ACS Physical Chemistry Au最新文献

Two-Step Approach to Obtain Nitrogen-Doped Reduced Graphene Oxide Using Nitrogen-Containing Reducing Agents 利用含氮还原剂制备氮掺杂还原氧化石墨烯的两步法

IF 4.8

ACS Physical Chemistry Au Pub Date : 2026-09-23 Epub Date: 2026-08-06 DOI: 10.1021/acsphyschemau.6c00049

Carlos Belman-Rodriguez, Rodrigo Ponce-Pérez, Jose Ruiz-Marizcal, Gabriel Alonso-Nunez, Jose M. Romo-Herrera

{"title":"Two-Step Approach to Obtain Nitrogen-Doped Reduced Graphene Oxide Using Nitrogen-Containing Reducing Agents","authors":"Carlos Belman-Rodriguez, Rodrigo Ponce-Pérez, Jose Ruiz-Marizcal, Gabriel Alonso-Nunez, Jose M. Romo-Herrera","doi":"10.1021/acsphyschemau.6c00049","DOIUrl":"https://doi.org/10.1021/acsphyschemau.6c00049","url":null,"abstract":"N-doping of graphene has emerged as a very valuable alternativefor diverse applications. Nonetheless, further work is required toexplore the grafting of N-containing molecules onto graphene to incorporateN atoms into its graphitic network, thereby harnessing a wide varietyof available N-containing molecules. Here, the chemical reductionof graphene oxide (GO), using nitrogen-containing reducing agentssuch as ethylenediamine (EDA) and dimethylformamide (DMF), was exploredto evaluate their effect on the surface composition of the obtainedreduced graphene oxides (rGO). Afterward, an 800 °C thermal treatmentwas performed, and the samples were characterized before and afterthe thermal treatment, focusing on the nitrogen and oxygen functionalgroups present on the rGO. Several fingerprints were identified fromthe grafting of the EDA molecules functionalizing the rGO-EDA sampleby XPS, FTIR, and UV–visible spectroscopy measurements andby first-principles calculations. The 800 °C thermal treatmentled to significant changes in the surface chemistry, incorporatingnitrogen as a dopant into the rGO to imprint the obtained N-rGO samplewith electrocatalytic properties (Oxygen Reduction Reaction activity).Therefore, the proposed approach opens the possibility to explorea myriad of N-containing molecules for N-doping of rGO.","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"6 5","pages":"1115–1130"},"PeriodicalIF":4.8,"publicationDate":"2026-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149027865","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Accelerated OH Oxidation of Methyl Chloride via Surface Accumulation at the Air–Water Interface 通过空气-水界面的表面积累加速氯甲烷的OH氧化

IF 4.8

ACS Physical Chemistry Au Pub Date : 2026-09-23 Epub Date: 2026-08-19 DOI: 10.1021/acsphyschemau.6c00076

Yutong Yang, Chung Chi Chio, Ying-Lung Steve Tse

{"title":"Accelerated OH Oxidation of Methyl Chloride via Surface Accumulation at the Air–Water Interface","authors":"Yutong Yang, Chung Chi Chio, Ying-Lung Steve Tse","doi":"10.1021/acsphyschemau.6c00076","DOIUrl":"https://doi.org/10.1021/acsphyschemau.6c00076","url":null,"abstract":"Chemical reactions often proceed differently at the air–waterinterface than in bulk solution. In particular, “on-water”catalysis refers to cases where reactions appear to be acceleratedat aqueous surfaces. A growing body of work shows that rate accelerationcan arise from intertwined effects, including modified solvation andacid–base behavior, as well as enhanced reactant concentrations.Despite this progress, it remains difficult to quantify, for specificatmospheric reactions, how much interfacial rate enhancement arisesfrom (i) intrinsic changes in the free energy barrier versus (ii)concentration-driven effects, because fully converged interfacialfree energy profiles are costly to obtain with ab initio molecularsimulations. Here, we address this challenge for the reaction of methylchloride CH3Cl with hydroxyl radicals (OH), an importantatmospheric sink of CH3Cl, by developing a reaction-specificempirical valence bond (EVB) model parametrized against high-levelab initio data. The EVB model, combined with a flexible polarizablewater force field, enables efficient condensed-phase simulations andsystematic comparison of gas phase, bulk aqueous, and interfacialreactivity. Our results show that the reaction free energy barrieris only weakly affected by proximity to the air–water interface,whereas thermodynamic enrichment of the surface-active reactants increasesthe effective interfacial rate by more than 2 orders of magnituderelative to the aqueous bulk and by over 6 orders of magnitude relativeto the gas phase.","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"6 5","pages":"1252–1263"},"PeriodicalIF":4.8,"publicationDate":"2026-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149027881","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Controlling the Stereodynamics of the F– + NH2Cl SN2 Reaction by Vibrational Excitation: A Quasi-Classical Study 用振动激发控制F - + NH2Cl SN2反应的立体动力学：准经典研究

IF 4.8

ACS Physical Chemistry Au Pub Date : 2026-09-23 Epub Date: 2026-07-13 DOI: 10.1021/acsphyschemau.6c00092

Deján Drágity, Gábor Czakó, Dóra Papp

{"title":"Controlling the Stereodynamics of the F– + NH2Cl SN2 Reaction by Vibrational Excitation: A Quasi-Classical Study","authors":"Deján Drágity, Gábor Czakó, Dóra Papp","doi":"10.1021/acsphyschemau.6c00092","DOIUrl":"https://doi.org/10.1021/acsphyschemau.6c00092","url":null,"abstract":"Here we report howspecific reactant vibrational excitations impactthe dynamics of the F– + NH2Cl reaction,with a special emphasis on the stereoselectivity of its SN2 channel, by performing quasi-classical trajectory simulations ona high-quality ab initio analytical potential energy surface. Excitingthe N–Cl stretching is found to enhance the SN2reactivity the most, while N–H stretching excitation is themost efficient in promoting proton transfer. The stereospecificityof the title reaction can be drastically manipulated by exciting (1)the umbrella vibration, which facilitates repeated inversion througha H-bonded entrance channel minimum and transition state, therebymaking multi-inversion the dominant mechanism over a wide collisionenergy range, accompanied by the complete loss of stereoselectivity;(2) the N–H stretching motion, which helps the H-bonded complexto form and thus lowers the inversion barrier around the N atom, therebyalso promoting multi-inversion and racemization; and (3) the N–Clstretching mode, which favors direct Walden inversion over complex-formingmulti-inversion, resulting in reinforced stereoselectivity. The excessvibrational energy mainly flows into the internal degrees of freedomof the products, and while making the SN2 reaction moredirect, it has an overall moderate impact on proton-transfer dynamics.","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"6 5","pages":"1299–1307"},"PeriodicalIF":4.8,"publicationDate":"2026-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149022713","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Toward Expanded Genetic Alphabets: Insights into Functionalized Ds–Px Unnatural Base Pairs 走向扩展的基因字母表：洞察功能化的Ds-Px非自然碱基对

IF 4.8

ACS Physical Chemistry Au Pub Date : 2026-09-23 Epub Date: 2026-08-06 DOI: 10.1021/acsphyschemau.6c00082

Andreu Bermejo, Josep Maria Bofill, Jordi Poater

引用次数: 0

The Mechanism of Nucleophilic Substitution Reactions at an Iodine Center: Single-Well or Double-Well Potential Energy Surface? 碘中心的亲核取代反应机理：单阱还是双阱势能面？

IF 4.8

ACS Physical Chemistry Au Pub Date : 2026-09-23 Epub Date: 2026-07-18 DOI: 10.1021/acsphyschemau.6c00052

Ádám Horváth, Zoltán Benkő

{"title":"The Mechanism of Nucleophilic Substitution Reactions at an Iodine Center: Single-Well or Double-Well Potential Energy Surface?","authors":"Ádám Horváth, Zoltán Benkő","doi":"10.1021/acsphyschemau.6c00052","DOIUrl":"https://doi.org/10.1021/acsphyschemau.6c00052","url":null,"abstract":"Nucleophilic substitution (SN) reactions belongto themost important transformations in both organic and inorganic chemistry.Although SN reactivity is well-known for many main groupelements, its extension to halogen centers is restricted to a fewexamples, and the mechanism of such reactions lacks fundamental understanding.Recent achievements initiated our investigations to decipher the mechanismof the substitution reactions between various amide ions and elementalI2. Here, we present that these reactions follow an addition–eliminationpathway through a charge-transfer complex (single-well potential energysurface), opposing a classical bimolecular mechanism via a centraltransition state (double-well potential energy surface), as reportedrecently. In addition, inclusion of a continuum solvent model fora polar solvent (such as water) remarkably impacts the thermodynamicfeasibility of these reactions. Uncovering the mechanism of theseSN2 reactions is a key step to a general understandingof SN reactions involving other attacking nucleophilesand to possible future extensions toward further halogens.","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"6 5","pages":"1144–1150"},"PeriodicalIF":4.8,"publicationDate":"2026-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149027894","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A Minimalist Model for Navigating Conformational Landscape Uncovers the Activation Mechanism of β2-Adrenergic Receptor 一个导航构象景观的极简模型揭示了β2-肾上腺素能受体的激活机制

IF 4.8

ACS Physical Chemistry Au Pub Date : 2026-09-23 Epub Date: 2026-08-24 DOI: 10.1021/acsphyschemau.6c00090

Satyaki Saha, Anthony T. Bogetti, Ivet Bahar

{"title":"A Minimalist Model for Navigating Conformational Landscape Uncovers the Activation Mechanism of β2-Adrenergic Receptor","authors":"Satyaki Saha, Anthony T. Bogetti, Ivet Bahar","doi":"10.1021/acsphyschemau.6c00090","DOIUrl":"https://doi.org/10.1021/acsphyschemau.6c00090","url":null,"abstract":"A mechanistic understandingof GPCR activation is essentialtodesigning modulators for its function. The lower energy of the inactivestate under basal conditions, as well as the transient nature of intermediateshave impeded the characterization of GPCR’s activation mechanismsat full-atomic scale. In this study, we generate in silico thousands of full-atomic, continuous pathways, visualizing the completeactivation mechanism of a broadly studied GPCR, the β2 adrenergic receptor. To this aim, we adopted a minimalist modelthat prioritizes the intrinsic dynamics of the receptor, combinedwith weighted ensemble-enhanced molecular dynamics (WEMD) simulations.Clustering analysis of the generated trajectories reveals distinctclasses of activation, including an off-pathway transition, and conformationalswitches that enable activation. Simulations of two mutants, D1303.49A and E2686.30A, show their high propensityto get activated, consistent with experimental observations. Overall,WEMD emerges as a promising method for navigating GPCR’s conformationallandscape and predicting the effects of mutations, well beyond thereach of conventional simulations.","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"6 5","pages":"1283–1298"},"PeriodicalIF":4.8,"publicationDate":"2026-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149027955","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Mechanistic Insights into the Photochemical Formation of Carbenes from Phenyl-trifluoromethyl Diazirine and Its Diazo Isomer: An MS-CASPT2 Study 苯基三氟甲基重氮嘧啶及其重氮异构体光化学生成卡宾的机理：MS-CASPT2研究

IF 4.8

ACS Physical Chemistry Au Pub Date : 2026-09-23 Epub Date: 2026-08-03 DOI: 10.1021/acsphyschemau.6c00069

Juan Soto

{"title":"Mechanistic Insights into the Photochemical Formation of Carbenes from Phenyl-trifluoromethyl Diazirine and Its Diazo Isomer: An MS-CASPT2 Study","authors":"Juan Soto","doi":"10.1021/acsphyschemau.6c00069","DOIUrl":"https://doi.org/10.1021/acsphyschemau.6c00069","url":null,"abstract":"The photochemical formation of carbenes from 3-phenyl-3-(trifluoromethyl)-3H-diazirine(1) and its diazo isomer, phenyl-trifluoromethyl-diazomethane(2), was investigated using high-level multiconfigurationalwave function methods (MS-CASPT2) and density functional theory (DFT).Vertical excitation energies and the vibronic absorption spectrumof 1 were computed, confirming that the experimentalsignals reported in the literature originate from a single conformer.Our results demonstrate that S1 excitationin both isomers leads to ultrafast nonradiative deactivation througha shared S1/S0 conical intersection (CI1). In the condensed phase, this relaxationtriggers a branching mechanism: the system can either revert to theprecursor, undergo diazirine–diazo isomerization, or fragmentinto N2 and a closed-shell singlet carbene.Notably, the topology of the ground-state potential energy surfacesuggests that CI1 is a primary connection between the two isomers,relegating a conventional transition-state-mediated pathway to a lesslikely alternative for isomerization. Furthermore, a comparative assessmentshows that both MS-CASPT2 and DFT provide consistent descriptionsof the critical S1/S0 and S0/T0 crossing geometries. These findings provide a comprehensivemechanistic framework for the photolysis of aryl-trifluoromethyl diazirines.","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"6 5","pages":"1235–1243"},"PeriodicalIF":4.8,"publicationDate":"2026-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149022643","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Characterization of the pH-Dependent Stabilizing Forces of Insulin’s Native and Fibril States 胰岛素天然状态和原纤维状态的ph依赖性稳定力的表征

IF 4.8

ACS Physical Chemistry Au Pub Date : 2026-09-23 Epub Date: 2026-06-24 DOI: 10.1021/acsphyschemau.6c00045

Stefan Hervø-Hansen, Nobuyuki Matubayasi

{"title":"Characterization of the pH-Dependent Stabilizing Forces of Insulin’s Native and Fibril States","authors":"Stefan Hervø-Hansen, Nobuyuki Matubayasi","doi":"10.1021/acsphyschemau.6c00045","DOIUrl":"https://doi.org/10.1021/acsphyschemau.6c00045","url":null,"abstract":"Insulin fibrillation poses a major challenge for proteintherapeutics,yet the molecular origins of its strong pH dependence remain incompletelyunderstood. Here we employ constant-pH molecular dynamics simulationsto quantify residue-specific protonation behavior in native monomericinsulin and in fibrils of increasing size. While the native monomerexhibits largely uncoupled titration with modest pKa perturbations, conversion to the fibrillar fold inducessystematic upshifts of acidic residues driven by partial desolvationand reduced dielectric screening. Upon self-association, strong electrostaticcoupling emerges between neighboring glutamate residues aligned alongthe fibril axis, giving rise to cooperative and multistep titrationbehavior. In fibril assemblies, central residues consistently deprotonatefirst, despite residing in partially solvent-shielded environmentswithin the fibril core, indicating that collective electrostatic frustrationoverrides simple solvent accessibility effects. This cooperative chargeredistribution is accompanied by a progressive loss of intermonomercontacts, revealing pH-dependent weakening of fibril cohesion. Together,our results demonstrate that insulin fibrillation is governed by collectiveelectrostatics that arises only after conformational rearrangementand assembly, providing an atomistic framework for understanding pH-regulatedamyloid stability.","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"6 5","pages":"1102–1114"},"PeriodicalIF":4.8,"publicationDate":"2026-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149022800","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Implications of Intramolecular Interactions on the Fluorescence of a Highly Flexible Ethane-Bridged Porphyrin Dimer 分子内相互作用对高柔性乙烷桥联卟啉二聚体荧光的影响

IF 4.8

ACS Physical Chemistry Au Pub Date : 2026-09-23 Epub Date: 2026-06-03 DOI: 10.1021/acsphyschemau.6c00042

Sucheta Kundu, Arya Roychowdhury, Arkaprava Chowdhury, Achintya Kumar Dutta, Sankar Prasad Rath, Anindya Datta

{"title":"Implications of Intramolecular Interactions on the Fluorescence of a Highly Flexible Ethane-Bridged Porphyrin Dimer","authors":"Sucheta Kundu, Arya Roychowdhury, Arkaprava Chowdhury, Achintya Kumar Dutta, Sankar Prasad Rath, Anindya Datta","doi":"10.1021/acsphyschemau.6c00042","DOIUrl":"https://doi.org/10.1021/acsphyschemau.6c00042","url":null,"abstract":"Understanding therole of conformational flexibilityin multichromophoricsystems is crucial for elucidating excited-state processes such aselectronic coupling, energy transfer, and exciton–exciton annihilation,which are central to the rational design of artificial light-harvestingassemblies. In the present work, the excited-state dynamics of a highlyflexible free-base porphyrin dimer has been investigated and comparedwith its monomer using femtosecond transient absorption spectroscopyand femtosecond optical gating. While the excited-state kinetics ofthe dimer closely resemble those of the monomer at low pump fluence,pump-fluence-dependent transient absorption and femtosecond opticalgating measurements reveal additional ultrafast components of 1 psand 18–28 ps. Potential energy surface scan reveals a strongdependence of electronic coupling on the dihedral angle between thetwo porphyrin units. Comparison of the estimated electronic couplingwith the reorganization energy indicates that the dimer lies in theweak-coupling regime. Correlation of femtosecond optical gating measurementswith transition dipole moments calculated at different dihedral anglessuggests that conformers with more favorable transition-dipole orientationspredominantly contribute to the blue side of the emission spectrum.These components are attributed to Förster-mediated singlet–singletannihilation, arising from the significant spectral overlap betweenthe S0 ← S1 emission and the Sn ← S1 excited-state absorption.Overall, these results demonstrate that conformational flexibilitymodulates Förster-mediated annihilation dynamics in a porphyrindimer.","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"6 5","pages":"1083–1093"},"PeriodicalIF":4.8,"publicationDate":"2026-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149022747","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Tuning Spectral Properties of Anthracenes through Substitution 通过取代调整蒽类的光谱性质

IF 4.8

ACS Physical Chemistry Au Pub Date : 2026-09-23 Epub Date: 2026-09-14 DOI: 10.1021/acsphyschemau.6c00105

Vyshna Ratheesh, Anna M. Weidlich, Andreas Dreuw

{"title":"Tuning Spectral Properties of Anthracenes through Substitution","authors":"Vyshna Ratheesh, Anna M. Weidlich, Andreas Dreuw","doi":"10.1021/acsphyschemau.6c00105","DOIUrl":"https://doi.org/10.1021/acsphyschemau.6c00105","url":null,"abstract":"Heteroatom substitutionoffers a powerful means of tuningthe spectralproperties of acenes, yet a general structure–property relationshipvalid across different heteroacene families has been lacking. In thisstudy, we extend a previously applied analysis based on the algebraicdiagrammatic construction scheme for electronic excitations (ADC)framework to a broader family of heteroacenes, including aza-, phospha-,and halogen-substituted anthracenes. Decomposition of the ADC diagonalelements and the corresponding perturbative effects from ADC(2) →ADC(1) → ADC(0) reveals orbital energy differences as the primarydriver of excited state mixing and thus of the resulting oscillatorstrengths. This uncovers how substituent type and position shapesspectral intensities of the low-lying ππ* electronic transitions,namely, 1Ls (1Lb) and 1Bb. Tip substitution consistently enhances the orbital energydifference and leads to bright α-bands (1Ls/1Lb), whereasside substitution produces more symmetric mixing of configurationsand weak α-bands. Across halogen series, increasing electronegativitywhile keeping the position unchanged generally leads to higher oscillatorstrength of the 1Ls (1Lb) state. These results provide a unified,general rule for tuning the spectral properties by substitution and/orheteroatom replacement.","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"6 5","pages":"1340–1348"},"PeriodicalIF":4.8,"publicationDate":"2026-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149022686","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0