ACS Publications最新文献_第9页

Atmospheric Degradation Mechanism of Isoamyl Acetate Initiated by OH Radicals and Cl Atoms Revealed by Quantum Chemical Calculations and Kinetic Modeling. 通过量子化学计算和动力学建模揭示 OH 自由基和 Cl 原子引发的醋酸异戊酯大气降解机理。

IF 2.7 2区化学

The Journal of Physical Chemistry A Pub Date : 2024-09-24 DOI: 10.1021/acs.jpca.4c05204

Aulia Sukma Hutama, Lala Adetia Marlina, Muhammad Bahy Akram, Karna Wijaya, Reka Mustika Sari, Wahyu Dita Saputri

{"title":"Atmospheric Degradation Mechanism of Isoamyl Acetate Initiated by OH Radicals and Cl Atoms Revealed by Quantum Chemical Calculations and Kinetic Modeling.","authors":"Aulia Sukma Hutama, Lala Adetia Marlina, Muhammad Bahy Akram, Karna Wijaya, Reka Mustika Sari, Wahyu Dita Saputri","doi":"10.1021/acs.jpca.4c05204","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c05204","url":null,"abstract":"Isoamyl acetate is one of the volatile organic compound class molecules relevant to agricultural and industrial applications. With the growing interest in isoamyl acetate applications in industry, the atmospheric fate of isoamyl acetate must be considered. Reaction mechanisms, potential energy profiles, and rate constants of isoamyl acetate reaction with atmospheric relevant oxidant OH radicals and Cl atoms have been obtained from the quantum chemical calculations and kinetic modeling. The geometry optimizations were conducted using M06-2X/6-311++G(3df,3pd) followed by single point-energy calculations at the DLPNO-CCSD(T) method with an extrapolated complete basis set. The rate constants were calculated by solving the master equation. A hydrogen-abstraction reaction dominates the first step of isoamyl acetate degradation, while the addition-substitution reaction plays a small role in the degradation products. The kinetic study was conducted to evaluate the rate constants within a temperature range of 200-400 K. The total rate constants for the isoamyl acetate degradation reactions initiated by the OH radical and Cl atom were determined to be 6.96 × 10-12 and 1.27 × 10-10 cm3 molecule-1 s-1, respectively, under standard temperature and pressure conditions. The product degradation mechanism, ozone formation potential, and atmospheric impacts were discussed.","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306631","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}

引用次数: 0

Hypoxia-Responsive Biomimetic Nanobubbles for Oxygen Delivery Promote Synergistic Ischemic Stroke Protection. 缺氧反应性仿生纳米气泡输送氧气促进缺血性脑卒中的协同保护作用

IF 8.3 2区材料科学

ACS Applied Materials & Interfaces Pub Date : 2024-09-24 DOI: 10.1021/acsami.4c11009

Mingxi Li, Lijun Miao, Xuan Xu, Yang Liu, Yakun Wang, Fang Yang

{"title":"Hypoxia-Responsive Biomimetic Nanobubbles for Oxygen Delivery Promote Synergistic Ischemic Stroke Protection.","authors":"Mingxi Li, Lijun Miao, Xuan Xu, Yang Liu, Yakun Wang, Fang Yang","doi":"10.1021/acsami.4c11009","DOIUrl":"https://doi.org/10.1021/acsami.4c11009","url":null,"abstract":"Effective, precise, and controllable oxygen delivery is crucial for regulating the oxygenation balance of brain tissue at the early stages of acute ischemic stroke (AIS) because the absence of oxygen may result in a series of highly interconnected vascular-neural pathological events, including oxidative stress, inflammation, and neuroapoptosis. In this study, platelet membrane-reassembled oxygen nanobubbles (PONBs) were constructed for oxygen delivery to protect AIS. Benefiting from the preserved natural targeting ability of platelet membranes, oxygen can be controlled release into the hypoxia lesion at the preperfusion stage due to vascular injury targeting and oxygen sustained diffusion capability after PONBs administration. Furthermore, synergizing with bioactive components carried by platelet membranes, PONBs can inhibit post-AIS vascular occlusion and maintain blood-brain barrier integrity, thereby facilitating enhanced oxygen delivery of PONBs, establishing a positive feedback loop between oxygen delivery and AIS protection. Additionally, the accumulation of PONBs enhances the ultrasound imaging contrast, enabling precise localization and dynamic monitoring of AIS lesions. Thus, PONBs represent a promising strategy for the diagnosis and treatment of AIS.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":null,"pages":null},"PeriodicalIF":8.3,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306541","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Capturing Different Intermediate Phases during Zeolite Synthesis. 在沸石合成过程中捕捉不同的中间相。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-09-24 DOI: 10.1021/jacs.4c07414

Jinjin Zeng, German Sastre, Suk Bong Hong

{"title":"Capturing Different Intermediate Phases during Zeolite Synthesis.","authors":"Jinjin Zeng, German Sastre, Suk Bong Hong","doi":"10.1021/jacs.4c07414","DOIUrl":"https://doi.org/10.1021/jacs.4c07414","url":null,"abstract":"Despite extensive efforts over the past several decades, the current mechanistic understanding of zeolite crystallization is still far from satisfactory, thus precluding the synthesis of designer zeolites. Here we show that the nucleation and in situ transformation pathways during the synthesis of medium-pore zeolite TNU-9 can be altered by controlling the extent of cooperative structure direction between Na+ and Cs+ ions in the presence of 1,4-bis(N-methylpyrrolidinium)butane cations as an organic structure-directing agent. The intermediate phase selectivity was found to change from bikitaite to analcime to layered MCM-22 precursor when the gel Na/Cs ratio was adjusted to 7, 15, and 20, respectively. We also show that the transformation of bikitaite into TNU-9 begins at the surface of intermediate crystals, unlike that of analcime and MCM-22 precursor by a dissolution-recrystallization process. The force field simulation results suggest that the nucleation of different intermediate phases is not thermodynamically but kinetically controlled. This study provides a new basis for advancing the fundamental understanding of zeolite crystallization pathways.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306592","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}

引用次数: 0

Giant Thermosalient Effect in a Molecular Single Crystal: Dynamic Transformations and Mechanistic Insights. 分子单晶中的巨热盐流效应：动态转变和机理启示。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-09-24 DOI: 10.1021/jacs.4c09222

Mohammad Afsar Uddin, Raúl Martín, Sergio Gámez-Valenzuela, Marcelo Echeverri, M Carmen Ruiz Delgado, Enrique Gutiérrez Puebla, Angeles Monge, Berta Gómez-Lor

{"title":"Giant Thermosalient Effect in a Molecular Single Crystal: Dynamic Transformations and Mechanistic Insights.","authors":"Mohammad Afsar Uddin, Raúl Martín, Sergio Gámez-Valenzuela, Marcelo Echeverri, M Carmen Ruiz Delgado, Enrique Gutiérrez Puebla, Angeles Monge, Berta Gómez-Lor","doi":"10.1021/jacs.4c09222","DOIUrl":"https://doi.org/10.1021/jacs.4c09222","url":null,"abstract":"The exploration of mechanical motion in molecular crystals under external stimuli is of great interest because of its potential applications in diverse fields, such as electronics, actuation, or sensing. Understanding the underlying processes, including phase transitions and structural changes, is crucial for exploiting the dynamic nature of these crystals. Here, we present a novel organic compound, PT-BTD, consisting of five interconnected aromatic units and two peripheral alkyl chains, which forms crystals that undergo a drastic anisotropic expansion (33% in the length of one of its dimensions) upon thermal stimulation, resulting in a pronounced deformation of their crystal shape. Remarkably, the transformation occurs while maintaining the single-crystal nature, which has allowed us to follow the crystal-to-crystal transformation by single-crystal analysis of the initial and expanded polymorphs, providing valuable insights into the underlying mechanisms of this unique thermosalient behavior. At the molecular level, this transformation is associated with subtle, coordinated conformational changes, including slight rotations of the five interconnected aromatic units in its structure and increased dynamism in one of its peripheral alkyl chains as the temperature rises, leading to the displacement of the molecules. In situ polarized optical microscopy reveals that this transformation occurs as a rapidly advancing front, indicative of a martensitic phase transition. The results of this study highlight the crucial role of a soft and flexible structural configuration combined with a highly compact but loosely bound supramolecular structure in the design of thermoelastic materials.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306596","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}

引用次数: 0

Quantification of Anisotropy in Exchange and Dispersion Interactions: A Simple Model for Physics-Based Force Fields. 交换和弥散相互作用中各向异性的量化：基于物理的力场简单模型

IF 4.8 2区化学

The Journal of Physical Chemistry Letters Pub Date : 2024-09-24 DOI: 10.1021/acs.jpclett.4c02034

Kristian Kříž, David van der Spoel

{"title":"Quantification of Anisotropy in Exchange and Dispersion Interactions: A Simple Model for Physics-Based Force Fields.","authors":"Kristian Kříž, David van der Spoel","doi":"10.1021/acs.jpclett.4c02034","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02034","url":null,"abstract":"In some compounds, exchange repulsion is orientation dependent. However, in contrast to quantum chemical methods that treat exchange explicitly, empirical models assume exchange to be spherically symmetric, yielding an average description only. Here we quantify the anisotropy of exchange and dispersion energy for hydrogen halides and water by probing these compounds with a helium atom using the symmetry-adapted perturbation theory (SAPT). The exchange interaction is reduced by up to 33% due to the σ-hole in hydrogen iodide, depending on the location of the probe. We demonstrate how this anisotropy can be modeled in empirical force fields either using an angle-dependent potential or by introducing virtual sites, reducing the error in the empirical model by a factor of 5 compared to isotropic atoms. Lone-pairs on water, positioned close to perpendicular to the plane of the molecule, on a line with the oxygen atom, and, surprisingly, σ-holes on water both modulate the exchange interaction strongly. Both lone-pairs and σ-holes can be modeled by virtual sites, leading to an 80% reduced error.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":4.8,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306642","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}

引用次数: 0

Customizing Ionic Liquids Functionalized MOFs Composites with Hydrophobic Interface for Electrochemical CO₂ Reduction. 定制具有疏水性界面的离子液体功能化 MOFs 复合材料，用于电化学还原二氧化碳。

IF 8.3 2区材料科学

ACS Applied Materials & Interfaces Pub Date : 2024-09-24 DOI: 10.1021/acsami.4c10640

Jie Wang, Meng Shi, Li-Ping Tang, Sheng-Nan Ruan, Ying-Ying Chao, Peng Chen, Feng-Cui Shen

{"title":"Customizing Ionic Liquids Functionalized MOFs Composites with Hydrophobic Interface for Electrochemical CO2 Reduction.","authors":"Jie Wang, Meng Shi, Li-Ping Tang, Sheng-Nan Ruan, Ying-Ying Chao, Peng Chen, Feng-Cui Shen","doi":"10.1021/acsami.4c10640","DOIUrl":"https://doi.org/10.1021/acsami.4c10640","url":null,"abstract":"The electrochemical carbon dioxide reduction reaction (CO2RR) to generate feedstocks for chemical products (e.g., carbon monoxide, CO) offers a highly attractive method for achieving the closure of the carbon cycle. Ionic liquids (ILs)-functionalized Cu-based catalyst Cu2O-HKUST-1/IL1/PTFE was developed, configuring metal-organic frameworks(MOFs) based materials with high adsorption and multiple active sites. The modified electrocatalysts exhibited high specific surface area, strong CO2 adsorption capacity, abundant active sites, and fast charge transfer rate. The nucleophilic active site of deprotonation at the C2 site in imidazole ILs further improved the selectivity of proton migration and CO product generation, which was verified through DFT calculations for the low Gibbs free energy of the generated intermediate interactions. In addition, the hydrophobic interface constructed by PTFE facilitated the inhibition of the hydrogen evolution reaction (HER) and significantly improved the efficiency of CO2 electroreduction. The Cu2O-HKUST-1/IL1/PTFE catalyst manifested a high C1 Faraday efficiency (FE) up to 96.5% and in particular 92.7% for FECO at -1.7 V vs RHE. The present work provides an efficient strategy for configuring ILs-functionalized MOFs-based materials with good hydrophobic interfaces to enhance the efficiency of CO2 electroreduction to C1 products.","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":null,"pages":null},"PeriodicalIF":8.3,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306520","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Development and Preclinical Evaluation of ¹⁸F-Labeled PEGylated Sansalvamide A Decapeptide for Noninvasive Evaluation of Hsp90 Status in Pancreas Cancer. 用于胰腺癌 Hsp90 状态无创评估的 18F 标记 PEG 化 Sansalvamide A 十肽的开发和临床前评估

IF 4.5 2区医学

Molecular Pharmaceutics Pub Date : 2024-09-24 DOI: 10.1021/acs.molpharmaceut.4c00643

Xiaohui Wang, Zhijian Han, Jun Zhang, Ming Chen, Wenbo Meng

{"title":"Development and Preclinical Evaluation of 18F-Labeled PEGylated Sansalvamide A Decapeptide for Noninvasive Evaluation of Hsp90 Status in Pancreas Cancer.","authors":"Xiaohui Wang, Zhijian Han, Jun Zhang, Ming Chen, Wenbo Meng","doi":"10.1021/acs.molpharmaceut.4c00643","DOIUrl":"https://doi.org/10.1021/acs.molpharmaceut.4c00643","url":null,"abstract":"Heat shock protein 90 (Hsp90) is a promising target for cancer therapy and imaging. Accurate detection of Hsp90 levels in tumors via noninvasive PET imaging might be beneficial for management. To achieve this, the precursor compound Dimer-Sansalvamide A (Dimer-San A) was PEGylated and modified by conjugating it with the bifunctional chelator 1,4,7-triazacyclononane-1,4,7-triacetic acid (NOTA). The 18F-labeled PEGylated Dimer-SanA decapeptide (18F-PEGylated San A) was completed within 30 min using a two-step process. In vitro stability and specificity were assessed, including competition studies with the Hsp90 inhibitor 17-allylamino-17-demethoxygeldanamycin (17-AAG). MicroPET imaging was performed on PL45 tumor-bearing mice to evaluate probe accumulation and tumor-to-muscle ratios. Biodistribution studies determined the route of excretion. The probe resulted in a radiochemical yield of 23.11% with a purity exceeding 95%. In vitro, 18F-PEGylated San A exhibited high stability and selectively accumulated in Hsp90-positive PL45 cells, with binding effectively blocked by the Hsp90 inhibitor 17AAG, confirming its specificity. MicroPET imaging of PL45 tumor-bearing mice showed significant probe accumulation in tumor tissues at 1 and 2 h postinjection (4.06 ± 0.30 and 3.72 ± 0.61%ID/g, respectively), with optimal tumor-to-muscle ratios observed at 2 h postinjection (6.09 ± 1.92). While 18F-PEGylated San A demonstrates enhanced water solubility, as indicated by increased kidney uptake relative to liver accumulation. The study successfully incorporated PEG units to create the novel probe 18F-PEGylated San A targeting to Hsp90 without affecting its targeting capability, aimed at improving the pharmacokinetics and PET imaging of Hsp90 expression noninvasively.","PeriodicalId":52,"journal":{"name":"Molecular Pharmaceutics","volume":null,"pages":null},"PeriodicalIF":4.5,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306606","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}

引用次数: 0

The Beginnings of JCTC. JCTC 成立之初。

IF 5.7 1区化学

Journal of Chemical Theory and Computation Pub Date : 2024-09-24 DOI: 10.1021/acs.jctc.4c01146

William L Jorgensen

引用次数: 0

Electrochemical Sensing of Phenylalanine using Polyaniline-Based Molecularly Imprinted Polymers. 使用聚苯胺基分子印迹聚合物对苯丙氨酸进行电化学传感。

IF 2.8 2区化学

The Journal of Physical Chemistry B Pub Date : 2024-09-24 DOI: 10.1021/acs.jpcb.4c04029

Sonia Sarangi, Ravishankar Srivastava, Jully Gogoi-Tiwari, Rajiv K Kar

{"title":"Electrochemical Sensing of Phenylalanine using Polyaniline-Based Molecularly Imprinted Polymers.","authors":"Sonia Sarangi, Ravishankar Srivastava, Jully Gogoi-Tiwari, Rajiv K Kar","doi":"10.1021/acs.jpcb.4c04029","DOIUrl":"https://doi.org/10.1021/acs.jpcb.4c04029","url":null,"abstract":"Polyaniline (PANI)-based molecularly imprinted polymers were investigated for their efficacy in sensing phenylalanine (Phe) when fabricated on both glassy carbon electrode (GCE) and indium tin oxide (ITO) sheets. This study highlights the superior performance of PANI-MIP/ITO over PANI-MIP/GCE for sensing Phe, with clear and distinct redox responses. Molecular computation helps to understand the interaction mechanism between PANI and Phe, where molecular crowding, aggregated clusters, hydrogen bonding, and π-π stacking facilitate stable interactions. We tested the specificity of Phe sensing by PANI-MIP with different amino acids such as cysteine, tryptophan, and tyrosine as well as organic molecules such as ascorbic acid, allantoin, sucrose, and urea, confirming its remarkable electrochemical efficiency. The oxidation response curve yielded a limit of detection of 4.88 μM and a limit of quantification of 16.3 μM, comparable to or better than earlier reported sensors. This work demonstrates the promise of MIP-based electrochemical sensing. It also lays the groundwork for future investigations into optimizing PANI-MIPs with nanocomposites to develop more selective and stable sensors.","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":null,"pages":null},"PeriodicalIF":2.8,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306638","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}

引用次数: 0

Career Transitions That Require a Lot of Energy and Take You to Excited States Will Eventually Result in Brighter Professional Achievements. 职业转型需要大量精力，会让你进入兴奋状态，最终会取得更辉煌的职业成就。

IF 6.8 1区医学

Journal of Medicinal Chemistry Pub Date : 2024-09-24 DOI: 10.1021/acs.jmedchem.4c02145

Cristiano R W Guimarães

引用次数: 0