ACS Publications最新文献

{"title":"Iron-Catalyzed Thioarylation of Arenes Using Saccharin-Derived Reagents","authors":"Lachlan J. N. Waddell,&nbsp;Oluwajuwon A. M. Okunade,&nbsp;Amy C. Dodds,&nbsp;Michael C. H. Lok,&nbsp;R. Nisha Khanizeman and Andrew Sutherland*,&nbsp;","doi":"10.1021/acs.joc.5c0025010.1021/acs.joc.5c00250","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00250https://doi.org/10.1021/acs.joc.5c00250","url":null,"abstract":"<p >Biaryl sulfides are important scaffolds found in various natural products and pharmaceutically active compounds. One of the main approaches for the synthesis of this compound class involves the substitution of arenes using electrophilic thioaryl species. However, these methods generally require acidic activation of the electrophile, more forcing conditions, and long reaction times. Here, we describe the combination of the super Lewis acid iron(III) triflimide with saccharin-based thioarylation reagents for the rapid synthesis of unsymmetrical biaryl sulfides under mild conditions. This approach was effective with electron-deficient thioaryl species that performed poorly with previous methods, allowing the efficient functionalization of bioactive compounds.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 16","pages":"5564–5573 5564–5573"},"PeriodicalIF":3.3,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.joc.5c00250","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867568","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Excited-State Mixing in the LOV Domain Proteins: Possible Physics behind the Difference in the Transient Absorption and Transient Stimulated Raman Spectroscopy","authors":"Yingliang Liu*,&nbsp;Aditya S. Chaudhari,&nbsp;Alessandra Picchiotti,&nbsp;Mateusz Rebarz,&nbsp;Miroslav Kloz,&nbsp;Martin Přeček,&nbsp;Jakob Andreasson and Bohdan Schneider,&nbsp;","doi":"10.1021/acs.jpclett.4c0297810.1021/acs.jpclett.4c02978","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c02978https://doi.org/10.1021/acs.jpclett.4c02978","url":null,"abstract":"<p >It remains uncertain whether excited electronic state mixing occurs in the flavin cofactor of the light-oxygen-voltage-sensing (LOV) domain. In this study, we present transient absorption and femtosecond stimulated Raman spectra of both free and EL222 binding flavin mononucleotide (FMN). We observed a change in the shape of the excited-state absorption around 800 nm in the S₁ state transient absorption after binding to EL222, alongside a relative intensity increase of the N₁–C₂ and C₂═O₂ stretching modes in the S₁ state Raman spectra. Based on the previous calculated geometric differences between the ππ* and nπ* states, we propose a probable electronic state mixing in EL222 binding FMN. This mixing is favored by the nonsymmetric hydrogen bonding interaction between the flavin O₄ atom and the asparagine residue and fewer hydrogen bonds with the O₂ atom in EL222.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"16 16","pages":"4072–4080 4072–4080"},"PeriodicalIF":4.8,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143863237","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":"Unified Framework for Molecular Response Functions of Different Electronic-Structure Models","authors":"Bin Gao*,&nbsp; and ,&nbsp;Magnus Ringholm,&nbsp;","doi":"10.1021/acs.jpca.4c0778910.1021/acs.jpca.4c07789","DOIUrl":"https://doi.org/10.1021/acs.jpca.4c07789https://doi.org/10.1021/acs.jpca.4c07789","url":null,"abstract":"<p >A unified framework─SymResponse─has been developed as a versatile tool to aid the implementation of response theory for different electronic-structure models. The framework manipulates the quasi-energy formulation of response theory at a symbolic level by building on top of other well-developed symbolic libraries. Response functions can therefore be nicely represented by “symbolic expressions,” which can be further evaluated numerically by users by developing their own evaluation routines with the assistance of SymResponse. The design of SymResponse makes it extensible to different electronic-structure models with only a moderate further amount of development effort. Response theory at Hartree–Fock, density functional theory, and coupled-cluster levels has been implemented in the present work as a demonstration, where elimination rules [<contrib-group><span>Kristensen, K.</span></contrib-group> <cite><i>J. Chem. Phys.</i></cite> <span>2008</span>, <em>129</em>, <elocation-id>214103</elocation-id>] can also be applied to offer the possibility to reduce the size of computational tasks.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 16","pages":"3709–3721 3709–3721"},"PeriodicalIF":2.7,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpca.4c07789","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143863215","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Modifying Separators with a Multistrategy-Constructed (ZnCo)3S4–MoS2 Heterostructure for High-Performance Lithium–Sulfur Batteries","authors":"Tingting Zhao,&nbsp;Jin Wang*,&nbsp;Chenghui Du,&nbsp;Wenbin Li,&nbsp;Meiying Zhao,&nbsp;Rong Wang,&nbsp;Ying Xin,&nbsp;Kebin Zhou* and Zhaoliang Zhang*,&nbsp;","doi":"10.1021/acsanm.5c0074710.1021/acsanm.5c00747","DOIUrl":"https://doi.org/10.1021/acsanm.5c00747https://doi.org/10.1021/acsanm.5c00747","url":null,"abstract":"<p >Lithium–sulfur (Li–S) batteries are considered promising candidates for next-generation energy storage systems. Developing high-efficiency catalysts to improve kinetics and inhibit the shuttle effect is a challenging task. In this study, a three-dimensional (3D) (ZnCo)₃S₄–MoS₂ heterostructure was constructed at the nanoscale and used as a decoration for the separator of durable Li–S batteries. Benefiting from the generation of the built-in electric field between 3D (ZnCo)₃S₄ and in situ grown MoS₂ nanosheet, the rapid transport of ions and electrons and excellent polysulfide redox kinetics are observed in the (ZnCo)₃S₄–MoS₂, which results in a smooth ″adsorption–diffusion–conversion″ process of polysulfides. The Zn dopant effectively reduces the work function of Co₃S₄ via an electron transfer from Zn to Co₃S₄, strengthening the built-in electric field. The battery equipped with the (ZnCo)₃S₄–MoS₂ nanomaterial-modified separator delivers a high initial discharge capacity of 1180.5 mAh g^–1 at 1 C conditions and a low attenuation rate of 0.054% after 1000 cycles. In addition, the battery also exhibits good cycling stability at a high sulfur loading of 3 mg·cm^–2, maintaining a capacity of 704.4 mAh g^–1 (84.9% capacity retention) after 200 cycles at 0.1 C. This study provides a promising strategy to design highly efficient catalysts for durable Li–S batteries.</p>","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":"8 16","pages":"8220–8230 8220–8230"},"PeriodicalIF":5.3,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867288","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}

{"title":"Enhanced Luminescence Properties of ZnS Nanoparticles for LEDs Applications via Doping and Phase Control","authors":"Long Han,&nbsp;Yongwang Cao,&nbsp;Yankun Chen,&nbsp;Lu Tian,&nbsp;Wenhuai Tian* and Zhipeng Li*,&nbsp;","doi":"10.1021/acsanm.5c0110810.1021/acsanm.5c01108","DOIUrl":"https://doi.org/10.1021/acsanm.5c01108https://doi.org/10.1021/acsanm.5c01108","url":null,"abstract":"<p >Cu- and Al-doped ZnS nanoparticles (NPs) were synthesized via a hot-injection method. The results indicate that the addition of Cu initially increases and subsequently decreases the luminescence intensity, reaching a peak at a Cu content of 0.5%. Furthermore, Al doping leads to a significant increase in luminescence intensity, accompanied by a blue-shift of the emission peaks. Additionally, an increase in the concentration of the Cu dopant induces a phase transition of ZnS from cubic to hexagonal at a low temperature. Moreover, a positive correlation is observed between the dopant concentration and the average particle size. The addition of Al results in a significant decrease in the average particle size, which ranges from approximately 3.59 to 4.34 nm. Although the band gap of ZnS is slightly reduced after doping, it remains stable. This study suggests that the addition of Al primarily forms a donor–acceptor pair with Cu, thereby enhancing Cu’s emission. Modulating the doping concentrations of Cu and Al can adjust the emission position while significantly increasing the photoluminescence quantum yield (PL QY) after doping. The highest PL QY is achieved with ZnS:0.5% Cu, 2.0% Al, which is 21.8 times higher than that of the undoped ZnS. This material has the potential to be employed in a variety of applications, including light-emitting diodes, inorganic scintillators, and anticounterfeiting techniques.</p>","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":"8 16","pages":"8445–8454 8445–8454"},"PeriodicalIF":5.3,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867353","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}

{"title":"Influence of Bases on Surface Functionalities of Polydopamine Nanoparticles: Impact on Radical Trapping Properties","authors":"Gabrielle Rey,&nbsp;Trey Fricker and Ali Dhinojwala*,&nbsp;","doi":"10.1021/acsanm.5c0057710.1021/acsanm.5c00577","DOIUrl":"https://doi.org/10.1021/acsanm.5c00577https://doi.org/10.1021/acsanm.5c00577","url":null,"abstract":"<p >Melanin is a biological nanomaterial with a variety of functions, for example, its ability to quench free radicals. Even though the surface chemistry of melanin is important for these properties, this area has remained relatively unexplored. Here, we compare differences in surface properties of polydopamine (PDA, synthetic mimic of natural melanin) nanoparticles synthesized using three different bases commonly reported in the literature. We use a fluorescence assay and X-ray photoelectron spectroscopy (XPS) to characterize the surface functionalities of nanoparticles synthesized using these three bases. Fluorescence measurements reveal that the PDA synthesized using tris and bicine bases had higher concentrations of amine and carbonyl groups compared to PDA synthesized using ammonium hydroxide. XPS measurements confirmed the presence of carbonyl and amine groups. However, this technique was not able to distinguish the differences in surface chemistry that we observed using fluorescence spectroscopy. Using a 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical trap assay, we demonstrated that the PDA nanoparticles synthesized using tris and bicine were more effective in quenching free radicals compared to PDA synthesized using ammonium hydroxide, correlating with a higher fraction of carbonyl groups on the surface of the PDA nanoparticles.</p>","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":"8 16","pages":"8122–8132 8122–8132"},"PeriodicalIF":5.3,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867595","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}

{"title":"Optical Nonlinearity of Transparent Conducting Oxides: More Metallic than Realized","authors":"Ieng-Wai Un,&nbsp;Naama Harcavi and Yonatan Sivan*,&nbsp;","doi":"10.1021/acsphotonics.5c0038410.1021/acsphotonics.5c00384","DOIUrl":"https://doi.org/10.1021/acsphotonics.5c00384https://doi.org/10.1021/acsphotonics.5c00384","url":null,"abstract":"<p >Transparent conducting oxides (TCOs) have recently been shown to have a remarkably strong nonlinear optical response. We show that the popular ascription of their nonlinearity to the temperature-dependence of the plasma frequency is only a partial description of their response to intense illumination. Specifically, we show that an increase in the electron collision rate upon illumination and consequent heating contributes to the permittivity in a manner that can be quantitatively comparable to the contribution of the temperature-dependent plasma frequency. This behavior makes the optical nonlinearity of TCOs more similar to that of noble metals than realized so far, and as far as the imaginary part of the permittivity is concerned, this behavior is qualitatively opposite compared to that assumed so far.</p>","PeriodicalId":23,"journal":{"name":"ACS Photonics","volume":"12 4","pages":"1718–1721 1718–1721"},"PeriodicalIF":6.5,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsphotonics.5c00384","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143833004","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"物理与天体物理","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ubiquitin-Specific Protease 7 (USP7) as a Promising Therapeutic Target for Drug Discovery: From Mechanisms to Therapies","authors":"Yihui Song,&nbsp;Xiangli Ren,&nbsp;Jinbo Xiong,&nbsp;Wenwen Wang,&nbsp;Qianyan Zhao,&nbsp;Junbiao Chang* and Bin Yu*,&nbsp;","doi":"10.1021/acs.jmedchem.5c0010210.1021/acs.jmedchem.5c00102","DOIUrl":"https://doi.org/10.1021/acs.jmedchem.5c00102https://doi.org/10.1021/acs.jmedchem.5c00102","url":null,"abstract":"<p >Protein ubiquitination is a reversible post-translational modification regulated by ubiquitin-conjugating and deubiquitinating enzymes (DUBs). Ubiquitin-specific protease 7 (USP7), a well-characterized DUB, plays multifaceted roles in various cellular processes, making it a promising therapeutic target. The plasticity of its catalytic domain and unique allosteric regulation by substrates or external or intramolecular factors facilitate the identification of highly selective USP7 inhibitors. These inhibitors can engage distinct ubiquitin-binding sites through covalent or non-covalent mechanisms. Despite its therapeutic promise, no USP7 inhibitors have entered clinical trials, underscoring the urgent need for novel therapeutics. Here we provide a crystallographic and functional landscape of USP7’s multilayer regulation and analyze the structure–activity relationship of inhibitors by chemotypes. Additionally, we explore USP7’s roles in diseases and discuss the challenges in USP7-targeted drug discovery and future directions for therapeutic development. This Perspective aims to provide a systematic overview of USP7, from its regulatory mechanisms to its therapeutic potential.</p>","PeriodicalId":46,"journal":{"name":"Journal of Medicinal Chemistry","volume":"68 8","pages":"7914–7931 7914–7931"},"PeriodicalIF":6.8,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143863218","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nanoascorbate Promotes Clearance of Mutant Huntingtin Aggregates via Restoration of Blocked Autophagy","authors":"Nibedita Pradhan*,&nbsp;Santanu Shaw and Nihar Ranjan Jana*,&nbsp;","doi":"10.1021/acsanm.5c0024010.1021/acsanm.5c00240","DOIUrl":"https://doi.org/10.1021/acsanm.5c00240https://doi.org/10.1021/acsanm.5c00240","url":null,"abstract":"<p >Impaired autophagy is a key contributor to aging and a variety of protein aggregation-linked neurodegenerative disorders. In this direction, autophagy modulation is emerging as a therapeutic approach to combat protein aggregation-related neuronal diseases. Herein, we report that nanoascorbate, a biocompatible polymeric nanoform of vitamin C, accelerates the clearance of mutant Huntingtin protein aggregates in HD150Q, the cellular model of Huntington’s disease by restoring blocked autophagy. We have confirmed that nanoascorbate induces autophagic flux in autophagy-compromised Huntington’s model cells bearing mutant Huntingtin aggregates, evident from the altered expression level of the characteristic autophagy marker protein LC3BII and rapid degradation of crucial cargo receptor SQSTM/p62. In addition, blockade of autophagy induction using a potent autophagy inhibitor causes depression/failure of clearance of protein aggregates by nanoascorbate, indicating that nanoascorbate induces autophagy-mediated degradation. Furthermore, nanoascorbate-mediated upregulation of autophagic flux is ROS- and glutathione reductase-dependent. A brief incubation of 3h with a low micromolar concentration of nanoascorbate has shown an average 90% clearance of high-molecular-weight soluble aggregate of neurotoxic mutant Huntingtin protein, within 2 days. Nanoascorbate is faster, and a low micromolar concentration is sufficient compared to a high molar concentration of trehalose, a conventional autophagy inducer, that achieves only an average of 38% degradation after 96 h of prolonged incubation. In general, induced HD150Q cells bearing neurotoxic polyglutamine aggregates are prone to rapid apoptotic death. Nanoascorbate rescues mutant huntingtin aggregate-bearing cells from apoptotic insult which is evident from the lowered expression of cleaved caspase-3 manifolds, after brief incubation with nanoascorbate. In addition, dietary supplementation of nanoascorbate has shown moderate improvement in motor activity, an increase in life span, and suppression of progressive polyQ-induced eye degeneration to some extent in the transgenic <i>Drosophila</i> model of Huntington’s disease. Our findings manifest the remarkable neurotherapeutic potential of the nanoform of ascorbate via autophagy modulation in autophagy-compromised conditions as well as a moderate neuroprotective effect in the transgenic <i>Drosophila</i> model of Huntington’s disease. In addition, the current study emphasizes that modulation of autophagy can be considered as a promising therapeutic approach for proteinopathy-related neurodegenerative diseases.</p>","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":"8 16","pages":"7974–7988 7974–7988"},"PeriodicalIF":5.3,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867284","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}

{"title":"Synthetic Studies toward the Total Synthesis of Scabrolide A","authors":"Sabnam Begum,&nbsp; and ,&nbsp;Tushar Kanti Chakraborty*,&nbsp;","doi":"10.1021/acs.joc.5c0029810.1021/acs.joc.5c00298","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00298https://doi.org/10.1021/acs.joc.5c00298","url":null,"abstract":"<p >Herein, we report a concise route to the [5-5-6]-fused tricyclic core of scabrolide A and our efforts toward the construction of the fourth cycloheptane ring of the molecule via a 7-<i>endo-trig</i> radical cyclization. The tricyclic cyclohexenone core was assembled by a ring-closing metathesis (RCM) reaction followed by oxidation and concomitant isomerization of the double bond. These promising results have potential implications in the synthesis of similar tricyclic cores of many other congeners within this family of furanobutenolide-derived polycyclic cembranoids and norcembranoids.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 16","pages":"5614–5631 5614–5631"},"PeriodicalIF":3.3,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867564","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}