化学•材料最新文献

{"title":"Picosecond Dexter-Type Energy Transfer in Device-Grade InAs Quantum Dot Films","authors":"Pan Xia, Jiahui Gui, Chengming Nie, Yupeng Yang, Jingyi Zhu, Mostafa. F. Abdelbar, Kaifeng Wu","doi":"10.1021/acs.jpclett.5c00697","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00697","url":null,"abstract":"InAs quantum dots (QDs) have emerged as a promising replacement for highly toxic lead- and mercury-based QDs for infrared optoelectronic devices. In order to understand the performance of InAs QD-devices and exploit their full potential, it is essential to elucidate the mechanisms of exciton migration or energy transfer in the films of InAs QDs, which, however, have remained lacking. Here we investigate exciton transfer dynamics in device-grade InAs QD films used in infrared photodetectors using femtosecond transient absorption spectroscopy. Interdot distances were precisely controlled by using InAs QDs of different sizes capped with ligands of varying lengths. Through minimizing interdot distances with halide ligands, we observed an energy transfer time constant as short as 1.7 ps. The distance dependence of the energy transfer rates was found to follow a Dexter-like mechanism with a damping coefficient of β = 0.31 ± 0.03 Å^–1, which is a relatively small value compared to prior charge/energy transfer studies enabled by the strongly delocalized exciton wave functions of InAs QDs. These results provide hitherto lacking fundamental insights into the energy transfer/migration mechanisms inside device-grade InAs QD films, with direct relevance to optoelectronic devices ranging from photodetectors and solar cells to light-emitting diodes.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"183 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766938","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":"Looking Backward and Forward","authors":"Alec Wodtke","doi":"10.1021/acs.jpcc.5c01323","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01323","url":null,"abstract":"Published as part of <i>The Journal of Physical Chemistry C</i> special issue “Alec Wodtke Festschrift”. have the courage to try new things about which you may be ignorant. do not worry what others think. recognize that you cannot succeed without some luck and remember that 1) and 2) seem to help with 3). Figure 1. <b>My First Building Project.</b> The Experimental setup for the F+HD experiments. The effusive F atom source (6)–I am still proud of it–and the velocity selector (8) produced a slow F atom beam (7) with a narrow velocity spread. The H<sub>2</sub>, D<sub>2</sub>, and HD beams (5) were cooled with liquid nitrogen (3) to achieve best conditions. The small velocity of the F atom beam made the entire scattering map visible in the experiment. Its low intensity also reduced the signal substantially. The project was led by Dan Neumark as part of his Ph.D. thesis work. Figure reprinted from ref (1). with the permission of AIP Publishing. Copyright 1985 AIP Publishing. Figure 2. <b><b>T</b>he first vibrationally state resolved differential scattering distributions of a chemical reaction.</b> Note that HF(v = 3) is scattered forward while HF (v = 2) is scattered backward. Figure reprinted from ref (1). with the permission of AIP Publishing. Copyright 1985 AIP Publishing. Figure 3. <b>The reaction path for nitromethane decomposition:</b> (left) the relative energies of the simple bond rupture reaction and isomerization were deduced from the IRMPD data obtained with the rotating source machine in 1986. Figure reprinted with permission From ref (12). Copyright 1986 American Chemical Society. Those results agree well with (right) electronic structure theory calculations by MC Lin possible in 2013. Figure reprinted with permission from ref (10). Copyright 2013 American Chemical Society. Figure 4. <b>This probably got me tenure:</b> Laser-induced fluorescence spectrum of HCN obtained in the near Vacuum Ultraviolet using a Tunable ArF laser. Once this spectrum had been seen in the lab, stimulated emission transitions quickly followed. Figure reprinted with permission from ref (23). Copyright 1990 Optica Publishing Group. Figure 5. <b>My first beam surface scattering experiment.</b> (left panel) Dick Martin’s instrument. See ref (27). for details. (right panel) The spectrum obtained when monitoring electron emission as a function of laser wavelength. The observed transitions are assigned to the CO Cameron system. This is a way to measure the speed distribution of individual quantum states of molecules. Figures reprinted with permission from ref (27). Copyright 1992 AIP Publishing. Figure 6. <b>Born–Oppenheimer Failure:</b> Electron emission resulting from <i>NO(v = 18)</i> collisions with the Cs/Au(111) surface. Electron emission is detected simultaneously with DUMP laser’s wavelength for two PUMP transitions. We compare these spectra to fluorescence depletion (down-going signal) spectra observed under identical conditions. The observed spectral resonan","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"58 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766981","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Tribute to Alec M. Wodtke","authors":"Hua Guo*, Gerard Meijer* and Xueming Yang*, ","doi":"10.1021/acs.jpcc.5c0132110.1021/acs.jpcc.5c01321","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01321https://doi.org/10.1021/acs.jpcc.5c01321","url":null,"abstract":"","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"129 13","pages":"6059–6061 6059–6061"},"PeriodicalIF":3.3,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758756","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Analogue-Specific Transplacental Transfer of Organophosphate Flame Retardants in ICR Mouse Mediated by Active Transport","authors":"Jiaying Wang, Yongting Li, Jingcun Dong, Shuang Liu, Le Tao, Jia Yin, Qingqing Zhu, Mercè Garí, Chunyang Liao, Guibin Jiang","doi":"10.1021/acs.est.4c14153","DOIUrl":"https://doi.org/10.1021/acs.est.4c14153","url":null,"abstract":"Prenatal exposure to organophosphate flame retardants (OPFRs) may pose potential health risks to offspring. While prior studies have demonstrated that OPFRs can be transferred from mothers to fetuses, the mechanism underlying transplacental transfer remains unclear. The pregnant ICR mouse and JAR cell (a monolayer model), in combination with molecular docking, were used to explore the underlying mechanism. OPFRs were rapidly metabolized into diester metabolites following oral gavage in the ICR mouse, with considerable concentrations detected in maternal serum, amniotic fluid, and placenta, as well as fetus within 3 h. After 6 h, the accumulation ratios of OPFRs between the mother and fetus exhibited a parabolic relationship with log <i>K</i>_OW. Oral exposure resulted in a decrease in interstitial cells in the decidua and an expansion of vascular systems in the labyrinthine area. RT-qPCR analysis revealed upregulated expression levels of transporter mRNA in the placenta, suggesting a protective mechanism characterized by greater efflux than influx transport efficiency. Metabolic inhibitors applied during in vitro transepithelial transport experiments using the JAR cells significantly reduced the transport efficiency, indicating that active transport facilitated the transplacental transport of aryl-OPFRs, with reductions exceeding 50%. Molecular docking analysis indicated that aryl-OPFRs exhibited greater binding affinities to placental transporters compared to other types of OPFRs, with more bonding interactions. These findings offer new insights into the potential health impacts of OPFR exposure and highlight the importance of elucidating their transplacental transport mechanisms.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"31 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766820","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unusual Rearrangement of a 1,8-Naphthalene Derivative","authors":"Asmaa Habib, Estela Sánchez-Santos, Irene Boya del Teso, José J. Garrido-González, Francisca Sanz, Luis Simón, Joaquín R. Morán, Ángel L. Fuentes de Arriba","doi":"10.1021/acs.joc.5c00021","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00021","url":null,"abstract":"The steric strain between nitro and carboxylic acid groups in an 8-nitro-1-naphthoic acid derivative is able to unexpectedly disrupt the aromaticity of the naphthalene core under mild reaction conditions. The addition of H₂O to the aromatic ring of a highly strained naphtho oxazinium intermediate induces the fragmentation of a Csp²–Csp² bond, with a concomitant rearrangement to yield a conjugated aldehyde. Key intermediates have been characterized, and the X-ray structure of the derivative has been obtained. Density functional theory (DFT) studies were performed to confirm the proposed mechanism.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"41 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766875","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":"Advancing Molecular Simulations: Merging Physical Models, Experiments, and AI to Tackle Multiscale Complexity","authors":"Giorgio Bonollo, Gauthier Trèves, Denis Komarov, Samman Mansoor, Elisabetta Moroni, Giorgio Colombo","doi":"10.1021/acs.jpclett.5c00652","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00652","url":null,"abstract":"Proteins and protein complexes form adaptable networks that regulate essential biochemical pathways and define cell phenotypes through dynamic mechanisms and interactions. Advances in structural biology and molecular simulations have revealed how protein systems respond to changes in their environments, such as ligand binding, stress conditions, or perturbations like mutations and post-translational modifications, influencing signal transduction and cellular phenotypes. Here, we discuss how computational approaches, ranging from molecular dynamics (MD) simulations to AI-driven methods, are instrumental in studying protein dynamics from isolated molecules to large assemblies. These techniques elucidate conformational landscapes, ligand-binding mechanisms, and protein–protein interactions and are starting to support the construction of multiscale realistic representations of highly complex systems, ranging up to whole cell models. With cryo-electron microscopy, cryo-electron tomography, and AlphaFold accelerating the structural characterization of protein networks, we suggest that integrating AI and Machine Learning with multiscale MD methods will enhance fundamental understating for systems of ever-increasing complexity, usher in exciting possibilities for predictive modeling of the behavior of cell compartments or even whole cells. These advances are indeed transforming biophysics and chemical biology, offering new opportunities to study biomolecular mechanisms at atomic resolution.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"34 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766937","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":"Looking Backward and Forward","authors":"Alec Wodtke*,&nbsp;","doi":"10.1021/acs.jpca.5c0132410.1021/acs.jpca.5c01324","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c01324https://doi.org/10.1021/acs.jpca.5c01324","url":null,"abstract":"","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 13","pages":"2976–2987 2976–2987"},"PeriodicalIF":2.7,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758808","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":"Strong Photochemical Activity of Colored Microplastics Containing Cadmium Pigments: Mechanisms and Implications","authors":"Xiaojing Mo, Xuxing Lu, Shuxue Yang, Yi Tan, Heyun Fu, Dongqiang Zhu, Xiaolei Qu","doi":"10.1021/acs.est.4c14715","DOIUrl":"https://doi.org/10.1021/acs.est.4c14715","url":null,"abstract":"Plastics used in daily life are often colored for esthetic and functional purposes. Nevertheless, little is known about the photochemical activity of colored microplastics and the associated risks that are ubiquitous in the environment. In this study, we report the strong photochemical activity of microplastics colored with cadmium pigments. These colored microplastics can be excited by photons within the solar spectrum (&lt;514 nm), readily generating •OH, O₂^•–, and H₂O₂. Consequently, they can effectively degrade 17β-estradiol, achieving &gt;91% degradation within 23 h under simulated solar exposure. Among microplastics colored with different cadmium pigments, those with a cadmium pigment S/Se ratio of 2:5 exhibited the highest photoactivity. This is attributed to the narrow band gap, fast charge separation, and efficient charge transfer of the microplastics, as suggested by the energy band, photocurrent, and electrochemical impedance results. Meanwhile, hazardous Cd²⁺ was leached from colored microplastics mainly owing to the oxidation of pigment lattices by photogenerated holes. Our results reveal that microplastics colored with photoactive inorganic pigments behave drastically differently from uncolored counterparts. This highlights the importance of considering pigments as a critical factor for better assessing the environmental fate and risks of colored microplastics and plastic products.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"192 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766851","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"I2-Induced Metal-Free C(sp2)–H Functionalization of Indoles via One-Pot and Two-Step Reaction with 1-(2-Hydroxyphenyl)-propargyl Alcohols: Access to 3-(Benzofuran-3-yl)-1H-indoles","authors":"Yang Zhu, Guisheng Deng","doi":"10.1021/acs.joc.4c03109","DOIUrl":"https://doi.org/10.1021/acs.joc.4c03109","url":null,"abstract":"The I₂-catalyzed reaction of 1-(2-hydroxyphenyl)-propargyl alcohols with indoles and subsequent treatment with K₂CO₃ provided (benzofuran-3-yl)-1<i>H</i>-indoles in good to excellent yields with high regioselectivity. This one-pot and two-step strategy proved to be suitable for a wide range of substrates except for aliphatic alkynyl alcohols as well as the indoles bearing <i>N</i>-protected groups such as the Ts group possessing strong electron-withdrawing feature. The reaction procedure involved a cross-coupling and the construction of a benzofuran framework via 5-<i>exo-dig</i> cyclization.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"33 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766877","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":"Strong Hydrogen Bond Donating Solvents Accelerate the Passerini Three-Component Reaction","authors":"Claudio Ferdeghini, Minghui Wu, Prabhat Ranjan, Martien A. Würdemann, Jan Pyschik, Alexander Mitsos, Eelco Ruijter, Romano V.A. Orru, Thomas Hansen, Jordy M. Saya","doi":"10.1021/acs.joc.5c00236","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00236","url":null,"abstract":"We report enhanced reaction rates of the Passerini reaction (P-3CR) using 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) as a cosolvent. Although alcoholic solvents typically increase the energy barrier of the rate-determining step for the P-3CR, we observed significant rate enhancements even when employing strong hydrogen bond donating (HBD) alcohols as cosolvents. This rate enhancement was observed for most aprotic organic solvents, with the exception of strong hydrogen bond accepting (HBA) solvents such as DMF. Experimental kinetic studies and DFT calculations provided a mechanistic rationale for our observations. An investigation of the substrate scope showed that this rate enhancement generally resulted in a (slight) increase of the overall yield in the P-3CR.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"34 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766878","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}