The Journal of Physical Chemistry B最新文献

{"title":"","authors":"Zachary C. Drake, Alexa G. Fowler, Ashley A. Blum and Steffen Lindert*, ","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":"129 26","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":2.8,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.jpcb.5c02872","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144535296","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Self-consistent Field Analysis of Segregative Aqueous Dextran-Polyethylene Glycol Solutions: (1) Bulk Phase Diagrams.","authors":"F A M Leermakers, L Ruiz-Martínez, S D Stoyanov, J van der Gucht","doi":"10.1021/acs.jpcb.5c01284","DOIUrl":"10.1021/acs.jpcb.5c01284","url":null,"abstract":"<p><p>Quasi-ternary dextran-water-polyethylene glycol (D-W-PEG) systems can undergo a segregative phase transition from a homogeneous to two-phase state with one phase enriched in dextran, the other in PEG, and both phases typically dominated by the spectator-like water component. The relation between the driving forces and the resulting phase behavior for such aqueous two-phase systems (ATPSs) is systematically studied with a Scheutjens-Fleer self-consistent field (SF-SCF) theory. We consider both the repulsive interactions between the polymeric species (the major driving force) and the solvent quality disparity (the minor driving force). In a narrow parameter range, when the major driving force is very weak, a closed-loop two-phase region with two critical points may be found. However, in more realistic parameter settings, an ATPS has an'open' binodal with a single critical point. We report on the volume ratio, the composition of the phases, (structural) parameters of the interface, such as the width, and the interfacial tension, as a function of the (average) water fraction in the system. We show that the volume-management strategy influences the phase diagram when polymers are polydisperse. By fitting a set of experimental phase diagrams, SF-SCF model parameters for D-W-PEG systems are established, which will be used in future to underpin experiments for these systems.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"6632-6645"},"PeriodicalIF":2.8,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144323872","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tuning Microbasicity in Poly(vinyl alcohol) Films via Hydrogen-Bonding Network Disruption.","authors":"Siyu Hou, Qin Yu, Xiya Peng, Shufang Gao, Jian Luo","doi":"10.1021/acs.jpcb.5c03440","DOIUrl":"10.1021/acs.jpcb.5c03440","url":null,"abstract":"<p><p>The microstructural properties of poly(vinyl alcohol) (PVA) and its composites critically determine their mechanical and optoelectronic performance in flexible sensors, yet their micro acid-base characteristics remain poorly understood despite their importance for pH-responsive functionalities. Here, we report a combined experimental and theoretical study demonstrating that dimethyl sulfoxide (DMSO) incorporation significantly enhances the microbasicity of PVA films. By employing a fluorescent probe and density functional theory calculations, we established that DMSO disrupts water's hydrogen-bonding network, increasing the population of bound water with enhanced basicity. Furthermore, DMSO may also strengthen the hydrogen bonding between the lumichrome probe and bound water, promoting deprotonation. This work provides direct evidence that water with an unsaturated hydrogen-bonding network exhibits elevated basicity, which offers a simple yet effective strategy to tune PVA's acid-base properties. Our findings enable new design principles for advanced proton-transfer-based materials in flexible electronics and smart sensors.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"6750-6756"},"PeriodicalIF":2.8,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144336123","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Molecular Insight into the Coalescence Mechanism of Droplets Stabilized by Amphiphilic Polymer-Grafted Nanoparticles.","authors":"Chiho Inada, Yusei Kobayashi, Masashi Yamakawa","doi":"10.1021/acs.jpcb.5c01676","DOIUrl":"10.1021/acs.jpcb.5c01676","url":null,"abstract":"<p><p>Recent progress in developing amphiphilic polymer-grafted nanoparticles (PGNPs) has led to extensive research on efficiently preparing emulsion droplets stabilized by these PGNPs. However, the molecular-level mechanism of droplet coalescence remains unclear. This study examines the relationship between the interfacial structures of PGNPs and the resistance force of emulsion droplets during coalescence, focusing on various grafting architectures and graft densities. A hybrid simulation approach combining dissipative particle dynamics and steered molecular dynamics is used to investigate this process. We observed various coalescence mechanisms at the molecular level based on the graft density. At low graft densities, the monolayered structure of the PGNP core between two oil droplets significantly contributes to the resistance against droplet-droplet coalescence due to the insufficient number of grafted polymers. Thus, diblock PGNPs with inner hydrophilic blocks are promising candidates for stabilizing emulsions, as they are pushed out from the droplet surface by the block immersed in the oil phase. Conversely, at higher graft density, this graft design causes the formation of the \"sticky\" point, promoting coalescence. On the other hand, diblock PGNPs with outer hydrophilic blocks exhibited a larger resistance force, accompanied by (multiple) layered structures between the two droplets during collision. More interestingly, the layer of Janus PGNPs had insufficient structural robustness, even at a high graft density, due to the penetration of the grafted homopolymers. These results improve the understanding of emulsion droplet coalescence and offer a theoretical guideline for designing optimal PGNPs for specific grafting architectures and graft densities.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"6684-6693"},"PeriodicalIF":2.8,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144339695","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Self-Assembly of 2-Hydroxyethyl-1H-imidazolium-Based Surface Active Ionic Liquids and Utilization of Their Aqueous Solution in Superactivity of Cytochrome-c.","authors":"Manpreet Singh, Rajwinder Kaur, Sugam Kumar, Vinod Kumar Aswal, Gurbir Singh, Tejwant Singh Kang","doi":"10.1021/acs.jpcb.5c01449","DOIUrl":"10.1021/acs.jpcb.5c01449","url":null,"abstract":"<p><p>Imidazolium-based surface active ionic liquids (SAILs) appended with a hydroxyethyl moiety at a cationic headgroup at a position opposite to an alkyl chain ([C₁₂ImOH][Br] and [C₁₆ImOH][Br]) and alkyl chain functionalized with amide ([C₁₂AImOH][Br]) and ester ([C₁₂EImOH][Br]) groups have been synthesized. Different techniques, i.e., surface tension, ionic conductance, fluorescence, dynamic light scattering, small angle neutron scattering, and isothermal titration calorimetry, have been exploited for establishing their micellization behavior, followed by the utilization of aqueous SAILs to offer enhanced enzymatic activity to cytochrome-c (Cyt-c). The hydrophobic hydration of the hydroxyethyl group retards the micellization in bulk but disturbs the water structure at and beneath the air-solution interface, resulting in better surface-active behavior as compared to their nonhydroxyethyl functionalized counterparts. The variation of characteristic micellar properties, i.e., cmc, counterion binding (β), aggregation number (<i>N</i>_agg), size, compactness, and thermodynamic parameters of micellization, is supported by the increasing hydrophobicity of the cationic SAIL along with contrastingly different <i>H</i>-bonding and stiffness of ester or amide moiety present near the cationic headgroup. The aqueous solutions of SAILs (below cmc) favored the enzyme activity governed predominantly by hydrophobic as well as polar interactions between SAILs and Cyt-c corroborated by molecular docking and circular dichroism (CD) spectroscopy investigations. Cyt-c shows a retarded activity in aqueous micelles of SAILs (above cmc) with the exception of [C₁₂AImOH][Br], where enzyme activity increased further to ∼2.1-fold compared to that observed in buffer. It is anticipated that the current results would pave a new way to synthesize SAILs not only to be used for enzyme activation and prolonged storage in aqueous medium but also for other biological applications.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"6661-6673"},"PeriodicalIF":2.8,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144482520","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"","authors":"Dan-Yang Zhao,&nbsp;Shengyang Zhou,&nbsp;Yan-Fei Huang,&nbsp;Han-Cheng Huang,&nbsp;Hongli Yang,&nbsp;Han Liu,&nbsp;Hao Lin,&nbsp;Gan-Ji Zhong* and Zhong-Ming Li*,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":"129 26","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":2.8,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.jpcb.5c02193","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144535228","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"","authors":"Thanh-Trị Châu,&nbsp; and ,&nbsp;Giovanni Zocchi*,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":"129 26","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":2.8,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.jpcb.5c01795","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144535292","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"","authors":"William L. Jorgensen*,&nbsp; and ,&nbsp;Julian Tirado-Rives,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":"129 26","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":2.8,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.jpcb.5c02405","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144535293","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Faster Diffusion of Water along Carbon Nanotubes near the Wall.","authors":"Golam Rosul Khan, Shinji Saito, Snehasis Daschakraborty","doi":"10.1021/acs.jpcb.5c02233","DOIUrl":"10.1021/acs.jpcb.5c02233","url":null,"abstract":"<p><p>The diffusion of water in carbon nanotubes (CNTs) is debated, particularly whether it is faster near the CNT wall or at the center and how the temperature influences this effect. Using molecular dynamics (MD) simulations, we study radially resolved water diffusion in CNT(26,26) (3.57 nm diameter) over a wide temperature range. Diffusion along the CNT axis is significantly enhanced compared to that of bulk water, with the effect intensifying at lower temperatures. Supercooling further amplifies this enhancement following near-Arrhenius behavior. Confinement has a smaller impact on the rotational dynamics. By resolving water motion into radial layers, we find that both translational and rotational dynamics are higher near the CNT wall due to weakened hydrogen bonding. The presence of dangling O-H bonds reduces friction at the CNT-water interface. Revisiting an NMR study, we suggest that the high-intensity peak corresponds to central layers, aligning with our MD results and refining our insights into confined water dynamics.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"6561-6573"},"PeriodicalIF":2.8,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144323870","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unravelling the Thermophysical Properties of Trisodium Citrate and Disodium Tartrate in Aqueous 1-Ethyl-3-methylimidazolium Ethyl Sulfate Solutions: Insights from Volumetric, Acoustic, Viscometric and Computational Studies.","authors":"Himani Singh, Amir Fayaz, Richu, Akshita Bandral, Ashwani Kumar","doi":"10.1021/acs.jpcb.5c00871","DOIUrl":"10.1021/acs.jpcb.5c00871","url":null,"abstract":"<p><p>The research focuses on studying the thermophysical properties of trisodium citrate and disodium tartrate in aqueous solutions of 1-ethyl-3-methylimidazolium ethyl sulfate, i.e., (0.05, 0.10, and 0.15) mol kg^-1 at different temperatures. The experiment involved measuring density, sound speed, and viscosity to calculate various parameters related to volume, compressibility, and viscosity like apparent molar volumes (<i>V</i>_ϕ), partial molar volumes (<i>V</i>^o_ϕ), limiting apparent molar expansibilities (<i>E</i>^o_ϕ), apparent molar isentropic compressibilities (<i>K</i>_ϕ,s), transfer properties, hydration number (<i>n</i>_H), viscosity <i>B</i>-coefficients, and thermodynamic parameters of viscous flow (Δμ^o₁, Δμ^o₂, Δ<i>H</i>^o₂ and <i>T</i>Δ<i>S</i>^o₂), etc. These parameters were used to analyze the interactions between trisodium citrate and disodium tartrate and 1-ethyl-3-methylimidazolium ethyl sulfate in the aqueous medium. The results indicated the prevalence of hydrophilic-hydrophilic interactions in the systems under investigation. Additionally, the density functional theory (DFT) calculations were performed to explore further the interactions and the characteristics of the studied systems.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"6528-6547"},"PeriodicalIF":2.8,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144336124","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}