ACS Physical Chemistry Au最新文献

{"title":"Rational Design of Far-Red Archaerhodopsin-3-Based Fluorescent Genetically Encoded Voltage Indicators: from Elucidation of the Fluorescence Mechanism in Archers to Novel Red-Shifted Variants","authors":"Dmitrii M. Nikolaev,&nbsp;Vladimir N. Mironov,&nbsp;Ekaterina M. Metelkina,&nbsp;Andrey A. Shtyrov,&nbsp;Andrey S. Mereshchenko,&nbsp;Nikita A. Demidov,&nbsp;Sergey Yu. Vyazmin,&nbsp;Tatiana B. Tennikova,&nbsp;Svetlana E. Moskalenko,&nbsp;Stanislav A. Bondarev,&nbsp;Galina A. Zhouravleva,&nbsp;Andrey V. Vasin,&nbsp;Maxim S. Panov and Mikhail N. Ryazantsev*,&nbsp;","doi":"10.1021/acsphyschemau.3c0007310.1021/acsphyschemau.3c00073","DOIUrl":"https://doi.org/10.1021/acsphyschemau.3c00073https://doi.org/10.1021/acsphyschemau.3c00073","url":null,"abstract":"<p >Genetically encoded voltage indicators (GEVIs) have found wide applications as molecular tools for visualization of changes in cell membrane potential. Among others, several classes of archaerhodopsin-3-based GEVIs have been developed and have proved themselves promising in various molecular imaging studies. To expand the application range for this type of GEVIs, new variants with absorption band maxima shifted toward the first biological window and enhanced fluorescence signal are required. Here, we integrate computational and experimental strategies to reveal structural factors that distinguish far-red bright archaerhodopsin-3-based GEVIs, Archers, obtained by directed evolution in a previous study (McIsaac et al., <i>PNAS,</i> 2014) and the wild-type archaerhodopsin-3 with an extremely dim fluorescence signal, aiming to use the obtained information in subsequent rational design. We found that the fluorescence can be enhanced by stabilization of a certain conformation of the protein, which, in turn, can be achieved by tuning the p<i>K</i>_a value of two titratable residues. These findings were supported further by introducing mutations into wild-type archeorhodopsin-3 and detecting the enhancement of the fluorescence signal. Finally, we came up with a rational design and proposed previously unknown Archers variants with red-shifted absorption bands (λ_max up to 640 nm) and potential-dependent bright fluorescence (quantum yield up to 0.97%).</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.3c00073","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141955179","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Important Elements of Spin-Exciton and Magnon-Exciton Coupling","authors":"Nicholas J. Brennan,&nbsp;Cora A. Noble,&nbsp;Jiacheng Tang,&nbsp;Michael E. Ziebel* and Youn Jue Bae*,&nbsp;","doi":"10.1021/acsphyschemau.4c0001010.1021/acsphyschemau.4c00010","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00010https://doi.org/10.1021/acsphyschemau.4c00010","url":null,"abstract":"<p >The recent discovery of spin-exciton and magnon-exciton coupling in a layered antiferromagnetic semiconductor, CrSBr, is both fundamentally intriguing and technologically significant. This discovery unveils a unique capability to optically access and manipulate spin information using excitons, opening doors to applications in quantum interconnects, quantum photonics, and opto-spintronics. Despite their remarkable potential, materials exhibiting spin-exciton and magnon-exciton coupling remain limited. To broaden the library of such materials, we explore key parameters for achieving and tuning spin-exciton and magnon-exciton couplings. We begin by examining the mechanisms of couplings in CrSBr and drawing comparisons with other recently identified two-dimensional magnetic semiconductors. Furthermore, we propose various promising scenarios for spin-exciton coupling, laying the groundwork for future research endeavors.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00010","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141955354","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Physical, Thermal, and Optical Properties of Mn2+ and Nd3+ Containing Barium Phosphate Glasses","authors":"José A. Jiménez","doi":"10.1021/acsphyschemau.4c00020","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00020","url":null,"abstract":"This work reports on various properties and analysis of optical interactions in phosphate glasses containing red-emitting Mn²⁺ and near-infrared (NIR)-emitting Nd³⁺ ions, which are of interest for energy applications and solar spectral converters. The glasses were made by melting with 50P₂O₅–(48 – <i>x</i>)BaO–2MnO–<i>x</i>Nd₂O₃ (<i>x</i> = 0, 0.5, 1.0, and 2.0 mol %) nominal compositions and characterized by X-ray diffraction, density and related physical properties, differential scanning calorimetry, dilatometry, UV–vis–NIR optical absorption, and photoluminescence spectroscopy with decay kinetics analysis. The glasses were X-ray amorphous, wherein the physical and thermal properties of the Mn²⁺/Nd³⁺-codoped glasses were largely impacted by Nd₂O₃ contents. The optical absorption spectra supported the occurrence of Mn²⁺ ions and the lack of Mn³⁺ in the codoped glasses, while the absorption due to Nd³⁺ ions increased steadily with Nd₂O₃ contents. Analyzing the glass absorption edges via Tauc and Urbach plots was further pursued for a comparison. The photoluminescence evaluation showed a consistent suppression of the emission from Mn²⁺ ions with increasing Nd³⁺ concentration, while the decay kinetics revealed shorter lifetimes in connection with increased Mn²⁺ → Nd³⁺ transfer efficiencies. Excitation of Mn²⁺ at 410 nm, however, led to the Nd³⁺ NIR emission being most intense for 1.0 mol % Nd₂O₃, despite the ⁴F_3/2 emission decay analysis showing lifetime shortening throughout. Considering the compromise between red and NIR emissions, the Mn-containing glass doped with 0.5 mol % Nd₂O₃ is put in perspective with the concept of solar spectral conversion.","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140801901","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}

{"title":"Rotational Symmetry Effects on Multibody Lateral Interactions between Co-Adsorbates at Heterogeneous Interfaces","authors":"Shuqiao Wang, Alyssa J.R. Hensley","doi":"10.1021/acsphyschemau.4c00019","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00019","url":null,"abstract":"Heterogeneous interfaces are critical in a wide range of applications, and their material properties can be tuned via changes in the coverage and configuration of chemical adsorbates. However, the tunability of such adlayers is limited by a lack of knowledge surrounding the impact of adsorbate internal structure and rotational symmetry on lateral interactions between coadsorbates. Using density functional theory (DFT) and cluster expansions, we systematically determine the impacts of rotational symmetry on lateral interactions between coadsorbates as a function of DFT functional, adsorbate type, metal type, and cluster configuration. Results indicate that the rotational symmetry effects can be nearly exclusively partitioned into the shortest 2-body clusters. By electronic analysis, the nature and strength of such effects on the lateral interactions are attributed to a balance of repulsive and attractive electrostatic interactions that are dependent on the adsorbate and metal types. Taken together, our characterization of the impacts of adsorbate internal structure and rotational symmetry on lateral interactions enables improved accuracy within multiscale modeling of multibody adsorbates at heterogeneous interfaces.","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140801785","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}

{"title":"Physical, Thermal, and Optical Properties of Mn2+ and Nd3+ Containing Barium Phosphate Glasses","authors":"José A. Jiménez*,&nbsp;","doi":"10.1021/acsphyschemau.4c0002010.1021/acsphyschemau.4c00020","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00020https://doi.org/10.1021/acsphyschemau.4c00020","url":null,"abstract":"<p >This work reports on various properties and analysis of optical interactions in phosphate glasses containing red-emitting Mn²⁺ and near-infrared (NIR)-emitting Nd³⁺ ions, which are of interest for energy applications and solar spectral converters. The glasses were made by melting with 50P₂O₅–(48 – <i>x</i>)BaO–2MnO–<i>x</i>Nd₂O₃ (<i>x</i> = 0, 0.5, 1.0, and 2.0 mol %) nominal compositions and characterized by X-ray diffraction, density and related physical properties, differential scanning calorimetry, dilatometry, UV–vis–NIR optical absorption, and photoluminescence spectroscopy with decay kinetics analysis. The glasses were X-ray amorphous, wherein the physical and thermal properties of the Mn²⁺/Nd³⁺-codoped glasses were largely impacted by Nd₂O₃ contents. The optical absorption spectra supported the occurrence of Mn²⁺ ions and the lack of Mn³⁺ in the codoped glasses, while the absorption due to Nd³⁺ ions increased steadily with Nd₂O₃ contents. Analyzing the glass absorption edges via Tauc and Urbach plots was further pursued for a comparison. The photoluminescence evaluation showed a consistent suppression of the emission from Mn²⁺ ions with increasing Nd³⁺ concentration, while the decay kinetics revealed shorter lifetimes in connection with increased Mn²⁺ → Nd³⁺ transfer efficiencies. Excitation of Mn²⁺ at 410 nm, however, led to the Nd³⁺ NIR emission being most intense for 1.0 mol % Nd₂O₃, despite the ⁴F_3/2 emission decay analysis showing lifetime shortening throughout. Considering the compromise between red and NIR emissions, the Mn-containing glass doped with 0.5 mol % Nd₂O₃ is put in perspective with the concept of solar spectral conversion.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00020","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141955356","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rotational Symmetry Effects on Multibody Lateral Interactions between Co-Adsorbates at Heterogeneous Interfaces","authors":"Shuqiao Wang,&nbsp; and ,&nbsp;Alyssa J.R. Hensley*,&nbsp;","doi":"10.1021/acsphyschemau.4c0001910.1021/acsphyschemau.4c00019","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00019https://doi.org/10.1021/acsphyschemau.4c00019","url":null,"abstract":"<p >Heterogeneous interfaces are critical in a wide range of applications, and their material properties can be tuned via changes in the coverage and configuration of chemical adsorbates. However, the tunability of such adlayers is limited by a lack of knowledge surrounding the impact of adsorbate internal structure and rotational symmetry on lateral interactions between coadsorbates. Using density functional theory (DFT) and cluster expansions, we systematically determine the impacts of rotational symmetry on lateral interactions between coadsorbates as a function of DFT functional, adsorbate type, metal type, and cluster configuration. Results indicate that the rotational symmetry effects can be nearly exclusively partitioned into the shortest 2-body clusters. By electronic analysis, the nature and strength of such effects on the lateral interactions are attributed to a balance of repulsive and attractive electrostatic interactions that are dependent on the adsorbate and metal types. Taken together, our characterization of the impacts of adsorbate internal structure and rotational symmetry on lateral interactions enables improved accuracy within multiscale modeling of multibody adsorbates at heterogeneous interfaces.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00019","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141955355","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Important Elements of Spin-Exciton and Magnon-Exciton Coupling","authors":"Nicholas J. Brennan, Cora A. Noble, Jiacheng Tang, Michael E. Ziebel, Youn Jue Bae","doi":"10.1021/acsphyschemau.4c00010","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00010","url":null,"abstract":"The recent discovery of spin-exciton and magnon-exciton coupling in a layered antiferromagnetic semiconductor, CrSBr, is both fundamentally intriguing and technologically significant. This discovery unveils a unique capability to optically access and manipulate spin information using excitons, opening doors to applications in quantum interconnects, quantum photonics, and opto-spintronics. Despite their remarkable potential, materials exhibiting spin-exciton and magnon-exciton coupling remain limited. To broaden the library of such materials, we explore key parameters for achieving and tuning spin-exciton and magnon-exciton couplings. We begin by examining the mechanisms of couplings in CrSBr and drawing comparisons with other recently identified two-dimensional magnetic semiconductors. Furthermore, we propose various promising scenarios for spin-exciton coupling, laying the groundwork for future research endeavors.","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140801950","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}

{"title":"Double-Layer Distribution of Hydronium and Hydroxide Ions in the Air–Water Interface","authors":"Pengchao Zhang,&nbsp;Muye Feng and Xuefei Xu*,&nbsp;","doi":"10.1021/acsphyschemau.3c0007610.1021/acsphyschemau.3c00076","DOIUrl":"https://doi.org/10.1021/acsphyschemau.3c00076https://doi.org/10.1021/acsphyschemau.3c00076","url":null,"abstract":"<p >The acid–base nature of the aqueous interface has long been controversial. Most macroscopic experiments suggest that the air–water interface is basic based on the detection of negative charges at the interface that indicates the enrichment of hydroxides (OH^–), whereas microscopic studies mostly support the acidic air–water interface with the observation of hydronium (H₃O⁺) accumulation in the top layer of the interface. It is crucial to clarify the interfacial preference of OH^– and H₃O⁺ ions for rationalizing the debate. In this work, we perform deep potential molecular dynamics simulations to investigate the preferential distribution of OH^– and H₃O⁺ ions at the aqueous interfaces. The neural network potential energy surface is trained based on density functional theory calculations with the SCAN functional, which can accurately describe the diffusion of these two ions both in the interface and in the bulk water. In contrast to the previously reported single ion enrichment, we show that both OH^– and H₃O⁺ surprisingly prefer to accumulate in interfaces but at different interfacial depths, rendering a double-layer ionic distribution within ∼1 nm near the Gibbs dividing surface. The H₃O⁺ preferentially resides in the topmost layer of the interface, but the OH^–, which is enriched in the deeper interfacial layer, has a higher equilibrium concentration due to the more negative free energy of interfacial stabilization [−0.90 (OH^–) vs −0.56 (H₃O⁺) kcal/mol]. The present finding of the ionic double-layer distribution may qualitatively offer a self-consistent explanation for the long-term controversy about the acid–base nature of the air–water interface.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.3c00076","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141954745","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Double-Layer Distribution of Hydronium and Hydroxide Ions in the Air–Water Interface","authors":"P. Zhang, Muye Feng, Xuefei Xu","doi":"10.1021/acsphyschemau.3c00076","DOIUrl":"https://doi.org/10.1021/acsphyschemau.3c00076","url":null,"abstract":",","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140680911","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}

{"title":"Physicochemical Perspective of Biological Heterogeneity","authors":"Karina Kwapiszewska*,&nbsp;","doi":"10.1021/acsphyschemau.3c0007910.1021/acsphyschemau.3c00079","DOIUrl":"https://doi.org/10.1021/acsphyschemau.3c00079https://doi.org/10.1021/acsphyschemau.3c00079","url":null,"abstract":"<p >The vast majority of chemical processes that govern our lives occur within living cells. At the core of every life process, such as gene expression or metabolism, are chemical reactions that follow the fundamental laws of chemical kinetics and thermodynamics. Understanding these reactions and the factors that govern them is particularly important for the life sciences. The physicochemical environment inside cells, which can vary between cells and organisms, significantly impacts various biochemical reactions and increases the extent of population heterogeneity. This paper discusses using physical chemistry approaches for biological studies, including methods for studying reactions inside cells and monitoring their conditions. The potential for development in this field and possible new research areas are highlighted. By applying physical chemistry methodology to biochemistry <i>in vivo</i>, we may gain new insights into biology, potentially leading to new ways of controlling biochemical reactions.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-04-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.3c00079","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141955249","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}