The Journal of Physical Chemistry Letters最新文献_第6页

Unraveling the Hidden Pathway of Catalyst-Free Direct Photochemical Conversion of Sulfides to Sulfoxides: A Universal Pathway under UVA Radiation. 揭示无催化剂的硫化物直接光化学转化为亚砜的隐藏途径：UVA辐射下的普遍途径。

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-06-19 Epub Date: 2025-06-09 DOI: 10.1021/acs.jpclett.5c01122

Shivendra Singh, Supritam Datta, Souvik Manna, Biswarup Pathak, Tushar Kanti Mukherjee

{"title":"Unraveling the Hidden Pathway of Catalyst-Free Direct Photochemical Conversion of Sulfides to Sulfoxides: A Universal Pathway under UVA Radiation.","authors":"Shivendra Singh, Supritam Datta, Souvik Manna, Biswarup Pathak, Tushar Kanti Mukherjee","doi":"10.1021/acs.jpclett.5c01122","DOIUrl":"10.1021/acs.jpclett.5c01122","url":null,"abstract":"Selective conversion of sulfides to sulfoxides is an important class of chemical transformation that has enormous potential in medicinal chemistry. However, the primary process associated with photoexcitation during the direct photochemical conversion of sulfides to sulfoxides is poorly understood and misrepresented in the literature. Herein, we discover a hidden pathway responsible for the direct photochemical conversion of sulfides to sulfoxides in the absence of any catalysts under UVA illumination (λex = 370 nm). We show that this hidden pathway directly generates singlet oxygen (a1Δg,1O2) via solvent-oxygen (X3∑g-,3O2) charge transfer (CT) excitation in neat solvents under ambient conditions. Our findings reveal efficient and selective oxidation of sulfides to sulfoxides in the presence of 1O2 through the generation of persulfoxide intermediates. In addition, we found that the presence of a marginal amount of water favors faster kinetics and prevents overoxidation to sulfones due to the stabilization of the sulfoxide products via specific hydrogen-bonding interactions.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"6106-6115"},"PeriodicalIF":4.8,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144256780","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

Aminosulfonate-Modified Buried Interface Coordination-Induced Defect Dassivation and Strain Relief toward Efficient Perovskite Solar Cells. 氨基磺酸修饰的埋藏界面配位诱导的高效钙钛矿太阳能电池缺陷钝化和应变缓解。

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-06-19 Epub Date: 2025-06-11 DOI: 10.1021/acs.jpclett.5c01507

Yanqiang Hu, Min Zhang, Yiqiong Zhang, Shuai Xu, Jiapei Xu, Yirui Wang, Xiangqian Cui, Xinyi Zhang, Jing Li, Yipu Wang, Qiang Huang, Tongming Sun, Minmin Wang, Wenming Tian, Yanfeng Tang

{"title":"Aminosulfonate-Modified Buried Interface Coordination-Induced Defect Dassivation and Strain Relief toward Efficient Perovskite Solar Cells.","authors":"Yanqiang Hu, Min Zhang, Yiqiong Zhang, Shuai Xu, Jiapei Xu, Yirui Wang, Xiangqian Cui, Xinyi Zhang, Jing Li, Yipu Wang, Qiang Huang, Tongming Sun, Minmin Wang, Wenming Tian, Yanfeng Tang","doi":"10.1021/acs.jpclett.5c01507","DOIUrl":"10.1021/acs.jpclett.5c01507","url":null,"abstract":"Continuous breakthroughs in the photovoltaic performance of perovskite solar cells (PSCs) have demonstrated the enormous potential for commercial application. However, accumulating numerous defects at the buried interface and residual stresses in the perovskite film severely restrict the further improvement of photovoltaic conversion efficiency (PCE) and device stability. Herein, an environmentally friendly and economical sodium sulfamate (SS) was employed as a versatile buried interface modifier to achieve simultaneous interface defect passivation, regulation of energy levels, and residual stress regulation through the synergistic effects among various functional groups. As a result, the average PCE of the optimized PSC increased from 23.02% to 24.83%, along with the champion efficiency of 25.07%. Meanwhile, the unencapsulated optimized device can still retain 80% of its initial PCE after 1048 h of continuous operation, which was significantly higher than the 36.50% of the controlled device. This work provides valuable insights for further leveraging interfacial modification strategies to achieve multifunctionality and break through the photovoltaic performance of PSCs.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"6163-6170"},"PeriodicalIF":4.8,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144264869","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

Structural Changes in the Retinal Chromophore and Ion-Conducting Pathway of an Anion Channelrhodopsin GtACR1. 视网膜发色团的结构变化和阴离子通道视紫质GtACR1的离子传导途径。

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-06-19 Epub Date: 2025-06-12 DOI: 10.1021/acs.jpclett.5c01008

Keisei Shibata, Yuma Kawasaki, Shunki Takaramoto, Masaya Watanabe, Masahiro Fukuda, Ryohei Ono, Hideaki E Kato, Hidefumi Akiyama, Keiichi Inoue

{"title":"Structural Changes in the Retinal Chromophore and Ion-Conducting Pathway of an Anion Channelrhodopsin GtACR1.","authors":"Keisei Shibata, Yuma Kawasaki, Shunki Takaramoto, Masaya Watanabe, Masahiro Fukuda, Ryohei Ono, Hideaki E Kato, Hidefumi Akiyama, Keiichi Inoue","doi":"10.1021/acs.jpclett.5c01008","DOIUrl":"10.1021/acs.jpclett.5c01008","url":null,"abstract":"Guillardia theta anion-conducting channelrhodopsin 1 (GtACR1) is a light-gated anion channel and is widely used as a representative optogenetic tool for neuronal silencing. However, its gating mechanism is unclear due to the lack of insight into its structural changes and kinetics. Here, we measured the structural changes in the retinal chromophore of GtACR1 throughout its photocycle using time-resolved resonance Raman spectroscopy. Moreover, we investigated the rate-limiting factors of the gating through transient absorption spectroscopy and laser patch clamp electrophysiology. Our results provided the following understanding: the retinal chromophore keeps planar structure even in the open state. The ion-conducting pathway extends to the retinal Schiff base (RSB) as the channel opens. The channel closes in a two-step process, rate-limited by the RSB deprotonation and reprotonation. These findings reveal that the gating mechanism of GtACR1 differs markedly from that of a cation channelrhodopsin C1C2 and contribute to the development of next-generation optogenetic tools.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"6234-6241"},"PeriodicalIF":4.8,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144273728","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

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-06-19

Ding Peng, Zhaoxi Yu, Sangen Zhao, Junhua Luo, Lin Shen* and Wei-Hai Fang,

引用次数: 0

Revealing the Electronic Structure of Water Imprinted in the Chiral Molecular Environment. 揭示手性分子环境中水印迹的电子结构。

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-06-19 Epub Date: 2025-06-09 DOI: 10.1021/acs.jpclett.5c00948

Bo Peng, Yisong Zhu, Meng Ding, Belen Albela, Laurent Bonneviot, Kun Zhang

{"title":"Revealing the Electronic Structure of Water Imprinted in the Chiral Molecular Environment.","authors":"Bo Peng, Yisong Zhu, Meng Ding, Belen Albela, Laurent Bonneviot, Kun Zhang","doi":"10.1021/acs.jpclett.5c00948","DOIUrl":"10.1021/acs.jpclett.5c00948","url":null,"abstract":"Water plays a crucial role in determining the functions of biomolecules and nanomaterials. However, the electronic structure of water molecules at the nanoscale remains elusive. In this study, we investigate the electronic structure of water molecules imprinted in chiral Ag(I) thiolate complexes (-SRs) by using cysteine as a probe ligand. By employing a chirality transfer strategy and analyzing absorption and circular dichroism (CD) spectra, we identify three types of structural water molecules (SWs) within the Ag(I)-SRs. These SWs exhibit unique electronic interactions between the outermost p-orbitals of oxygen atoms due to spatial confinement, forming electronic states with a molecule-like structure. Notably, the distinctive electronic structure of SWs generates a pair of absorption signals with opposite Cotton effects, which can be captured by CD spectroscopy in a chiral molecular environment. Our theoretical calculations using the one-dimensional free electron gas model align well with experimental results, and the Cotton effect exhibited by these SWs is explained by a simple octant rule. This study provides novel insights into the electronic structure of water in confined nanospaces and highlights its potential role in various biological and material systems.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"6116-6124"},"PeriodicalIF":4.8,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144256777","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

Electronic and Structural Relaxation of Photoexcited WO₃ Observed by Femtosecond Resonant X-ray Emission Spectra. 飞秒共振x射线发射光谱观测光激发WO3的电子和结构弛豫。

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-06-19 Epub Date: 2025-06-10 DOI: 10.1021/acs.jpclett.5c01062

Yohei Uemura, Kohei Yamamoto, Yasuhiro Niwa, Thomas Buttiens, Hebatalla Elnaggar, Ru-Pan Wang, Masoud Lazemi, Frank de Groot, Tetsuo Katayama, Makina Yabashi, Christopher J Milne, Toshihiko Yokoyama

{"title":"Electronic and Structural Relaxation of Photoexcited WO3 Observed by Femtosecond Resonant X-ray Emission Spectra.","authors":"Yohei Uemura, Kohei Yamamoto, Yasuhiro Niwa, Thomas Buttiens, Hebatalla Elnaggar, Ru-Pan Wang, Masoud Lazemi, Frank de Groot, Tetsuo Katayama, Makina Yabashi, Christopher J Milne, Toshihiko Yokoyama","doi":"10.1021/acs.jpclett.5c01062","DOIUrl":"10.1021/acs.jpclett.5c01062","url":null,"abstract":"Photoexcited states of tungsten trioxide (WO3) were observed using femtosecond high-energy-resolution fluorescence detection X-ray Absorption Spectra (HERFD-XAS) and resonant X-ray emission spectra (RXES). In the initial state of the photoexcitation (∼100 fs), the W L3 edge XAS shifts to lower energy and the energy levels of the t2g and eg peaks are modulated due to the photoexcited electrons in the conduction band. The electronic state of the photoexcited W atoms is modified by 500 fs. The crystal field splitting between the t2g and eg peaks shrinks by 500 fs, which indicates local structural changes around the W atoms due to the formation of polarons. HERFD-XAS and RXES provide more details about the early state of the photoexcited states of WO3. This work demonstrates that the detailed dynamics of 5d elements in the femtosecond range can be addressed with HERFD-XAS/RXES.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"6138-6145"},"PeriodicalIF":4.8,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144256813","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

Competition between Coherent Ultrafast Energy Redistribution and Photochemistry in the Collective Strong Coupling Regime: The Role of Static Disorder. 集体强耦合中相干超快能量重分布与光化学的竞争：静态无序的作用。

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-06-19 Epub Date: 2025-06-11 DOI: 10.1021/acs.jpclett.5c01117

Federico Mellini, Oriol Vendrell

{"title":"Competition between Coherent Ultrafast Energy Redistribution and Photochemistry in the Collective Strong Coupling Regime: The Role of Static Disorder.","authors":"Federico Mellini, Oriol Vendrell","doi":"10.1021/acs.jpclett.5c01117","DOIUrl":"10.1021/acs.jpclett.5c01117","url":null,"abstract":"We explore the dynamics of coherent, ultrafast energy redistribution in disordered molecular ensembles mediated by a cavity under electronic strong coupling and their competition with the onset of a photochemical process. Quantum dynamics simulations show that the amount of energy redistribution between different molecules depends on their individual coupling strength to the cavity. This collective dynamical process is determined by the initial state of the system and by the relative time-scales of the Rabi-cycling and the onset of the photoreaction. Even in the large ensemble limit, where each molecule is weakly coupled, the relative reaction probability of each individual molecule differs significantly from its reaction probability in an uncoupled ensemble, which is due to the dynamic energy reorganization promoted by the cavity. We investigate this mechanism by considering different types of initial conditions of a disordered ensemble of tens of NOCl molecules, each treated in full dimensionality. The multilayer multiconfiguration time-dependent Hartree method is used to describe the ensemble and the cavity.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"6155-6162"},"PeriodicalIF":4.8,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144264870","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

Nonadiabatic Dynamics with Constrained Nuclear-Electronic Orbital Theory 约束核电子轨道理论的非绝热动力学

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-06-18 DOI: 10.1021/acs.jpclett.5c01020

Zhe Liu, Zehua Chen, Yang Yang

引用次数: 0

Perspective on Fluid-Interface-Involved Physiochemistry: From Static to Dynamic 涉及流体界面的物理化学透视：从静态到动态

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-06-18 DOI: 10.1021/acs.jpclett.5c01280

Yitan Li, Hangchen Liu, Min Li, Zuankai Wang

{"title":"Perspective on Fluid-Interface-Involved Physiochemistry: From Static to Dynamic","authors":"Yitan Li, Hangchen Liu, Min Li, Zuankai Wang","doi":"10.1021/acs.jpclett.5c01280","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c01280","url":null,"abstract":"Fluid interfaces are commonly observed in natural phenomena and industrial applications where heat and mass transfer behaviors as well as the associated energy conversions inevitably impact both material fabrication and chemical reactions. It is known that fluid interfaces, including both air–liquid and liquid–liquid interfaces, are proven to involve a series of spatiotemporal physicochemical effects that dominate the fluid-interface-involved processes, instead of being a simple medium. However, it remains a challenge to understand and utilize the underlying mechanisms of the interfacial effects. This perspective focuses on the latest progress in fluid-involved interfacial behaviors, emphasizing the fundamental “heat and mass transfer” and corresponding “energy transfer” on both liquid–air and liquid–liquid interfaces, which can be regulated by external fields, such as temperature fields, shear fields, acoustic fields, and electric fields. Additionally, we discuss the ongoing challenges and potential evolutionary influences of fluid interfaces, pointing out that by orchestrating various external fields, fluid interfaces can be harnessed to play more important roles in chemical reactions, material assemblies, crystal growth, and fluidic devices.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"60 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144312046","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

Controlling Intramolecular Vibrational Redistribution with an Infrared Photonic Cavity 用红外光子腔控制分子内振动重分布

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-06-18 DOI: 10.1021/acs.jpclett.5c01342

Bar Cohn, Artem Sribnyi, Sithara U. Nawagamuwage, Junhan Zhou, Muhammad Shakeel, Igor V. Rubtsov, Lev Chuntonov

{"title":"Controlling Intramolecular Vibrational Redistribution with an Infrared Photonic Cavity","authors":"Bar Cohn, Artem Sribnyi, Sithara U. Nawagamuwage, Junhan Zhou, Muhammad Shakeel, Igor V. Rubtsov, Lev Chuntonov","doi":"10.1021/acs.jpclett.5c01342","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c01342","url":null,"abstract":"Using ultrafast dual-frequency two-dimensional infrared spectroscopy (DF-2DIR), we probed how the strong coupling of high-frequency molecular vibrations to surface lattice resonances of infrared antennas, which act as a photonic cavity, affects intramolecular vibrational relaxation (IVR). DF-2DIR allows one to probe the IVR pathways beyond the vibrational state subspace of the polaritons and reservoir states, which is typically accessed in conventional 2DIR experiments. We observed anharmonic coupling between lower polariton and high-frequency molecular vibrational modes not coupled to the cavity directly, which appeared in the strongly coupled system by virtue of the polariton’s molecular component, and alternation of the rate of excitation energy excess transfer from the polariton to a distant molecular vibrational mode, which depended on the polariton transition frequency. These are in contrast with the weak coupling regime, where enhanced fields magnify molecular vibrational signals without affecting their dynamics. Our work demonstrates a promising experimental approach toward understanding of polariton chemistry phenomena.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"14 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144312048","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