The Journal of Physical Chemistry Letters最新文献

{"title":"Steric Control of Copper(II) Coordination by Carnosine: Role of the β-Alanyl Methylene Spacer","authors":"Xueyu Feng, Chunyang Wang, Yangfan He, Kaijun Yuan, Xin-Xing Zhang","doi":"10.1021/acs.jpclett.5c01255","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c01255","url":null,"abstract":"Carnosine (β-alanyl-<span>l</span>-histidine), the shortest histidine-containing natural peptide in mammalian tissues, regulates crucial biological processes through Cu(II) chelation. Using a multitechnique approach combining potentiometric titration and UV–vis, EPR, FTIR, and 2D IR spectroscopy, we identified and characterized three distinct Cu(II)-carnosine complexes with pH-dependent speciation. Structural comparison with glycyl-<span>l</span>-histidine demonstrates that the extended methylene spacer of carnosine introduces unique steric constraints that (i) inhibits amide hydrogen substitution by Cu(II), (ii) facilitates formation of the binuclear species [Cu₂LH_–1]^II, and (iii) promotes subsequent dimerization to [Cu₂L₂H_–2] under acidic to neutral conditions. At alkaline pH, the protonation state of carnosine N-terminus serves as a critical regulator of Cu(II) coordination geometry, dictating metal binding affinity and determining site preference between N- and C-terminal coordination motifs.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"70 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-06-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144335190","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":"Insight into the Origin of Strong Metal-Support Interaction Obtained on an Inverse TiOx/Au/Al2O3 Quasi-Model Catalyst.","authors":"Xiaorui Du,Mi Luo,Yike Huang,Xiaoli Pan,Chaobin Zeng,Chenguang Wang,Botao Qiao","doi":"10.1021/acs.jpclett.5c01146","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c01146","url":null,"abstract":"Strong metal-support interaction (SMSI) is one of the most important phenomena in the history of heterogeneous catalysis and has gained renewed attention in the past decade due to the emergence of various new types of SMSI. However, the origin of SMSI still remains in debate. Both minimizing surface energy and electron transfer have been regarded as the origin of SMSI because these two are hard to decouple in traditional supported metal catalysts. In this work, a TiOx/Au/Al2O3 quasi-model catalyst was fabricated by inversely depositing a minimal amount of TiOx on the surface of Au nanoparticles, where the charge transfer between TiOx and Au was minimized. As experimentally demonstrated, under high-temperature reduction-reoxidation treatment, the surface TiOx undergoes a wetting-dewetting process, accompanied by the reversible suppression and recovery of the adsorption capability, during which the electron transfer between TiOx and Au is negligible. This work suggests that charge transfer may not be the driving force for the occurrence of SMSI, contributing to a deeper understanding of the SMSI mechanism.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 1","pages":"6661-6666"},"PeriodicalIF":6.475,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144328903","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":"Allegro-FM: Toward an Equivariant Foundation Model for Exascale Molecular Dynamics Simulations","authors":"Ken-ichi Nomura, Shinnosuke Hattori, Satoshi Ohmura, Ikumi Kanemasu, Kohei Shimamura, Nabankur Dasgupta, Aiichiro Nakano, Rajiv K. Kalia, Priya Vashishta","doi":"10.1021/acs.jpclett.5c00605","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00605","url":null,"abstract":"We present a foundation model for exascale molecular dynamics simulations by leveraging an E(3) equivariant network architecture (Allegro) and a set of large-scale organic and inorganic materials data sets merged by the Total Energy Alignment framework. The obtained model (Allegro-FM) is versatile for various material simulations for diverse downstream tasks covering 89 elements in the training sets. Allegro-FM exhibits excellent agreement with high-level quantum chemistry theories in describing structural, mechanical, and thermodynamic properties, while exhibiting emergent capabilities for structural correlations, reaction kinetics, mechanical strengths, fracture, and solid/liquid dissolution, for which the model has not been trained. Furthermore, we demonstrate the robust predictability and generalizability of Allegro-FM for chemical reactions using Transition1x, which consists of tens of thousands of organic reactions and 9.6 million configurations including transition state data, in addition to reactive simulations using calcium silicate hydrates as a test bed. With its computationally efficient, strictly local network architecture, Allegro-FM scales up to multibillion-atom systems with a parallel efficiency of 0.975 on the exaflop/s Aurora supercomputer at Argonne Leadership Computing Facility. The approach presented in this work demonstrates the potential of the foundation model for novel materials design and discovery based on large-scale atomistic simulations.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"12 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144329402","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":"A Constructive Study Based on Gloeobacter Rhodopsin to Explore the Origin of Extreme Redshift and Nontypical Isomerization of Bestrhodopsin.","authors":"Takashi Nagata,Yuma Kawasaki,Masae Konno,Keiichi Inoue","doi":"10.1021/acs.jpclett.5c00869","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00869","url":null,"abstract":"Bestrhodopsins are recently discovered microbial rhodopsins comprising one or two photosensitive rhodopsin domains and an ion channel. Their rhodopsin domains exhibit extremely red-shifted absorption spectra and a nontypical all-trans-to-11-cis photoisomerization of the retinal chromophore. To determine the origin of these characteristics, we reconstituted a bestrhodopsin-like retinal-binding pocket in a prototypical microbial rhodopsin, Gloeobacter rhodopsin (GR). A triple mutation, D121E/T125D/A256M, in GR induced a 70-nm redshift of its absorption maximum and a pH-dependent spectral shift mirroring Tara-RRB, the best-characterized bestrhodopsin. The D121E/T125D/A256M substitutions also changed the isomerization position on the retinal chromophore from the typical C13=C14 to the C9=C10 bond, whereas an additional mutation, V126A, was found to be critical for efficient photoreaction. Thus, the present study identified four amino acid residues from bestrhodopsin that partially confer unique bestrhodopsin-like spectroscopic and photochemical properties on GR, providing insights into the mechanisms determining the photoisomerization pattern among rhodopsins.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"11 1","pages":"6622-6626"},"PeriodicalIF":6.475,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144328920","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":"Growth and Application of MAPbI3 Single-Crystal Films through LIPSS on an ITO Surface.","authors":"Wenpan Tao,Jingya Sun,Shengjia Li,Binhang Gao,Yifan Deng,Ziqi Ding,Yiling Lian,Ruochen Zhang,Yang Yang,Lan Jiang","doi":"10.1021/acs.jpclett.5c00471","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00471","url":null,"abstract":"Metal halide perovskite has attracted great interest as a promising optoelectronic device material due to its inherent excellent photoelectric properties. Currently, perovskites have made significant strides in enhancing their efficiency, yet their industrial advancement and multiscenario applications remain hampered by manufacturing technology. In this work, high-quality MAPbI3 single-crystal films were prepared through low spatial frequency laser-induced periodic surface structures (LIPSS) with a depth of 139 nm on the surface of ITO processed by femtosecond laser. Femtosecond laser processing revealed that the period of LIPSS decreases with the increase of laser fluence and increases with the increase of scanning speed. Meanwhile, the depth of LIPSS grows with increasing laser fluence and first ascends and then descends as scanning speed goes up. Ultrafast pump probe experiments revealed that the coulomb explosion dominated the interaction mechanism between the femtosecond laser and material at low laser fluence, while the phase explosion became the main mechanism at high laser fluence. The LIPSS with a depth of 139 nm was selected as the substrate to prepare MAPbI3 single-crystal films based on the spatially confined growth method as it greatly facilitates the light absorption rate of MAPbI3 single-crystal films by FDTD simulation. SEM, EDS, and XRD analyses proved that the MAPbI3 single-crystal films have excellent surface quality morphology and uniform element distribution. The average lifetime of an MAPbI3 single crystal obtained by time-resolved photoluminescence spectroscopy is about 24.05 ns, which indicates the low defect density and a long carrier lifetime in MAPbI3 single-crystal films. Transient absorption spectroscopy revealed that Auger recombination is the primary carrier recombination mode at high excitation fluence, which proposed a strong carrier band filling effect and energy structure with two conduction bands in MAPbI3 single-crystal films. The accumulated carriers promoted the excited-state absorption and slowed down the recombination, which is meaningful for the further application of MAPbI3 single-crystal films in optoelectronic devices.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"606 1","pages":"6645-6660"},"PeriodicalIF":6.475,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144328902","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":"Relationship between Morphology and Performance of Manganese-Derived Catalysts for Rechargeable Zinc-Air Batteries","authors":"Sheraz Ahmed, Jiwon An, Muhammad Zubair, Ho-Jung Sun, Joongpyo Shim, Gyungse Park","doi":"10.1021/acs.jpclett.5c01560","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c01560","url":null,"abstract":"Porous carbon derived from a zeolitic imidazolate framework containing zinc (ZIF-8) was used as a precursor, and Mn was deposited on it, which improves the catalytic performance and stability for both ORR and OER. Mn-deposited porous carbon was obtained by the thermal decomposition of Zn-ZIF-8 at 1000 °C, which removes most of the Zn atoms from Zn-ZIF-8 and yields porous carbon (PC) to form Mn/C-ZIF. The Mn/C-ZIF has a higher surface area of 60 m²/g. The Mn/C-ZIF catalyst shows significant performance for ORR (oxygen reduction reactions) and OER (oxygen evolution reactions). The Mn/C-ZIF has high stability and low overpotential for rechargeable zinc-air batteries. The Mn-deposited porous carbon has potential application toward rechargeable zinc-air batteries as a cathode material and generates catalytically active sites for ORR/OER.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"237 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144334974","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":"Watching Vibrations Steer Electrons: Ultrafast Vibration-Induced Absorption Switching through Real-Time Orbital Modulation in a Confined Quantum System","authors":"Yang Liu, Shanshan Feng, Xiufang Song, Xinyu Song, Yuxiang Bu","doi":"10.1021/acs.jpclett.5c01367","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c01367","url":null,"abstract":"Excess electrons (EEs), transient anionic species pivotal in radiation chemistry, catalysis, and optoelectronics, have long been stabilized via solvent interactions such as hydrogen bonding in water or polar solvent traps. While these systems enable electron localization, their environmental sensitivity, limited spectral tunability, and static confinement mechanisms restrict applications requiring dynamic control. Here, we introduce a solvent-free paradigm using a supramolecular electropositive cage (C₆₀F₆₀) to confine and strongly couple an electron with a triatomic CO₂ molecule, bypassing traditional solvation limitations. Through <i>ab initio</i> molecular dynamics, we uncover CO₂’s dual role as a nonlinear quantum actuator: Its bending vibration (∠_OCO = 122–156°) steers sub-50 fs electron oscillation via synchronized <i>s</i>/<i>p</i>-orbital hybridization and polarity switching. Crucially, this vibration-EE coupling modulates the EE-orbital’s symmetry, switching Laporte-forbidden (∠_OCO &lt; 133°/UV-dark) to allowed (∠_OCO ≈ 133–140°/invisible-light and ∠_OCO &gt; 140°/visible-light) transitions, thereby enabling vibration-induced absorption switching spanning 380–760 nm. The C₆₀F₆₀ cage enhances CO₂’s electron affinity by 6.1 eV through noncovalent electrostatic stabilization, creating a vibrationally active yet chemically inert environment, a stark contrast to solvent-dependent systems. This platform reveals ultrafast coherence between molecular vibrations and electron redistribution, establishing a dynamic quantum confinement model in which mechanical motion directly dictates optical responses. By bridging triatomic molecular dynamics to macroscopic tunable luminescence, this work advances the design of stimuli-responsive optoelectronic materials, offering applications in wavelength-adaptive scintillators and ultrafast optical switches while redefining the role of vibrations in quantum state manipulation.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"150 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144335200","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":"Direct Monitoring of Vacancy Thermal Equilibration.","authors":"Hao Wang,Yongquan Wu","doi":"10.1021/acs.jpclett.5c01596","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c01596","url":null,"abstract":"Vacancy thermal equilibration (VTE) is ubiquitous, and it plays a crucial role in many complex physical and chemical processes. However, because it has not yet been possible to directly monitor the VTE process, the mechanism of VTE remains unclear. In this work, we realize such direct monitoring for the first time via molecular dynamics (MD) simulations of aluminum slabs with free surfaces and an innovative method for identifying vacancies. By developing a diffusion model to fit the MD data, we verify that the VTE process obeys Fick's second law. The vacancy concentration to which the system eventually converges is found to be the thermodynamic equilibrium concentration, independent of the structure and orientation of the surface. The key diffusion coefficient is found to be an equivalent value. It decreases as the degree of vacancy aggregation increases. This first monitoring of VTE will have profound implications for many vacancy-mediated fields.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"70 1","pages":"6608-6614"},"PeriodicalIF":6.475,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144328672","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":"Toward Generalized Solution-State 1H DNP NMR via Particle-Mediated Cross-Relaxation.","authors":"Sungsool Wi,Angeliki Giannouli,Korin Butbul,Jenica Lumata,Thierry Dubroca,Faith Scott,Zachary Dowdell,Robert W Schurko,Hans Van Tol,Lucio Frydman","doi":"10.1021/acs.jpclett.5c01398","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c01398","url":null,"abstract":"This study discusses a potential route for enhancing 1H NMR signals in the liquid phase at high magnetic fields for samples on the 100 μL volume scale using dynamic nuclear polarization (DNP). The approach involves dispersing an inert powder that is both rich in protons and capable of undergoing DNP with good efficiency at noncryogenic temperatures, and letting the solid 1H polarization thus enhanced pass from the dispersed particles onto the surrounding liquid via spontaneous cross relaxation effects. To this end, BDPA-doped polystyrene (PS) particles in the μm range were suspended in 30 μL of heptane, loaded into 3.2 mm sapphire rotors, and spun at ≈500 Hz for homogeneity purposes in a 14.1 T magnet. Irradiation with ≈13 W at 395 GHz while maintaining temperature in the 185-220 K range thus enhanced the PS proton polarization ≈12-fold within ≈2 s; after ca. 6 s of irradiation, this resulted in ca. 3-fold enhancements of the heptane proton resonances, while preserving their ≤2 Hz line widths. The conditions over which such particle-mediated transfer occurs were explored over a range of sample composition, deuteration and molecular weight; best results were obtained when polarizing a ball-milled powder made of deuterated-PS/PS/BDPA = 86.4/9.6/4.0 suspended on perdeuterated heptane-d16. While the solution-state enhancements provided by this approach are still relatively modest, its generality could open new avenues in DNP-enhanced 1H NMR that do not sacrifice on the volumes, on the high-resolution conditions, or on the multiscan averaging that is customary in contemporary applications.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"236 1","pages":"6627-6636"},"PeriodicalIF":6.475,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144328904","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":"Simulation of Pump–Push Molecular Dynamics in the Heptazine–H2O Complex","authors":"Sebastian V. Pios, Maxim F. Gelin, Wolfgang Domcke, Lipeng Chen","doi":"10.1021/acs.jpclett.5c01352","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c01352","url":null,"abstract":"Pump–push–probe spectroscopy was employed for the exploration of charge-separation processes in organic photovoltaic blends as well as for proton-coupled electron-transfer (PCET) reactions in hydrogen-bonded complexes of trianisole–heptazine with substituted phenols in organic solvents. In the present work, the electron and proton transfer dynamics driven by a femtosecond pump pulse and a time-delayed femtosecond push pulse has been studied with <i>ab initio</i> on-the-fly non-adiabatic trajectory calculations for the hydrogen-bonded heptazine–H₂O complex. While the dynamics following the pump pulse is dominated by ultrafast radiationless energy relaxation to the long-lived lowest singlet excited state (S₁) of the heptazine chromophore with only minor PCET reactivity, the re-excitation of the transient S₁ population by the push pulse results in a much higher PCET reaction probability. These results illustrate that pump–push excitation has the potential to unravel the individual electron and proton transfer processes of PCET reactions on femtosecond time scales.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"6 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144329403","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}