ACS Physical Chemistry Au最新文献

{"title":"Roundabout Mechanism of Ion–Molecule Nucleophilic Substitution Reactions","authors":"Xiangyu Wu, Fei Ying, Hongyi Wang, Li Yang, Jiaxu Zhang, Jing Xie","doi":"10.1021/acsphyschemau.4c00061","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00061","url":null,"abstract":"Roundabout (RA) is an important indirect mechanism for gas-phase X^– + CH₃Y → XCH₃ + Y^– S_N2 reactions at a high collision energy. It refers to the rotation of the CH₃-group by half or multiple circles upon the collision of incoming nucleophiles before substitution takes place. The RA mechanism was first discovered in the Cl^– + CH₃I S_N2 reaction to explain the energy transfer observed in crossed molecular beam imaging experiments in 2008. Since then, the RA mechanism and its variants have been observed not only in multiple C-centered S_N2 reactions, but also in N-centered S_N2 reactions, proton transfer reactions, and elimination reactions. This work reviewed recent studies on the RA mechanism and summarized the characteristics of RA mechanisms in terms of variant types, product energy partitioning, and product velocity scattering angle distribution. RA mechanisms usually happen at small impact parameters and tend to couple with other mechanisms at relatively low collision energy, and the available energy of roundabout trajectories is primarily partitioned to internal energy. Factors that affect the importance of the RA mechanism were analyzed, including the type of leaving group and nucleophile, collision energy, and microsolvation. A massive leaving group and relatively high collision energy are prerequisite for the occurrence of the roundabout mechanism. Interestingly, when reacting with CH₃I, the importance of RA mechanisms follows an order of Cl^– > HO^– > F^–, and such a nucleophile dependence was attributed to the difference in proton affinity and size of the nucleophile.","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142256285","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ultrafast Spin Relaxation of Charge Carriers in Strongly Quantum Confined Methylammonium Lead Bromide Perovskite Magic-Sized Clusters","authors":"David C. Zeitz, Vivien L. Cherrette, Sarah A. Creech, Yan Li, Yuan Ping, Jin Z. Zhang","doi":"10.1021/acsphyschemau.4c00051","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00051","url":null,"abstract":"Spin relaxation of charge carriers in strongly quantum confined perovskite magic-sized clusters has been probed, for the first time, by using polarization-controlled femtosecond transient absorption (fs-TA) spectroscopy. Fs-TA measurements with a circularly polarized pump and probe allowed for the determination of the exciton spin relaxation lifetime (∼1.5 ps) at room temperature based on the dynamics of a photoinduced absorption (PIA) feature peaked at 458 nm. This spin lifetime is shorter than that of perovskite quantum dots (PQDs) with a larger size, and the results suggest that exciton confinement and defects likely play a more important role in these strongly quantum confined magic-sized clusters with a larger surface-to-volume ratio.","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142256287","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Direct Detection of Bound Water in Hydrated Powders of Lysozyme by Differential Scanning Calorimetry","authors":"Judith Peters, Karin Kornmueller, Rim Dannaoui, Ejona Syla, Annalisa Pastore","doi":"10.1021/acsphyschemau.4c00029","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00029","url":null,"abstract":"While exploring the behavior of lysozyme powders at different percentages of rehydration by differential scanning calorimetry, we noticed a small peak persistently on the left of the melting point of bulk water, which, when heating up the system, was always around −10 °C. The intensity of the transition was maximal at 160% rehydration and disappeared at higher values. By comparing the premelting peak properties in H₂O and D₂O, we attributed it to freezable water bound on the protein surface. This is the first time that such an observation has been reported.","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142219238","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"GO@β-Ag2MoO4 Composite: One-Step Synthesis, Characterization, and Photocatalytic Performance against RhB Dye","authors":"Pedro Hyug de Almeida da Silva, Dalete Araújo de Souza, Rubens Lucas de Freitas Filho, Ana Paula de Carvalho Teixeira, Rochel Montero Lago, Walter Ricardo Brito, Edgar Alves Araújo Junior, Litiko Lopes Takeno, Francimauro Sousa Morais, José Fábio de Lima Nascimento, Yurimiler Leyet Ruiz, Libertalamar Brilhalva Saraiva, Francisco Xavier Nobre","doi":"10.1021/acsphyschemau.4c00038","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00038","url":null,"abstract":"The combination of materials to improve properties of interest has become one of the strategies widely used for numerous applications, including new catalysts, over the last few decades. In this study, silver molybdate (β-Ag₂MoO₄) microcrystals were efficiently obtained by the hydrothermal method, obtaining composites with different amounts of graphene oxide (GO) (1, 2.5, 5, 7.5, and 10%, w/w) using the conventional hydrothermal method. The incorporation of GO on silver molybdate was confirmed by X-ray diffraction (XRD) and Raman spectroscopy, where the vibrational modes and crystallographic planes characteristic of the materials of interest were highlighted. The images collected by scanning electron microscopy (SEM) revealed the occurrence of plate-shaped structures (shells) anchored to the surface of the silver molybdate microcrystals (core). The optical properties showed that the materials presented <i>E</i>_gap between 3.34 and 3.39 eV, where the sample with 7.5% of GO (GO@β-AgMo_7.5) was the one that presented energy for the conduction band, largely favorable to the formation of superoxide radicals through the photoexcitation process of electrons. The catalytic tests demonstrated that, among the samples obtained in this study, the sample with 7.5% of GO (GO@β-AgMo_7.5) exhibits superior photocatalytic performance against the dye rhodamine B (RhB) in an aqueous medium. Thus, the kinetics constant for photolysis (absence of catalysts) and for the sample β-AgMo and the sample with 7.5% of GO (GO@β-AgMo_7.5) are 0.38 × 10^–3, 12 × 10^–3, and 23.72 × 10^–3 min^–1, respectively. Therefore, it is 62.5 times more efficient in the degradation of the RhB dye, which confirms the promising photocatalytic properties of the obtained composite.","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142227335","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Time-Resolved Spatial Distributions of Individual Components of Electroactive Films during Potentiodynamic Electrodeposition","authors":"Rachel M. Sapstead, Robert M. Dalgliesh, Virginia C. Ferreira, Charlotte Beebee, Erik Watkins, A. Robert Hillman, Karl S. Ryder, Emma L. Smith, Nina-Juliane Steinke","doi":"10.1021/acsphyschemau.4c00055","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00055","url":null,"abstract":"Of the attributes that determine the performance of electroactive film-based devices, the least well quantified and understood is the spatial distribution of the component species. This is critical since it dictates the transport rates of <i>all</i> the mobile species (electrons, counterions, solvent, analyte, and reactant) and the film mechanical properties (as exploited in actuator devices). One of the few techniques able to provide individual species population profiles <i>in situ</i> is specular neutron reflectivity (NR). Historically, this information is obtained at the cost of poor time resolution (hours). Here we show how NR measurements with <i>event mode</i> data acquisition enable both spatial <i>and</i> temporal resolution; the latter can be selected postexperiment and varied during the transient. We profile individual species at “buried” interfaces under dynamic electrochemical conditions during polypyrrole electrodeposition and Cu deposition/dissolution. In the case of polypyrrole, the film is homogeneous throughout growth; there is no evidence of dendrite formation followed by solvent (water) displacement. Correlation of NR-derived film thickness and coulometric assay allows calculation of the solvent volume fraction, ϕ_S = 0.48. In the case of Cu in a deep eutectic solvent, the complexing nature of the medium results in time-dependent metal speciation: mechanistically, dissolution does not simply follow the deposition pathway in reverse.","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142219240","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"An Unexpected Water Channel in the Light-Harvesting Complex of a Diatom: Implications for the Switch between Light Harvesting and Photoprotection","authors":"Vangelis Daskalakis, Sayan Maity, Ulrich Kleinekathöfer","doi":"10.1021/acsphyschemau.4c00069","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00069","url":null,"abstract":"Many important processes in cells depend on the transfer of protons through water wires embedded in transmembrane proteins. Herein, we have performed more than 55 μs all-atom simulations of the light-harvesting complex of a diatom, i.e., the fucoxanthin and chlorophyll a/c binding protein (FCP) from the marine diatom <i>Phaeodactylum tricornutum</i>. Diatoms are unique models to study natural photosynthesis as they exert an efficient light-harvesting machinery with a robust pH-dependent photoprotective mechanism. The present study reports on the dynamics of an FCP monomer, a dimer, and a tetramer at varying pH values. Surprisingly, we have identified at low pH a water channel across FCP that selectively hydrates and protonates the acrylate of a Chl-c2 pigment located in the middle of the membrane. These results are further supported by QM/MM calculations and steered MD simulations on the proton dynamics. It is shown that proton hopping events between the lumenal and stromal sides of the membrane through the observed water channel are highly disfavored. This hindrance is due to the presence of residues Arg31 and Lys82 close to the acrylate, along with an hydronium desolvation penalty that shows close similarities to the water conductance in aquaporins. Furthermore, we provide strong evidence that this identified water channel is governing the transition between light-harvesting and photoprotective states of the major FCP complex in the diatom <i>P. tricornutum</i>.","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142219241","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Time-Resolved Probing of the Iodobenzene C-Band Using XUV-Induced Electron Transfer Dynamics","authors":"J. Unwin, Weronika O. Razmus, F. Allum, James Harries, Yoshiaki Kumagai, K. Nagaya, Mathew Britton, M. Brouard, P. Bucksbaum, Mizuho Fushitani, I. Gabalski, T. Gejo, P. Hockett, A. J. Howard, H. Iwayama, E. Kukk, Chow-shing Lam, Joseph W McManus, R. Minns, A. Niozu, Sekito Nishimuro, J. Niskanen, S. Owada, James D. Pickering, D. Rolles, James Somper, K. Ueda, Shin-Ichi Wada, Tiffany Walmsley, J. Woodhouse, Ruaridh J G Forbes, M. Burt, E. Warne","doi":"10.1021/acsphyschemau.4c00036","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00036","url":null,"abstract":"","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141920544","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Prominent Role of Charge Transfer in the Spectral Tuning of Photosynthetic Light-Harvesting I Complex","authors":"Kazuhiro J. Fujimoto*,&nbsp;Rio Tsuji,&nbsp;Zheng-Yu Wang-Otomo and Takeshi Yanai*,&nbsp;","doi":"10.1021/acsphyschemau.4c0002210.1021/acsphyschemau.4c00022","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00022https://doi.org/10.1021/acsphyschemau.4c00022","url":null,"abstract":"<p >Purple bacteria possess two ring-shaped protein complexes, light-harvesting 1 (LH1) and 2 (LH2), both of which function as antennas for solar energy utilization for photosynthesis but exhibit distinct absorption properties. The two antennas have differing amounts of bacteriochlorophyll (BChl) <i>a</i>; however, their significance in spectral tuning remains elusive. Here, we report a high-precision evaluation of the physicochemical factors contributing to the variation in absorption maxima between LH1 and LH2, namely, BChl <i>a</i> structural distortion, protein electrostatic interaction, excitonic coupling, and charge transfer (CT) effects, as derived from detailed spectral calculations using an extended version of the exciton model, in the model purple bacterium <i>Rhodospirillum rubrum</i>. Spectral analysis confirmed that the electronic structure of the excited state in LH1 extended to the BChl <i>a</i> 16-mer. Further analysis revealed that the LH1-specific redshift (∼61% in energy) is predominantly accounted for by the CT effect resulting from the closer inter-BChl distance in LH1 than in LH2. Our analysis explains how LH1 and LH2, both with chemically identical BChl <i>a</i> chromophores, use distinct physicochemical effects to achieve a progressive redshift from LH2 to LH1, ensuring efficient energy transfer to the reaction center special pair.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00022","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142318194","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Prominent Role of Charge Transfer in the Spectral Tuning of Photosynthetic Light-Harvesting I Complex","authors":"Kazuhiro J. Fujimoto, Rio Tsuji, Zheng-Yu Wang-Otomo, Takeshi Yanai","doi":"10.1021/acsphyschemau.4c00022","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00022","url":null,"abstract":"Purple bacteria possess two ring-shaped protein complexes, light-harvesting 1 (LH1) and 2 (LH2), both of which function as antennas for solar energy utilization for photosynthesis but exhibit distinct absorption properties. The two antennas have differing amounts of bacteriochlorophyll (BChl) <i>a</i>; however, their significance in spectral tuning remains elusive. Here, we report a high-precision evaluation of the physicochemical factors contributing to the variation in absorption maxima between LH1 and LH2, namely, BChl <i>a</i> structural distortion, protein electrostatic interaction, excitonic coupling, and charge transfer (CT) effects, as derived from detailed spectral calculations using an extended version of the exciton model, in the model purple bacterium <i>Rhodospirillum rubrum</i>. Spectral analysis confirmed that the electronic structure of the excited state in LH1 extended to the BChl <i>a</i> 16-mer. Further analysis revealed that the LH1-specific redshift (∼61% in energy) is predominantly accounted for by the CT effect resulting from the closer inter-BChl distance in LH1 than in LH2. Our analysis explains how LH1 and LH2, both with chemically identical BChl <i>a</i> chromophores, use distinct physicochemical effects to achieve a progressive redshift from LH2 to LH1, ensuring efficient energy transfer to the reaction center special pair.","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141931921","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ultrafast Production of NiCO and Ni Following 197 nm Photodissociation of Nickel Tetracarbonyl","authors":"Neil C. Cole-Filipiak, Jan Troß, Paul Schrader, Laura M. McCaslin, Krupa Ramasesha","doi":"10.1021/acsphyschemau.4c00033","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00033","url":null,"abstract":"Herein, we report on the ultrafast photodissociation of nickel tetracarbonyl─a prototypical metal–ligand model system─at 197 nm. Using mid-infrared transient absorption spectroscopy to probe the bound C≡O stretching modes, we find evidence for the picosecond time scale production of highly vibronically excited nickel dicarbonyl and nickel monocarbonyl, in marked contrast with a prior investigation at 193 nm. Further spectral evolution with a 50 ps time constant suggests an additional dissociation step; the absence of any corresponding growth in signal strongly indicates the production of bare Ni, a heretofore unreported product from single-photon excitation of nickel tetracarbonyl. Thus, by probing the deep UV-induced photodynamics of a prototypical metal carbonyl, this Letter adds time-resolved spectroscopic signatures of these dynamics to the sparse literature at high excitation energies.","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141881714","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}