ACS Publications最新文献

{"title":"Modeling Uterine Fibroids Using Bioengineered Hydrogels.","authors":"Allison K Moses, Miriam Tamaño-Blanco, Erika Moore","doi":"10.1021/acsbiomaterials.5c01026","DOIUrl":"https://doi.org/10.1021/acsbiomaterials.5c01026","url":null,"abstract":"<p><p>Uterine fibroids are the most common gynecological tumors, characterized by excessive production of extracellular matrix. Despite their prevalence, the cellular mechanisms governing fibroid growth remain poorly understood. Current in vitro models for fibroids do not replicate the complex 3D tissue mechanics, structure, and extracellular matrix components of fibroids, which may limit our understanding of fibroid pathogenesis. To address this gap, we aimed to develop a 3D in vitro model to mimic aspects of the fibroid microenvironment. By encapsulating human uterine fibroblasts in poly(ethylene glycol) (PEG)-based hydrogels comprising collagen- and fibronectin-derived peptides, this model allows for incorporation of fibroid cellular components, extracellular matrix components, and fibroid or myometrial tissue stiffness. Due to its mechanistic role in fibroblast activation and subsequent extracellular matrix production seen in fibroids, we treated uterine fibroblasts with transforming growth factor beta 3 (TGF-β3) to demonstrate quantification of fibrotic markers observed in fibroids. Here, we establish that human uterine fibroblasts increase α smooth muscle actin, extracellular matrix proteins, and cell elongation, as well as high metabolic activity and matrix remodeling in PEG-based hydrogels in response to TGF-β3. This research represents a physiologically relevant in vitro platform to investigate uterine fibroblast function within a 3D environment that mimics uterine fibroids, with the potential to advance our understanding of the cellular and molecular mechanisms driving fibroid growth and development.</p>","PeriodicalId":8,"journal":{"name":"ACS Biomaterials Science & Engineering","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145032378","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":"Amphiphilic Poly(SBMA-<i>co</i>-EGDEA) Coatings for Marine Antifouling: Insights into Design Criteria for Hydrophobic Monomers.","authors":"Jinhyeok Jeong, Jinwoo Lee, Sang Uk Jeong, Jae Woo Park, Sung Min Kang","doi":"10.1021/acs.biomac.5c00875","DOIUrl":"https://doi.org/10.1021/acs.biomac.5c00875","url":null,"abstract":"<p><p>Marine biofouling poses significant economic and environmental challenges, highlighting the need for effective antifouling coatings. We report amphiphilic poly(SBMA-<i>co</i>-EGDEA) copolymer coatings that resist both marine diatom adhesion and sediment adsorption. The coatings were synthesized via surface-initiated ATRP and RAFT polymerization using hydrophilic sulfobetaine methacrylate (SBMA) and hydrophobic ethylene glycol dicyclopentenyl ether acrylate (EGDEA). Interestingly, EGDEA exhibited a partial negative charge when coated on a surface, as confirmed by computational analyses. Since marine sediments are typically negatively charged and adhere strongly to hydrophilic surfaces, EGDEA's combination of hydrophobicity and negative charge effectively minimized sediment adsorption while maintaining resistance to diatom adhesion. Experimental results further showed that coatings with higher EGDEA content exhibited superior antifouling performance. These findings highlight the unique role of EGDEA in amphiphilic copolymers and provide valuable design insights for next-generation marine antifouling coatings.</p>","PeriodicalId":30,"journal":{"name":"Biomacromolecules","volume":" ","pages":""},"PeriodicalIF":5.4,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145032494","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":"Aufbau Suppressed Coupled Cluster As a Post-Linear-Response Method.","authors":"Trine Kay Quady, Harrison Tuckman, Eric Neuscamman","doi":"10.1021/acs.jctc.5c01027","DOIUrl":"https://doi.org/10.1021/acs.jctc.5c01027","url":null,"abstract":"<p><p>We investigate the ability of Aufbau suppressed coupled cluster theory to act as a post-linear-response correction to widely used linear response methods for electronically excited states. We find that the theory is highly resilient to shortcomings in the underlying linear response method, with final results from less accurate starting points nearly as good as those from the best starting points. This pattern is especially stark in charge transfer states, where the approach converts starting points with multi-eV errors into post-linear-response results with errors on the order of 0.1 eV. These findings highlight the ability of Aufbau suppressed coupled cluster to perform its own orbital relaxations and raise the question of whether initializing it with an orbital relaxed reference is worth the trouble.</p>","PeriodicalId":45,"journal":{"name":"Journal of Chemical Theory and Computation","volume":" ","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145028510","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":"Characterization of Fluorescent Reporters for Flow Cytometry-Based Single-Cell Studies in <i>Saccharomyces cerevisiae</i>.","authors":"Samuel Evans, Masahiro Tominaga, Zeyu Lu, Naga Chandra Bandari, Liam McDonnell, Chengqiang Wang, Robert E Speight, Jun Ishii, Claudia E Vickers, Bingyin Peng","doi":"10.1021/acssynbio.5c00432","DOIUrl":"https://doi.org/10.1021/acssynbio.5c00432","url":null,"abstract":"<p><p>Fluorescent proteins (FPs) are commonly used as reporters to examine intracellular genetic, molecular, and biochemical status. Flow cytometry is a powerful technique for accurate quantification of single-cell fluorescent levels. Here, we characterize green, red, and blue FPs for use in yeast <i>Saccharomyces cerevisiae</i>. Fluorophore-containing FPs and fluorogen-activating FPs (YFAST and FrFAST) were characterized dynamically in batch cultivation. FPs with a low p<i>K</i>_a, StayGold, E2-Crimson, mTagBFP2, and mScarlet-I3, showed relatively stable fluorescence in diauxic growth when they were expressed under the control of the <i>TEF1</i> promoter. A pH sensor, based on the fusion of mNeonGreen and mTagBFP2, was used to investigate the dynamic change of intracellular pH in batch cultivation. High-concentration acetate (200 mM) interfered with intracellular pH dramatically, whereas low-concentration acetate (20 mM) could not. Using StayGold and mScarlet-I3, an Epac-based cAMP sensor was constructed, showing varied Förster resonance energy transfer (FRET) patterns in different growth phases in <i>S. cerevisiae</i> CEN.PK113-7D and EBY100 backgrounds. In summary, the change in intracellular pH can significantly affect the brightness of pH-sensitive FPs. It is important to use FPs with a low p<i>K</i>_a, neutralize intracellular pH, or compensate pH impacts when FPs are used as reporters.</p>","PeriodicalId":26,"journal":{"name":"ACS Synthetic Biology","volume":" ","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145028573","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}

{"title":"Electronegativity-Induced Jahn-Teller Distortion Boosts Li-S Conversion on Asymmetric Cu Single-Atom Catalysts.","authors":"Hengyue Xu","doi":"10.1021/acs.jpca.5c03527","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c03527","url":null,"abstract":"<p><p>A series of Cu-based single-atom catalysts (SACs) with asymmetric coordination were designed to accelerate lithium-sulfur (Li-S) chemistry. The electronegativity contrast from the dopant induces a localized electronic asymmetry that amplifies Jahn-Teller distortion at the Cu center. This distortion profoundly modulates the Cu 3d electronic structure and its interaction with Li-S intermediates. Among the series, the CuN₃F site exhibits the strongest Cu(II) Jahn-Teller distortion and the lowest free-energy step (Δ<i>G</i> ≈ 0.19 eV) for sulfur reduction, indicating superior catalytic activity. To rigorously capture the underlying electronic and structural effects, we establish a quantitative Jahn-Teller distortion index (<i>Q</i>_JT), defined as the product of the local spin magnetic moment and the standard deviation of integrated crystal orbital Hamilton population (iCOHP) values among Cu-ligand bonds. This descriptor effectively distinguishes true electronic Jahn-Teller activity from mere geometric or steric asymmetry, providing a physically grounded metric to assess and engineer the active site electronic structure. Mechanistic analysis reveals that the dynamic Jahn-Teller distortion at CuN₃F leads to an ideal alignment of Cu d orbitals with the LUMO of key Li-S intermediates, enhancing electronic coupling and reaction kinetics. This work demonstrates a novel Jahn-Teller distortion engineering strategy for Li-S catalysis, wherein electronegativity-driven local asymmetry is harnessed to tune the electronic structure and boost catalytic performance in energy storage system technologies.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145028568","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":"Dynamic Coupling and Disorder in Aggregation of Light-Harvesting Complex II in Plant Thylakoid Membranes.","authors":"Avinash Garg, Renu Saini, Ananya Debnath","doi":"10.1021/acs.jpcb.5c05377","DOIUrl":"10.1021/acs.jpcb.5c05377","url":null,"abstract":"<p><p>The dynamics of the aggregated light-harvesting complex (LHCII) associated with its antenna pigments can be crucial for a transition between light-harvesting and dissipative states, which is pivotal for nonphotochemical quenching (NPQ). To this end, aggregation of pigment-binding LHCII monomers and PsbS-associated trimers in neutral and low lumenal pH respectively, has been investigated when embedded in the plant thylakoid membranes, using coarse-grained molecular dynamics simulations. Both pigment-binding LHCII monomers and PsbS-associated trimers dynamically form and break dimers and higher-order aggregates in thylakoids within the simulation time. During aggregation of the monomeric and the PsbS-associated trimeric LHCII, survival probability representing conformations of the N-terminus, helices, and the respective antennae pigments follows a nonexponential decay with multiple residence time scales. The dimer residence time of the trimers at low lumenal pH is higher than that of the monomers at neutral pH. The conformational fluctuations of the proteins occur under a fast fluctuation limit in the presence of slower interpigment distance fluctuations, highlighting the presence of disorder in LHCII for both monomeric and trimeric LHCII aggregations in neutral and low lumenal pH. The multiple residence times lead to a time-dependent rate, unlike conventional rate theory. As the rate becomes a stochastic function of time, disorder emerges. Thus, LHCII aggregation does not proceed through a single uniform pathway. Instead, it involves a range of coupled dynamics, with some contacts forming and breaking with various time scales and transitions among multistates originating from dimer, trimer, and higher-order aggregates in thylakoids relevant for regulating NPQ.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145028522","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":"Microwave Spectroscopy and Structure of the 1-Fluoronaphthalene···H₂O Complex: Two Hydrogen Bonds Make the Complex a Rigid Rotor.","authors":"Surabhi Gupta, Charlotte N Cummings, Nicholas R Walker, Elangannan Arunan","doi":"10.1021/acs.jpca.5c02931","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c02931","url":null,"abstract":"<p><p>The microwave spectrum of the complex formed between 1-fluoronaphthalene and H₂O has been recorded using a chirped pulse Fourier transform microwave spectrometer within the frequency range of 2.0 to 8.0 GHz, with neon as the carrier gas. The rotational spectra of the isotopologues 1-fluoronaphthalene···H₂O, 1-fluoronaphthalene···D₂O, 1-fluoronaphthalene···DOH, and 1-fluoronaphthalene···H₂¹⁸O have been assigned and analyzed. By considering the rotational constants of all four isotopologues, the structure of the complex has been determined. Specifically, H₂O interacts with 1-fluoronaphthalene in an in-plane orientation, acting as a hydrogen bond donor and a weak hydrogen bond acceptor, resulting in the formation of O-H···F and C-H···O hydrogen bonds, respectively. The observed rotational spectra could be fit as a rigid rotor without any centrifugal distortion constants, a rare observation for a weakly bound complex formed in a supersonic beam. Atoms in molecules (AIM) and natural bond orbital (NBO) theoretical analyses of the complex confirm the presence of O-H···F and C-H···O hydrogen bonds.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145032465","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":"Biomimetic Multinuclear Nickel-Polyphenol Artificial Enzyme with Synergistic Catalytic Centers for Broad-Spectrum RONS Scavenging: A Therapeutic Strategy against LPS-Induced Septic Cardiomyopathy.","authors":"Yuying Wang, Ruifang Li, Longwu Xu, Xiufeng Xu, Shulan Pang, Xiaotong Zhang, Qiuhong Jiao, Xiaoxin Lv, Yulin Shen, Yudan Zhao, Xiaohong Liu, Xinjun Yu, Baolong Zhou, Tao Wang","doi":"10.1021/acs.molpharmaceut.5c00644","DOIUrl":"https://doi.org/10.1021/acs.molpharmaceut.5c00644","url":null,"abstract":"<p><p>Myocardial injury constitutes a life-threatening complication of sepsis, driven by synergistic oxidative-inflammatory pathology involving dysregulated production of reactive oxygen species (ROS), reactive nitrogen species (RNS), and proinflammatory cytokines. This pathophysiological cascade remarkably elevates morbidity and mortality rates in septic patients, emerging as a key contributor to poor clinical outcomes. Despite its clinical significance, no clinically validated therapeutics currently exist for managing septic cardiomyopathy. Here, we present a novel nickel-salvianolic acid B metallopolymer (Ni-SalB) engineered through metal-coordination-driven self-assembly. This biohybrid therapeutic demonstrates multimodal catalytic efficacy in counteracting lipopolysaccharide (LPS)-induced myocardial injury through coordinated oxidative stress mitigation and inflammation regulation. The integration of catechol-carboxyl dual coordination centers with phenolic frameworks creates a synergistic system enhancing structural stability while enabling tandem catalytic cascade: (1) superoxide dismutase (SOD)-mimetic conversion of superoxide radicals (O₂^•-) to H₂O₂, followed by (2) glutathione peroxidase (GPx)-like decomposition of H₂O₂ to water. Mechanistic studies revealed the multifunctional scavenging capacity of Ni-SalB against diverse cytotoxic species, including hydroxyl radicals (^•OH) and reactive nitrogen species(RNS), through electron transfer and radical recombination pathways. In murine sepsis models, Ni-SalB administration markedly attenuated myocardial oxidative damage, while enhancing endogenous antioxidant defenses. Histopathological analysis demonstrated therapeutic preservation of myocardial architecture, showing not only a great reduction in inflammatory infiltration but also a remarkably decrease in collagen deposition compared to septic controls. The catechol-carboxyl coordination architecture conferred enhanced pharmacokinetic properties with prolonged circulation life, while maintaining favorable biosafety profiles. This study introduces a metallo-polymeric artificial enzyme strategy with dual catalytic antioxidant systems, presenting a paradigm-shifting approach for managing sepsis-induced cardiac complications and expanding the translational promise of redox-modulation therapies.</p>","PeriodicalId":52,"journal":{"name":"Molecular Pharmaceutics","volume":" ","pages":""},"PeriodicalIF":4.5,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145032471","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":"Probing the Dipole-Bound State of the Cryogenically Cooled 2-Chlorothiophenoxide Anion via Photoelectron Imaging and Photodetachment Spectroscopy.","authors":"Jisoo Kang, Lai-Sheng Wang","doi":"10.1021/acs.jpca.5c05303","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c05303","url":null,"abstract":"<p><p>Chlorothiophenols are key precursors for polychlorinated dibenzothiophenes, which are a class of persistent organic pollutants environmentally, but little is known about their electronic and spectroscopic properties. We report a high-resolution spectroscopic investigation of the cryogenically cooled 2-chlorothiophenoxide (2-CTP^-) anion using photoelectron imaging, photodetachment spectroscopy, and resonant photoelectron spectroscopy. High-resolution photoelectron spectroscopy yields an accurate electron affinity of 21,005 ± 5 cm^-1 (2.6043 ± 0.0006 eV) for the 2-chlorothiophenoxy radical as well as an excited electronic state at 0.295 eV above the ground state. Photodetachment spectroscopy reveals a dipole-bound state (DBS) for the 2-CTP^- anion at 113 cm^-1 below the detachment threshold and 14 vibrational Feshbach resonances. Resonant photoelectron spectra via vibrational autodetachment are obtained, resulting in rich spectroscopic information about the ground state of the 2-CTP radical. A resonant two-photon detachment experiment via the zero-point level of the DBS indicates relaxation from the DBS to a lower-lying excited state of the 2-CTP^- anion as well as low-lying vibrational levels of the anion ground state. The current study yields a wealth of spectroscopic information for the 2-CTP radical and the 2-CTP^- anion, which is valuable for understanding the energetics and reactivities of these environmentally important species.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145032514","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":"Perovskite Nanozyme-Mediated Sonocatalytic Therapy: A Mitochondrion-Targeted Strategy for Enhanced Cancer Therapy.","authors":"Li Yang, Jialun Li, Xiaomin Sun, Wangzixi Zhang, Tiedong Sun, Yuan Sun, Jinyu Wu, Lei Wang","doi":"10.1021/acsabm.5c01087","DOIUrl":"https://doi.org/10.1021/acsabm.5c01087","url":null,"abstract":"<p><p>The generation of reactive oxygen species (ROS) through nanozyme-mediated sonocatalytic therapy has demonstrated remarkable therapeutic efficacy in the field of cancer. Nevertheless, it remains a significant challenge for nanozymes with a single catalytic active center to generate sufficient ROS via Fenton or Fenton-like reactions to effectively induce tumor cell death. In order to enhance the catalytic efficacy, we devised and synthesized a multiple active centre and mitochondrial-targeted perovskite nanozyme (NCFP), doped with cobalt (Co) element, and incorporated 4-carboxybutyltriphenylphosphonium bromide (TPP) as a mitochondrial targeting marker for ultrasound (US)-assisted enzyme-like catalytic treatment of tumors. Considering that perovskite nanozymes have the advantages of long carrier diffusion length, tunable direct band gap, and strong quantum confinement, it can be used as a substrate to increase the production rate of ROS. Therefore, on the basis of the intrinsic catalytic reaction, US is introduced to improve the catalytic reaction efficiency. The cavitation effect releases energy to promote the electron-hole pair separation of NCFP, increase the rate of electron-hole-mediated reaction, and enhance the degree of reaction, thereby helping it to produce more ROS and effectively kill tumor cells. Moreover, NCFP also has mitochondrial targeting ability, which can damage mitochondria more accurately and kill tumor cells. In summary, the successful preparation of NCFP provides a strategy for perovskite nanozyme-mediated sonocatalytic therapy for tumor therapy.</p>","PeriodicalId":2,"journal":{"name":"ACS Applied Bio Materials","volume":" ","pages":""},"PeriodicalIF":4.7,"publicationDate":"2025-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145032402","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}