The Journal of Physical Chemistry B最新文献_第4页

Revealing Interaction Mechanisms between Mechanical Properties and Structural Conformations–Interfacial Interactions in Materials Using Molecular Dynamics Simulations: A Natural Rubber–Lignin Composite Case 揭示力学性能与结构构象之间的相互作用机制——利用分子动力学模拟材料中的界面相互作用：以天然橡胶-木质素复合材料为例

IF 3.2 2区化学

The Journal of Physical Chemistry B Pub Date : 2026-10-08 Epub Date: 2026-09-23 DOI: 10.1021/acs.jpcb.6c03828

Hua Long, Junjie Lei, Jinze Dai, Fangjun Chen, Weifeng Liu, Qingang Xiong, Xueqing Qiu, Fengshan Zhang, Yanchao Zhao

{"title":"Revealing Interaction Mechanisms between Mechanical Properties and Structural Conformations–Interfacial Interactions in Materials Using Molecular Dynamics Simulations: A Natural Rubber–Lignin Composite Case","authors":"Hua Long, Junjie Lei, Jinze Dai, Fangjun Chen, Weifeng Liu, Qingang Xiong, Xueqing Qiu, Fengshan Zhang, Yanchao Zhao","doi":"10.1021/acs.jpcb.6c03828","DOIUrl":"https://doi.org/10.1021/acs.jpcb.6c03828","url":null,"abstract":"Inthis paper, the natural rubber-lignin system is usedas an example,and molecular dynamics simulations are employed to reveal the interactionmechanisms linking mechanical properties with structural conformation–interfacialinteractions. The results indicate that when the number of ligninchains is below 20 mol, interfacial interactions dominate the reinforcementbehavior of the system, and chain-segment extensibility, system packingefficiency, network confinement, and mechanical properties exhibitpositive correlations with lignin chain number. When the number oflignin chains reaches 20 mol, lignin agglomeration becomes the dominantfactor governing the reinforcement behavior, resulting in negativecorrelations between these structural characteristics and mechanicalproperties. Furthermore, increasing the lignin degree of polymerizationenhances lignin-chain extensibility, system packing efficiency, networkchain density, and mechanical properties, with interfacial interactionsserving as the primary contributor to reinforcement. These findingsprovide a theoretical foundation for the design and enhancement ofcomposite materials.","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":"130 40","pages":"10758–10770"},"PeriodicalIF":3.2,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149124774","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}

引用次数: 0

Solution-Phase Protein Adsorption to ss(GT)15-DNA-Wrapped Single-Walled Carbon Nanotubes ss(GT)15- dna包裹单壁碳纳米管的液相蛋白质吸附

IF 3.2 2区化学

The Journal of Physical Chemistry B Pub Date : 2026-10-08 Epub Date: 2026-09-23 DOI: 10.1021/acs.jpcb.6c03127

Gabriel Sánchez-Velázquez, Thomas K. Porter, Lucas Ospina, Ali A. Alizadehmojarad, Wonjun Yim, Xiaoyi Wang, Michael S. Strano

{"title":"Solution-Phase Protein Adsorption to ss(GT)15-DNA-Wrapped Single-Walled Carbon Nanotubes","authors":"Gabriel Sánchez-Velázquez, Thomas K. Porter, Lucas Ospina, Ali A. Alizadehmojarad, Wonjun Yim, Xiaoyi Wang, Michael S. Strano","doi":"10.1021/acs.jpcb.6c03127","DOIUrl":"https://doi.org/10.1021/acs.jpcb.6c03127","url":null,"abstract":"Proteins in solution adsorb to the corona of nanoparticlessuchas single-walled carbon nanotubes (SWCNTs), but these interactionsare difficult to predict and analyze due to ambiguities in the structureof the latter. In this work, we employ ss(GT)15-DNA-wrappedSWCNTs, a commonly used fluorescent sensor construct, to examine proteinadsorption by quantifying binding dissociation constants and characterizingthe corresponding photophysical effects. A library of 20 proteinsis used to evaluate adsorption-induced changes in photoluminescence(PL) intensity (ΔI/I0) and emission wavelength upon solution phase binding. We find that15 proteins produce monotonic dose–response behavior well describedusing a single-site Langmuir model. Alternatively, five proteins exhibitedmore complex, nonmonotonic behavior consistent with a two-step bindingmodel representing protein–protein interactions coupled toadsorption. The study reveals that metalloproteins, which comprised12 of the 20 proteins in the library, induced, on average, greaterPL quenching compared with metal-free proteins for this system, withmaximum binding-associated quenching (ΔI/I0) of 94% for metalloproteins versus 20% formetal-free proteins. For metalloproteins, we introduce a proximity-basedquenching framework in which protein size provides a coarse proxyfor cofactor–SWCNT separation, offering a mechanistic interpretationof the observed quenching variation across proteins. Together, theseresults establish the use of metal coordination sites, such as thosein metalloproteins, to assist the transduction of certain nanoparticlefluorescent sensors, helping with sensor probe design and interpretationin biological environments.","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":"130 40","pages":"10735–10748"},"PeriodicalIF":3.2,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149124912","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}

引用次数: 0

Tuning the Dynamic Fragility of Aromatic Acrylic Polymers: Effects of Associating Strength, Ether Linkages, and Alkyl Substituents 芳香丙烯酸聚合物动态脆性的调整：缔合强度、醚键和烷基取代基的影响

IF 3.2 2区化学

The Journal of Physical Chemistry B Pub Date : 2026-10-08 Epub Date: 2026-09-24 DOI: 10.1021/acs.jpcb.6c05329

Xuhong Zheng, Linghui Cui, Gaopeng Shi

{"title":"Tuning the Dynamic Fragility of Aromatic Acrylic Polymers: Effects of Associating Strength, Ether Linkages, and Alkyl Substituents","authors":"Xuhong Zheng, Linghui Cui, Gaopeng Shi","doi":"10.1021/acs.jpcb.6c05329","DOIUrl":"https://doi.org/10.1021/acs.jpcb.6c05329","url":null,"abstract":"Dynamic fragility is a critical parameter for understandingmaterialfunctionality, processability, and the fundamental nature of the glasstransition. However, achieving low fragility remains particularlychallenging for aromatic polyacrylates due to their high chain rigidityand weak cohesive energy. In this study, we aimed to reduce the fragilityof poly(benzyl acrylate) by tuning associative interactions, introducingether linkages, and incorporating alkyl substituents. It was foundthat hindered phenols exhibiting weak intermolecular hydrogen bondingwith the host polymer, along with high rigidity or significant sterichindrance, failed to achieve a substantial reduction in fragility.This result is attributed to the significantly enhanced rigidity,which increases fragility and thereby counterbalances the reductionin fragility induced by the moderately strengthened cohesive energy.In contrast, introducing either flexible ether linkages or bulky methylsubstituents into the host polymer led to a significant reductionin fragility, even in the presence of hindered phenols with high rigidity.We propose that both modification strategies enhance the flexibilitybalance between side groups and the polymer backbone and thus leadto an increase in configurational entropy, as confirmed by the generalizedentropy theory. These design principles offer a synergistic pathwayto tame the fragility of aromatic polyacrylates.","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":"130 40","pages":"10812–10822"},"PeriodicalIF":3.2,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149124851","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}

引用次数: 0

Separate-Gradient and Continuous-Gradient Langmuir–Blodgett Films 分离梯度和连续梯度Langmuir-Blodgett膜

IF 3.2 2区化学

The Journal of Physical Chemistry B Pub Date : 2026-10-08 Epub Date: 2026-09-24 DOI: 10.1021/acs.jpcb.6c05268

Gangyao Wen

{"title":"Separate-Gradient and Continuous-Gradient Langmuir–Blodgett Films","authors":"Gangyao Wen","doi":"10.1021/acs.jpcb.6c05268","DOIUrl":"https://doi.org/10.1021/acs.jpcb.6c05268","url":null,"abstract":"The classic Langmuir–Blodgett (LB) film techniqueis anadvanced and powerful tool to prepare highly ordered ultrathin filmsat the molecular and atomic levels; however, it cannot totally revealthe aggregation mechanism and conformation change of Langmuir monolayers.In this work, the separate-gradient and continuous-gradient LB filmmethods are proposed to resolve these problems. Two kinds of gradientLB monolayer films of an asymmetric block copolymer polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA)were successfully prepared, and their structures were compared withthose of conventional single LB films by atomic force microscopy (AFM).At the air/water interface, initial nontypical aggregates/micellesof PS-b-PMMA spontaneously form, and each copolymermolecule forms several connected intramolecular PS-rich domains (smallcores) tailed/surrounded with a PMMA block/shell. Upon monolayer compression,the small PS cores coalesce or connect into large cores or rods/networksthrough compression-driven morphological evolution. Combining withthe continuous-gradient LB films, the time-consuming “ex-situ”AFM can be regarded as a “quasi-in-situ” approach tostudy interfacial structures/aggregation behavior. The above two gradientLB film methods are great contributions to the development and complementaryto the classic LB film technique.","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":"130 40","pages":"10804–10811"},"PeriodicalIF":3.2,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149130670","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}

引用次数: 0

Assessing the Competition between Bulk and Interfacial Nucleation of H2S Hydrates via Molecular Dynamics 基于分子动力学的硫化氢水合物体积成核与界面成核竞争研究

IF 3.2 2区化学

The Journal of Physical Chemistry B Pub Date : 2026-10-08 Epub Date: 2026-09-25 DOI: 10.1021/acs.jpcb.6c04569

Joanna Grabowska, Eduardo Sanz

{"title":"Assessing the Competition between Bulk and Interfacial Nucleation of H2S Hydrates via Molecular Dynamics","authors":"Joanna Grabowska, Eduardo Sanz","doi":"10.1021/acs.jpcb.6c04569","DOIUrl":"https://doi.org/10.1021/acs.jpcb.6c04569","url":null,"abstract":"Understanding the mechanisms by which gas hydrates nucleatefromaqueous solutions is essential for predicting and controlling theirformation. Experimental observations have suggested that hydrate nucleationoccurs preferentially at interfaces between the aqueous phase andhydrate-forming reservoirs. However, recent simulation studies haveraised questions regarding the general validity of this assumption.Here, we investigate the spontaneous nucleation of H2Shydrates at 500 bar using molecular dynamics simulations employingthe TIP4P/Ice water model and a four-site H2S potential,with the aim of clarifying the competition between bulk and interfacialnucleation pathways. To ensure rigorous control of the thermodynamicconditions, we first determine the three-phase coexistence temperature(T3) from the intersection of the aqueoussolubility and hydrate–solution equilibrium curves; our calculatedvalue of T3 = 314(3) K shows excellentagreement with an experimentally inferred value of approximately316 K. Then, under deeply supercooled conditions, we directly comparenucleation kinetics across two distinct configurations: an interfacialsystem with an aqueous solution in contact with an H2Sreservoir and a standalone bulk solution at identical saturation.Our results show that nucleation rates in bulk systems are comparableto those obtained in the presence of an interface, indicating thatthe interface does not promote hydrate nucleation under the conditionsexplored. This behavior is consistent with our previous findings forCO2 hydrates and suggests that bulk nucleation can be theprevailing pathway under deep supercooling conditions.","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":"130 40","pages":"10601–10608"},"PeriodicalIF":3.2,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149124925","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}

引用次数: 0

Distinguishing Free Cytosolic and Vesicle-Confined Nanoparticle Motion by Fluorescence Correlation Spectroscopy 荧光相关光谱法鉴别自由胞质和囊泡纳米颗粒运动

IF 3.2 2区化学

The Journal of Physical Chemistry B Pub Date : 2026-10-08 Epub Date: 2026-09-25 DOI: 10.1021/acs.jpcb.6c05465

Karina Kwapiszewska, Grzegorz Bubak, Krzysztof Bielec, Aneta Magiera, Alicja Zgorzelska, Robert Hołyst

{"title":"Distinguishing Free Cytosolic and Vesicle-Confined Nanoparticle Motion by Fluorescence Correlation Spectroscopy","authors":"Karina Kwapiszewska, Grzegorz Bubak, Krzysztof Bielec, Aneta Magiera, Alicja Zgorzelska, Robert Hołyst","doi":"10.1021/acs.jpcb.6c05465","DOIUrl":"https://doi.org/10.1021/acs.jpcb.6c05465","url":null,"abstract":"Understanding whetherinternalized nanoparticles remainconfinedwithin intracellular vesicles or are released into the cytosol isessential for evaluating their biological activity and potential useas delivery systems. However, this distinction is often difficultto establish by using fluorescence imaging alone, particularly atnanomolar probe concentrations. Here, we propose fluorescence correlationspectroscopy (FCS) combined with length-scale-dependent viscosityanalysis and appropriate diffusion models as an approach for assessingnanoparticle uptake and intracellular localization. The method wasevaluated in HeLa cells using fluorescent polystyrene nanoparticles,cell-penetrating peptide-coated nanoparticles, dextran of two molecularweights, and receptor-internalized transferrin. Cytosolic probes wereidentified by autocorrelation curves that fit an anomalous diffusionmodel and by diffusion coefficients consistent with those predictedby the cytoplasmic length scale-dependent viscosity profile. In contrast,vesicle-associated probes produced characteristic two-step autocorrelationcurves that were modeled as the sum of probe diffusion within a confinedspace, vesicle translation, and directed intracellular transport.Bare nanoparticles, pinocytosed dextrans, and transferrin displayedpredominantly vesicle-associated mobility, whereas microinjected dextransand cell-penetrating-peptide-associated nanoparticles exhibited diffusionin the cytosol. Our results demonstrate that FCS can complement fluorescenceimaging by detecting cytosolic probe populations and distinguishingbetween cytosolic release and vesicular retention.","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":"130 40","pages":"10477–10487"},"PeriodicalIF":3.2,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149124890","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}

引用次数: 0

Molecular Motion of Viscous Solvents from Solid-State NMR 固体核磁共振黏性溶剂的分子运动

IF 3.2 2区化学

The Journal of Physical Chemistry B Pub Date : 2026-10-08 Epub Date: 2026-09-12 DOI: 10.1021/acs.jpcb.6c04720

Wanli Zhang, Yuling Feng, Hong Ye, Kai Xue

{"title":"Molecular Motion of Viscous Solvents from Solid-State NMR","authors":"Wanli Zhang, Yuling Feng, Hong Ye, Kai Xue","doi":"10.1021/acs.jpcb.6c04720","DOIUrl":"https://doi.org/10.1021/acs.jpcb.6c04720","url":null,"abstract":"Liquid–liquid phase separation (LLPS) is a ubiquitousphenomenonin biological systems and involves molecular motions across multipletime scales, especially in viscous, crowded environments. These dynamicsinclude not only biomacromolecules but also small solutes, ions, andwater. To establish an NMR framework for characterizing such heterogeneousdynamic regimes, we employ two homogeneous viscous model systems,glycerol and PEG400, which reproduce the slowed molecular motionscharacteristic of condensed biomolecular environments while avoidingthe structural complexity of phase-separated systems. Using solid-stateNMR relaxometry, we investigate multi-time scale dynamics in thesemodel solvents and examine water behavior under crowded conditions.Nanosecond motions are characterized by heteronuclear Overhauser effectsand 13C T1 relaxation, while microsecond dynamicsare probed via T2 and T1ρ relaxation;and translational self-diffusion is quantified using diffusion-orderedspectroscopy (DOSY). Glycerol and PEG400 exhibit similar fast nanosecondrotational motions (∼ 0.7–1.0 ns), yet their distinctviscosities are associated with differences in slower rotational dynamicsand translational self-diffusion. Water exhibits constrained nanosecondmotion in both systems, indicating partially immobilized populationsshaped by variations in free volume. This work establishes an NMR-basedframework for resolving multi-time scale dynamics in viscous systems,providing insights into LLPS and hydration behavior.","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":"130 40","pages":"10783–10791"},"PeriodicalIF":3.2,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149124862","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}

引用次数: 0

Cation-Dependent Water Dynamics in Concentrated Aqueous Tetrafluoroborate Solutions: Insights from Ultrafast IR Spectroscopy and Molecular Dynamics Simulations 浓缩四氟硼酸盐水溶液中阳离子依赖的水动力学：来自超快红外光谱和分子动力学模拟的见解

IF 3.2 2区化学

The Journal of Physical Chemistry B Pub Date : 2026-10-08 Epub Date: 2026-09-29 DOI: 10.1021/acs.jpcb.6c04067

Mengyu Wang, Xinyu Yang, Han Jiang, Jiajia Kang, Hongtao Bian

{"title":"Cation-Dependent Water Dynamics in Concentrated Aqueous Tetrafluoroborate Solutions: Insights from Ultrafast IR Spectroscopy and Molecular Dynamics Simulations","authors":"Mengyu Wang, Xinyu Yang, Han Jiang, Jiajia Kang, Hongtao Bian","doi":"10.1021/acs.jpcb.6c04067","DOIUrl":"https://doi.org/10.1021/acs.jpcb.6c04067","url":null,"abstract":"The freezing behavior of aqueous tetrafluoroborate solutionsdiffersmarkedly between Li+ and Zn2+, yet the microscopicorigin remains unclear. By combining ultrafast infrared spectroscopyand molecular dynamics (MD) simulations, we compare the dynamics ofbulk-like water and water molecules hydrogen-bonded to BF–4 in LiBF4 and Zn(BF4)2 solutions. Our resultsreveal that the vibrational lifetime of both water species is onlyslightly affected by the cation identity. The rotational dynamics,however, show a clear cation-dependent slowing: in Zn(BF4)2, the rotational time constant of bulk-like water increasesfrom ∼2.7 to ∼4.6 ps, while that of anion-bound waterincreases from ∼5.1 to ∼8.7 ps. These observations indicatethat Zn2+ imposes orientational constraints on water molecules,particularly on anion-bound water, suggesting a cation-dependent influenceon water–anion interactions. The different freezing behaviorof the two electrolytes is therefore proposed to be associated withcollective changes in the intermolecular interactions and water structure,rather than being determined solely by individual water rotationaldynamics. These changes include hydrogen-bond network disruption andsuppressed diffusion, as supported by our MD simulations. Our findingsprovide a molecular-level understanding of how cation identity modulateswater dynamics. These insights help explain the distinct freezingbehavior of aqueous electrolytes and may guide the design of low-temperatureaqueous electrolytes.","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":"130 40","pages":"10561–10570"},"PeriodicalIF":3.2,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149125000","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}

引用次数: 0

Calcium and Magnesium Ions in Glyme and Ether Sulfone-Based Electrolytes: Insights into Solvation Structure and Dynamics 钙和镁离子在甘氨酸和醚砜基电解质：洞察溶剂化结构和动力学

IF 3.2 2区化学

The Journal of Physical Chemistry B Pub Date : 2026-10-08 Epub Date: 2026-09-28 DOI: 10.1021/acs.jpcb.6c04886

Heigo Ers, Mathieu Cancade, Agílio A. H. Pádua

{"title":"Calcium and Magnesium Ions in Glyme and Ether Sulfone-Based Electrolytes: Insights into Solvation Structure and Dynamics","authors":"Heigo Ers, Mathieu Cancade, Agílio A. H. Pádua","doi":"10.1021/acs.jpcb.6c04886","DOIUrl":"https://doi.org/10.1021/acs.jpcb.6c04886","url":null,"abstract":"Energy-storage devices based on Ca2+ and Mg2+ ions are promising alternatives for moving beyond lithium-ionbatteries.The design of novel electrolytes for divalent metal ions requiresa detailed knowledge of the coordination environment and ion transport.In this regard, glymes and ether sulfones form various multidentatesolvation complexes with metal ions in electrolytes, promoting reversibleelectrodeposition of Ca2+ and Mg2+ by displacingthe coordinating anion, while offering good electrochemical stability.To provide insights into the structural and dynamic properties ofa wide variety of glyme and ether-sulfone electrolytes with Ca2+ and Mg2+ salts, we used molecular dynamic simulationswith an extended CL&Pol polarizable force field, which is basedon a fragment approach and is transferable to many families of molecules.Our simulation results show the dependence of the cation solvationenvironment structure on the choice of metal ion and salt anion inboth classes of solvents, and reveal the interplay between the coordinationof the metal ion by the ether and sulfonyl oxygens in ether sulfones.Additionally, we examine the impact of the solvent and additives onelectrolyte viscosity and conductivity.","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":"130 40","pages":"10619–10630"},"PeriodicalIF":3.2,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149124902","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}

引用次数: 0

Regioselective Counterion Association Governs Organohalogenochromism in Ferrocenyl Ionic Push-Pull Chromophores 二茂铁离子推拉发色团的区域选择性反离子缔合控制有机卤色

IF 3.2 2区化学

The Journal of Physical Chemistry B Pub Date : 2026-10-08 Epub Date: 2026-09-29 DOI: 10.1021/acs.jpcb.6c05161

Ignacio Aburto, Raúl Mera-Adasme, Fabián Martínez-Gómez, Carolina Aliaga, Moisés Domínguez

{"title":"Regioselective Counterion Association Governs Organohalogenochromism in Ferrocenyl Ionic Push-Pull Chromophores","authors":"Ignacio Aburto, Raúl Mera-Adasme, Fabián Martínez-Gómez, Carolina Aliaga, Moisés Domínguez","doi":"10.1021/acs.jpcb.6c05161","DOIUrl":"https://doi.org/10.1021/acs.jpcb.6c05161","url":null,"abstract":"Two organometallic cationic D-π-A dyes incorporatingferrocene donors and pyridinium or quinolinium acceptors were synthesizedand evaluated for their organohalogenochromic (OHC) behavior in halogenatedand non-halogenated solvents. Both dyes exhibited pronounced bathochromicshifts in halogenated media that cannot be explained solely by conventionalsolvent polarity effects. Triflate titration experiments demonstratedthat ICT transition energies are directly controlled by counterionassociation, while 1H NMR measurements revealed a regioselectiveinteraction centered at the azaheterocyclic acceptor. Benesi–Hildebrandanalysis yielded association constants of 4.82 × 10–2 M–1 and 1.38 × 10–2 M–1 for the pyridinium and quinolinium derivatives, respectively.Complementary T1 measurements and TD-DFTcalculations further supported a solvent-dependent ion-pairing model.Collectively, the results indicate that organohalogenochromism arisesfrom solvent-controlled modulation of ion-pair equilibria, highlightingregioselective counterion association as a key factor governing theoptical response of ferrocenyl ionic push-pull chromophores.","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":"130 40","pages":"10666–10673"},"PeriodicalIF":3.2,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149125002","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}

引用次数: 0