ACS Physical Chemistry Au最新文献

{"title":"Ultrafast Spin Relaxation of Charge Carriers in Strongly Quantum Confined Methylammonium Lead Bromide Perovskite Magic-Sized Clusters","authors":"David C. Zeitz,&nbsp;Vivien L. Cherrette,&nbsp;Sarah A. Creech,&nbsp;Yan Li,&nbsp;Yuan Ping and Jin Z. Zhang*,&nbsp;","doi":"10.1021/acsphyschemau.4c0005110.1021/acsphyschemau.4c00051","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00051https://doi.org/10.1021/acsphyschemau.4c00051","url":null,"abstract":"<p >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.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"4 6","pages":"610–614 610–614"},"PeriodicalIF":3.7,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00051","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142719287","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":"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":"203 1","pages":""},"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*,&nbsp;Karin Kornmueller,&nbsp;Rim Dannaoui,&nbsp;Ejona Syla and Annalisa Pastore*,&nbsp;","doi":"10.1021/acsphyschemau.4c0002910.1021/acsphyschemau.4c00029","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00029https://doi.org/10.1021/acsphyschemau.4c00029","url":null,"abstract":"<p >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.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"4 6","pages":"593–597 593–597"},"PeriodicalIF":3.7,"publicationDate":"2024-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00029","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142713736","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":"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":"69 1","pages":""},"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,&nbsp;Dalete Araújo de Souza,&nbsp;Rubens Lucas de Freitas Filho,&nbsp;Ana Paula de Carvalho Teixeira,&nbsp;Rochel Montero Lago,&nbsp;Walter Ricardo Brito,&nbsp;Edgar Alves Araújo Junior,&nbsp;Litiko Lopes Takeno,&nbsp;Francimauro Sousa Morais,&nbsp;José Fábio de Lima Nascimento,&nbsp;Yurimiler Leyet Ruiz,&nbsp;Libertalamar Brilhalva Saraiva and Francisco Xavier Nobre*,&nbsp;","doi":"10.1021/acsphyschemau.4c0003810.1021/acsphyschemau.4c00038","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00038https://doi.org/10.1021/acsphyschemau.4c00038","url":null,"abstract":"<p >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.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"4 6","pages":"632–646 632–646"},"PeriodicalIF":3.7,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00038","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142719285","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":"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":"12 1","pages":""},"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,&nbsp;Robert M. Dalgliesh,&nbsp;Virginia C. Ferreira,&nbsp;Charlotte Beebee,&nbsp;Erik Watkins,&nbsp;A. Robert Hillman*,&nbsp;Karl S. Ryder,&nbsp;Emma L. Smith and Nina-Juliane Steinke,&nbsp;","doi":"10.1021/acsphyschemau.4c0005510.1021/acsphyschemau.4c00055","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00055https://doi.org/10.1021/acsphyschemau.4c00055","url":null,"abstract":"<p >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.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"4 6","pages":"615–619 615–619"},"PeriodicalIF":3.7,"publicationDate":"2024-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00055","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142713751","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":"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":"77 1","pages":""},"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*,&nbsp;Sayan Maity and Ulrich Kleinekathöfer,&nbsp;","doi":"10.1021/acsphyschemau.4c0006910.1021/acsphyschemau.4c00069","DOIUrl":"https://doi.org/10.1021/acsphyschemau.4c00069https://doi.org/10.1021/acsphyschemau.4c00069","url":null,"abstract":"<p >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>.</p>","PeriodicalId":29796,"journal":{"name":"ACS Physical Chemistry Au","volume":"5 1","pages":"47–61 47–61"},"PeriodicalIF":3.7,"publicationDate":"2024-08-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphyschemau.4c00069","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143084803","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":"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":"13 1","pages":""},"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}