ACS Publications最新文献

{"title":"Theoretical Insights into Halogen Substitution Effects on Room Temperature Phosphorescence in Twisted Halogenated Tetraphenylene Derivatives.","authors":"Songsong Liu, Huanling Liu, Yang Gao, Lili Lin, Chuan-Kui Wang, Yuzhi Song, Zhen Xie, Jianzhong Fan","doi":"10.1021/acs.jpca.5c01904","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c01904","url":null,"abstract":"<p><p>The introduction of heavy atoms, halogen atoms and heteroatoms into organic room-temperature phosphorescence (RTP) molecules can effectively enhance the spin-orbit coupling (SOC) effect. However, this strategy often simultaneously accelerates both radiative and nonradiative decay rates, significantly reducing the RTP efficiency and lifetime. As a wise molecular design strategy, the synergistic effect between twisted molecular conformations and halogen substitution can overcome the limitations. Therefore, this study aims to provide a theoretical elucidation of the regulatory mechanism underlying this synergistic effect on RTP performance. Building upon this foundation, we employ twisted tetraphenylene (TeP) and its halogenated derivatives (TeP-F, TeP-Cl, and TeP-Br) as model to theoretically investigate their excited-state properties and luminescence mechanisms based on first-principles calculations. Results indicate that, compared with the molecule in solvent, the solid state effect in crystal significantly inhibits the molecular geometry changes, leading to reduced nonradiative decay rates, both RTP efficiency and lifetime are increased. In addition, the increase in the atomic number of halogen substitutions increases the degree of molecular distortion that changes the distribution of electrons within the molecule, increasing the proportion of n-π* transitions, which in turn leads to an enhanced SOC effect and an increased intersystem crossing (ISC) rate. However, heavy halogen atoms excessively enhance the SOC effect and increase the reorganization energy, thereby accelerating the nonradiative decay rate. Consequently, both the lifetime and efficiency do not monotonically increase with the atomic number of halogen substituents. Among these systems, TeP-F molecule is verified to possess high efficiency and long lifetime primarily due to its moderate SOC strength and low nonradiative decay rate. Furthermore, to explore the influence of the number of halogen substitutions, we theoretically construct two new molecular aggregates (difluoro-substituted TeP-2F and tetrafluoro-substituted TeP-4F) using atomic replacement in the TeP-F crystal framework for ONIOM models. The results indicate that the SOC effect is enhanced compared with that of TeP-F, while the RTP performance is not improved due to the remarkably increased nonradiative decay rate. This study theoretically elucidates the influence of the type and number of halogen substitutions on the RTP performance of twisted halogenated TeP derivatives, providing important theoretical insights for the design of efficient, long-persistent pure organic RTP materials.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232630","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":"l-Lactate Oxidase-Based Biosensor Enables Quasi-Calibration-Free Detection of l-Lactate in Sweat of Acidic to Neutral pH.","authors":"Kosuke Ike, Kousuke Muto, Takahiro Hioki, Noya Loew, Isao Shitanda, Masafumi Takesue, Mitsuyoshi Okuda","doi":"10.1021/acssensors.5c01238","DOIUrl":"https://doi.org/10.1021/acssensors.5c01238","url":null,"abstract":"<p><p>l-lactate biosensing has attracted attention in recent years in sports, medicine, and nursing care fields as well as in food manufacturing and biotechnology industries. In particular, l-lactate in human sweat, a biological indicator that can be collected noninvasively, has driven rapid progress in the research and development of sensing technology, positioning sweat as a new target to replace blood and interstitial fluid. The key to l-lactate sensing in human sweat, which contains various biological components, is using l-lactate oxidase (LOX) as a recognition element. l-lactate can be specifically, continuously, and quantitatively measured using this enzyme electrode. However, as conventional LOX is affected by acidic pH, biosensors must be calibrated for each individual for accurate l-lactate quantification owing to individual differences in sweat pH. Furthermore, fluctuations in sweat pH during exercise lead to inaccuracies in the detected l-lactate levels. Therefore, identifying LOX active in acidic pH is crucial. Here, we report a novel LOX with acidic pH tolerance and a technology that enables constant detection of l-lactate levels in acidic to neutral pH sweat. Phylogenetic analysis of α-hydroxy acid oxidase in a public protein database, with the evaluation of heterologously expressed enzymes, revealed the existence of a novel LOX with better acidic pH tolerance compared to that observed with conventional LOX. Furthermore, applying the novel LOX to a paper electrode screen-printed with MgO-templated carbon enhanced the l-lactate response at acidic pH compared to that observed with conventional enzyme electrodes while maintaining a pH-independent response to l-lactate. Overall, biosensors utilizing this novel LOX will be quasi-calibration-free, by eliminating the need for adjusting the calibration according to changes in pH. Thus, our findings contribute to expanding the use of l-lactate biosensors targeting sweat and accelerating their societal application.</p>","PeriodicalId":24,"journal":{"name":"ACS Sensors","volume":" ","pages":""},"PeriodicalIF":8.2,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232641","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ginsenoside Rh2 Exerts a Therapeutic Effect against Myocardial Infarction via Promoting Angiogenesis and Mitochondrial Bioenergetics.","authors":"Zikun Duan, Baohong Yuan, Hongbin Li, Jun Yang, Xiaoqiu Xiao, Ke Wei","doi":"10.1021/acs.jafc.5c00479","DOIUrl":"https://doi.org/10.1021/acs.jafc.5c00479","url":null,"abstract":"<p><p>Ginsenoside Rh2 (Rh2), an important phytochemical derived from <i>Panax ginseng</i>, has demonstrated anticancer activity, amelioration of ischemic brain injury, and mitigation of doxorubicin-induced cardiac damage. The cardioprotective effects of Rh2 were evaluated in a mouse model of acute myocardial infarction (AMI). Mice received Rh2 treatment for 14 days postsurgery, and the cardiac function was assessed by echocardiography. Rh2 treatment significantly improved left ventricular function, reduced infarct size, and suppressed cardiac fibrosis in the MI model. Furthermore, it promoted angiogenesis in the border zone, enhanced mitochondrial membrane potential and ATP production, and reduced hypoxia-induced ROS accumulation, excessive mitochondrial fission, and cardiomyocyte apoptosis. In vitro, Rh2 enhanced human umbilical vein endothelial cell (HUVEC) migration in wound-healing assays, an effect associated with an increased level of ERK phosphorylation. These effects were abolished by U0126, an ERK inhibitor. In conclusion, Rh2 protects against MI-induced cardiac injury by improving mitochondrial bioenergetics and activating an ERK-dependent pathway.</p>","PeriodicalId":41,"journal":{"name":"Journal of Agricultural and Food Chemistry","volume":" ","pages":""},"PeriodicalIF":5.7,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232662","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"农林科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Path-Based Nonequilibrium Binding Free Energy Estimation, from Protein-Ligand to RNA-Ligand Binding.","authors":"Eleonora Serra, Alessia Ghidini, Riccardo Aguti, Mattia Bernetti, Sergio Decherchi, Andrea Cavalli","doi":"10.1021/acs.jcim.5c00452","DOIUrl":"https://doi.org/10.1021/acs.jcim.5c00452","url":null,"abstract":"<p><p>In this study, we addressed the challenge of estimating binding free energies in complex biological systems of pharmaceutical relevance, including both protein-ligand and RNA-ligand complexes. As case studies, we examined the intricate binding of the drug Gleevec to Abl-tyrosine kinase and two ligands binding to the preQ1 RNA riboswitch. By refining our approach based on nonequilibrium steered molecular dynamics simulations and path-based collective variables, we tackled the specific difficulties posed by these systems. In particular, the Abl-Gleevec complex is characterized by significant system size and extensive conformational rearrangements of the protein, whereas the systems involving RNA are characterized by marked conformational flexibility. For the Abl-Gleevec system, our method produced binding free energy estimates closely aligned with experimental values, demonstrating its reliability. For the RNA-ligand complexes investigated, we found that the simpler water model TIP3P yields more accurate free energy estimates than the TIP4P-D model, offering practical insight for future research. In this case, the agreement with the experimental results is reasonable. Overall, this work underscores the effectiveness of the proposed path-based workflow in handling complex biomolecular systems with unique characteristics, enabling systematic binding free energy predictions across a variety of targets.</p>","PeriodicalId":44,"journal":{"name":"Journal of Chemical Information and Modeling ","volume":" ","pages":""},"PeriodicalIF":5.6,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232672","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":"Efficacy Evaluation and Mechanism Study of Nonantibiotic Nanoplatform for Clearing MRSA.","authors":"Xiangjun Chen, Xinzhong Zhang, Qing Fan, Menglin Cao, Sai Zhang, Wenting Li, Rui Ma, Xiuping Zhang, Wei Hong","doi":"10.1021/acs.molpharmaceut.5c00097","DOIUrl":"https://doi.org/10.1021/acs.molpharmaceut.5c00097","url":null,"abstract":"<p><p>The effective treatment of infections induced by biofilms has remained a substantial challenge in clinical practice. Presently, there is an imperative demand for innovative antimicrobial strategies that can not only eliminate biofilms but also incorporate controlled delivery and intelligent release mechanisms. In this research, the charge-reversible nonantibiotic nanodelivery system (MPDA/AuNCs/ICG@Lip NPs) is synthesized. Initially, AuNCs and indocyanine green (ICG) were introduced onto MPDA NPs via adsorption and mesoporous loading, followed by the modification of the phospholipids on the exterior surface. Within the biofilm microenvironment, the surface charge was reversed, thereby improving its affinity for methicillin-resistant <i>Staphylococcus aureus</i> (MRSA) and facilitating enhanced biofilm permeability. Owing to the ultrasmall AuNCs, they were internalized by the bacteria and, in conjunction with ICG, contributed to the elevation of local ROS concentrations under the 808 nm laser. As anticipated, the <i>in vitro</i> findings confirmed that MPDA/AuNCs/ICG@Lip NPs demonstrated superior biofilm-clearing capabilities and antibacterial effect. <i>In vivo</i> experiments corroborated that MPDA/AuNCs/ICG@Lip NPs successfully targeted the cyst site and remained localized for an extended period, resulting in excellent therapeutic efficacy. This discovery offers a novel perspective for the development of nonantibiotic nanoplatform for clearing MRSA.</p>","PeriodicalId":52,"journal":{"name":"Molecular Pharmaceutics","volume":" ","pages":""},"PeriodicalIF":4.5,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232686","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Lithography-Defined Semiconductor Moirés with Anomalous In-Gap Quantum Hall States.","authors":"Wei Pan, D Bruce Burckel, Catalin D Spataru, Keshab R Sapkota, Aaron J Muhowski, Samuel D Hawkins, John F Klem, Layla S Smith, Doyle A Temple, Zachery A Enderson, Zhigang Jiang, Komalavalli Thirunavukkuarasu, Li Xiang, Mykhaylo Ozerov, Dmitry Smirnov, Chang Niu, Peide D Ye, Praveen Pai, Fan Zhang","doi":"10.1021/acs.nanolett.5c02180","DOIUrl":"https://doi.org/10.1021/acs.nanolett.5c02180","url":null,"abstract":"<p><p>Quantum materials and phenomena have attracted great interest for their potential applications in next-generation microelectronics and quantum-information technologies. In one especially interesting class of quantum materials, moiré superlattices (MSLs) formed by twisted bilayers of 2D materials, a wide range of novel phenomena are observed. However, there exist daunting challenges such as reproducibility and scalability of utilizing 2D MSLs for microelectronics and quantum technologies due to their exfoliate-tear-stack method. Here, we propose lithography-defined semiconductor MSLs, in which three fundamental parameters─electron-electron interaction, spin-orbit coupling, and band topology─are designable. We experimentally investigate quantum-transport properties in a moiré specimen made in an InAs quantum well. Strong anomalous in-gap states are observed within the same integer quantum Hall state. Our work opens up new horizons for studying 2D quantum-materials phenomena in semiconductors featuring superior industry-level quality and state-of-the-art technologies, and they may potentially enable new quantum-information and microelectronics technologies.</p>","PeriodicalId":53,"journal":{"name":"Nano Letters","volume":" ","pages":""},"PeriodicalIF":9.6,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232693","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Alkali-Metal-Catalyzed Deprotonative Addition of Toluenes with Styrenes.","authors":"Yuanyun Gu, Yufei Zhang, Yaqi Yuan, Yan-En Wang, Dan Xiong, Jianyou Mao","doi":"10.1021/acs.orglett.5c01842","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c01842","url":null,"abstract":"<p><p>A LiN(SiMe₃)₂/CsF-catalyzed benzylic C-H bond addition of toluene to styrene is reported, which enables the functionalization of weakly acidic C-H bonds (p<i>K</i>_a ≈ 43) with high efficiency and a broad substrate scope. This method overcomes the limitations of traditional strong base systems by utilizing a bimetallic catalyst that reversibly deprotonates benzylic positions, achieving yields of 62-89% across 34 examples. Key advantages include excellent functional group tolerance, scalability, and operational simplicity. Mechanistic studies, supported by kinetic isotope effects, confirm that benzylic deprotonation is the turnover-limiting step.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":" ","pages":""},"PeriodicalIF":4.9,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232702","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Collective Biomimetic Synthesis of Myrcaulones A and C and Myrcauones B-D.","authors":"Zi-Jian Peng, Zhi-Zhang Duan, Xiao-Xia Chen, Wang-Ling Fang, Yi-Fan Liu, Zi-Zhe Cai, Jian-Guo Song, Xiao-Jun Huang, Wen-Cai Ye, Ying Wang, Li-Jun Hu","doi":"10.1021/acs.orglett.5c01758","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c01758","url":null,"abstract":"<p><p>We report the first collective biomimetic synthesis of noncanonical phloroglucinol derivatives myrcaulones A (<b>1</b>) and C (<b>3</b>), featuring a unique ring-contracted phloroglucinol skeleton, along with three biosynthetically related canonical phloroglucinol derivatives myrcauones B-D (<b>4</b>-<b>6</b>). These compounds were synthesized in only 6-9 steps, starting from the commercially available 3,4,5-trimethoxyphenol. Key features of the synthetic strategy include a <i>hetero</i>-Diels-Alder reaction to construct the canonical phloroglucinol framework and an α-ketol rearrangement-driven ring contraction reaction to form the noncanonical phloroglucinol skeleton.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":" ","pages":""},"PeriodicalIF":4.9,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232704","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enantioselective Synthesis of Highly Functionalized 2,3-Dihydrobenzofuran Derivatives via Steric Hindrance-Overcoming Strategy.","authors":"Dong-Qun Huang, Shi-Ying Wu, Hui Zhang, Jian-Qiang Zhao, Yong You, Yan-Ping Zhang, Lei Yang, Zhen-Hua Wang, Wei-Cheng Yuan","doi":"10.1021/acs.joc.5c00764","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00764","url":null,"abstract":"<p><p>The asymmetric cycloaddition reaction of <i>p</i>-quinone monoimides is a significant research focus for constructing benzofused heterocycles. However, due to steric effects, achieving efficient cycloaddition at highly sterically hindered site is challenging but practically valuable. Herein, we develop an asymmetric [3 + 2] cycloaddition reaction of <i>p</i>-quinone monoimides with 1-vinylnaphthalen-2-ols and 3-vinylindoles via steric hindrance-overcoming strategy. Binaphthalene-based chiral phosphoric acid catalyzes the asymmetric cycloaddition reaction to synthesize highly functionalized 2,3-dihydrobenzofurans in generally good yields with good to excellent stereoselectivities.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":" ","pages":""},"PeriodicalIF":3.3,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144232625","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":"Metaproteomics as a Powerful Tool for an Extensive Characterization of Ambient Bioaerosols.","authors":"Mathieu Galmiche, Lauriane Kuhn, Maurice Millet, Yannis-Nicolas François","doi":"10.1021/acs.jproteome.4c00936","DOIUrl":"10.1021/acs.jproteome.4c00936","url":null,"abstract":"<p><p>Bioaerosols are of great health and environmental concern. Current techniques for their characterization are generally designed to detect individual species or oppositely unspecific molecular tracers. Metaproteomics on the other hand features the possibility to cover a broad range of taxonomies in a single analysis. This work presents a successful application of metaproteomics to characterize the biological fraction of airborne particulate matter (PM). A bottom-up proteomic strategy was employed, including protein extraction by ultrasonication in aqueous buffer, in-solution tryptic digestion, and nanoflow liquid chromatography-high-resolution mass spectrometry analysis. Extraction parameters were optimized to enhance proteins' recovery. The method was validated on <i>Escherichia coli</i> extracts before its application on ambient PM₁₀ samples collected over 12 weeks in Strasbourg, France. A total of 1,087 peptides were detected across all samples, with a weekly average of 223 ± 104 peptides corresponding to 111 ± 40 proteins. Peptides from species belonging to animals, plants, fungi, bacteria, and archaea kingdoms were inventoried. Many of them proved to be very relevant, as they were related to human allergens and pathogens, plant pathogens, or ecological indicators. In this work, the major benefits of metaproteomics, yet rather unexploited, as well as its pitfalls and challenges for a broader application in atmospheric chemistry, are discussed.</p>","PeriodicalId":48,"journal":{"name":"Journal of Proteome Research","volume":" ","pages":"2657-2674"},"PeriodicalIF":3.8,"publicationDate":"2025-06-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144118408","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}