,the temperature variance was calculated to identify the time nodes where the temperature gradient of the roadbed soil was maximum and minimum.Subsequently,corresponding roadbed temperature distribution maps were drawn,illustrating the changes in the temperature and position of the lowtemperature core near the TPCT over time.Furthermore,using small-scale indoor model experiments,we qualitatively concluded that moisture in the soil migrates toward the TPCT due to the temperature gradient.Thereafter,combining borehole water content data and precipitation data from the sloped terrain construction site,the formation mechanisms and timing characteristics of roadside water accumulation were analyzed.Ultimately,by integrating the ground temperature data,air temperature data,roadside water formation mechanisms,and the operating characteristics of the TPCT,it was concluded that roadside water,while in a thawed state during TPCT operation,acts as a supplementary source for moisture migration in the roadbed soil.This migration leads to cracking in the TPCT roadbed.Therefore,this study reveals a novel damage mechanism:asynchronous freeze-thaw processes induce temperature gradients,which drive the migration of roadside water into the roadbed and are responsible for the cracking damage.展开更多
Water molecules can form hydrogen bonds.At the solid surfaces,the preferential alignment of water molecules due to the heterogeneous atomic distributions can induce ordered hydrogen bond networks of water molecules wi...Water molecules can form hydrogen bonds.At the solid surfaces,the preferential alignment of water molecules due to the heterogeneous atomic distributions can induce ordered hydrogen bond networks of water molecules with spatially heterogeneous patterns and slower dynamics compared to bulk water.Both the confinement and the surface atomic structures can induce the water phase transitions at low dimensional spaces.Here,we review how the phase transitions of interfacial water affect the surface physical behaviors,such as wetting,ice nucleation and the terahertz-wave-water interactions,from solid materials to the biological surfaces.These works help extend our knowledge of the physics properties of the interfacial water,particularly the multi-phase behaviors in materials and biology sciences.展开更多
Herein,we have developed a straightforward wet-chemical method to synthesize a series of Pd-based alloy nanowires(NWs),including Pd Pt NWs,Pd Au NWs,Pd Ir NWs,and Pd Ru NWs,which exhibits high mass activity and turnov...Herein,we have developed a straightforward wet-chemical method to synthesize a series of Pd-based alloy nanowires(NWs),including Pd Pt NWs,Pd Au NWs,Pd Ir NWs,and Pd Ru NWs,which exhibits high mass activity and turnover frequency(TOF) for HER,surpassing Pt/C by 4.6-fold and 1.5-fold in acidic and alkaline electrolytes,respectively.It also demonstrates high stability in alkaline electrolyte at a current density of 220 m A/cm^(2) for 280 h,highlighting its potential for practical applications under industrial current conditions.Pd Pt NWs exhibited ultrathin structures with head-to-tail kinks and inherent defects,significantly increasing the density of active sites and precisely tuning the electronic structure,which could accelerate reaction kinetics and boost water-splitting electrocatalytic performance.This study highlights the potential of Pd Pt NWs as highly efficient catalysts,offering outstanding catalytic performance and stability for practical applications.展开更多
Sustainable water,energy and food(WEF)supplies are the bedrock upon which human society depends.Solar-driven interfacial evaporation,combined with electricity generation and cultivation,is a promising approach to miti...Sustainable water,energy and food(WEF)supplies are the bedrock upon which human society depends.Solar-driven interfacial evaporation,combined with electricity generation and cultivation,is a promising approach to mitigate the freshwater,energy and food crises.However,the performance of solar-driven systems decreases significantly during operation due to uncontrollable weather.This study proposes an integrated water/electricity cogeneration-cultivation system with superior thermal management.The energy storage evaporator,consisting of energy storage microcapsules/hydrogel composites,is optimally designed for sustainable desalination,achieving an evaporation rate of around 1.91 kg m^(-2)h^(-1).In the dark,heat released from the phase-change layer supported an evaporation rate of around 0.54kg m^(-2)h^(-1).Reverse electrodialysis harnessed the salinity-gradient energy enhanced during desalination,enabling the long-running WEC system to achieve a power output of~0.3 W m^(-2),which was almost three times higher than that of conventional seawater/surface water mixing.Additionally,an integrated crop irrigation platform utilized system drainage for real-time,on-demand wheat cultivation without secondary contaminants,facilitating seamless WEF integration.This work presents a novel approach to all-day solar water production,electricity generation and crop irrigation,offering a solution and blueprint for the sustainable development of WEF.展开更多
Distributions of nuclear magnetic resonance(NMR)relaxation times provide detailed information about the water in wood.This study documents the water dynamics analysis of T_(2)and T_(1)distributions for saturated delig...Distributions of nuclear magnetic resonance(NMR)relaxation times provide detailed information about the water in wood.This study documents the water dynamics analysis of T_(2)and T_(1)distributions for saturated delignified sapwood(DSW),delignified heartwood(DHW)and lignocellulose(LC)samples at different temperatures.Results indicate that below the freezing point of bulk water,free water freezes,causing its signal to disappear from the distribution.Then,the low temperature distributions of the unfrozen bound water contain more information about its components,with DSW,DHW and LC containing two distinct states of bound water(OH bound water(B-water)and more freely bound water(C-water)).Furthermore,it was observed that within the temperature range of−3°C to−60°C,B-water in DSW,DHW and LC maintained a higher unfrozen water content(UWC)value than C-water,and the T_(1)/T_(2)ratios for B-water were consistently higher than that for C-water,indicating that B-water has a greater antifreeze capacity.T_(2)and T_(1)distributions offer different kinds of information about water components,and all peaks within the distribution have been assigned.展开更多
Boron(B)doping serves as a promising strategy to enhance the quantum yield,photostability and environmental robustness of graphene quantum dots(GQDs).In this study,we reported a light-driven strategy for the facile sy...Boron(B)doping serves as a promising strategy to enhance the quantum yield,photostability and environmental robustness of graphene quantum dots(GQDs).In this study,we reported a light-driven strategy for the facile synthesis of boron-doped graphene quantum dots(B-GQDs).Specifically,under continuous stirring at room temperature,ultraviolet irradiation induces the progressive polymerization of o-phenylenediamine(o-PDA)precursors,resulting in the formation of GQDs;meanwhile,2-hydroxyphenylboronic acid(2-HPBA),acting as the B source,participates in the polymerization reaction with o-PDA intermediates,ultimately yielding B-GQDs.This approach significantly improves the technology of preparing QDs,yielding B-GQDs with a remarkably high fluorescence quantum yield of 71.2%.Detailed investigations reveal that the abundant surface functional groups on B-GQDs facilitate hydrogen-bonding interactions with water molecules,enabling their application as fluorescent probes for the quantitative detection of water content in various organic solvents.By integrating B-GQDs,a paper-based fluorescent sensor was successfully designed,achieving ultra-portable water content detection with excellent performance(0%-100%).展开更多
基金supported by the Youth Foundation of Education Bureau,Sichuan Province(13ZB0003)
文摘New descriptors were constructed and structures of some oxygen-containing organic compounds were parameterized. The multiple linear regression（MLR） and partial least squares regression（PLS） methods were employed to build two relationship models between the structures and octanol/water partition coefficients（LogP） of the compounds. The modeling correlation coefficients（R） were 0.976 and 0.922, and the ＂leave one out＂ cross validation correlation coefficients（R（CV）） were 0.973 and 0.909, respectively. The results showed that the structural descriptors could well characterize the molecular structures of the compounds; the stability and predictive power of the models were good.
基金This work was supported by the National Natural Science Foundation of China (No. 20737001)
文摘The n-octanol/water partition coefficients （lgKow） of 18 substituted anilines were determined at 25 ℃ by shake-flask method. The geometrical optimization of substituted anilines has been performed at B3LYP/6-311G^＊＊ level with Gaussian98 program, and the molecular surface areas of substituted anilines were calculated using ChemOffice 2004 program. The calculated structural parameters of substituted anilines were used as theoretical descriptors and the two-parameter （molecular surface area （MA） and the energy of the highest occupied molecular orbital （EaoMo）） quantitative structure-property relationship （QSPR） model of lgKow for substituted aniline with molecular structural parameters was developed by multi-linear regression method. The regression coefficient square （r^2） is 0.990 and the standard deviation SE 0.109. The model was validated by variance inflation factors （VIF） and t-test, and the results show that there exists small self-correlation between variables of the model with perfect stability. The model gives results in good qualitative agreement with experimental data. At last, the model was applied to predict lgKow values of five substituted anilines whose lgKow values have not been determined experimentally.
基金This work was supported by the National Natural Science Foundation of China (No. 20737001)(2003CB415002)China Postdoctoral Science Foundation (No. 2003033486)
文摘Optimized calculations of 75 PCDDs and their parent DD were carded out at the B3LYP/6-31G＊ level by density functional theory （DFT） method. The structural parameters were obtained and significant correlation between the C1 substitution position and some structural parameters was found. Consequently, the number of C1 substitution positions was taken as theoretical descriptors to establish two novel QSPR models for predicting lgKow and -lgSw of all PCDD congeners. The two models achieved in this work contain two variables （Na and Nβ）, of which r = 0.9312, 0.9965 and SD = 0.27, 0.12 respectively, and t values are all large. The variation inflation factors （VIF） of variables in the two models herein are both less than 5.0, suggesting high accuracy of the lgKow and -lgSw predicting models, and the results of cross-validation test also show that the two models exhibit optimum stability and good predictive power. By comparison, the correlation and predictive ability of the present work are more advantageous than those obtained using semi-empirical AM1 and GC-RI methods.
基金Supported by the Key Program of National Natural Science Foundation of China (No. 20737001)the National Science Foundation for Post-doctoral Scientists of China (No. 2003033486)
文摘Quantum chemistry parameters of 28 alkyl（1-phenylsulfonyl） cycloalkane-carboxy-lates were computed at the 6-31G＊ level in fully optimal manner using B3LYP method of density functional theory （DFT）. With GQSARF2.0 program, the correlation equations that can predict n-octanol/water partition coefficient （lgKow） were developed using the structural and thermodynamic parameters of 28 alkyl（1-phenylsulfonyl） cycloalkane-carboxylates with experimental data of lgKow as theoretical descriptors; the correlation coefficient （R^2） was 0.9452 and the cross-validation squared correlation coefficient （Rcv^2） 0.9312. Furthermore, a four-variable model from MEDV was obtained, of which R2 = 0.9497 and Rov^2 =0.9388. The models were validated by variance inflation factor （VIF） and t-test. Cross-validation indicates that the correlation and predicting ability of the model based on both DFT method and MEDV are more advantageous than those obtained from semi-empirical AM1 method.
基金the State Science Foundation of China (No. 20477018)
文摘Optimized calculation of 35 dialkyl phenyl phosphate compounds （OPs） was carded out at the B3LYP/6-31G^＊ level in Gaussian 98 program. Based on the theoretical linear solvation energy relationship （TLSER） model, the obtained parameters were taken as theoretical descriptors to establish the novel QSPR model for predicting n-octanol/water partition coefficients （lgKow） of OPs. The new model achieved in this work contains three variables, i.e., molecular volume （Vm）, dipole moment of the molecules （μ） and enthalpy （H^0）. For this model, R^2 = 0.9167 and SD = 0.31 at large t values. In addition, the variation inflation factors （VIF） of variables are all close to 1.0, suggesting high accuracy of the predicting model. And the results of cross-validation test （q^2 = 0.8993） and method validation also showed the model of this study exhibited optimum stability and better predictive power than that from semi-empirical method. The model achieved can be used to predict IgKow of congeneric compounds.
基金the China Post Doctoral Research Fund (No. 2003033486)
文摘Structural parameters of 24 substituted naphthalin compounds were computed at four levels using Hartree-Fock and DFT methods. Based on the experimental data of octanol/water partition coefficient （lgKow）, three-parameter （energy of the highest occupied molecular orbital （EHOMO）, the most positive, atomic net charges of molecule （q^＋） and molecular average polarizability （α）） dependent equations were developed using structural parameters as theoretical descriptors. Especially, lgKow dependent equation calculated at the HF/6-311G^＊＊ level is more advantageous than others in view of their correlation and predictive abilities. This dependent equation was validated by variance inflation factors （VIF） and t-test methods and used to predict lgKow of eight designed compounds. Upon comparison, the predictive abilities of our work are all more advantageous than those calculated from molecular property calculator program.
基金Supported by the NNSF of China (No. 20737001)Program for Environment Protection in Jiangsu Province (201140)
文摘Octanol/water partition coefficient （Kow） is a crucial property for evaluating the environmental behavior and fate of organic compound. Herein, some quantitative structure-property relationship （QSPR） studies were performed to estimate and predict the lgK ow of substituted anilines. 2D method （multiple linear regression, MLR） and 3D method （comparative molecular field analysis, CoMFA） were applied in this study. Successful 2D and 3D models yielded the correlation coefficient （R2） values of 0.981 and 0.966 and the Leave-One-Out （LOO） cross-validated correlation coefficient （q2） values of 0.933 and 0.820, respectively. The developed models have a highly predictive ability in both internal and external validation. In addition, the results were interpreted in terms of physical and chemical meanings of descriptors and field contribution maps. It showed that the steric and electrostatic properties are the primary factors that govern the lgK ow of substituted anilines. The information obtained from the QSPR models would be helpful to the interpretation of structural features pertinent to the lgK ow of substituted anilines, which may be helpful in estimating the organic compounds＇ potential harm to the environment.
基金Supported by the Natural Science Foundation of Henan Province,China(No.0611033400)
文摘A shake-flask method was used to determine 1-octanol/water partition coefficients of ofloxacin, norfloxacin, lomefloxacin, ciprofloxacin, pefloxacin and pipemidic acid from 293.15 K to 323.15 K. The results show that 1-octanol/water partition coefficient of each quinolone increased with the increase of temperature. Based on the fluid phase equilibrium theory, the thermodynamic relationship of 1-octanol/water partition coefficient depending on the temperature was proposed, and the changes of enthalpy, entropy, and Gibbs free energy for quinolones partitioning in 1-octanol/water were determined, respectively. Quinolones molecules partitioning in 1-octanol/water was mainly an entropy driving process, during which the order degree of system decreased. The temperature effects of 1-octanol/water partition coefficient were investigated. The results show that its magnitude is the same as the values in the literature.
基金This work was supported by the China Postdoctoral Science Foundation (No. 2003033486)
文摘Optimized calculation of dibenzofuran （DF） and 135 polychlorinated dibenzofurans （PCDFs） was carried out at the B3LYP/6-31G＊ level in GAUSSIAN 98 program. Based on the theoretical linear solvation energy relationship （TLSER） model, the obtained structural parameters were taken as theoretical descriptors to establish the novel quantitative structureproperty relationship （QSPR） model for predicting n-octanol/water partition coefficients （lgKow） of PCDFs. The new model of lgKow achieved in this work contains three variables： energy of the highest occupied molecular orbital （EHOMO）, the most negative atomic partial charge （q^-） and average molecular polarizability （a）, of which R^2= 0.9011 and SD = 0,17 with larger t values. In addition, the variation inflation factors （VIF） of variables in the present model are all less than 5.5, suggesting high accuracy of the lgKow model. And the results of cross-validation test （q^2 = 0.8688） and method validation also show this model exhibits optimum stability and better predictive power than semi-empirical method. At the same time, it is found that the aqueous solubility （-lgSw） has high relative correlation with constant volume molar heat capacity （Cv^0）, of which R^2 = 0.9777 and SD = 0.22. Moreover, lgKow and -lgSw values of all PCDF congeners were predicted respectively.
基金Supported by the National Natural Science Foundation of China(No.52273056)the Science and Technology Development Program of Jilin Province,China(No.YDZJ202501ZYTS305)。
文摘Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen evolution reaction(HER)and the anodic oxygen evolution reaction(OER).Transition metal-based catalysts have garnered significant research interest as promising alternatives to noble-metal catalysts,owing to their low cost,tunable composition,and noble-metal-like catalytic activity.Nevertheless,systematic reviews on their application as bifunctional catalysts for overall water splitting(OWS)are still limited.This review comprehensively outlines the principal categories of bifunctional transition metal electrocatalysts derived from electrospun nanofibers(NFs),including metals,oxides,phosphides,sulfides,and carbides.Key strategies for enhancing their catalytic performance are systematically summarized,such as heterointerface engineering,heteroatom doping,metal-nonmetal-metal bridging architectures,and single-atom site design.Finally,current challenges and future research directions are discussed,aiming to provide insightful perspectives for the rational design of high-performance electrocatalysts for OWS.
基金supported by the National Key Research and Development Program of China (2022YFE0138900)the “Scientific and Technical Innovation Action Plan” Basic Research Field of Shanghai Science and Technology Committee (19JC1410500)。
文摘Ion-solvaing membranes(ISMs)have received extensive attention in recent years as a key component in electrochemical energy conversion and storage devices.This article provides an overview of structural composition,performance advan-tages,research progress,ion conduction mechanism and existing issues of ISMs,primarily classifying them according to the matrix structure.A detailed analysis of performance enhancement methods,key performance indicators of ISMs and performance influencing factors is also presented.The article contributes to further optimizing the design and application of ion-solvation membranes,providing theoretical support for the development of fields such as hydrogen production through electrolysis of water and electrochemical energy in the future.
基金supported by National Key R&D Program of China (2022YFD1900104)。
文摘To maintain soil quality under long-term saline water irrigation,the influence of manure on soil physical properties was examined.Long-term saline irrigation has been conducted from 2015 to 2024 at the Nanpi Eco-Agricultural Experimental Station of Chinese Academy Sciences in the Low Plain of the North China Plain,comprising four irrigation treatments:irrigation once at the jointing stage for winter wheat with irrigation water containing salt at fresh water,3,4 and 5 g·L^(–1),and maize irrigation at sowing using fresh water.Manure application was conducted under all irrigation treatments,with treatments without manure application used as controls.The results showed that under long-term irrigation with saline water,the application of manure increased the soil organic matter content,exchangeable potassium,available phosphorus,and total nitrogen content in the 0–20 cm soil layer by 46.8%,117.0%,75.7%,and 45.5%,respectively,compared to treatments without manure application.The application of manure reduced soil bulk density.It also increased the proportion of water-stable aggregates and the abundance of bacteria,fungi,and actinomycetes in the tillage soil layer compared to the controls.Because of the salt contained in the manure,the application of manure had dual effects on soil salt content.During the winter wheat season,manure application increased soil salt content.The salt content was significantly reduced during the summer maize season,owing to the strong salt-leaching effects under manure application,resulting in a smaller difference in salt content between the manure and non-manure treatments.During the summer rainfall season,improvements in soil structure under manure application increased the soil desalination rate for the 1 m top soil layer.The desalination rate for 0–40 cm and 40–100 cm was averagely by 39.1%and 18.9%higher,respectively,under manure application as compared with that under the nomanure treatments.The yield of winter wheat under manure application was 0.12%lower than that of the control,owing to the higher salt content during the winter wheat season.In contrast,the yield of summer maize improved by 3.9%under manure application,owing to the increased soil nutrient content and effective salt leaching.The results of this study indicated that manure application helped maintain the soil physical structure,which is important for the long-term use of saline water.In practice,using manure with a low salt content is suggested to reduce the adverse effects of saline water irrigation on soil properties and achieve sustainable saline water use.
文摘In Bom Jesus Municipality,a cool breeze drifts in from the Kwanza River,softening the edges of a town marked by landmarks such as António Agostinho Neto International Airport.Yet beneath Luanda’s scenic façade,daily life for many residents is defined by a persistent struggle for water.“We have to walk 5 to 15 km to access water.This perennial problem is so depressing.What’s more,the lack of clean water causes waterborne diseases in our community,”local resident Isabel Fernando told ChinAfrica.
基金supported by the National Natural Science Foundation of China(Grant Nos.52225404 and 52404121)the Key Research and Development Program Projects of Xinjiang Uygur Autonomous Region(Grant No.2024B03017).
文摘The mining industry is frequently subjected to various disasters,one of the major concerns is water-related disasters,particularly seam floor water inrush.These disasters pose significant threats to the safety and production of deep coal mines.The primary reason for this is that the fracturing of the rock mass induces the formation of a fluid(water)with both kinetic and potential energy.In this paper,a novel water inrush mechanism for deep floor failure due to water hammer effects is proposed based on the Xingdong coal mine in China.The water hammer pressure within rock pore channels has a different impact on the surrounding rock,leading to the degradation of the rock mass channel through repeated conduction and instantaneous cutoff.To further investigate this phenomenon,a progressive corrosion fracture mechanics(PCFM)model induced by a water hammer is established.The results show that the water hammer pressure caused by instantaneous channel truncation increases with increasing water flow velocity.The chemical damage factor(i.e.,stress corrosion fracture)is also incorporated into the Dugdale-Barenblatt(D-B)model to analyze the factors influencing the PCFM.These findings indicate that the greater the degree of damage is,the more likely the concealed fault is to experience water inrush.Finally,methods for controlling water inrush caused by the water hammer effects of deep floors are proposed.The failure mechanisms of the water hammer and the PCFM provide theoretical and practical guidance for controlling water inrush from the deep floor.
基金supported by the Major Science and Technology Project of Gansu Province(Grant No.24ZD13FA003 and 23ZDWA005)National Natural Science Foundation of China(Grant No.42371140,42301163,41971087 and 42272332)the program of the State Key Laboratory of Cryospheric Science and Frozen Soil Engineering,CAS(No.CSFSEZZ-2411)。
文摘In permafrost regions of the QinghaiXizang Plateau,embankments of the Qinghai-Xizang Highway and Qinghai-Xizang Railway experiencing roadside water accumulation exhibit more pronounced engineering deteriorations.A widely accepted view is that the accumulated water adjacent to the embankment possesses substantial thermal energy,which accelerates the degradation-even disappearance-of the underlying permafrost.Moreover,the presence of roadside water keeps the embankment soil in a persistently high-moisture state,thereby making the frozen-soil embankment more susceptible to deformation under traffic loading.However,in the permafrost regions of the QinghaiXizang Plateau,deteriorations of embankments affected by roadside water are more commonly manifested as undulating pavement surfaces,and extensive crack networks appear on the embankment crest even where thermosyphons are installed.These manifestations are not fully consistent with the deterioration mechanisms proposed by existing viewpoints.We propose the hypothesis that temperature gradients,formed due to the freezing and thawing processes between the roadside wateraffected soil and the roadbed soil,lead to moisture migration under the influence of temperature gradients,resulting in frost heave and thaw settlement in the roadbed soil.To validate this hypothesis,we conducted the following investigations sequentially.Initially,we selected a roadbed with a thermosyphon(TPCT)system,which has a significant cooling effect,as the study object.By analyzing the temperature monitoring data of the roadbed section,the temperature variance was calculated to identify the time nodes where the temperature gradient of the roadbed soil was maximum and minimum.Subsequently,corresponding roadbed temperature distribution maps were drawn,illustrating the changes in the temperature and position of the lowtemperature core near the TPCT over time.Furthermore,using small-scale indoor model experiments,we qualitatively concluded that moisture in the soil migrates toward the TPCT due to the temperature gradient.Thereafter,combining borehole water content data and precipitation data from the sloped terrain construction site,the formation mechanisms and timing characteristics of roadside water accumulation were analyzed.Ultimately,by integrating the ground temperature data,air temperature data,roadside water formation mechanisms,and the operating characteristics of the TPCT,it was concluded that roadside water,while in a thawed state during TPCT operation,acts as a supplementary source for moisture migration in the roadbed soil.This migration leads to cracking in the TPCT roadbed.Therefore,this study reveals a novel damage mechanism:asynchronous freeze-thaw processes induce temperature gradients,which drive the migration of roadside water into the roadbed and are responsible for the cracking damage.
基金supported by the National Natural Science Foundation of China(Grant Nos.22576126,12074394,12022508).
文摘Water molecules can form hydrogen bonds.At the solid surfaces,the preferential alignment of water molecules due to the heterogeneous atomic distributions can induce ordered hydrogen bond networks of water molecules with spatially heterogeneous patterns and slower dynamics compared to bulk water.Both the confinement and the surface atomic structures can induce the water phase transitions at low dimensional spaces.Here,we review how the phase transitions of interfacial water affect the surface physical behaviors,such as wetting,ice nucleation and the terahertz-wave-water interactions,from solid materials to the biological surfaces.These works help extend our knowledge of the physics properties of the interfacial water,particularly the multi-phase behaviors in materials and biology sciences.
基金the financial support from the National Natural Science Foundation of China (Nos.21805170,22172093)Natural Science Foundation of Shandong Province (Nos.ZR2023QB219,ZR2021QB161)Qingdao Postdoctoral Innovation Project (No.QDBSH20220202031)。
文摘Herein,we have developed a straightforward wet-chemical method to synthesize a series of Pd-based alloy nanowires(NWs),including Pd Pt NWs,Pd Au NWs,Pd Ir NWs,and Pd Ru NWs,which exhibits high mass activity and turnover frequency(TOF) for HER,surpassing Pt/C by 4.6-fold and 1.5-fold in acidic and alkaline electrolytes,respectively.It also demonstrates high stability in alkaline electrolyte at a current density of 220 m A/cm^(2) for 280 h,highlighting its potential for practical applications under industrial current conditions.Pd Pt NWs exhibited ultrathin structures with head-to-tail kinks and inherent defects,significantly increasing the density of active sites and precisely tuning the electronic structure,which could accelerate reaction kinetics and boost water-splitting electrocatalytic performance.This study highlights the potential of Pd Pt NWs as highly efficient catalysts,offering outstanding catalytic performance and stability for practical applications.
基金supported by the National Natural Science Foundation of China(No.52070057)China Postdoctoral Science Foundation(No.2023M730855)Heilongjiang Postdoctoral Fund(No.LBH-Z22183)for financial support。
文摘Sustainable water,energy and food(WEF)supplies are the bedrock upon which human society depends.Solar-driven interfacial evaporation,combined with electricity generation and cultivation,is a promising approach to mitigate the freshwater,energy and food crises.However,the performance of solar-driven systems decreases significantly during operation due to uncontrollable weather.This study proposes an integrated water/electricity cogeneration-cultivation system with superior thermal management.The energy storage evaporator,consisting of energy storage microcapsules/hydrogel composites,is optimally designed for sustainable desalination,achieving an evaporation rate of around 1.91 kg m^(-2)h^(-1).In the dark,heat released from the phase-change layer supported an evaporation rate of around 0.54kg m^(-2)h^(-1).Reverse electrodialysis harnessed the salinity-gradient energy enhanced during desalination,enabling the long-running WEC system to achieve a power output of~0.3 W m^(-2),which was almost three times higher than that of conventional seawater/surface water mixing.Additionally,an integrated crop irrigation platform utilized system drainage for real-time,on-demand wheat cultivation without secondary contaminants,facilitating seamless WEF integration.This work presents a novel approach to all-day solar water production,electricity generation and crop irrigation,offering a solution and blueprint for the sustainable development of WEF.
基金supported by Natural Science Foundation of Inner Mongolia Autonomous Region of China (2023MS03027)the National Natural Science Foundation of China (31860185 and 31160141)
文摘Distributions of nuclear magnetic resonance(NMR)relaxation times provide detailed information about the water in wood.This study documents the water dynamics analysis of T_(2)and T_(1)distributions for saturated delignified sapwood(DSW),delignified heartwood(DHW)and lignocellulose(LC)samples at different temperatures.Results indicate that below the freezing point of bulk water,free water freezes,causing its signal to disappear from the distribution.Then,the low temperature distributions of the unfrozen bound water contain more information about its components,with DSW,DHW and LC containing two distinct states of bound water(OH bound water(B-water)and more freely bound water(C-water)).Furthermore,it was observed that within the temperature range of−3°C to−60°C,B-water in DSW,DHW and LC maintained a higher unfrozen water content(UWC)value than C-water,and the T_(1)/T_(2)ratios for B-water were consistently higher than that for C-water,indicating that B-water has a greater antifreeze capacity.T_(2)and T_(1)distributions offer different kinds of information about water components,and all peaks within the distribution have been assigned.
基金support from Sichuan Science and Technology Project(Nos.2023zYD0034 and 2024NSFJQ0061)the State Key Lab of Geohazard Prevention&Geoenvironment Protection Independent Research Project(No.SKLGP 2023Z009).
文摘Boron(B)doping serves as a promising strategy to enhance the quantum yield,photostability and environmental robustness of graphene quantum dots(GQDs).In this study,we reported a light-driven strategy for the facile synthesis of boron-doped graphene quantum dots(B-GQDs).Specifically,under continuous stirring at room temperature,ultraviolet irradiation induces the progressive polymerization of o-phenylenediamine(o-PDA)precursors,resulting in the formation of GQDs;meanwhile,2-hydroxyphenylboronic acid(2-HPBA),acting as the B source,participates in the polymerization reaction with o-PDA intermediates,ultimately yielding B-GQDs.This approach significantly improves the technology of preparing QDs,yielding B-GQDs with a remarkably high fluorescence quantum yield of 71.2%.Detailed investigations reveal that the abundant surface functional groups on B-GQDs facilitate hydrogen-bonding interactions with water molecules,enabling their application as fluorescent probes for the quantitative detection of water content in various organic solvents.By integrating B-GQDs,a paper-based fluorescent sensor was successfully designed,achieving ultra-portable water content detection with excellent performance(0%-100%).
