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
Green hydrogen from water splitting has emerged as a critical energy vector with the potential to spearhead the global transition to a fossil fuel-independent society.The field of catalysis has been revolutionized by ...Green hydrogen from water splitting has emerged as a critical energy vector with the potential to spearhead the global transition to a fossil fuel-independent society.The field of catalysis has been revolutionized by single-atom catalysts(SACs),which exhibit unique and intricate interactions between atomically dispersed metal atoms and their supports.Recently,bimetallic SACs(bimSACs)have garnered significant attention for leveraging the synergistic functions of two metal ions coordinated on appropriately designed supports.BimSACs offer an avenue for rich metal–metal and metal–support cooperativity,potentially addressing current limitations of SACs in effectively furnishing transformations which involve synchronous proton–electron exchanges,substrate activation with reversible redox cycles,simultaneous multi-electron transfer,regulation of spin states,tuning of electronic properties,and cyclic transition states with low activation energies.This review aims to encapsulate the growing advancements in bimSACs,with an emphasis on their pivotal role in hydrogen generation via water splitting.We subsequently delve into advanced experimental methodologies for the elaborate characterization of SACs,elucidate their electronic properties,and discuss their local coordination environment.Overall,we present comprehensive discussion on the deployment of bimSACs in both hydrogen evolution reaction and oxygen evolution reaction,the two half-reactions of the water electrolysis process.展开更多
In recent years,smart materials have emerged as a groundbreaking innovation in the field of water filtration,offering sustainable,efficient,and environmentally friendly solutions to address the growing global water cr...In recent years,smart materials have emerged as a groundbreaking innovation in the field of water filtration,offering sustainable,efficient,and environmentally friendly solutions to address the growing global water crisis.This review explores the latest advancements in the application of smart materials—including biomaterials,nanocomposites,and stimuli-responsive polymers—specifically for water treatment.It examines their effectiveness in detecting and removing various types of pollutants,including organic contaminants,heavy metals,and microbial infections,while adapting to dynamic environmental conditions such as fluctuations in temperature,pH,and pressure.The review highlights the remarkable versatility of these materials,emphasizing their multifunctionality,which allows them to address a wide range of water quality issues with high efficiency and low environmental impact.Moreover,it explores the potential of smart materials to overcome significant challenges in water purification,such as the need for real-time pollutant detection and targeted removal processes.The research also discusses the scalability and future development of these materials,considering their cost-effectiveness and potential for large-scale application.By aligning with the principles of sustainable development,smart materials represent a promising direction for ensuring global water security,offering both innovative solutions for current water pollution issues and long-term benefits for the environment and public health.展开更多
River ethics,a significant advancement inspired by Chinese President XI Jinping's ecological civilization thought,embodies the philosophical essence of river governance and represents a legacy of innovation by gen...River ethics,a significant advancement inspired by Chinese President XI Jinping's ecological civilization thought,embodies the philosophical essence of river governance and represents a legacy of innovation by generations of water resources professionals.Rooted in river ecology,it offers a framework for advancing modern water governance systems and capabilities.This paper examines eight dimensions of river ethics to provide actionable recommendations:enhancing knowledge systems on water,rivers,and lakes;addressing critical challenges in water governance to strengthen the foundational role of water authorities in ensuring water security,resource management,ecological sustainability and environmental protection;optimizing water project planning to mitigate ecological impacts;ensuring high standards in the lifecycle management of water projects;refining water diversion strategies for precise scheduling;utilizing ecosystem complexity for river and lake restoration;implementing tiered management of water-related disasters;and driving reforms to modernize water governance systems and mechanisms.展开更多
Water use efficiency(WUE),as a pivotal indicator of the coupling degree within the carbon–water cycle of ecosystems,holds considerable importance in assessment of the carbon–water balance within terrestrial ecosyste...Water use efficiency(WUE),as a pivotal indicator of the coupling degree within the carbon–water cycle of ecosystems,holds considerable importance in assessment of the carbon–water balance within terrestrial ecosystems.However,in the context of global warming,WUE evolution and its primary drivers on the Tibetan Plateau remain unclear.This study employed the ensemble empirical mode decomposition method and the random forest algorithm to decipher the nonlinear trends and drivers of WUE on the Tibetan Plateau in 2001–2020.Results indicated an annual mean WUE of 0.8088 gC/mm·m^(2)across the plateau,with a spatial gradient reflecting decrease from the southeast toward the northwest.Areas manifesting monotonous trends of increase or decrease in WUE accounted for 23.64%and 9.69%of the total,respectively.Remarkably,66.67%of the region exhibited trend reversals,i.e.,39.94%of the area of the Tibetan Plateau showed transition from a trend of increase to a trend of decrease,and 26.73%of the area demonstrated a shift from a trend of decrease to a trend of increase.Environmental factors accounted for 70.79%of the variability in WUE.The leaf area index and temperature served as the major driving forces of WUE variation.展开更多
Water content, whether as free or lattice-bound water, is a crucial factor in determining the Earth's internal thermal state and plays a key role in volcanic eruptions, melting phenomena, and mantle convection rat...Water content, whether as free or lattice-bound water, is a crucial factor in determining the Earth's internal thermal state and plays a key role in volcanic eruptions, melting phenomena, and mantle convection rates. As electrical conductivity in the Earth's interior is highly sensitive to water content, it is an important geophysical parameter for understanding the deep Earth water content. Since its launch on May 21, 2023, the MSS-1(Macao Science Satellite-1) mission has operated for nearly one year, with its magnetometer achieving a precision of higher than 0.5 nT after orbital testing and calibration. Orbiting at 450 kilometers with a unique 41-degree inclination, the satellite enables high-density observations across multiple local times, allowing detailed monitoring of low-latitude regions and enhancing data for global conductivity imaging. To better understand the global distribution of water within the Earth's interior, it is crucial to study internal conductivity structure and water content distribution. To this aim, we introduce a method for using MSS-1 data to estamate induced magnetic fields related to magnetospheric currents. We then develop a trans-dimensional Bayesian approach to reveal Earth's internal conductivity, providing probable conductivity structure with an uncertainty analysis. Finally, by integrating known mineral composition, pressure, and temperature distribution within the mantle, we estimate the water content range in the mantle transition zone, concluding that this region may contain the equivalent of up to 3.0 oceans of water, providing compelling evidence that supports the hypothesis of a deep water cycle within the Earth's interior.展开更多
The accelerated decline of Arctic sea ice since the 1980s has paradoxically amplified greenhouse gas(GHG)emissions through increased shipping activities in this ecologically vulnerable region.This study investigates h...The accelerated decline of Arctic sea ice since the 1980s has paradoxically amplified greenhouse gas(GHG)emissions through increased shipping activities in this ecologically vulnerable region.This study investigates how to reconcile the decarbonization of Arctic shipping with conflicting environmental,economic,and geopolitical interests.Through systematic literature review and interest-balancing analysis,our findings identify three systemic barriers:(1)inadequate adaptation of International Maritime Organization(IMO)regulations to Arctic-specific environmental risks,(2)fragmented enforcement mechanisms among Arctic and non-Arctic States,and(3)technological limitations in clean fuel adoption for ice-class vessels.To address these challenges,a tripartite governance framework is proposed.First,legally binding amendments to International Convention for the Prevention of Pollution from Ships(MARPOL)Annex VI introducing Arctic-specific Energy Efficiency eXisting ship Index(EEXI)standards and extending energy efficiency regulations to fishing vessels.Second,a phased fuel transition prioritizing liquefied natural gas(LNG)and methanol,followed by hydrogen-ammonia synthetics.Third,enhanced multilateral cooperation through an Arctic Climate Shipping Alliance to coordinate joint research and development in cold-adapted technologies and ice-route optimization.By integrating United Nations Convention on the Law of the Sea(UNCLOS)obligations with IMO Polar Code implementation,this study advances a dynamic interest-balancing framework for policymakers,offering actionable pathways to achieve Paris Agreement targets while safeguarding Arctic ecosystems.展开更多
This study presents a novel method to fabricate metal-decorated,sulfur-doped layered double hydroxides(M/SLDH)through spontaneous redox and sulfurization processes.The developed Ag/SLDH and Pt/SLDH catalysts with abun...This study presents a novel method to fabricate metal-decorated,sulfur-doped layered double hydroxides(M/SLDH)through spontaneous redox and sulfurization processes.The developed Ag/SLDH and Pt/SLDH catalysts with abundant heterogeneous interfaces and hierarchical nanostructures demonstrated outstanding oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)performance,achieving low overpotentials of 212 and 35 mV at 10 mA cm^(-2)in 1 M KOH,respectively.As both anode and cathode in water splitting,they required only 1.47 V to reach 10 mA cm^(-2)and exhibited high structural robustness,maintaining stability at 1000 mA cm^(-2)for 300 h.In-situ Raman analysis revealed that the synergistic effects of metal nanoparticles and S doping significantly promote the transformation into the S-Co1-xFexOOH layer,which serves as the active phase for water oxidation.Additionally,ultraviolet photoelectron spectroscopy(UPS)and density functional theory(DFT)analyses indicated that incorporating metal nanoparticles and S doping increase electron density near the Fermi level and reduce reaction energy barriers,thus enhancing intrinsic OER and HER activities.This study provides a scalable strategy for synthesizing high-performance electrocatalysts for water splitting,with promising potential for broader applications.展开更多
Understanding the levels,causes,and sources of fluoride in groundwater is critical for public health,effective water resource management,and sustainable utilization.This study employs multivariate statistical methods,...Understanding the levels,causes,and sources of fluoride in groundwater is critical for public health,effective water resource management,and sustainable utilization.This study employs multivariate statistical methods,hazard quotient assessment,and geochemical analyses,such as mineral saturation index,ionic activities,and Gibbs diagrams,to investigate the hydrochemical characteristics,causes,and noncarcinogenic risks of fluoride in Red bed groundwater and geothermal water in the Guang'an area and neighboring regions.Approximately 9%of the Red bed groundwater samples contain fluoride concentrations exceeding 1 mg·L^(-1).The predominant water types identified are Cl-Na and HCO_(3)-Na,primarily influenced by evapotranspiration.Low-fluoride groundwater and high-fluoride geothermal water exhibit distinct hydrochemical types HCO_(3)-Ca and SO_(4)-Ca,respectively,which are mainly related to the weathering of carbonate,sulfate,and fluorite-containing rocks.Correlation analysis reveals that fluoride content in Red bed groundwater is positively associated with Na^(+),Cl^(-),SO_(4)^(2-),and TDS(r^(2)=0.45-0.64,p<0.01),while in geothermal water,it correlates strongly with pH,K^(+),Ca^(2+),and Mg^(2+)(r^(2)=0.52-0.80,p<0.05).Mineral saturation indices and ionic activities indicate that ion exchange processes and the dissolution of minerals such as carbonatite and fluorite are important sources of fluoride in groundwater.The enrichment of fluorine in the Red bed groundwater is linked to evaporation,cation exchange and dissolution of fluorite,caused by the lithologic characteristics of the red bed in this area.However,it exhibits minimal correlation with the geothermal water in the adjacent area.The noncarcinogenic health risk assessment indicates that 7%(n=5)of Red bed groundwater points exceed the fluoride safety limit for adults,while 12%(n=8)exceed the limit for children.These findings underscore the importance of avoiding highly fluoridated red bed groundwater as a direct drinking source and enhancing groundwater monitoring to mitigate health risks associated with elevated fluoride levels.展开更多
Increasing the grain yield(GY) and water use efficiency(WUE) of winter wheat in the Huaibei Plain(HP), China are essential. However, the effects of micro-sprinkler irrigation and topsoil compaction after wheat seed so...Increasing the grain yield(GY) and water use efficiency(WUE) of winter wheat in the Huaibei Plain(HP), China are essential. However, the effects of micro-sprinkler irrigation and topsoil compaction after wheat seed sowing on the GY and WUE are unclear. Therefore, a two-year field experiment was conducted during the 2021–2023 winter wheat growing seasons with a total six treatments: rain-fed(RF), conventional irrigation(CI) and micro-sprinkler irrigation(MI), as well as topsoil compaction after seed sowing under these three irrigation methods(RFC, CIC, and MIC). The results in the two years indicated that MI significantly increased GY compared to CI and RF, by averages of 17.9 and 42.1%, respectively. The increase in GY of MI was due to its significant increases in the number of spikes, kernels per spike, and grain weight. The chlorophyll concentration in flag leaves of MI after the anthesis stage maintained higher levels than with CI and RF, and was the lowest in RF. This was due to the dramatically enhanced catalase and peroxidase activities and lower malondialdehyde content under MI. Compared with RF and CI, MI significantly promoted dry matter remobilization and production after anthesis, as well as its contribution to GY. In addition, MI significantly boosted root growth, and root activity during the grain-filling stage was remarkably enhanced compared to CI and RF. In 2021–2022, there was no significant difference in WUE between MI and RF, but the WUE of RF was significantly lower than that of MI in 2022–2023. However, the WUE in MI was significantly improved compared to CI, and it increased by averages of 15.1 and 17.6% for the two years. Topsoil compaction significantly increased GY and WUE under rain-fed conditions due to improved spike numbers and dry matter production. Overall, topsoil compaction is advisable for enhancing GY and WUE in rain-fed conditions, whereas micro-sprinkler irrigation can be adopted to simultaneously achieve high GY and WUE in the HP.展开更多
The electrochemical corrosion of ductile pipes(DPs)in drinking water distribution systems(DWDS)has a crucial impact on cement-mortar lining(CML)failure and metal release,potentially leading to drinking water quality d...The electrochemical corrosion of ductile pipes(DPs)in drinking water distribution systems(DWDS)has a crucial impact on cement-mortar lining(CML)failure and metal release,potentially leading to drinking water quality deterioration and posing a risk to public health.An in-situ scanning vibrating electrode technique(SVET)with micron-scale resolution,microscopic scale detection and water quality analysis were used to investigate the corrosion behavior and metal release from DPs throughout the whole CML failure process.Metal pollutants release occurred at three different stages of CML failure process,and there are potential risks of water quality deterioration exceeding the maximum allowable levels set by national standards in the partial failure stage and lining peeling stage.Furthermore,the effects of water chemistry(Cl^(−),SO_(4)^(2−),NO_(3)−,and Ca^(2+))on corrosion scale growth and iron release activity,were investigated during the CML partial failure stage.Results showed that the CML failure process in DPs was accelerated by the autocatalysis of localized corrosion.Cl^(−)was found to damage the uncorroded metal surface,while SO_(4)^(2−)mainly dissolved the corrosion scale surface,increasing iron release.Both the oxidation of NO_(3)−and selective sedimentation of Ca2+were found to enhance the stability of corrosion scales and inhibit iron release.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support from the Czech Science Foundation,project EXPRO,No 19-27454Xsupport by the European Union under the REFRESH—Research Excellence For Region Sustainability and High-tech Industries project number CZ.10.03.01/00/22_003/0000048 via the Operational Programme Just Transition from the Ministry of the Environment of the Czech Republic+1 种基金Horizon Europe project EIC Pathfinder Open 2023,“GlaS-A-Fuels”(No.101130717)supported from ERDF/ESF,project TECHSCALE No.CZ.02.01.01/00/22_008/0004587).
文摘Green hydrogen from water splitting has emerged as a critical energy vector with the potential to spearhead the global transition to a fossil fuel-independent society.The field of catalysis has been revolutionized by single-atom catalysts(SACs),which exhibit unique and intricate interactions between atomically dispersed metal atoms and their supports.Recently,bimetallic SACs(bimSACs)have garnered significant attention for leveraging the synergistic functions of two metal ions coordinated on appropriately designed supports.BimSACs offer an avenue for rich metal–metal and metal–support cooperativity,potentially addressing current limitations of SACs in effectively furnishing transformations which involve synchronous proton–electron exchanges,substrate activation with reversible redox cycles,simultaneous multi-electron transfer,regulation of spin states,tuning of electronic properties,and cyclic transition states with low activation energies.This review aims to encapsulate the growing advancements in bimSACs,with an emphasis on their pivotal role in hydrogen generation via water splitting.We subsequently delve into advanced experimental methodologies for the elaborate characterization of SACs,elucidate their electronic properties,and discuss their local coordination environment.Overall,we present comprehensive discussion on the deployment of bimSACs in both hydrogen evolution reaction and oxygen evolution reaction,the two half-reactions of the water electrolysis process.
文摘In recent years,smart materials have emerged as a groundbreaking innovation in the field of water filtration,offering sustainable,efficient,and environmentally friendly solutions to address the growing global water crisis.This review explores the latest advancements in the application of smart materials—including biomaterials,nanocomposites,and stimuli-responsive polymers—specifically for water treatment.It examines their effectiveness in detecting and removing various types of pollutants,including organic contaminants,heavy metals,and microbial infections,while adapting to dynamic environmental conditions such as fluctuations in temperature,pH,and pressure.The review highlights the remarkable versatility of these materials,emphasizing their multifunctionality,which allows them to address a wide range of water quality issues with high efficiency and low environmental impact.Moreover,it explores the potential of smart materials to overcome significant challenges in water purification,such as the need for real-time pollutant detection and targeted removal processes.The research also discusses the scalability and future development of these materials,considering their cost-effectiveness and potential for large-scale application.By aligning with the principles of sustainable development,smart materials represent a promising direction for ensuring global water security,offering both innovative solutions for current water pollution issues and long-term benefits for the environment and public health.
基金Three Gorges Follow-up Work Fund,Grant/Award Number:WE0161A042024National Key Research Program of China,Grant/Award Number:2024YFC3210900。
文摘River ethics,a significant advancement inspired by Chinese President XI Jinping's ecological civilization thought,embodies the philosophical essence of river governance and represents a legacy of innovation by generations of water resources professionals.Rooted in river ecology,it offers a framework for advancing modern water governance systems and capabilities.This paper examines eight dimensions of river ethics to provide actionable recommendations:enhancing knowledge systems on water,rivers,and lakes;addressing critical challenges in water governance to strengthen the foundational role of water authorities in ensuring water security,resource management,ecological sustainability and environmental protection;optimizing water project planning to mitigate ecological impacts;ensuring high standards in the lifecycle management of water projects;refining water diversion strategies for precise scheduling;utilizing ecosystem complexity for river and lake restoration;implementing tiered management of water-related disasters;and driving reforms to modernize water governance systems and mechanisms.
基金National Nonprofit Institute Research Grant of CAF,No.CAFYBB2018ZA004,No.CAFYBB2023ZA009Fengyun Application Pioneering Project,No.FY-APP-ZX-2023.02。
文摘Water use efficiency(WUE),as a pivotal indicator of the coupling degree within the carbon–water cycle of ecosystems,holds considerable importance in assessment of the carbon–water balance within terrestrial ecosystems.However,in the context of global warming,WUE evolution and its primary drivers on the Tibetan Plateau remain unclear.This study employed the ensemble empirical mode decomposition method and the random forest algorithm to decipher the nonlinear trends and drivers of WUE on the Tibetan Plateau in 2001–2020.Results indicated an annual mean WUE of 0.8088 gC/mm·m^(2)across the plateau,with a spatial gradient reflecting decrease from the southeast toward the northwest.Areas manifesting monotonous trends of increase or decrease in WUE accounted for 23.64%and 9.69%of the total,respectively.Remarkably,66.67%of the region exhibited trend reversals,i.e.,39.94%of the area of the Tibetan Plateau showed transition from a trend of increase to a trend of decrease,and 26.73%of the area demonstrated a shift from a trend of decrease to a trend of increase.Environmental factors accounted for 70.79%of the variability in WUE.The leaf area index and temperature served as the major driving forces of WUE variation.
基金financially supported by the National Natural Science Foundation of China(42250102,42250101)the Macao Foundation.
文摘Water content, whether as free or lattice-bound water, is a crucial factor in determining the Earth's internal thermal state and plays a key role in volcanic eruptions, melting phenomena, and mantle convection rates. As electrical conductivity in the Earth's interior is highly sensitive to water content, it is an important geophysical parameter for understanding the deep Earth water content. Since its launch on May 21, 2023, the MSS-1(Macao Science Satellite-1) mission has operated for nearly one year, with its magnetometer achieving a precision of higher than 0.5 nT after orbital testing and calibration. Orbiting at 450 kilometers with a unique 41-degree inclination, the satellite enables high-density observations across multiple local times, allowing detailed monitoring of low-latitude regions and enhancing data for global conductivity imaging. To better understand the global distribution of water within the Earth's interior, it is crucial to study internal conductivity structure and water content distribution. To this aim, we introduce a method for using MSS-1 data to estamate induced magnetic fields related to magnetospheric currents. We then develop a trans-dimensional Bayesian approach to reveal Earth's internal conductivity, providing probable conductivity structure with an uncertainty analysis. Finally, by integrating known mineral composition, pressure, and temperature distribution within the mantle, we estimate the water content range in the mantle transition zone, concluding that this region may contain the equivalent of up to 3.0 oceans of water, providing compelling evidence that supports the hypothesis of a deep water cycle within the Earth's interior.
基金supported by the Major Research Projects of the National Social Science Fund of China(NSFC,Grant no.23VHQ015).
文摘The accelerated decline of Arctic sea ice since the 1980s has paradoxically amplified greenhouse gas(GHG)emissions through increased shipping activities in this ecologically vulnerable region.This study investigates how to reconcile the decarbonization of Arctic shipping with conflicting environmental,economic,and geopolitical interests.Through systematic literature review and interest-balancing analysis,our findings identify three systemic barriers:(1)inadequate adaptation of International Maritime Organization(IMO)regulations to Arctic-specific environmental risks,(2)fragmented enforcement mechanisms among Arctic and non-Arctic States,and(3)technological limitations in clean fuel adoption for ice-class vessels.To address these challenges,a tripartite governance framework is proposed.First,legally binding amendments to International Convention for the Prevention of Pollution from Ships(MARPOL)Annex VI introducing Arctic-specific Energy Efficiency eXisting ship Index(EEXI)standards and extending energy efficiency regulations to fishing vessels.Second,a phased fuel transition prioritizing liquefied natural gas(LNG)and methanol,followed by hydrogen-ammonia synthetics.Third,enhanced multilateral cooperation through an Arctic Climate Shipping Alliance to coordinate joint research and development in cold-adapted technologies and ice-route optimization.By integrating United Nations Convention on the Law of the Sea(UNCLOS)obligations with IMO Polar Code implementation,this study advances a dynamic interest-balancing framework for policymakers,offering actionable pathways to achieve Paris Agreement targets while safeguarding Arctic ecosystems.
基金National Programs for NanoKey Project(2022YFA1504002)National Natural Science Foundation of China(22078233)。
文摘This study presents a novel method to fabricate metal-decorated,sulfur-doped layered double hydroxides(M/SLDH)through spontaneous redox and sulfurization processes.The developed Ag/SLDH and Pt/SLDH catalysts with abundant heterogeneous interfaces and hierarchical nanostructures demonstrated outstanding oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)performance,achieving low overpotentials of 212 and 35 mV at 10 mA cm^(-2)in 1 M KOH,respectively.As both anode and cathode in water splitting,they required only 1.47 V to reach 10 mA cm^(-2)and exhibited high structural robustness,maintaining stability at 1000 mA cm^(-2)for 300 h.In-situ Raman analysis revealed that the synergistic effects of metal nanoparticles and S doping significantly promote the transformation into the S-Co1-xFexOOH layer,which serves as the active phase for water oxidation.Additionally,ultraviolet photoelectron spectroscopy(UPS)and density functional theory(DFT)analyses indicated that incorporating metal nanoparticles and S doping increase electron density near the Fermi level and reduce reaction energy barriers,thus enhancing intrinsic OER and HER activities.This study provides a scalable strategy for synthesizing high-performance electrocatalysts for water splitting,with promising potential for broader applications.
基金supported by the China Geological Survey Project(Nos.DD20220864 and DD20243077).
文摘Understanding the levels,causes,and sources of fluoride in groundwater is critical for public health,effective water resource management,and sustainable utilization.This study employs multivariate statistical methods,hazard quotient assessment,and geochemical analyses,such as mineral saturation index,ionic activities,and Gibbs diagrams,to investigate the hydrochemical characteristics,causes,and noncarcinogenic risks of fluoride in Red bed groundwater and geothermal water in the Guang'an area and neighboring regions.Approximately 9%of the Red bed groundwater samples contain fluoride concentrations exceeding 1 mg·L^(-1).The predominant water types identified are Cl-Na and HCO_(3)-Na,primarily influenced by evapotranspiration.Low-fluoride groundwater and high-fluoride geothermal water exhibit distinct hydrochemical types HCO_(3)-Ca and SO_(4)-Ca,respectively,which are mainly related to the weathering of carbonate,sulfate,and fluorite-containing rocks.Correlation analysis reveals that fluoride content in Red bed groundwater is positively associated with Na^(+),Cl^(-),SO_(4)^(2-),and TDS(r^(2)=0.45-0.64,p<0.01),while in geothermal water,it correlates strongly with pH,K^(+),Ca^(2+),and Mg^(2+)(r^(2)=0.52-0.80,p<0.05).Mineral saturation indices and ionic activities indicate that ion exchange processes and the dissolution of minerals such as carbonatite and fluorite are important sources of fluoride in groundwater.The enrichment of fluorine in the Red bed groundwater is linked to evaporation,cation exchange and dissolution of fluorite,caused by the lithologic characteristics of the red bed in this area.However,it exhibits minimal correlation with the geothermal water in the adjacent area.The noncarcinogenic health risk assessment indicates that 7%(n=5)of Red bed groundwater points exceed the fluoride safety limit for adults,while 12%(n=8)exceed the limit for children.These findings underscore the importance of avoiding highly fluoridated red bed groundwater as a direct drinking source and enhancing groundwater monitoring to mitigate health risks associated with elevated fluoride levels.
基金funding from the Scientific Research Program of the Higher Educational Institutions in Anhui Province, China (2023AH050986)the Natural Science Foundation of Anhui Province, China (240805MC063)+1 种基金the National Natural Science Foundation of China (32172119)the Talent Introduction Project of Anhui Agricultural University, China (rc312212 and yj2019-01)。
文摘Increasing the grain yield(GY) and water use efficiency(WUE) of winter wheat in the Huaibei Plain(HP), China are essential. However, the effects of micro-sprinkler irrigation and topsoil compaction after wheat seed sowing on the GY and WUE are unclear. Therefore, a two-year field experiment was conducted during the 2021–2023 winter wheat growing seasons with a total six treatments: rain-fed(RF), conventional irrigation(CI) and micro-sprinkler irrigation(MI), as well as topsoil compaction after seed sowing under these three irrigation methods(RFC, CIC, and MIC). The results in the two years indicated that MI significantly increased GY compared to CI and RF, by averages of 17.9 and 42.1%, respectively. The increase in GY of MI was due to its significant increases in the number of spikes, kernels per spike, and grain weight. The chlorophyll concentration in flag leaves of MI after the anthesis stage maintained higher levels than with CI and RF, and was the lowest in RF. This was due to the dramatically enhanced catalase and peroxidase activities and lower malondialdehyde content under MI. Compared with RF and CI, MI significantly promoted dry matter remobilization and production after anthesis, as well as its contribution to GY. In addition, MI significantly boosted root growth, and root activity during the grain-filling stage was remarkably enhanced compared to CI and RF. In 2021–2022, there was no significant difference in WUE between MI and RF, but the WUE of RF was significantly lower than that of MI in 2022–2023. However, the WUE in MI was significantly improved compared to CI, and it increased by averages of 15.1 and 17.6% for the two years. Topsoil compaction significantly increased GY and WUE under rain-fed conditions due to improved spike numbers and dry matter production. Overall, topsoil compaction is advisable for enhancing GY and WUE in rain-fed conditions, whereas micro-sprinkler irrigation can be adopted to simultaneously achieve high GY and WUE in the HP.
基金supported by the National Natural Science Foundation of China(Nos.51808158,52170101,and 52200116)Tianjin Natural Science Foundation(No.23JCYBJC00640).
文摘The electrochemical corrosion of ductile pipes(DPs)in drinking water distribution systems(DWDS)has a crucial impact on cement-mortar lining(CML)failure and metal release,potentially leading to drinking water quality deterioration and posing a risk to public health.An in-situ scanning vibrating electrode technique(SVET)with micron-scale resolution,microscopic scale detection and water quality analysis were used to investigate the corrosion behavior and metal release from DPs throughout the whole CML failure process.Metal pollutants release occurred at three different stages of CML failure process,and there are potential risks of water quality deterioration exceeding the maximum allowable levels set by national standards in the partial failure stage and lining peeling stage.Furthermore,the effects of water chemistry(Cl^(−),SO_(4)^(2−),NO_(3)−,and Ca^(2+))on corrosion scale growth and iron release activity,were investigated during the CML partial failure stage.Results showed that the CML failure process in DPs was accelerated by the autocatalysis of localized corrosion.Cl^(−)was found to damage the uncorroded metal surface,while SO_(4)^(2−)mainly dissolved the corrosion scale surface,increasing iron release.Both the oxidation of NO_(3)−and selective sedimentation of Ca2+were found to enhance the stability of corrosion scales and inhibit iron release.
