ACS Publications最新文献_第8页

Tuning Electron Transfer Coupling and Exchange Interaction in Bis-triarylamine Radical Cations and Dications by Bridge Electron Density. 通过桥电子密度调节双三芳基胺阳离子和阳离子中的电子转移耦合和交换相互作用。

IF 14.4 1区化学

Journal of the American Chemical Society Pub Date : 2024-09-24 DOI: 10.1021/jacs.4c09221

Leon Euringer, Marco Holzapfel, Ivo Krummenacher, Michael Franz, Sabine Richert, Holger Braunschweig, Christoph Lambert

{"title":"Tuning Electron Transfer Coupling and Exchange Interaction in Bis-triarylamine Radical Cations and Dications by Bridge Electron Density.","authors":"Leon Euringer, Marco Holzapfel, Ivo Krummenacher, Michael Franz, Sabine Richert, Holger Braunschweig, Christoph Lambert","doi":"10.1021/jacs.4c09221","DOIUrl":"https://doi.org/10.1021/jacs.4c09221","url":null,"abstract":"The influence of the electron density of a bridge connecting two redox centers on both the intervalence hole transfer and the magnetic superexchange was investigated in a series of bridged bis-triarylamine mono- and dications. In this series, the bridge was 2,7-fluorenyl, where the bridge electron density was modified by substituents at the 9-position. For the mixed-valence monocations, the observation of both an intervalence charge transfer (IVCT) band and an absorption band associated with an electron transfer from the bridging fluorene to the triarylamine radical cation centers allowed determination of the electron transfer couplings in the framework of the three-state generalized Mulliken-Hush theory. Comparison of the derived couplings with those obtained from a classical two-state approach demonstrates an enhancement of the electronic coupling which increases with decreasing bridge state energy. For the dicationic diradical counterparts, the singlet-triplet gap (exchange interaction) was determined both experimentally and by quantum chemical methods. Hereby, an increase of antiferromagnetic coupling with a lowering of the bridge state energy by electron donating substituents was observed. Analysis of the involved molecular orbitals suggests that the ferromagnetic coupling is inversely proportional to the square of the bridge energy, which is also supported by the experimental findings. This influence of the bridge state energy on both types of interactions, electron transfer and magnetic exchange, provides a design guideline for fine-tuning the properties of electronically coupled organic redox dyads by variation of the bridge electron density.","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":"142306599","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

Fundamental Understanding of Interface Chemistry and Electrical Contact Properties of Bi and MoS₂. 从根本上了解 Bi 和 MoS2 的界面化学和电接触特性。

IF 8.3 2区材料科学

ACS Applied Materials & Interfaces Pub Date : 2024-09-24 DOI: 10.1021/acsami.4c10082

Seong Yeoul Kim, Zheng Sun, Joy Roy, Xinglu Wang, Zhihong Chen, Joerg Appenzeller, Robert M Wallace

{"title":"Fundamental Understanding of Interface Chemistry and Electrical Contact Properties of Bi and MoS2.","authors":"Seong Yeoul Kim, Zheng Sun, Joy Roy, Xinglu Wang, Zhihong Chen, Joerg Appenzeller, Robert M Wallace","doi":"10.1021/acsami.4c10082","DOIUrl":"https://doi.org/10.1021/acsami.4c10082","url":null,"abstract":"The interface properties and thermal stability of bismuth (Bi) contacts on molybdenum disulfide (MoS2) shed light on their behavior under various deposition conditions and temperatures. The examination involves extensive techniques including X-ray photoelectron spectroscopy, scanning tunneling microscopy (STM), and scanning tunneling spectroscopy (STS). Bi contacts formed a van der Waals interface on MoS2 regardless of deposition conditions, such as ultrahigh vacuum (UHV, 3 × 10-11 mbar) and high vacuum (HV, 4 × 10-6 mbar), while the oxidation on MoS2 has been observed. However, the semimetallic properties of Bi suppress the impact of defect states, including oxidized-MoS2 and vacancies. Notably, the n-type characteristic of Bi/MoS2 remains unaffected, and no significant changes in the local density of states near the conduction band minimum are observed despite the presence of defects detected by STM and STS. As a result, the Fermi level (EF) resides below the conduction band of MoS2. The study also examines the impact of annealing on the contact interface, revealing no interface reaction between Bi and MoS2 up to 300 °C. These findings enhance our understanding of semimetal (Bi) contacts on MoS2, with implications for improving the performance and reliability of electronic devices.","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":"142306537","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

Research on Drug Efficacy using a Terahertz Metasurface Microfluidic Biosensor Based on Fano Resonance Effect. 基于法诺共振效应的太赫兹元表面微流控生物传感器的药效研究

IF 8.3 2区材料科学

ACS Applied Materials & Interfaces Pub Date : 2024-09-24 DOI: 10.1021/acsami.4c12247

Yuhan Zhao, Zeyu Hou, Bingxin Yan, Xueting Cao, Bo Su, Mi Lv, Hailin Cui, Cunlin Zhang

{"title":"Research on Drug Efficacy using a Terahertz Metasurface Microfluidic Biosensor Based on Fano Resonance Effect.","authors":"Yuhan Zhao, Zeyu Hou, Bingxin Yan, Xueting Cao, Bo Su, Mi Lv, Hailin Cui, Cunlin Zhang","doi":"10.1021/acsami.4c12247","DOIUrl":"https://doi.org/10.1021/acsami.4c12247","url":null,"abstract":"Advanced biosensors must exhibit high sensitivity, reliability, and convenience, making them suitable for detecting trace samples in biological or medical applications. Currently, biometric identification is the predominant method in clinical practice, but it is complex and time-consuming. In this study, we propose an optical metasurface utilizing the Fano resonance effect, which exhibits a sharp resonance with a transmittance of 32% at 0.65 THz. The resonance dip has a narrow bandwidth of 0.07 THz and a high Q-factor of 42. This resonance arises from the coupling of bright and dark modes, underpinned by the electromagnetic mechanism of Fano resonance. We integrated the metasurface into a microfluidic platform and fabricated low-temperature gallium arsenide photoconductive antennas (LT-GaAs-PCAs) on both sides of the microfluidics to efficiently generate and detect THz waves, significantly reducing the system's volume. The biosensor's detection limits for Escherichia coli (E. coli) and cefamandole nafate are 5 × 103 cells/mL and 5 μg/mL, respectively. Experimentally, when E. coli and cefamandole nafate solutions were sequentially injected into the microfluidic chip, a blue shift in the spectrum was observed. The sensor measured a 95.2% killing rate of E. coli by 40 μg/mL cefamandole nafate solution, with only a 3% deviation from biological experiments. Additionally, a timed killing experiment using 40 μg/mL cefamandole nafate on E. coli revealed a 93.7% killing rate within 3 min. This research presents a THz microfluidic biosensor with rapid detection, high sensitivity, and enhanced portability and integration, offering a promising approach for biomedical research, including antibiotic efficacy assessment and bacterial concentration monitoring.","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":"142306548","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

Efficient Simulation of Viral Transduction and Propagation for Biomanufacturing. 高效模拟生物制造中的病毒转导和传播。

IF 3.7 2区生物学

ACS Synthetic Biology Pub Date : 2024-09-24 DOI: 10.1021/acssynbio.4c00227

Francesco Destro, Richard D Braatz

{"title":"Efficient Simulation of Viral Transduction and Propagation for Biomanufacturing.","authors":"Francesco Destro, Richard D Braatz","doi":"10.1021/acssynbio.4c00227","DOIUrl":"https://doi.org/10.1021/acssynbio.4c00227","url":null,"abstract":"The design of biomanufacturing platforms based on viral transduction and/or propagation poses significant challenges at the intersection between synthetic biology and process engineering. This paper introduces vitraPro, a software toolkit composed of a multiscale model and an efficient numeric technique that can be leveraged for determining genetic and process designs that optimize transduction-based biomanufacturing platforms and viral amplification processes. Viral infection and propagation for up to two viruses simultaneously can be simulated through the model, considering viruses in either the lytic or lysogenic stage, during batch, perfusion, or continuous operation. The model estimates the distribution of the viral genome(s) copy number in the cell population, which is an indicator of transduction efficiency and viral genome stability. The infection age distribution of the infected cells is also calculated, indicating how many cells are in an infection stage compatible with recombinant product expression or viral amplification. The model can also consider the presence of defective interfering particles in the system, which can severely compromise the productivity of biomanufacturing processes. Model benchmarking and validation are demonstrated for case studies of the baculovirus expression vector system and influenza A propagation in suspension cultures.","PeriodicalId":26,"journal":{"name":"ACS Synthetic Biology","volume":null,"pages":null},"PeriodicalIF":3.7,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306534","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}

引用次数: 0

Peptide-Coated Polycaprolactone-Benzalkonium Chloride Nanocapsules for Targeted Drug Delivery to the Pancreatic β-Cell. 肽包覆聚己内酯-苯扎氯铵纳米胶囊用于胰腺β细胞靶向给药

IF 4.6

ACS Applied Bio Materials Pub Date : 2024-09-24 DOI: 10.1021/acsabm.4c00621

Jillian Collins, Jessie M Barra, Keifer Holcomb, Andres Ocampo, Ashton Fremin, Austin Kratz, Jubril Akolade, Julianna K Hays, Ali Shilleh, Amit Sela, David J Hodson, Johannes Broichhagen, Holger A Russ, Nikki L Farnsworth

{"title":"Peptide-Coated Polycaprolactone-Benzalkonium Chloride Nanocapsules for Targeted Drug Delivery to the Pancreatic β-Cell.","authors":"Jillian Collins, Jessie M Barra, Keifer Holcomb, Andres Ocampo, Ashton Fremin, Austin Kratz, Jubril Akolade, Julianna K Hays, Ali Shilleh, Amit Sela, David J Hodson, Johannes Broichhagen, Holger A Russ, Nikki L Farnsworth","doi":"10.1021/acsabm.4c00621","DOIUrl":"https://doi.org/10.1021/acsabm.4c00621","url":null,"abstract":"Targeting current therapies to treat or prevent the loss of pancreatic islet β-cells in Type 1 Diabetes (T1D) may provide improved efficacy and reduce off-target effects. Current efforts to target the β-cell are limited by a lack of β-cell-specific targets and the inability to test multiple targeting moieties with the same delivery vehicle. Here, we fabricate a tailorable polycaprolactone nanocapsule (NC) in which multiple different targeting peptides can be interchangeably attached for β-cell-specific delivery. Incorporation of a cationic surfactant in the NC shell allows for the attachment of Exendin-4 and an antibody for ectonucleoside triphosphate diphosphohydrolase 3 (ENTPD3) for β-cell-specific targeting. The average NC size ranges from 250 to 300 nm with a polydispersity index under 0.2. The NCs are nontoxic, stable in media culture, and can be lyophilized and reconstituted. NCs coated with a targeting peptide were taken up by human cadaveric islet β-cells and human stem cell-derived β-like cells (sBC) in vitro with a high level of specificity. Furthermore, NCs successfully delivered both hydrophobic and hydrophilic cargo to human β-cells. Additionally, Exendin-4-coated NCs were stable and targeted the mouse pancreatic islet β-cell in vivo. Overall, our tailorable NCs have the potential to improve cell-targeted drug delivery and can be utilized as a screening platform to test the efficacy of cell-targeting peptides.","PeriodicalId":2,"journal":{"name":"ACS Applied Bio Materials","volume":null,"pages":null},"PeriodicalIF":4.6,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142309733","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}

引用次数: 0

Metal and Photocatalyst-Free Amide Synthesis via Decarbonylative Condensation of Alkynes and Photoexcited Nitroarenes. 通过炔烃和光激发硝基烯烃的脱羰基缩合合成无金属和光催化剂的酰胺。

IF 4.9 1区化学

Organic Letters Pub Date : 2024-09-24 DOI: 10.1021/acs.orglett.4c02513

Rongqi Cui, Qian Liao, Yuanxia Zhao, Lifang Wang, Yongqiang Zhang, Shuyang Liu, Ziyu Gan, Yufei Chen, Yi Shi, Lei Shi, Min Li, Yunhe Jin

引用次数: 0

Role of DNA Double-Strand Break Formation in Gyrase Inhibitor-Mediated Killing of Nonreplicating Persistent Mycobacterium tuberculosis in Caseum. 回旋酶抑制剂介导的 DNA 双链断裂在杀灭酪氨酸中的非复制持久性结核分枝杆菌中的作用

IF 4 2区医学

ACS Infectious Diseases Pub Date : 2024-09-24 DOI: 10.1021/acsinfecdis.4c00499

Priyanka Ashwath, Paulina Osiecki, Danielle Weiner, Laura E Via, Jansy P Sarathy

{"title":"Role of DNA Double-Strand Break Formation in Gyrase Inhibitor-Mediated Killing of Nonreplicating Persistent Mycobacterium tuberculosis in Caseum.","authors":"Priyanka Ashwath, Paulina Osiecki, Danielle Weiner, Laura E Via, Jansy P Sarathy","doi":"10.1021/acsinfecdis.4c00499","DOIUrl":"https://doi.org/10.1021/acsinfecdis.4c00499","url":null,"abstract":"Tuberculosis is the leading cause of mortality by infectious agents worldwide. The necrotic debris, known as caseum, which accumulates in the center of pulmonary lesions and cavities is home to nonreplicating drug-tolerant Mycobacterium tuberculosis that presents a significant hurdle to achieving a fast and durable cure. Fluoroquinolones such as moxifloxacin are highly effective at killing this nonreplicating persistent bacterial population and boosting TB lesion sterilization. Fluoroquinolones target bacterial DNA gyrase, which catalyzes the negative supercoiling of DNA and relaxes supercoils ahead of replication forks. In this study, we investigated the potency of several other classes of gyrase inhibitors against M. tuberculosis in different states of replication. In contrast to fluoroquinolones, many other gyrase inhibitors kill only replicating bacterial cultures but produce negligible cidal activity against M. tuberculosis in ex vivo rabbit caseum. We demonstrate that while these inhibitors are capable of inhibiting M. tuberculosis gyrase DNA supercoiling activity, fluoroquinolones are unique in their ability to cleave double-stranded DNA at low micromolar concentrations. We hypothesize that double-strand break formation is an important driver of gyrase inhibitor-mediated bactericidal potency against nonreplicating persistent M. tuberculosis populations in the host. This study provides general insight into the lesion sterilization potential of different gyrase inhibitor classes and informs the development of more effective chemotherapeutic options against persistent mycobacterial infections.","PeriodicalId":17,"journal":{"name":"ACS Infectious Diseases","volume":null,"pages":null},"PeriodicalIF":4.0,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306512","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

Litchi Procyanidins Ameliorate DSS-Induced Colitis through Gut Microbiota-Dependent Regulation of Treg/Th17 Balance. 荔枝原花青素通过肠道微生物群对Treg/Th17平衡的依赖性调节改善DSS诱导的结肠炎

IF 5.7 1区农林科学

Journal of Agricultural and Food Chemistry Pub Date : 2024-09-24 DOI: 10.1021/acs.jafc.4c05577

Benyue Sun, Yunhui Wang, Jingjing Bai, Xuejiao Li, Long Ma, Shuli Man

{"title":"Litchi Procyanidins Ameliorate DSS-Induced Colitis through Gut Microbiota-Dependent Regulation of Treg/Th17 Balance.","authors":"Benyue Sun, Yunhui Wang, Jingjing Bai, Xuejiao Li, Long Ma, Shuli Man","doi":"10.1021/acs.jafc.4c05577","DOIUrl":"https://doi.org/10.1021/acs.jafc.4c05577","url":null,"abstract":"Ulcerative colitis (UC) is a common chronic, relapsing inflammatory bowel condition. Procyanidins (PC) are known for their antiangiogenic, anti-inflammatory, antioxidant, and antimetastatic properties. However, there is comparatively limited information on how PC interacts with UC. In this study, 5 mg/10 mL/kg body weight of PC was administered to mice with dextran sulfate sodium (DSS)-induced colitis mice. PC treatment prolonged the survival period of mice, ameliorated UC symptoms, reduced damage to the intestinal mucosal barrier, and increased the protein expression of ZO-1 and occludin in the DSS-treated mice. Importantly, PC treatment significantly reduced gene expression related to Th17 cell differentiation, including STAT3, SMAD3, TGF-β, and JAK1. The results of the flow cytometry analysis indicated significant increase in the number of Treg cells and a concomitant decrease in the proportion of Th17 cells in the colon following PC treatment. Additionally, PC increased the abundance of gut microbiota such as Bacteroidota, Oscillospiraceae, Muribaculaceae, and Desulfovibrionaceae, as well as the concentrations of acetate acid, propionate acid, and butyrate acid in the feces. PC also activated short-chain fatty acid receptors, such as G-protein coupled receptor 43 in the colon, which promoted the proliferation of Treg cells. The depletion of gut microbiota and subsequent transplantation of fecal microbiota demonstrated that PC's effects on gut microbiota were effective in improving UC and restoring intestinal Th17/Treg homeostasis in a microbiota-dependent manner. This suggests that PC could be a promising functional food for the prevention and treatment of UC in the future.","PeriodicalId":41,"journal":{"name":"Journal of Agricultural and Food Chemistry","volume":null,"pages":null},"PeriodicalIF":5.7,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306574","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}

引用次数: 0

Structure of Multi-State Correlation in Electronic Systems. 电子系统中的多态相关结构。

IF 5.7 1区化学

Journal of Chemical Theory and Computation Pub Date : 2024-09-24 DOI: 10.1021/acs.jctc.4c00545

Yangyi Lu, Jiali Gao

{"title":"Structure of Multi-State Correlation in Electronic Systems.","authors":"Yangyi Lu, Jiali Gao","doi":"10.1021/acs.jctc.4c00545","DOIUrl":"https://doi.org/10.1021/acs.jctc.4c00545","url":null,"abstract":"Beyond the Hohenberg-Kohn density functional theory for the ground state, it has been established that the Hamiltonian matrix for a finite number (N) of lowest eigenstates is a matrix density functional. Its fundamental variable─the matrix density D(r)─can be represented by, or mapped to, a set of auxiliary, multiconfigurational wave functions expressed as a linear combination of no more than N2 determinant configurations. The latter defines a minimal active space (MAS), which naturally leads to the introduction of the correlation matrix functional, responsible for the electronic correlation effects outside the MAS. In this study, we report a set of rigorous conditions in the Hamiltonian matrix functional, derived by enforcing the symmetry of a Hilbert subspace, namely the subspace invariance property. We further establish a fundamental theorem on the correlation matrix functional. That is, given the correlation functional for a single state in the N-dimensional subspace, all elements of the correlation matrix functional for the entire subspace are uniquely determined. These findings reveal the intricate structure of electronic correlation within the Hilbert subspace of lowest eigenstates and suggest a promising direction for efficient simulation of excited states.","PeriodicalId":45,"journal":{"name":"Journal of Chemical Theory and Computation","volume":null,"pages":null},"PeriodicalIF":5.7,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306577","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

Stereo- and Regioselective Installation of Vinyl Sulfonyl Fluoride onto Indoles without Transition-Metal Catalyst. 在无过渡金属催化剂的情况下，将乙烯基磺酰氟立体和区域选择性地安装到吲哚上。

IF 3.3 2区化学

The Journal of Organic Chemistry Pub Date : 2024-09-24 DOI: 10.1021/acs.joc.4c01689

Shu-Zhen Zheng, Eman Fayad, Najla A Alshaye, Hua-Li Qin

引用次数: 0