The Journal of Physical Chemistry Letters最新文献_第5页

Conformational Dynamics and Activation of Membrane-Associated Human Group IVA Cytosolic Phospholipase A₂ (cPLA₂). 膜相关人IVA胞质磷脂酶A2 （cPLA2）的构象动力学和激活。

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.5c00860

Mac Kevin E Braza, Edward A Dennis, Rommie E Amaro

{"title":"Conformational Dynamics and Activation of Membrane-Associated Human Group IVA Cytosolic Phospholipase A2 (cPLA2).","authors":"Mac Kevin E Braza, Edward A Dennis, Rommie E Amaro","doi":"10.1021/acs.jpclett.5c00860","DOIUrl":"10.1021/acs.jpclett.5c00860","url":null,"abstract":"Cytosolic phospholipase A2 (cPLA2) associates with membranes, where it hydrolyzes phospholipids containing arachidonic acid to initiate an inflammatory cascade. All-atom molecular dynamics simulations were employed to understand the activation process when cPLA2 associates with the endoplasmic reticulum (ER) membrane of macrophages, where it acts. We found that membrane association causes the lid region of cPLA2 to undergo a closed-to-open state transition that is accompanied by the sideways movement of loop 495-540, allowing the exposure of a cluster of lysine residues (K488, K541, K543, and K544), which are known to bind allosteric activator PIP2 from the membrane. The active site of the open form of cPLA2, containing catalytic dyad residues S228 and D549, exhibited a 3-fold larger cavity than the closed form of cPLA2 in aqueous solution. These findings provide mechanistic insight into how cPLA2-ER membrane association promotes major transitions between conformational states critical to allosteric activation and enzymatic phospholipid hydrolysis.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"6059-6065"},"PeriodicalIF":4.8,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144256809","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

Aaron Forde*, Carlos MoraPerez, Nikhil Singh, Dibyajyoti Ghosh, Amanda J Neukirch and Sergei Tretiak*,

引用次数: 0

IF 4.8 2区化学

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

Jacob J. Krich*, Luisa Brenneis, Peter A. Rose, Katja Mayershofer, Simon Büttner, Julian Lüttig, Pavel Malý and Tobias Brixner*,

引用次数: 0

Effect of Hydrostatic Pressure on the g Tensor and Hyperfine Coupling Constants of the Nitroxide Radical Characterized by Ab Initio Calculations. 静水压力对氮氧自由基g张量和超精细耦合常数的影响

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-06-19 Epub Date: 2025-06-05 DOI: 10.1021/acs.jpclett.5c00677

Ana Gurgenidze, Anna I Krylov, Susumu Takahashi

{"title":"Effect of Hydrostatic Pressure on the g Tensor and Hyperfine Coupling Constants of the Nitroxide Radical Characterized by Ab Initio Calculations.","authors":"Ana Gurgenidze, Anna I Krylov, Susumu Takahashi","doi":"10.1021/acs.jpclett.5c00677","DOIUrl":"10.1021/acs.jpclett.5c00677","url":null,"abstract":"We present a computational study characterizing the effect of hydrostatic pressure on magnetic spin parameters that are used to analyze the electron paramagnetic resonance (EPR) spectra. Site-directed spin labeling (SDSL) in combination with EPR spectroscopy is a powerful tool for investigating the structure and dynamics of biological molecules. In studies using SDSL-based EPR spectroscopy, it is essential to know the spin parameters, such as the g factor and the hyperfine constants, precisely. However, the experimental characterization of these spin parameters under extreme conditions is often challenging. We report quantum chemistry calculations of g tensors and hyperfine coupling tensors (A tensors) for the nitroxide radical spin label in the pressure range of 0-15 GPa. The hydrostatic pressure causes structural changes, which, in turn, result in linear changes of the g and A tensors. The observed linear dependence of the g and A tensors suggests that these quantities can serve as reporters of local pressure in complex environments. The corresponding simulated EPR spectra at 9 and 230 GHz reveal that the changes of the EPR spectrum are more pronounced in the former. Our results indicate that the computational approach can address the challenge of determining magnetic spin parameters under extreme conditions, such as under high hydrostatic pressure.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"5906-5911"},"PeriodicalIF":4.8,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232636","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

Ion-π Interactions Unveil a Universal Mechanism for Boosting Electrochemiluminescence. 离子-π相互作用揭示了促进电化学发光的普遍机制。

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.5c01134

Yunxiu Jia, Li Zhang, Weijiang Guan, Haoke Zhang, Xiong Liu, Zhiqin Yuan, Chao Lu

{"title":"Ion-π Interactions Unveil a Universal Mechanism for Boosting Electrochemiluminescence.","authors":"Yunxiu Jia, Li Zhang, Weijiang Guan, Haoke Zhang, Xiong Liu, Zhiqin Yuan, Chao Lu","doi":"10.1021/acs.jpclett.5c01134","DOIUrl":"10.1021/acs.jpclett.5c01134","url":null,"abstract":"Improving the electro-oxidation efficiency of neutral tertiary amines has long been considered crucial for achieving efficient electrochemiluminescence (ECL) in physiological environments. However, they are predominantly present as protonated cations at neutral pH. Recognizing this distinction might lead to significant improvements in ECL performance. In this study, we examine the contribution of such protonated amines by introducing electrodes modified with π-conjugated moieties designed to engage in cation-π interactions. Comparative experiments with a series of π-modified electrodes indicate that cation-π interactions can stabilize the amine-derived radical intermediates and facilitate their electro-oxidation, resulting in higher ECL intensities. More interestingly, the effect is most pronounced when the π-conjugated moieties are located at the outermost layer of the electrode/solution interface. The findings of this work highlight the potential of cation-π interactions to improve ECL systems, encouraging further exploration of ion-π interactions across various ECL platforms.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"6023-6031"},"PeriodicalIF":4.8,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144256773","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

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