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

Isomerism and Solvent Interaction in Octamethyl Calix[4]pyrrole Complexed with Formate

IF 2.8 2区化学

The Journal of Physical Chemistry B Pub Date : 2025-03-26 DOI: 10.1021/acs.jpcb.5c0039310.1021/acs.jpcb.5c00393

Lane M. Terry, Madison M. Foreman and J. Mathias Weber*,

{"title":"Isomerism and Solvent Interaction in Octamethyl Calix[4]pyrrole Complexed with Formate","authors":"Lane M. Terry, Madison M. Foreman and J. Mathias Weber*, ","doi":"10.1021/acs.jpcb.5c0039310.1021/acs.jpcb.5c00393","DOIUrl":"https://doi.org/10.1021/acs.jpcb.5c00393https://doi.org/10.1021/acs.jpcb.5c00393","url":null,"abstract":"We investigate the binding motifs of host–guest complexes of the anion receptor octamethyl calix[4]pyrrole (omC4P) with the formate anion using cryogenic ion vibrational spectroscopy in concert with density functional theory. The resulting infrared spectrum in vacuo is compared to that in deuterated acetonitrile and acetone solutions. The combination of the strong host–guest interaction and the charge distribution that the formate ion presents to the chemical environment results in complex behavior of the NH stretching features in the two solvents. The formate–omC4P complex has three low energy isomers in vacuo: (i) one with an oxygen atom of formate interacting with three of the NH groups of omC4P and the other oxygen atom interacting with the remaining NH group; (ii) one with a single oxygen atom of formate interacting with all four NH groups of omC4P; and (iii) one with each oxygen atom interacting with two NH groups. Each complex geometry lowers the C4v symmetry of the receptor to C1, Cs, or C2v, respectively, and both symmetry breaking and isomerism are reflected in the pattern and broad line shapes of the NH stretching modes of omC4P.","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":"129 13","pages":"3436–3442 3436–3442"},"PeriodicalIF":2.8,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758790","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

Resonant Soft X-ray Scattering for Organic Photovoltaics

IF 2.8 2区化学

The Journal of Physical Chemistry B Pub Date : 2025-03-26 DOI: 10.1021/acs.jpcb.5c0036210.1021/acs.jpcb.5c00362

Dean M. DeLongchamp*,

{"title":"Resonant Soft X-ray Scattering for Organic Photovoltaics","authors":"Dean M. DeLongchamp*, ","doi":"10.1021/acs.jpcb.5c0036210.1021/acs.jpcb.5c00362","DOIUrl":"https://doi.org/10.1021/acs.jpcb.5c00362https://doi.org/10.1021/acs.jpcb.5c00362","url":null,"abstract":"Resonant Soft X-ray Scattering (RSoXS) has emerged as a powerful technique for probing the morphology in organic bulk heterojunction (BHJ) solar cells, frequently employed as a measurement of phase purity and compositional length scales. Here we use the National Institute of Standards and Technology RSoXS Simulation Suite to systematically examine how structural features common to BHJs would contribute to RSoXS patterns in the PM6:Y6 BHJ system. Starting from experimentally determined anisotropic optical constants, we simulate scattering from controlled morphological variations including compositional heterogeneity, interfacial sharpness, surface roughness, and molecular orientation. Our results demonstrate that noncompositional features can cause increases in scattering intensity exceeding those from compositional phase separation. Surface roughness of just a few nanometers produces substantial scattering due to the high contrast between organic materials and vacuum, and molecular orientation effects─whether random, interface-aligned, or independently correlated─can dramatically influence pattern intensity and shape. However, each structural feature exhibits a distinct energy-dependent scattering signature across the carbon K-edge, suggesting that careful analysis of the complete spectral response could enable deconvolution of multiple contributions. These findings provide a broader interpretation of the excellent correlations between RSoXS measurements and BHJ solar cell device performance, while highlighting the potential of forward simulation approaches to leverage the full information content of energy-dependent RSoXS measurements.","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":"129 13","pages":"3529–3545 3529–3545"},"PeriodicalIF":2.8,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpcb.5c00362","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758841","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}

引用次数: 0

Catalytic Effects of Water-Solvated Metal Cations in Epoxy-Amine Curing through Hydrogen Bonds and Metal-Ligand Interactions.

IF 2.8 2区化学

The Journal of Physical Chemistry B Pub Date : 2025-03-25 DOI: 10.1021/acs.jpcb.4c05874

Dipak Prasad, Nilanjan Mitra

引用次数: 0

The Enhanced Proton-Accepting Ability of Bound Water in Poly(vinyl alcohol) Films.

IF 2.8 2区化学

The Journal of Physical Chemistry B Pub Date : 2025-03-25 DOI: 10.1021/acs.jpcb.5c00861

Qin Yu, Siyu Hou, Mengrong Hu, Zheng Li, Jian Luo

引用次数: 0

Molecular-Level Understanding of Water Transport Mechanisms in Functionalized Ti₃C₂T_X MXene Membrane-Combined Experimental Approaches.

IF 2.8 2区化学

The Journal of Physical Chemistry B Pub Date : 2025-03-25 DOI: 10.1021/acs.jpcb.4c08655

Yang He, Guowei Chen, Yiping Zhao, Li Chen

{"title":"Molecular-Level Understanding of Water Transport Mechanisms in Functionalized Ti3C2TX MXene Membrane-Combined Experimental Approaches.","authors":"Yang He, Guowei Chen, Yiping Zhao, Li Chen","doi":"10.1021/acs.jpcb.4c08655","DOIUrl":"https://doi.org/10.1021/acs.jpcb.4c08655","url":null,"abstract":"The hydrophilicity of two-dimensional (2D) transition-metal carbides, carbonitrides, and nitrides (MXene) nanochannels plays a critical role in water transport during filtration, yet its specific effects on MXene membranes remain inadequately understood. Herein, we systematically investigated water transport through Ti3C2TX MXene nanochannels using molecular dynamics simulations coupled with experimental validation, addressing a significant knowledge gap in MXene-based separation membranes. Our simulations demonstrated that strong interactions between water molecules and hydrophilic nanochannel MXene surfaces (Ti3C2(OH)2 MXene or Ti3C2(NH)2 MXene) facilitated the formation of ordered molecular arrangements, substantially improving water permeability. Conversely, hydrophobic nanochannels (Ti3C2O2 MXene or Ti3C2F2 MXene) exhibited disordered water molecule distributions, leading to reduced permeability. Experimental validation corroborated these simulation results, demonstrating a direct correlation between the hydrophilicity of the Ti3C2TX surface and the water flux. The highly hydrophilic Ti3C2(OH)2 MXenes exhibited water flux maximum, whereas the more hydrophobic Ti3C2F2 MXenes had the lowest water flux. By integrating molecular dynamics simulations with experimental analyses, we gained comprehensive insights into the influence of nanochannel hydrophilicity on water transport mechanisms in MXene membranes. These findings provide critical guidelines for designing high-performance MXene-based membranes for advanced water treatment and separation applications.","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143707791","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-Level Understanding of Water Transport Mechanisms in Functionalized Ti3C2TX MXene Membrane-Combined Experimental Approaches

IF 2.8 2区化学

The Journal of Physical Chemistry B Pub Date : 2025-03-25 DOI: 10.1021/acs.jpcb.4c0865510.1021/acs.jpcb.4c08655

Yang He, Guowei Chen, Yiping Zhao and Li Chen*,

{"title":"Molecular-Level Understanding of Water Transport Mechanisms in Functionalized Ti3C2TX MXene Membrane-Combined Experimental Approaches","authors":"Yang He, Guowei Chen, Yiping Zhao and Li Chen*, ","doi":"10.1021/acs.jpcb.4c0865510.1021/acs.jpcb.4c08655","DOIUrl":"https://doi.org/10.1021/acs.jpcb.4c08655https://doi.org/10.1021/acs.jpcb.4c08655","url":null,"abstract":"The hydrophilicity of two-dimensional (2D) transition-metal carbides, carbonitrides, and nitrides (MXene) nanochannels plays a critical role in water transport during filtration, yet its specific effects on MXene membranes remain inadequately understood. Herein, we systematically investigated water transport through Ti3C2TX MXene nanochannels using molecular dynamics simulations coupled with experimental validation, addressing a significant knowledge gap in MXene-based separation membranes. Our simulations demonstrated that strong interactions between water molecules and hydrophilic nanochannel MXene surfaces (Ti3C2(OH)2 MXene or Ti3C2(NH)2 MXene) facilitated the formation of ordered molecular arrangements, substantially improving water permeability. Conversely, hydrophobic nanochannels (Ti3C2O2 MXene or Ti3C2F2 MXene) exhibited disordered water molecule distributions, leading to reduced permeability. Experimental validation corroborated these simulation results, demonstrating a direct correlation between the hydrophilicity of the Ti3C2TX surface and the water flux. The highly hydrophilic Ti3C2(OH)2 MXenes exhibited water flux maximum, whereas the more hydrophobic Ti3C2F2 MXenes had the lowest water flux. By integrating molecular dynamics simulations with experimental analyses, we gained comprehensive insights into the influence of nanochannel hydrophilicity on water transport mechanisms in MXene membranes. These findings provide critical guidelines for designing high-performance MXene-based membranes for advanced water treatment and separation applications.","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":"129 13","pages":"3396–3407 3396–3407"},"PeriodicalIF":2.8,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758908","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

Discrimination and Translocation of Charged Proteinogenic Amino Acids through a Single-Walled Carbon Nanotube.

IF 2.8 2区化学

The Journal of Physical Chemistry B Pub Date : 2025-03-25 DOI: 10.1021/acs.jpcb.4c08692

Yingjun Shen, Mingming Ding

引用次数: 0

The Enhanced Proton-Accepting Ability of Bound Water in Poly(vinyl alcohol) Films

IF 2.8 2区化学

The Journal of Physical Chemistry B Pub Date : 2025-03-25 DOI: 10.1021/acs.jpcb.5c0086110.1021/acs.jpcb.5c00861

Qin Yu, Siyu Hou, Mengrong Hu, Zheng Li and Jian Luo*,

{"title":"The Enhanced Proton-Accepting Ability of Bound Water in Poly(vinyl alcohol) Films","authors":"Qin Yu, Siyu Hou, Mengrong Hu, Zheng Li and Jian Luo*, ","doi":"10.1021/acs.jpcb.5c0086110.1021/acs.jpcb.5c00861","DOIUrl":"https://doi.org/10.1021/acs.jpcb.5c00861https://doi.org/10.1021/acs.jpcb.5c00861","url":null,"abstract":"Poly(vinyl alcohol) (PVA) films have been widely used as flexible matrixes in advanced optical materials. Most studies concern the rigidification strategy of PVA films, while the physicochemical properties of inside bound water are ignored. In this study, we have employed lumichrome as the fluorescent probe to explore the acid–base property of bound water, which was demonstrated to exhibit an enhanced proton-accepting ability than bulk water, evidenced by the promoted deprotonation of lumichrome in the ground state. Decreasing the water content in a PVA film is demonstrated to further improve the proton-accepting ability. Different from that in bulk solution, a selective prototropism of lumichrome is determined in PVA films, which is induced by the formation of an anchored lumichrome–PVA complex through three hydrogen bonds. This work first points out the enhanced proton-accepting ability of bound water in PVA films, opening a new avenue for the development of flexible optical materials based on proton transfer.","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":"129 13","pages":"3546–3552 3546–3552"},"PeriodicalIF":2.8,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758785","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

Pterin-Thymidine Adducts: From Their Photochemical Synthesis to Their Photosensitizing Properties.

IF 2.8 2区化学

The Journal of Physical Chemistry B Pub Date : 2025-03-25 DOI: 10.1021/acs.jpcb.5c00185

Gricelda Godoy-Ortega, Gemma M Rodríguez-Muñiz, Virginie Lhiaubet-Vallet, Carolina Lorente, Andrés H Thomas

{"title":"Pterin-Thymidine Adducts: From Their Photochemical Synthesis to Their Photosensitizing Properties.","authors":"Gricelda Godoy-Ortega, Gemma M Rodríguez-Muñiz, Virginie Lhiaubet-Vallet, Carolina Lorente, Andrés H Thomas","doi":"10.1021/acs.jpcb.5c00185","DOIUrl":"https://doi.org/10.1021/acs.jpcb.5c00185","url":null,"abstract":"Pterin (Ptr) is the model compound of aromatic pterins, which are efficient photosensitizers present in human skin and are able to oxidize biomolecules upon UVA irradiation. Photosensitization involves chemical alteration of a biomolecule as a result of the initial absorption of radiation by another chemical species, the photosensitizer. Under anaerobic conditions, Ptr reacts with thymine (T) to form photoadducts (T-Ptr). In this work, we present a method to prepare and purify T-Ptr adducts, using 2'-deoxythymidine 5'-monophosphate (dTMP) and single stranded oligonucleotide 5'-d(TTTTT)-3' (dT5), and investigate their photosensitizing properties. Interestingly, the Ptr moiety, when attached to T, retains its photophysical properties. The adduct dTMP-Ptr, upon excitation, forms singlet and triplet excited states, the latter being capable of transferring energy to dissolved O2 and generating singlet oxygen, with an efficiency similar to Ptr. In air-equilibrated solutions, both dTMP-Ptr and dT5-Ptr adducts can photosensitize the oxidation of tryptophan and 2'-deoxyguanosine 5'-monophosphate, two of the main targets of photosensitization in biological systems, with efficiencies close to that of free Ptr. The mechanisms involved in the oxidation of biomolecules can be either type I (electron transfer) or type II (singlet oxygen).","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143699117","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 Excited-State Charge Transfer Character in Cofacial Core-Substituted Perylenediimide Dimers.

IF 2.8 2区化学

The Journal of Physical Chemistry B Pub Date : 2025-03-25 DOI: 10.1021/acs.jpcb.5c00617

Samuel B Tyndall, Jonathan R Palmer, Nikolai A Tcyrulnikov, Ryan M Young, Michael R Wasielewski

{"title":"Tuning Excited-State Charge Transfer Character in Cofacial Core-Substituted Perylenediimide Dimers.","authors":"Samuel B Tyndall, Jonathan R Palmer, Nikolai A Tcyrulnikov, Ryan M Young, Michael R Wasielewski","doi":"10.1021/acs.jpcb.5c00617","DOIUrl":"https://doi.org/10.1021/acs.jpcb.5c00617","url":null,"abstract":"Understanding the interplay between excimer formation and symmetry-breaking charge separation is important for optimizing charge separation in organic photovoltaic materials. To explore this connection, we synthesized four 1,6,7,12-tetrakis(p-X-phenoxy)perylene-(3,4:9,10)-bisdicarboximide cofacially stacked dimers, where X = MeO, tert-butyl, Br, and CF3. Steady-state spectroscopy reveals H-type aggregation and excimer formation in all four dimers, while transient absorption spectroscopy shows relatively small changes in their excited-state absorptions. However, time-resolved fluorescence (TRF) spectroscopy shows that relaxation occurs from an initial Frenkel exciton-dominated excimer state to one in which charge transfer (CT) character contributes. Relaxation to the lower-lying state with CT character is attributed to a combination of structural and charge distribution changes elicited by varying the substituents. This study illustrates how subtle changes in charge distribution and structure can combine to influence the excited state dynamics that influence charge separation in molecular dimers.","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143707795","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