化学•材料最新文献

{"title":"Distal Heteroaryl Ipso-Migration of Unactivated Alkenes via Cobalt/Photoredox-Catalyzed Hydrogen/Deuterium Atom Transfer.","authors":"Masaaki Yamashita, Akihiko Suzuki, Tatsuhiko Yoshino, Kosuke Higashida, Masahiro Kojima, Shigeki Matsunaga","doi":"10.1002/asia.202500448","DOIUrl":"https://doi.org/10.1002/asia.202500448","url":null,"abstract":"<p><p>A structural isomerization of alkenyl alcohols via 1,4- or 1,5-heteroaryl migration initiated by metal-hydride hydrogen atom transfer (MHAT) under cobalt/photoredox dual catalysis is described. The remote migration method provided various heteroaryl-containing ketones inaccessible through conventional MHAT 1,2-migration pathways. The cobalt/photoredox catalysis was further applied to the synthesis of deuterium-labeled heteroaryl-containing ketones.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00448"},"PeriodicalIF":3.5,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144223824","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":"Effects of Bases on the Mechanism of Ag(I)-Catalyzed Selectivity of CO₂ Incorporation into Conjugated Ynones: A Computational Study.","authors":"Binfang Yuan, Junyi Ma, Guangzhao Wang, Xiaogang Guo, Huisheng Huang, Jinyang Chen, Bing Li, Rongxing He","doi":"10.1002/asia.202401903","DOIUrl":"https://doi.org/10.1002/asia.202401903","url":null,"abstract":"<p><p>The mechanisms of AgOAc-catalyzed CO₂ incorporation into conjugated ynones are studied using density functional theory (DFT) calculations to explore the selectivity of reaction (5-exo-dig P1 versus 6-endo-dig P2) and to understand the effects of bases (MTBD versus TMG versus DMAP) on the reactions. The bases have the function of proton-shuttle, assisting the transfer of H1 (H2) from C4 (C4) to C1 (O1) by the four-step proton-transfer strategy. More importantly, the differences of base strength are revealed to be the primary factor that determines the catalytic activities of MTBD, TMG, and DMAP, and the order of catalytic activity is MTBD > TMG > DMAP, which does match with the increased trend of base strength MTBD > TMG > DMAP. Moreover, the selectivity of Ag(I)-catalyzed reaction is controlled via the intramolecular cyclization to selectively generate 5-exo-dig P1, which could be reasonably explained by the analysis of electronic interactions and bond lengths on the base of theoretical calculations. In a word, the studies provide indispensable understanding for the transition-metals catalyzed CO₂ conversion with assistance of bases to synthesize various high-value chemicals.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e01903"},"PeriodicalIF":3.5,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144223825","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":"Chiral Orbital Modifying Dipolar Polarization and Recombination in Chiral Perovskites.","authors":"Yuan Yu, Xiangping Zhao, Chenghao Liu, Zhiyong Pang, Wei Qin","doi":"10.1021/acs.jpclett.5c01227","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c01227","url":null,"abstract":"<p><p>The chiral spatial structure of chiral perovskite materials enriches the physical and optical properties of perovskite materials, making them an excellent platform to deeply understand charge-spin-photon interactions. In this work, we fabricated chiral perovskite crystals and their nonchiral isomeric counterparts. The significant differences in the crystal structures of these two types of materials lead to notable variations in their fluorescence lifetimes and electron-phonon coupling strength, which present an externally presentable change in physical properties, such as the dielectric constant. Moreover, inside chiral structures, the chiral orbit should be taken into account. Under the effect of a magnetic field versus a chiral orbit, dipolar polarization and charge recombination will be rebalanced after disruption, where the dielectric constants and photoluminescence intensities of the S- and R-type chiral perovskites display opposite trends. It is also noted that chiral orbit-induced spin relaxation determined the spin dependence of recombination, which presents a potential materials platform to fabricate devices resisting external signal interference well.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"5912-5917"},"PeriodicalIF":4.8,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232635","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":"Correction to \"Identifying Allosteric Hotspots in <i>Mycobacterium tuberculosis</i> cAMP Receptor Protein through Structural Homology\".","authors":"Stephen P Dokas, Daniel K Taylor, Lydia L Good, Sanuja Mohanaraj, Anna Park, Rodrigo A Maillard","doi":"10.1021/acs.biochem.5c00102","DOIUrl":"https://doi.org/10.1021/acs.biochem.5c00102","url":null,"abstract":"","PeriodicalId":28,"journal":{"name":"Biochemistry Biochemistry","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232647","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synthesis of SeCF₃-Substituted Oxazines and Oxazolines through Electrophilic Trifluoromethylselenolation Cyclization of Propargylic Amides.","authors":"Jia Wang, Jia-Qi Niu, Jia-Cheng Li, Lixia Liu, Xuefang Shang, Ping-Xin Zhou, Shujun Chao","doi":"10.1021/acs.joc.5c00930","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00930","url":null,"abstract":"<p><p>The electrophilic trifluoromethylselenolation cyclizations of propargylic amides are disclosed. The transformations undergo the 6-<i>endo</i>-dig and 5-<i>exo</i>-dig cyclizations to synthesize SeCF₃-substituted oxazines and oxazolines, respectively, which are induced by <i>N</i>-trifluoromethylselenophthalimide. This protocol is suitable for late-stage applications of complex natural products and drug molecules.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232628","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":"A systematic review of the intersection between energy justice and human rights","authors":"Chioma Vivian Basil ,&nbsp;Raphael Heffron","doi":"10.1016/j.rser.2025.115892","DOIUrl":"10.1016/j.rser.2025.115892","url":null,"abstract":"<div><div>This article systematically reviews the relationship between energy justice and human rights, recognising the shared responsibility of equity, inclusivity, respect, acknowledgement, and accountability for historical injustices. The energy justice theory is applied to checkmate the activities of the energy sector through the energy chain to manage its adverse impact on the environment and communities. This is anchored on five principles of distributional, procedural, recognition, restorative, and cosmopolitan justice principles. These principles are equally advocated for in the human rights framework to ensure universal energy access for well-being and a healthy environment. Therefore, this article explores how these energy justice and human rights principles have converged in the energy sector to tackle energy poverty, environmental degradation, community rights violations, and accountability concerns. The aim being to establish an intersection between the justice of energy activities and fundamental rights across academic journals and policy materials. Thus, by utilising a method of systematic review, this article analyses research materials spanning from January 2000 to October 2024. To understand the evolution of the relationship between human rights and energy justice, reflecting shifts in priorities and responses to contemporary issues. In this review, we find that very few studies have begun analysing human rights violations of energy activities as an energy justice concern. Therefore, this systematic review offers insights into creating a sustainable, accountable, and equitable energy system devoid of fundamental rights violations; through inclusive energy policies and implementation mechanisms that prioritize the rights, and well-being of vulnerable populations.</div></div>","PeriodicalId":418,"journal":{"name":"Renewable and Sustainable Energy Reviews","volume":"221 ","pages":"Article 115892"},"PeriodicalIF":16.3,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144223173","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Correction to \"High-Level Calculation for Assessing the Atmospheric Reactivity of Pentachlorophenol with Hydroxyl Radical: Mechanism and Kinetics\".","authors":"Nissrin Alharzali, Ivan Černušák, Hisham K Al Rawas, Sonia Taamalli, Abderrahman El Bakali, Florent Louis, Duy Quang Dao","doi":"10.1021/acs.jpca.5c02803","DOIUrl":"10.1021/acs.jpca.5c02803","url":null,"abstract":"","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"4968"},"PeriodicalIF":2.7,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144118337","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":"Low-Energy Isomers of the Magic Number H⁺(H₂O)₂₁ Cluster.","authors":"T-H Choi, E V Henderson, K D Jordan","doi":"10.1021/acs.jpca.5c01977","DOIUrl":"10.1021/acs.jpca.5c01977","url":null,"abstract":"<p><p>Electronic structure calculations are used to characterize low-energy isomers of H⁺(H₂O)₂₁. Eleven different classes of isomers, based on the (H₂O)₂₀ pentagonal dodecahedron with the excess proton localized on the surface (as a hydrated hydronium ion) and the \"extra\" water molecule located in the interior of the cluster, are characterized. In 10 of these classes, the internal water molecule is engaged in six 5-membered rings, but in the remaining class, which is predicted to start at only 0.6 kcal/mol above the global minimum, the internal water is engaged in a 4-membered ring, an additional 6-membered ring, and four 5-membered rings. In addition, isomers with two 4-membered rings and two 6-membered rings on the cluster surface are predicted to start at only ∼1.3 kcal/mol above the lowest-energy dodecahedral-based structure.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"4927-4935"},"PeriodicalIF":2.7,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144118339","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":"Oxygen Dependence on Hydrated Electron Yields: Pulsed Radiolysis Studies Using Proton Beams.","authors":"Sarra Terfas, Guillaume Blain, Emeline Craff, Charbel Koumeir, Ferid Haddad, Freddy Poirier, Gregory Delpon, Johan Vandenborre","doi":"10.1021/acs.jpca.5c00629","DOIUrl":"10.1021/acs.jpca.5c00629","url":null,"abstract":"<p><p>Understanding the yield and kinetics of the hydrated electron (e^-_aq) is critical for applications in both biological and chemical systems, especially in the context of innovative FLASH radiation therapy. Most studies have employed chemical scavenging methods to measure radical yields. Although these techniques have undeniable advantages, such as probing early processes down to nanosecond time scale, and are easy to implement, they also have significant limitations. The main one is that they are not appropriate to longer time scales, especially the microsecond one, which is a key part of the homogeneous chemistry stage. Direct measurements of hydrated electron using pulsed ion beams are rare, especially with lighter particles such as protons used in radiotherapy, mainly due to instrumental complexity. This study addresses this gap by employing a dedicated time-resolved UV-visible absorption spectrometer coupled to a pulsed ion beam to measure transient hydrated electron radiolytic yield (<i>G</i>-value) in pure water, under both aerated and deaerated conditions. Pulsed radiolysis experiments were conducted at the Arronax cyclotron facility (Nantes, France) with a 68 MeV extracted H⁺ ion beam under ultra-high-dose rate (UHDR) conditions. The pulsed proton beam provides a radiolytic yield at <i>t</i> = 2 μs as well as e^-_aq formation and decay times. The results present the following track segment (TS) yields <b><i>G</i></b>_{<b>TS_2μ<i>s</i></b>}(e^-_aq) = (1.00 ± 0.17) × 10^-7 mol·J^-1 under deaerated conditions (≤0.04% O₂) with a half-life of 8.8 ± 1.5 μs, and <b><i>G</i></b>_{<b>TS_2μ<i>s</i></b>}(e^-_aq) = (0.90 ± 0.20) × 10^-7 mol·J^-1, <b><i>G</i></b>_{<b>TS_2μ<i>s</i></b>}(e^-_aq) = (0.62 ± 0.24)×10^-7 mol·J^-1, and <b><i>G</i></b>_{<b>TS_2μ<i>s</i></b>}(e^-_aq) = (0.13 ± 0.04) × 10^-7 mol·J^-1 under oxygen concentrations of 0.4, 1, and 21% O₂, respectively. These results represent the yields measured directly at the homogeneous chemistry stage, without the use of scavengers, and offer new data within several oxygen contents, allowing a better understanding of the dependence of oxygen on <i>G</i>_TS(e^-_aq). They are essential to explore UHDR chemistry dedicated to FLASH radiation therapy and to produce reliable data to validate Monte Carlo codes, such as Geant4-DNA and Topas-nBio.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":"4861-4869"},"PeriodicalIF":2.7,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144118341","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":"Formation and Disruption of Hydrogen Bond in 1-Ethyl-3-methylimidazolium Ethylsulfate and Glycerol Binary Mixtures: A Molecular Perspective.","authors":"Md Ahad Ali, Md Abu Bin Hasan Susan","doi":"10.1021/acs.jpcb.5c01519","DOIUrl":"10.1021/acs.jpcb.5c01519","url":null,"abstract":"<p><p>This study focuses on the hydrogen bonding interactions that govern the physicochemical properties of the binary mixtures of 1-ethyl-3-methylimidazolium ethylsulfate ([C₂mim]C₂H₅SO₄) and glycerol. Various thermodynamic properties of [C₂mim]C₂H₅SO₄ and glycerol mixtures were investigated by using density and viscosity across a range of compositions and temperatures, while structural properties were explored by using temperature-dependent near-infrared (NIR) spectroscopy, two-dimensional (2D) correlation spectroscopy, and principal component analyses (PCA). In order to better understand hydrogen bonding interactions, both analyses were employed. The NIR spectroscopic analysis shows the presence of various types of hydrogen-bonded clusters in the structure of glycerol and a strong hydrogen bond between the hydrogen of the imidazole ring and the oxygen of ethylsulfate anions. In the binary mixtures, hydrogen-bonded clusters of glycerol were sustained upon addition of [C₂mim]C₂H₅SO₄ up to a mole fraction of 0.6. Further addition of [C₂mim]C₂H₅SO₄ causes breakdown of the cluster of glycerol and forms solvated ions of [C₂mim]C₂H₅SO_4. The variation of excess molar volume, dynamic viscosity deviation, excess molar Gibbs free energy of activation, and thermodynamic activation parameters also show transitions at this particular composition. Hence, the dynamic interaction between the formation and disruption of hydrogen bonds in these compounds controls the thermodynamic properties, which is the key factor to apply this binary system in various fields.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"5541-5549"},"PeriodicalIF":2.8,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144126234","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}