The Journal of Physical Chemistry Letters最新文献

{"title":"Ultrafast Dynamics Simulations in the Plasmon-Induced Photocatalysis of Benzyl Alcohol by Nanoparticles.","authors":"Weichuang Zhang, Qi Xiao, Jin Wen","doi":"10.1021/acs.jpclett.5c01072","DOIUrl":"10.1021/acs.jpclett.5c01072","url":null,"abstract":"<p><p>The solvent-free metal-catalyzed synthesis of benzaldehyde from benzyl alcohol requires high temperatures or pressures to achieve high reaction efficiencies, which can reduce the stability of the catalyst. To address this issue, utilizing solar energy to facilitate the photocatalytic conversion of benzyl alcohol into benzaldehyde via the plasmonic effects of metal nanoparticles under ambient conditions has emerged as a promising approach. However, the microscopic mechanism underlying the plasmon-induced photocatalytic conversion of benzyl alcohol remains unclear. In this work, we employ time-dependent density functional theory to investigate the ultrafast carrier dynamics during the plasmon-driven photocatalysis mediated by PdAu₃ nanoparticles, revealing the electron transfer process at the atomic scale during the photochemical reactions. Our findings indicate that the reaction is governed by multiple charge transfer mechanisms, with indirect charge transfer driven by hot carriers within the metal being predominant. Direct charge transfer between the metal and the adsorbed molecule, as well as within the adsorbed molecule, plays secondary roles. This study provides a detailed pathway for understanding the plasmon-driven photocatalytic conversion of benzyl alcohol to benzaldehyde and offers valuable insights into the design of catalysts for various organic syntheses under ambient conditions using light.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"6073-6080"},"PeriodicalIF":4.8,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144256779","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":"Dynamic Potential-pH Diagrams of Ni-Based Anodes for Durable Oxygen Evolution in the Presence of Cl^- Impurity.","authors":"Hiroki Komiya, Swastik Laha, Keisuke Obata, Kalishankar Bhattacharyya, Kazuhiro Takanabe","doi":"10.1021/acs.jpclett.5c00704","DOIUrl":"10.1021/acs.jpclett.5c00704","url":null,"abstract":"<p><p>The corrosion of anode materials caused by dissolved chloride ions (Cl^-) is considered one of the most significant issues in the long term durability of seawater electrolysis systems. This study examined the corrosion behaviors of Ni-based electrodes based on a dynamic potential-pH (Pourbaix) diagram with various buffered electrolytes (borate, carbonate, and phosphate). It was found that NiFeO_<i>x</i>/Ni plate electrodes degraded faster in media with mild pH than those with alkaline pH, and the corrosion rate depended on the dissolved ionic species in the presence of Cl^-, which could be explained in terms of the thermodynamic stability of the formed compounds on the surface. No significant corrosion was observed in phosphate-containing electrolytes, which could be explained by the high formation constant and the low solubility of the Ni-PO₄ product with the formed complex. The density functional theory calculation was used to clarify the preferable phosphate adsorption on the Ni site over Cl^-, which stabilized Ni.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"6052-6058"},"PeriodicalIF":4.8,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144256812","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":"Enhancing FRET Efficiency through Synergistic Influences of Surfactants and Quantum Dots on Zinc Quinolate Complex-Dye Interactions.","authors":"Sumit Singha, Manideepa Paul, Prokash Ghosh, Mihir Manna, Sabyasachi Pramanik, Anirban Misra, Satyapriya Bhandari","doi":"10.1021/acs.jpclett.5c01269","DOIUrl":"10.1021/acs.jpclett.5c01269","url":null,"abstract":"<p><p>Herein, we present a pioneering approach to enhancing Förster resonance energy transfer (FRET) efficiency through the synergistic integration of cetyltrimethylammonium bromide (CTAB) surfactants and ZnS quantum dots (QDs) within a zinc quinolate complex (ZQC)-dye (Rhodamine B: RhB) system. FRET efficiency is elevated from 13.1% to 49% with surfactants alone and further to an impressive 93.6% with the addition of QDs. This advancement highlights the vital role of chemical environment modifications in regulating energy transfer mechanisms. Employing nuclear magnetic resonance (NMR) and Fourier-transform infrared (FTIR) spectroscopy alongside density functional theory (DFT) calculations, the study provides comprehensive insights into molecular interactions, electronic behavior, and structural transformations driving enhanced energy transfer. The findings set a benchmark for high-performance FRET systems, offering a robust platform for applications in bioimaging, biosensors, optoelectronics, and nanophotonics. By blending experimental innovation with theoretical validation, this work paves the way for transformative advancements in optical- and nanomaterial-based technologies.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"6066-6072"},"PeriodicalIF":4.8,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144256772","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":"Origin of Stabilization of Ligand-Centered Mixed Valence Ruthenium Azopyridine Complexes: DFT Insights for Neuromorphic Applications.","authors":"A Avilés, S Perez Beltran, M Ghotbi, A J Ferguson, J L Blackburn, M Y Darensbourg, P B Balbuena","doi":"10.1021/acs.jpclett.5c00812","DOIUrl":"10.1021/acs.jpclett.5c00812","url":null,"abstract":"<p><p>Redox-driven conductance changes are critical processes in molecular- and coordination-complex-based memristive thin films and devices that are envisioned for neuromorphic technologies, but fundamental mechanisms of conductance switching are not fully understood. Here, we explore charge disproportionation (CD) processes in [Ru^IIL₂](PF₆)₂ molecular systems that intrinsically involve interfragment charge transfer (IFCT). Using a combination of <i>ab initio</i> molecular dynamics simulation (AIMD), time-dependent density functional theory (TD-DFT), and density functional theory (DFT) calculations, we investigate the electron transfer mechanisms and the roles of temperature and cell volumetric expansion in facilitating the counterion movements and electronic transitions required for low-cost IFCT and charge redistribution. A detailed analysis of the density of states and TD-DFT calculations highlights that unpaired electrons play a crucial role in low-energy transitions, with the azo (N═N) groups of the ligand serving as the primary sites for electronic transport between molecular fragments, further stabilizing the asymmetric state. Localization of added electrons on azo ligands occurs with negligible change at the Ru centers, supported by atomic volume expansions up to +4.74 bohr³, and goes along with a progressive reduction of the HOMO-LUMO gap across redox states, suggesting enhanced conductivity. The TD-DFT analysis reveals a dominant IFCT excitation at 2082.76 nm in the doubly reduced (22) state, while a stabilization energy of 1.20 eV of the asymmetric (13) state relative to the symmetric (22) state is predicted by constrained DFT. Periodic DFT and AIMD simulations emulating a molecular film show that the stabilization of the asymmetric state, relative to a symmetric one, translates in net charge separation values (order of ∼0.33 e) that are strongly linked to increased counterion mobility (average counterion displacements exceeding 0.7 Å per atom during CD events) and the involvement of azo groups in electron redistribution. These findings, which align with previously reported experimental and computational data, provide key insights into the IFCT mechanisms and electronic transport facilitated by azo groups, with important implications for redox-driven memristive and neuromorphic technologies.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"6125-6137"},"PeriodicalIF":4.8,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144256775","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":"Enhanced Quantum Yield and Long-Term Stability of Eco-Friendly Water-Dispersed InP/ZnSe/ZnS Quantum Dots via Photochemical Surface Passivation.","authors":"Hyeonmin Yim, Borim Shim, Hyeongwoo Kim, Seokyu Park, Cheolwan Park, Woo-Byoung Kim","doi":"10.1021/acs.jpclett.5c00188","DOIUrl":"10.1021/acs.jpclett.5c00188","url":null,"abstract":"<p><p>Quantum dots (QDs) are essential in fields such as bioimaging and electronics due to their unique optical properties. However, traditional cadmium (Cd)-based QDs pose significant environmental and health risks. This study aimed to develop efficient, Cd-free QDs suitable for water dispersion and long-term stability. We synthesized InP/ZnSe/ZnS multi-shell QDs and employed a photochemical surface passivation method using a halogen lamp to enhance their photoluminescence. For water dispersion, we used ligand exchange with hydrophilic agents, such as 3-mercaptopropionic acid (3-MPA) and 11-mercaptoundecanoic acid (11-MUA). This process facilitated the dispersion of QDs in water while maintaining their quantum yield (QY). The results revealed that the water-dispersed QDs retained 92.5% of their initial QY after 2 months, a notable improvement compared to the 47.3% retention of QDs dispersed in chloroform solvents. This demonstrates that our photochemical passivation method and ligand exchange effectively stabilize QDs in aqueous environments. These Cd-free, water-dispersed QDs offer significant advantages for sustainable electronics, water treatment, and biomedical applications. The study highlights the potential for broader commercialization and further research into optimizing QD performance through advanced ligand and synthesis techniques.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"6008-6014"},"PeriodicalIF":4.8,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144256814","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":"Insights into the Influence of the Potassium Ion on the Charge Carrier Kinetics of Potassium Poly(heptazine imides).","authors":"Yuna Kang, Rong Lu, Xin Zou, Jun Lin, Anchi Yu","doi":"10.1021/acs.jpclett.5c01209","DOIUrl":"10.1021/acs.jpclett.5c01209","url":null,"abstract":"<p><p>Understanding the influence of potassium ions (K⁺) on the charge carrier kinetics of potassium poly(heptazine imide) (K-PHI) is crucial for the rational design of efficient PHI-based photocatalytic materials. Herein, we prepare a series of K-PHI photocatalysts with varying K⁺ contents while maintaining constant cyanamide group content and conduct comprehensive femtosecond transient absorption (fs-TA) studies on them. The successful modulation of the K⁺ content in K-PHI samples was confirmed through FTIR, XRD, SEM-EDX, and ICP-OES measurements. A decay process with an ∼62 ps time constant was observed in the fs-TA kinetics of K-PHI samples, in which its amplitude increases linearly with K⁺ content in K-PHI samples, indicating that K⁺ plays a crucial role in modulating the ∼62 ps decay process of K-PHI materials. These findings provide valuable insights into the influence of K⁺ on the charge carrier kinetics and photophysical properties of K-PHI, offering a theoretical foundation for the design of efficient PHI-based photocatalytic materials.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"6146-6154"},"PeriodicalIF":4.8,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144264871","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":"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":"<p><p>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.</p>","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}

{"title":"Effect of Hydrostatic Pressure on the <i>g</i> Tensor and Hyperfine Coupling Constants of the Nitroxide Radical Characterized by <i>Ab Initio</i> Calculations.","authors":"Ana Gurgenidze, Anna I Krylov, Susumu Takahashi","doi":"10.1021/acs.jpclett.5c00677","DOIUrl":"10.1021/acs.jpclett.5c00677","url":null,"abstract":"<p><p>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 <i>g</i> 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 <i>g</i> tensors and hyperfine coupling tensors (<i>A</i> 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 <i>g</i> and <i>A</i> tensors. The observed linear dependence of the <i>g</i> and <i>A</i> 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.</p>","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}

{"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":"<p><p>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.</p>","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}

{"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":"<p><p>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 (λ_ex = 370 nm). We show that this hidden pathway directly generates singlet oxygen (a¹Δ_g,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.</p>","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}