The Journal of Physical Chemistry Letters最新文献

{"title":"Formation of Nitrile Imine in the Ground and Excited States from Photolysis of 2-N-Methylpyrrole-5-formylamino-tetrazole","authors":"Lei Zhao,&nbsp;, ,&nbsp;Ye-Guang Fang,&nbsp;, ,&nbsp;Bin-Bin Xie,&nbsp;, ,&nbsp;Qiu Fang*,&nbsp;, ,&nbsp;Haobin Wang,&nbsp;, and ,&nbsp;Wei-Hai Fang*,&nbsp;","doi":"10.1021/acs.jpclett.5c02521","DOIUrl":"10.1021/acs.jpclett.5c02521","url":null,"abstract":"<p >Photo-cross-linking reactions have been widely used for exploring the network of dynamic protein–protein interaction, and photolysis of cross-linker plays an extremely important role in the formation of the reactive intermediate and subsequent linking reaction. However, the detailed mechanism of the relevant reactions has been rarely reported up to date. In this work, 2-<i>N</i>-methylpyrrole-5-formylamino-tetrazole (<b>MPFT</b>) was chosen as a representative of the photo-cross-linkers developed recently. Structures and properties of <b>MPFT</b> in the three lowest-lying electronic states have been determined at the level of multistate complete active space second-order perturbation theory (MS-CASPT2). Meanwhile, the direct <i>ab initio</i> quantum trajectory mean-field (QTMF) method has been used to simulate nonadiabatic dynamics initiated from the first excited singlet state of <b>MPFT</b>. The combination of the MS-CASPT2 calculation and the QTMF simulation not only provided new insights into the mechanism of the <b>MPFT</b> photolysis but also revealed that the singlet excited-state nitrile imine is likely to be the reactive intermediate that is responsible for the cross-linking reaction with the site of target protein. Our conclusions obtained from MS-CASPT2 calculations and QTMF dynamical simulations are supported by the experimental findings.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 39","pages":"10149–10158"},"PeriodicalIF":4.6,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145103307","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}

{"title":"Fano Factor as the Key Measure of Sensitivity in Biological Networks","authors":"Kinshuk Banerjee,&nbsp;, ,&nbsp;Pintu Patra,&nbsp;, ,&nbsp;Anatoly B. Kolomeisky*,&nbsp;, and ,&nbsp;Biswajit Das*,&nbsp;","doi":"10.1021/acs.jpclett.5c02317","DOIUrl":"10.1021/acs.jpclett.5c02317","url":null,"abstract":"<p >Sensitivity is a crucial feature for proper function and regulation of biological processes. Cooperative protein–ligand binding, which can be described as transitions in biological networks, is a fundamental mechanism for such sensitivity. The phenomenological sensitivity measure is the empirical Hill slope. However, a measure of sensitivity directly related to network dynamics at the cellular level is still lacking. In this study, using discrete-state stochastic analysis of seminal ligand-binding networks, we establish that the Fano factor is a crucial measure of sensitivity. Nonlinear variation of the Fano factor with fractional saturation of the network gives the criterion of cooperativity, with noncooperative binding producing a linear trend. The positive (negative) deviation of the Fano factor curve from linearity indicates positive (negative) cooperativity. Finally, the ratio of Fano factor values in cooperative and noncooperative binding becomes equal to the Hill slope, affirming its role as the essential measure of sensitivity in biological networks.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 39","pages":"10174–10179"},"PeriodicalIF":4.6,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145117229","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}

{"title":"Atomic-Scale Modulation of Charge Carrier Dynamics by Intrinsic Defects in Monolayer MoSi2N4","authors":"Chenyi You,&nbsp;, ,&nbsp;Jingkui Gao,&nbsp;, ,&nbsp;Bao Liu,&nbsp;, and ,&nbsp;Shuping Huang*,&nbsp;","doi":"10.1021/acs.jpclett.5c02350","DOIUrl":"10.1021/acs.jpclett.5c02350","url":null,"abstract":"<p >The atomic-scale mechanisms by which intrinsic defects influence charge carrier dynamics in monolayer MoSi₂N₄ remain poorly understood in current studies of this emerging two-dimensional material. By combining first-principles density functional theory (DFT) and <i>ab initio</i> nonadiabatic molecular dynamics (NAMD) simulations, we investigated the static properties and carrier dynamics of MoSi₂N₄ monolayers with and without intrinsic defects. MoSi₂N₄ reveals strong band dispersion near the conduction band minimum, with weak coupling between the K-valley states and other states, leading to delayed electron relaxation and suppressed energy dissipation. Notably, the Mo_Si defect (Mo substituting Si) induces a pronounced spin-polarized lifetime contrast, where spin-down carriers exhibit extended lifetimes in comparison to those in pristine MoSi₂N₄. In contrast, an internal N vacancy introduces deep defect states that significantly accelerate electron–hole recombination. The Si_Mo defect (Si substituting Mo) contributes negligibly to defect-assisted recombination. These findings provide new insights for designing high-performance MoSi₂N₄-based optoelectronic and nanoelectronic devices.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 39","pages":"10134–10141"},"PeriodicalIF":4.6,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145103349","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}

{"title":"Pressure-Modulated Near-Infrared Photoluminescence of a Two-Dimensional Germanium Halide Perovskite","authors":"Ya-Si Fang,&nbsp;, ,&nbsp;Yi-Fan Guo,&nbsp;, ,&nbsp;Hao-Jin Xu,&nbsp;, ,&nbsp;Xiao-Gang Chen,&nbsp;, ,&nbsp;Lin Zhou*,&nbsp;, ,&nbsp;Zhong-Xia Wang,&nbsp;, ,&nbsp;Yuan-Yuan Tang*,&nbsp;, and ,&nbsp;Yan Qin*,&nbsp;","doi":"10.1021/acs.jpclett.5c02131","DOIUrl":"10.1021/acs.jpclett.5c02131","url":null,"abstract":"<p >Two-dimensional (2D) metal halide perovskites have received considerable attention among researchers in recent years owing to their potential use in light-emitting diodes. However, deep-red and near-infrared (NIR) emissions are usually absent in such perovskites owing to their intrinsic quantum and dielectric confinement effects, warranting further exploration. Herein, we report the pressure-modulated NIR emission of a 2D perovskite, (benzimidazolium)₂GeI₄ [(BIM)₂GeI₄], the photoluminescence (PL) of which can be regulated from broadband NIR emission to tunable narrowband deep-red to NIR emission under hydrostatic pressure. The dramatic PL change is attributed to pressure-induced exciton transfer from self-trapped excitons to free excitons and structural rearrangement, which can be fully reversed upon pressure release. A remarkable reversible piezochromism from orange to red to black is also observed. This study extends the PL emission of 2D halide perovskites to the deep-red to NIR region through pressure engineering, demonstrating their potential use in red light emission applications and bioimaging.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 39","pages":"10126–10133"},"PeriodicalIF":4.6,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145103582","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}

{"title":"Tunable Circularly Polarized Afterglow from Cholesteric Liquid Crystalline Polymer Networks","authors":"Peipei Guan,&nbsp;, ,&nbsp;Fengyun Shi,&nbsp;, ,&nbsp;Chenqingliang Xu,&nbsp;, ,&nbsp;Yonggang Yang,&nbsp;, and ,&nbsp;Hongkun Li*,&nbsp;","doi":"10.1021/acs.jpclett.5c02487","DOIUrl":"10.1021/acs.jpclett.5c02487","url":null,"abstract":"<p >Circularly polarized afterglow (CPA) materials have demonstrated significant potential in diverse applications. Nevertheless, the development of organic CPA materials simultaneously possessing large luminescence dissymmetry factors (<i>g</i>_lum) and ultralong lifetimes remains a formidable challenge. Herein, a series of liquid crystalline polymer network films with tunable CPA properties were fabricated via photopolymerization of liquid crystalline mixtures doped with varying amounts of binaphthyl derivatives. The resulting polymer films exhibit structural colors, room-temperature phosphorescence (RTP), and circularly polarized RTP properties, with phosphorescence dissymmetry factors reaching up to 0.70 and tunable lifetimes extending to 730 ms. Through further photopolymerization of cholesteric liquid crystalline mixtures doped with rhodamine 6G (Rh6G), a commercially available fluorescent dye, lifetime- and color-tunable CPA with enhanced <i>g</i>_lum values and quantum yields as high as 8.6% was achieved via phosphorescence energy transfer. Furthermore, the fabricated film patterns display distinct colors in reflection, fluorescence, and phosphorescence modes. This work presents a facile strategy for preparing CPA films with large <i>g</i>_lum values as well as tunable lifetimes and colors, which hold promise for applications in image encryption and anticounterfeiting technology.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 39","pages":"10142–10148"},"PeriodicalIF":4.6,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145103348","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}

{"title":"Anion Engineering of Ionic Liquid-Based Polymer Electrolytes for Interfacial Stabilization in Lithium Metal Batteries","authors":"Runhong Wei*,&nbsp;, ,&nbsp;Li Niu,&nbsp;, ,&nbsp;Yanlei Zhang,&nbsp;, ,&nbsp;Jinhai You*,&nbsp;, and ,&nbsp;Michael Wübbenhorst,&nbsp;","doi":"10.1021/acs.jpclett.5c02147","DOIUrl":"10.1021/acs.jpclett.5c02147","url":null,"abstract":"<p >Polymer solid-state electrolytes promise safer Li-metal batteries but face slow Li⁺ transport and unstable Li–electrolyte interfaces. The anion is an underused handle despite governing both bulk ion dynamics and interphase chemistry. A unified cation platform was constructed to isolate the roles of Br^–, I^–, and BF₄^–, revealing that bromide delivers a dual benefit. This mild, self-limiting halide reaction seeds a uniform LiBr-rich interphase that blocks electrons yet permits Li⁺, while bromide weakens Li⁺ coordination in the polymer and accelerates segmental relaxation. This synergy increases interfacial ion flux and enhances bulk conductivity, yielding smooth plating and durable cycling. The bromide electrolyte enables 158 mAh g^–1 at 0.2 C in full cells, 92.5% retention after 200 cycles at 0.5 C, and Coulombic efficiency exceeding 99.3%. The results establish anion-focused design as a practical route to polymer electrolytes that are simultaneously stable and fast-ion conducting.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 39","pages":"10117–10125"},"PeriodicalIF":4.6,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145103350","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}

{"title":"Unlocking Tetravalent Iron Reactivity at Mildly Acidic pH through Decay Kinetics Technique","authors":"Huixin Shao,&nbsp;, ,&nbsp;Chengyu Gu,&nbsp;, ,&nbsp;Shuchang Wang,&nbsp;, and ,&nbsp;Xiaohong Guan*,&nbsp;","doi":"10.1021/acs.jpclett.5c02491","DOIUrl":"10.1021/acs.jpclett.5c02491","url":null,"abstract":"<p >Tetravalent iron (Fe_aq^IVO²⁺) is a short-lived, high-valent intermediate of broad interest in physical chemistry due to its strong oxidizing potential, tunable redox properties, and pH-dependent speciation. These features make Fe_aq^IVO²⁺ not only a subject of fundamental interest in physical chemistry but also a promising oxidant in wastewater treatment for the degradation of trace organic contaminants (TrOCs). However, previous kinetic studies have been restricted to highly acidic conditions (pH ≤ 1.0) to mitigate Fe(III) absorbance interference at 320 nm, limiting understanding under environmentally relevant pH regimes. Here, we developed a modified decay-kinetics method by monitoring Fe_aq^IVO²⁺ at 425 nm, thereby eliminating Fe(III) interference and enabling direct determination of second-order rate constants (<i>k</i>_{Fe_aq^IV}_O²⁺,TrOC) at pH 3.0. The measured <i>k</i>_{Fe_aq^IV}_O²⁺,TrOC values reveal selective reactivity toward sulfonamides (4.17–8.24 × 10⁵ M^–¹ s^–¹) and phenols (0.22–5.49 × 10⁵ M^–¹ s^–¹) and support quantitative structure–activity analysis of phenol oxidation, advancing the mechanistic basis for selective oxidation in both catalysis and wastewater treatment.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 39","pages":"10159–10164"},"PeriodicalIF":4.6,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145117107","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}

{"title":"Design of Ultraviolet Multiple-Resonance TADF Materials Enabled by Phosphine Oxide/Sulfide-Based Polycyclics with Accelerated Reverse Intersystem Crossing","authors":"Peng Zhang,&nbsp;, ,&nbsp;Ping Li*,&nbsp;, ,&nbsp;Chang Zeng,&nbsp;, ,&nbsp;Xianjie Wang,&nbsp;, ,&nbsp;Ye Tao,&nbsp;, and ,&nbsp;Runfeng Chen*,&nbsp;","doi":"10.1021/acs.jpclett.5c02457","DOIUrl":"10.1021/acs.jpclett.5c02457","url":null,"abstract":"<p >Multiple-resonance thermally activated delayed fluorescence (MR-TADF) materials have attracted more attention owing to their theoretical 100% exciton utilization capability and narrowband emission. However, the development of ultraviolet (UV) narrowband MR-TADF emitters remains challenging, as such materials are still scarce and exhibit inadequate reverse intersystem crossing (RISC) efficiency. Herein, we employ a theoretical investigation of the design of high-performance UV MR-TADF materials based on phosphine oxide/sulfide polycyclic aromatics using acceptor modifications and peripheral fusion strategies. A series of UV emitters exhibit small reorganization energies and short-range charge transfer characteristics upon excitation, enabling narrowband emission. Notably, the designed molecules featuring bilateral P═S units or 2-position sulfur peripheral locking exhibit ultrahigh total RISC rates (<i>k</i>_toRISC) of ∼10⁵ s^–1 via efficient high-lying triplet-mediated RISC channels, where the significantly reduced energy difference between the first and second triplet states (Δ<i>E</i>_T₁-T₂) enhances the T₁ ↔ T₂ → S₁ transitions and leads to the accumulation of T₂ excitons. These findings provide deep physical insights into structure–property relationships and offer valuable design principles for high-performance optoelectronic materials.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 39","pages":"10165–10173"},"PeriodicalIF":4.6,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145117105","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}

{"title":"Impurity PbCO3 from Low-Purity Raw Material Improves MAPbBr3 Single-Crystalline X-ray Detectors","authors":"Nan Li,&nbsp;, ,&nbsp;Shuaishuai Yu,&nbsp;, ,&nbsp;Yuliang Yi,&nbsp;, ,&nbsp;Haipeng Di,&nbsp;, ,&nbsp;Yehao Deng,&nbsp;, and ,&nbsp;Jingjing Zhao*,&nbsp;","doi":"10.1021/acs.jpclett.5c02181","DOIUrl":"10.1021/acs.jpclett.5c02181","url":null,"abstract":"<p >Perovskite single crystals have been found to exhibit excellent X-ray detection and imaging performance. High-purity raw materials have generally been considered a prerequisite to guarantee crystal quality and device performance, which may lead to higher costs. However, we found that higher quality MAPbBr₃ single crystals can be obtained from low-purity lead bromide (PbBr₂). This is attributed to the presence of impurity lead carbonate (PbCO₃) in the raw material. PbCO₃ facilitates the suppression of crystal defects, leading to higher quality crystals. With the addition of a small amount of PbCO₃ to high-purity PbBr₂ raw material, MAPbBr₃ single crystals grow with a smoother surface, improved uniformity, and lower defect concentrations. The single crystal becomes more intrinsic. The product of carrier mobility and lifetime increases to 1.3 × 10^–2 cm² V^–1. With the addition of PbCO₃, the detector sensitivity is about twice as high and the lowest detection limit is approximately 300 times lower, down to 20 nGy_air/s. This work reveals the key factors for preparing high-quality perovskite single crystals using low-cost, low-purity raw materials, providing a new approach for producing high-yield perovskite single crystals.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 39","pages":"10102–10108"},"PeriodicalIF":4.6,"publicationDate":"2025-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145089012","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}

{"title":"Bubble-Guided Foam Nanochannels for Tunable Ionic Transport","authors":"Zhang-Rong Wu,&nbsp;, ,&nbsp;Tao Feng,&nbsp;, ,&nbsp;Ning Bao*,&nbsp;, and ,&nbsp;Zeng-Qiang Wu*,&nbsp;","doi":"10.1021/acs.jpclett.5c02401","DOIUrl":"10.1021/acs.jpclett.5c02401","url":null,"abstract":"<p >Biological nanochannels, as representative soft nanochannels, exhibit remarkably high efficiency, operating at energy levels only slightly above thermal noise. In contrast, solid-state nanochannels have garnered considerable attention across diverse fields due to their unique properties, including ionic current rectification, ionic Coulomb blockade, and ionic concentration polarization. However, their performance is strongly influenced by thermal noise, necessitating relatively high operating thresholds and, consequently, leading to substantial energy consumption. In this study, we report the fabrication of a bubble-regulated foam nanochannel on a nanocapillary platform and systematically investigate its ion-transport characteristics. Current–voltage (<i>I–V</i>) measurements reveal three distinct behaviors─rectification, linear, and voltage-activated─arising from variations in Tween 60 concentration and bubble volume. As the concentration of Tween 60 increases, a self-assembled monolayer (SAM) gradually forms on the surface of the foam nanochannel, leading to a reduction in the surface charge. This transition results in the progressive transformation of the <i>I–V</i> response from rectification to linear behavior. With further increases in Tween 60 concentration, a well-defined SAM layer develops at the gas–liquid interface, producing a confined nanochannel approximately 2 nm in diameter. Ion transport through this ultranarrow channel requires partial dehydration to overcome the energy barrier, likely driven by interactions between the hydrophilic SAM layer and solvated water molecules. The driving voltage is used to compensate for this ion dehydration, which results in voltage-activated transport behavior. The proposed mechanism was further validated using finite element method (FEM) simulations, which incorporate ionic hydration and size effects, offering quantitative insight into the observed phenomena. Overall, this work provides new mechanistic insights into the operation of soft nanofluidic systems and advances their potential for energy-efficient applications.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 39","pages":"10109–10116"},"PeriodicalIF":4.6,"publicationDate":"2025-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145088933","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}