The Journal of Physical Chemistry Letters最新文献

Ultrafast Charge Carrier Dynamics in Vanadium Dioxide, VO2: Nonequilibrium Contributions to the Photoinduced Phase Transitions

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-01-28 DOI: 10.1021/acs.jpclett.4c02951

John A. Tomko, Kiumars Aryana, Yifan Wu, Guoqing Zhou, Qiyan Zhang, Pat Wongwiset, Virginia Wheeler, Oleg V. Prezhdo, Patrick E. Hopkins

{"title":"Ultrafast Charge Carrier Dynamics in Vanadium Dioxide, VO2: Nonequilibrium Contributions to the Photoinduced Phase Transitions","authors":"John A. Tomko, Kiumars Aryana, Yifan Wu, Guoqing Zhou, Qiyan Zhang, Pat Wongwiset, Virginia Wheeler, Oleg V. Prezhdo, Patrick E. Hopkins","doi":"10.1021/acs.jpclett.4c02951","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02951","url":null,"abstract":"Vanadium oxide (VO2) is an exotic phase-change material with diverse applications ranging from thermochromic smart windows to thermal sensors, neuromorphic computing, and tunable metasurfaces. Nonetheless, the mechanism responsible for its metal–insulator phase transition remains a subject of vigorous debate. Here, we investigate the ultrafast dynamics of the photoinduced phase transition in VO2 under low perturbation conditions. By experimentally examining carrier relaxation dynamics at energy levels near the VO2 band gap (0.6–0.92 eV), we note that numerous optical features do not correspond to the first-order phase transition. Previous studies indeed induced such a phase transition, but they relied on fluences at least an order of magnitude higher, leading to temperature increases well above the transition threshold (340 K). Instead, for excitation fluences that correspond to lattice temperatures only in slight excess of the phase transition (absolute temperatures < 500 K), we find that the marked changes in optical properties are dominated by a shift in the electronic density of states/Fermi level. We find that this effect is a lattice-driven process and does not occur until sufficient energy has been transferred from the excited electrons into the phonon subsystem.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"47 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050283","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

Solvent-Free Artificial Light-Harvesting System in a Fluid Donor with Highly Efficient Förster Resonance Energy Transfer

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-01-28 DOI: 10.1021/acs.jpclett.4c03518

Longyue Yu, Xionghui Huang, Ning Feng, Wenwen Fu, Xia Xin, Jingcheng Hao, Hongguang Li

{"title":"Solvent-Free Artificial Light-Harvesting System in a Fluid Donor with Highly Efficient Förster Resonance Energy Transfer","authors":"Longyue Yu, Xionghui Huang, Ning Feng, Wenwen Fu, Xia Xin, Jingcheng Hao, Hongguang Li","doi":"10.1021/acs.jpclett.4c03518","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03518","url":null,"abstract":"Multi-step Förster resonance energy transfer (FRET) plays a vital role in photosynthesis. While the energy transfer efficiency (ΦET) of a naturally occurring system can reach 95%, that of most artificial light-harvesting systems (ALHSs) is still limited. Herein, we propose a strategy to construct highly efficient ALHSs using a blue-emitting, supercooled ionic compound of naphthalimide (NPI) as the donor, a green-emitting BODIPY derivate as a relay acceptor, and a commercially available, red-emitting dye [rhodamine B (RhB)] as the final acceptor. The broad emission of the fluid donor can overlap simultaneously with the absorption of BODIPY and RhB, enabling the occurrence of a sequential FRET from NPI to BODIPY to RhB as well as a parallel FRET directly from NPI to RhB. These two complementary energy transfer routes lead to an overall ΦET up to 97.4%, which is the champion among all of the reported ALHSs and is also higher than that found in plants and photosynthetic bacteria. This strategy is universal, and ΦET of the system could be further improved by optimizing the structures of the fluid donor and relay acceptor.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"117 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050286","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

Photochemistry of Microsolvated Nitrous Acid: Observation of the Water-Separated Complex of Nitric Oxide and Hydroxyl Radical

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-01-28 DOI: 10.1021/acs.jpclett.4c03483

Xiaolong Li, Wenbin Fan, Xin Shao, Wei Fang, Dong H. Zhang, Mingfei Zhou, Joseph S. Francisco, Xiaoqing Zeng

{"title":"Photochemistry of Microsolvated Nitrous Acid: Observation of the Water-Separated Complex of Nitric Oxide and Hydroxyl Radical","authors":"Xiaolong Li, Wenbin Fan, Xin Shao, Wei Fang, Dong H. Zhang, Mingfei Zhou, Joseph S. Francisco, Xiaoqing Zeng","doi":"10.1021/acs.jpclett.4c03483","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03483","url":null,"abstract":"The photochemistry of nitrous acid (HONO) plays a crucial role in atmospheric chemistry as it serves as a key source of hydroxyl radicals (OH) in the atmosphere; however, our comprehension of the underlying mechanism for the photochemistry of HONO especially in the presence of water is far from being complete as the transient intermediates in the photoreactions have not been observed. Herein, we report the photochemistry of microsolvated HONO by water in a cryogenic N2 matrix. Specifically, the 1:1 hydrogen-bonded water complex of HONO was facially prepared in the matrix through stepwise photolytic O2 oxidation of the water complex of imidogen (NH–H2O) via the intermediacy of the elusive water complex of peroxyl isomer HNOO. Upon photolysis at 193 nm, the matrix-isolated HONO–H2O complex decomposes by yielding the ternary water complex of OH and NO due to the matrix cage effect. The identification of this rare water-separated radical pair (OH–H2O–NO) with matrix-isolation infrared and ultraviolet–visible spectroscopy is aided by D, 15N, and 18O isotope labeling and quantum chemical calculations at the (U)CCSD/AVTZ level of theory, and its most stable structure exhibits separate hydrogen bonding interactions of the OH and NO radicals with H2O via OH···OH2 and ON···HOH contacts, respectively. This ternary complex is extremely unstable, as it undergoes spontaneous radical recombination to reform the HONO–H2O complex in the temperature range of 4–12 K through quantum-mechanical tunneling with 16/18O, H/D, 14/15N kinetic isotopic effects of 1.43, 2.33, and 0.91, respectively. At increased temperatures from 15 to 21 K, the recombination proceeds predominantly by overcoming the activation barrier with an estimated height of 0.12(1) kcal/mol.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"6 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050287","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

Small-Angle and Quasi-Elastic Neutron Scattering from Polydisperse Oligolamellar Vesicles Containing Glycolipids

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-01-28 DOI: 10.1021/acs.jpclett.4c03454

Lukas Bange, Amin Rahimzadeh, Tetiana Mukhina, Regine von Klitzing, Ingo Hoffmann, Emanuel Schneck

{"title":"Small-Angle and Quasi-Elastic Neutron Scattering from Polydisperse Oligolamellar Vesicles Containing Glycolipids","authors":"Lukas Bange, Amin Rahimzadeh, Tetiana Mukhina, Regine von Klitzing, Ingo Hoffmann, Emanuel Schneck","doi":"10.1021/acs.jpclett.4c03454","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03454","url":null,"abstract":"Glycolipids are known to stabilize biomembrane multilayers through preferential sugar–sugar interactions that act as weak transient membrane cross-links. Here, we use small-angle and quasi-elastic neutron scattering on oligolamellar phospholipid vesicles containing defined glycolipid fractions in order to elucidate the influence of glycolipids on membrane mechanics and dynamics. Small-angle neutron scattering (SANS) reveals that the oligolamellar vesicles (OLVs) obtained by extrusion are polydisperse with regard to the number of lamellae, n, which renders the interpretation of the quasi-elastic neutron spin echo (NSE) data nontrivial. To overcome this problem, we propose a method to model the NSE data in a rigorous fashion based on the obtained histograms of n and on their q-dependent intensity-weighted contribution. This procedure yields meaningful values for the bending rigidity of individual lipid membranes and insights into the mechanical coupling between adjacent membrane lamellae including the effect of the glycolipids.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"39 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050285","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

Depolarized Forward Light Scattering for Subnanometer Precision in Biomolecular Layer Analysis on Gold Nanorods

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-01-27 DOI: 10.1021/acs.jpclett.4c02956

Peter Johansson, Mikael Käll, Hana Šípová-Jungová

{"title":"Depolarized Forward Light Scattering for Subnanometer Precision in Biomolecular Layer Analysis on Gold Nanorods","authors":"Peter Johansson, Mikael Käll, Hana Šípová-Jungová","doi":"10.1021/acs.jpclett.4c02956","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02956","url":null,"abstract":"Functional gold nanoparticles have emerged as a cornerstone in targeted drug delivery, imaging, and biosensing. Their stability, distribution, and overall performance in biological systems are largely determined by their interactions with molecules in biological fluids as well as the biomolecular layers they acquire in complex environments. However, real-time tracking of how biomolecules attach to colloidal nanoparticles, a critical aspect for optimizing nanoparticle function, has proven to be experimentally challenging. To address this issue, we present a depolarized forward light scattering (DFLS) method that measures rotational relaxation constants. In DFLS, optically anisotropic nanoparticles are illuminated with linearly polarized light and the forward light scattering is analyzed in a cross-polarized configuration. We demonstrate the application of DFLS to characterize various functional coatings, analyze biomolecular binding kinetics to gold nanoparticles, and determine specific protein adsorption affinity constants. Our results indicate that DFLS offers a powerful approach to studying nanoparticle-biomolecule interactions in complex environments such as bodily fluids, thereby opening new pathways for advancements in nanomedicine and the optimization of nanoparticle-based drug delivery systems.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"9 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050288","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

Calprotectin’s Protein Structure Shields Ni–N(His) Bonds from Competing Agents

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-01-27 DOI: 10.1021/acs.jpclett.4c03229

Zhuojian Lu, Jingyuan Nie, Ziling Wang, Ziyi Wang, Panke Zhang, Yajun Jiang, Peng Zheng

{"title":"Calprotectin’s Protein Structure Shields Ni–N(His) Bonds from Competing Agents","authors":"Zhuojian Lu, Jingyuan Nie, Ziling Wang, Ziyi Wang, Panke Zhang, Yajun Jiang, Peng Zheng","doi":"10.1021/acs.jpclett.4c03229","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03229","url":null,"abstract":"The Ni–N(His) coordination bond, formed between the nickel ion and histidine residues, is essential for recombinant protein purification, especially in Ni-NTA-based systems for selectively binding polyhistidine-tagged (Histag) proteins. While previous studies have explored its bond strength in a synthetic Ni-NTA-Histag system, the influence of the surrounding protein structure remains less understood. In this study, we used atomic force microscopy-based single-molecule force spectroscopy (AFM-SMFS) to quantify the Ni–N(His) bond strength in calprotectin, a biologically relevant protein system. Our results demonstrate that the Ni–N(His) bond in protein exhibits a rupture force of ∼56 pN. Notably, kinetic analysis revealed a significantly lower off-rate compared to the synthetic system, suggesting that the protein environment plays a crucial role in stabilizing the bond. Moreover, we found that the bond is less susceptible to displacement by competing agents, such as imidazole, and experiences only a modest decrease in stability under acidic conditions, compared to the dramatic weakening seen in a synthetic system. These findings highlight the role of protein structure in protecting the mechanical and kinetic stability of the Ni–N(His) bond, offering insights into understanding the metal–ligand interactions in proteins in general.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"15 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044618","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

Synergistic Intramolecular Charge Transfer Promotes Au Nanoclusters with Enhanced NIR-II Photoluminescence

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-01-27 DOI: 10.1021/acs.jpclett.4c03410

Shuxian Li, Wei Ge, Xiaoyu Huang, Hong Du, Fu Wang

{"title":"Synergistic Intramolecular Charge Transfer Promotes Au Nanoclusters with Enhanced NIR-II Photoluminescence","authors":"Shuxian Li, Wei Ge, Xiaoyu Huang, Hong Du, Fu Wang","doi":"10.1021/acs.jpclett.4c03410","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03410","url":null,"abstract":"Gold nanoclusters (Au NCs) protected by molecular ligands represent a new class of second-generation near-infrared (NIR-II) luminescent materials that have been widely studied. However, the photoluminescence efficiencies of most NIR-II emitting Au NCs in aqueous solution are generally lower than 0.2%, and to fully exploit the advantages of AuNCs in the NIR-II region, improving their photoluminescence efficiency has become an urgent need. Considering the holistic nature of the core–shell structure of Au NCs, herein, we propose a synergistic intramolecular charge transfer (ICT) strategy to enhance the luminescence. The NIR-II fluorescence quantum yield of Au NCs was increased 6-fold to 5.59% by the synergistic effect of heteroatomic copper doping and ligand p-MBA deprotonation. Experimental characterization results show that the strong p-π conjugation between d10 metal and the deprotonated p-MBA enhances the charge transfer between the metal core and ligand. The synergistic ICT process strongly suppressed the nonradiative process, thereby enhancing the emission intensity. Our findings provide a facile method for understanding the integrity of the core–shell structure of Au NCs and regulating their photoluminescence properties.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"10 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044619","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

Far-Ultraviolet Plexciton Formation in Water-Covered Indium Clusters

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-01-27 DOI: 10.1021/acs.jpclett.5c00001

Naoki Nagatsuka, Ryoto Matsuguchi, Kazuya Watanabe, Takanori Koitaya, Daiki Yamamoto, Hiroshi Okuyama, Tomokazu Yasuike

引用次数: 0

Weak Antilocalization and Negative Magnetoresistance of the Gate-Tunable PbTe Thin Films

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-01-27 DOI: 10.1021/acs.jpclett.4c03425

Huizhen Li, Kang Li, Wenyu Hu, Jianyuan Zhao, Tong Su, Jielin Yang, Yiming Chen, Kuo Yang, Mei Du, Zhe Li, Weiwei Zhao

引用次数: 0

Pinpointing the CN Stretch Frequency of Neutral Cyano-Polycyclic Aromatic Hydrocarbons: A Laboratory and Quantum Chemical Spectroscopic Study of 9-Cyanoanthracene

IF 6.475 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2025-01-27 DOI: 10.1021/acs.jpclett.4c03396

Vincent J. Esposito, Piero Ferrari, C. Zachary Palmer, Christiaan Boersma, Alessandra Candian, Ryan C. Fortenberry, Wybren Jan Buma, Alexander G. G. M. Tielens

{"title":"Pinpointing the CN Stretch Frequency of Neutral Cyano-Polycyclic Aromatic Hydrocarbons: A Laboratory and Quantum Chemical Spectroscopic Study of 9-Cyanoanthracene","authors":"Vincent J. Esposito, Piero Ferrari, C. Zachary Palmer, Christiaan Boersma, Alessandra Candian, Ryan C. Fortenberry, Wybren Jan Buma, Alexander G. G. M. Tielens","doi":"10.1021/acs.jpclett.4c03396","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03396","url":null,"abstract":"The CN stretch frequency of neutral, gas-phase 9-cyanoanthracene is 2207 cm–1 (4.531 μm) based on high-resolution infrared absorption experiments coupled with a new hybrid anharmonic quantum chemical methodology. A broad band (full-width at half-maximum of 47 cm–1) is observed and assigned to multiple transitions, including the CN stretch fundamental and various combination bands that gather intensity from strong anharmonic coupling with the bright CN stretch. The new hybrid computational approach utilizes the harmonic force constants from the double-hybrid rev-DSDPBEP86 functional that includes MP2 electron correlation, and the cubic and quartic force constants from the B3LYP density functional. In combination, this method computes a band center of 2207 cm–1 for 9-cyanoanthracene, a direct match with experiment. Further, the hybrid method produces a difference of less than 1 cm–1 for the two isomers of cyanonaphthalene and cyanobenzene. As shown from comparison with CCSD(T)-F12b anharmonic frequency computations of cyanobenzene, inclusion of electron correlation is required to properly characterize the electronic structure of the highly electron withdrawing CN group on polycyclic aromatic hydrocarbons. In agreement with earlier studies, computation of the CN stretch of 14 small CN-PAHs produces a narrow (∼20 cm–1) band from 2207–2229 cm–1 (4.53–4.48 μm). The remainder of the spectrum below 2000 cm–1 and from 3000–3120 cm–1 shows good agreement between experiment and the hybrid theory with a mean absolute error of 16 and 14 cm–1, respectively.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 1 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050290","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