ACS Organic & Inorganic Au最新文献

{"title":"A New Water-Soluble Copper(II) Coordination Polymer for Electrocatalytic Oxygen Evolution Reaction","authors":"Renata P. P. Macedo,&nbsp;Joice L. Carvalho,&nbsp;P.R.A de Oliveira,&nbsp;Lorenzo C. Visentin,&nbsp;Nakédia M. F. Carvalho","doi":"10.1021/acsorginorgau.5c00077","DOIUrl":"10.1021/acsorginorgau.5c00077","url":null,"abstract":"<p>The development of efficient and low-cost catalysts topromotethe oxygen evolution reaction (OER) is a challenge for the generationof green hydrogen through water splitting electrolysis. This workdescribes the synthesis of a new water-soluble one-dimensional copper­(II)coordination polymer for application as an earth-abundant OER molecularelectrocatalyst. The ligand was designed to have nitrogenated andcarboxylate groups, inspired by the amino acid residues of the Mn₄CaO₅ cluster of photosystem II (PSII). The multiplecoordination sites with different Lewis basicity were envisioned toinfer structural stability and modulated electronic structure of theCu­(II) center allowing redox processes to occur during the OER. Furthermore,a <em>N</em>-propanoate linker allows structural flexibilityfor the formation of carboxylate bridges and the coordination polymer.The single-crystal diffraction structure reveals an unusual monatomicbridge involving the chelation of the carboxylate group to two adjacentCu­(II) ions. The electrocatalysis of the OER was conducted in a phosphatebuffer at pH 12.5, and an onset overpotential of 394 mV was achievedat a current density of 0.1 mA cm^–2, comparableto those reported for Cu^II molecular catalysts. Kineticdata show first-order electron transfer with a turnover frequencyof 2.1 s^–1. Stability tests by chronopotentiometryand cyclic voltammetry showed the formation of a CuOx-OH film at theworking electrode surface, indicating the contribution of heterogeneouselectrocatalysis for the OER.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 2","pages":"209–224"},"PeriodicalIF":5.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147623869","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}

{"title":"Non-Catalyzed Cascade Double Imination Reaction of 2‑Fluoro-alk-3-yn-1-ones: Sustainable Synthesis of 3‑Fluoro-1,5-benzodiazepines","authors":"Trevor L. Olson,&nbsp;Ariela W. Kaspi-Kaneti,&nbsp;Adrian Zając,&nbsp;Dominic Agyei Gyimah,&nbsp;Austin Walsh,&nbsp;Jacob A. Weston,&nbsp;Alexander A. Rusakov,&nbsp;Kraig A. Wheeler,&nbsp;Béla Török,&nbsp;Roman Dembinski","doi":"10.1021/acsorginorgau.5c00116","DOIUrl":"10.1021/acsorginorgau.5c00116","url":null,"abstract":"<p>The cascade reactions of 2-fluoroalk-3-yn-1-ones with <em>o</em>-phenylenediamines provide an effective synthetic methodwith highatom economy for the preparation of diversely substituted 3-fluoro-3<em>H</em>-benzo­[<em>b</em>]­[1,4]­diazepines (52–81%).This noncatalytic and sustainable process embraces formal hydroaminationand imination reactions, resulting in the formation of two C<span></span>Nand two C–H bonds. DFT modeling provided additional insightinto the reaction’s mechanism, favoring the pathway involvinginitial cyclization of nonconjugated enaminone, <em>o</em>-aminoanilino-2-fluorobut-3-en-1-one. The reaction may be divertedto the formation of conjugated enaminone (<em>o</em>-aminoanilino-2-fluorobut-2-en-1-one),whose presence was confirmed by ¹H NMR. The conformationalproperties of the 7-membered ring were investigated by the ¹H and ¹⁹F variable temperature NMR studies in solutionand by the X-ray structure determination of 3-fluoro-4-(4-methylbenzyl)-2-phenyl-3<em>H</em>-benzo­[<em>b</em>]­[1,4]­diazepine.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 2","pages":"237–247"},"PeriodicalIF":5.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147623919","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}

{"title":"Fluorine Chemistry","authors":"Thomas Poisson,&nbsp;Valentina Dichiarante","doi":"10.1021/acsorginorgau.6c00022","DOIUrl":"10.1021/acsorginorgau.6c00022","url":null,"abstract":"","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 2","pages":"177–178"},"PeriodicalIF":5.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147623935","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}

{"title":"C–C Bond Formation via Direct Functionalization of Indolizines with a Bichromophoric Ruthenium Photocatalyst","authors":"Kevin Klaus Stefanoni,&nbsp;René Wilhelm","doi":"10.1021/acsorginorgau.5c00110","DOIUrl":"10.1021/acsorginorgau.5c00110","url":null,"abstract":"<p>An unprecedented photocatalyzed radical C­(sp²)–C­(sp³) alkylation protocol to prepare a rangeof substituted 3-alkylatedindolizine derivatives, mediated by 2-mercaptothiazolidinium saltsas radical sources and a new dyad-like Ruthenium complex as a photoredoxcatalyst, under green light irradiation, resulted in yields of upto 99%. The mild, robust, and chemoselective procedure employs inexpensive,air-insensitive, and readily accessible reagents, enabling convenientsynthesis of the substituted indolizines. Moreover, different <em>N</em>-heteroarenes, such as 1<em>H</em>-indoles and2<em>H</em>-indazoles, were successfully alkylated under theoptimized conditions. The resulting alkylated products are scaffoldswith significance for drug design in medicinal chemistry.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 2","pages":"225–236"},"PeriodicalIF":5.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147623909","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}

{"title":"Synthetic Applications of Hydroxamic Acids and Their Derivatives in Organic Chemistry","authors":"Rui Wang,&nbsp;Wenbo H. Liu","doi":"10.1021/acsorginorgau.5c00120","DOIUrl":"10.1021/acsorginorgau.5c00120","url":null,"abstract":"<p>Hydroxamic acidsand their derivatives are a versatileclass oforganic compounds with broad utility in synthetic chemistry. Thisreview highlights key synthetic transformations involving these molecules,covering important reactions such as their use in Weinreb amide chemistry,rearrangement processes, C–H activation directed by hydroxamategroups, their role as precursors to <em>N</em>-centered radicalsand aza-oxyallyl cations, reduction reactions, and umpolung transformationsinitiated by the N–O bond cleavage.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 2","pages":"179–201"},"PeriodicalIF":5.2,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147623924","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}

{"title":"The “Missing Link”, Allostery and SynergismHosting of Metal Cations by Regular and Partial Cone Calix[4]arene Isomers","authors":"Matija Modrušan,&nbsp;Nikola Cindro,&nbsp;Marija Cvetnić,&nbsp;Andrea Usenik,&nbsp;Slavica Petrović,&nbsp;Jakov Borovec,&nbsp;Katarina Leko,&nbsp;Karla Kukina Gradečak,&nbsp;Vladimir Stilinović,&nbsp;Gordan Horvat,&nbsp;Tomica Hrenar,&nbsp;Josip Požar,&nbsp;Vladislav Tomišić","doi":"10.1021/acsorginorgau.5c00095","DOIUrl":"10.1021/acsorginorgau.5c00095","url":null,"abstract":"<p>The influence of the tetra-<em>O</em>-2-oxopropyl-substitutedcalix­[4]­arene conformation on its binding affinity toward first- andsecond-group metal cations, as well as on the solvent molecule (acetonitrileor methanol) inclusion in the calixarene hydrophobic cavity, was investigatedexperimentally and computationally. Misorientation of one monomericsubunit in the partial <em>cone</em> ligand (<strong>L</strong>_{<strong>p</strong>}) led to incomplete cation desolvation andsignificantly reduced its cation-binding ability compared to the regular <em>cone</em> isomer (<strong>L</strong>_{<strong>c</strong>}). Aromaticring inversion also precluded solvent inclusion in the calixarene <em>basket</em> of both free and complexed <strong>L</strong>_{<strong>p</strong>} (in contrast to <strong>L</strong>_{<strong>c</strong>}), which considerably affected the complex stabilities and highlightedthe pronounced cooperative allosteric effect of this process on thecation binding. Comprehensive structural and energetic studies, carriedout by classical molecular dynamics simulations and quantum chemicalcalculations, showed that inclusion of acetonitrile within the complexeswas favored over methanol, whereby the nitrile group of the solventcoordinated the second-group cations. Conversely, the methyl groupof included acetonitrile or methanol molecule faced the alkali metalcations in the corresponding adducts. Molecular and crystal structuresof free <strong>L</strong>_{<strong>p</strong>}, as well as sodium,calcium, and barium complexes of <strong>L</strong>_{<strong>c</strong>} with included acetonitrile, were determined by single-crystalX-ray diffraction. The orientations of solvent molecules within thecalixarene cavity in the solid state closely matched computationalpredictions, further supporting conclusions drawn from the experimentaldata. Overall, this work presents a particularly detailed accountof the thermodynamic and structural aspects of chelate, macrocyclic,and medium effects on the cation-hosting processes, providing valuableinsights into the driving forces governing supramolecular recognitionin solution.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"88–103"},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143532","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}

{"title":"Deoxyfluorination of Hydroxy-Substituted Boronates","authors":"Yaroslav Melnyk,&nbsp;Oleksandr S. Liashuk,&nbsp;Oleksandr Horulya,&nbsp;Olexiy D. Kachkovskiy,&nbsp;Oleksandr O. Grygorenko","doi":"10.1021/acsorginorgau.5c00112","DOIUrl":"10.1021/acsorginorgau.5c00112","url":null,"abstract":"<p>A practical and scalableprotocol for the deoxyfluorination ofhydroxyalkyl-substituted aryl- and alkenylboronates was developed.The optimized conditions (combining Deoxo-Fluor with TEA·3HFas the reagents and substrate preconversion to trifluoroborate salts)enabled efficient transformation across a wide range of (homo)­benzylicand allylic alcohols while tolerating protected carboxyl and aminogroups. The resulting fluorinated boronates performed well as versatilebuilding blocks in oxidation and Suzuki cross-coupling reactions.Furthermore, a telescoped one-pot strategy allowed direct utilizationof crude fluorinated intermediates, enabling access to complex molecularframeworks containing alcohol, carbonyl, and ester functionalities,typically intolerant to late-stage fluorination conditions. This methodologyoffers a general and efficient route for the incorporation of monofluorinatedaliphatic fragments into structures that are relevant for medicinalchemistry and materials science.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"169–176"},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143348","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}

{"title":"The Combined Role of Silanols and Oxidative Stress in Determining Engineered Stone Dust Toxicity","authors":"Cristina Pavan,&nbsp;Marianna Fimiani,&nbsp;Stefania Cananà,&nbsp;Aleandro Diana,&nbsp;Matteo Marafante,&nbsp;Stefano Bertinetti,&nbsp;Guillermo Escolano-Casado,&nbsp;Lorenzo Mino,&nbsp;Dino Pisaniello,&nbsp;Riccardo Leinardi,&nbsp;Maura Tomatis,&nbsp;Francesco Turci","doi":"10.1021/acsorginorgau.5c00089","DOIUrl":"10.1021/acsorginorgau.5c00089","url":null,"abstract":"<p>Engineered stone(ES) silicosis is emerging as a globaloccupationalhealth crisis, caused by exposure to respirable particles generatedduring the processing of ES composite materials. ES composites comprisecrystalline silica (predominantly quartz), inorganic aggregates, polymericresins, and pigments. The severity of lung disease in workers contrastswith the modest effects observed in short-term in vitro studies, exposinga critical gap in our mechanistic understanding of ES dust toxicity.In this work, we examined the surface chemistry and reactivity ofES dust obtained from a slab with high crystalline silica content,before and after incubation (up to two months) in simulated lung fluids:artificial lysosomal fluid (ALF, pH ∼ 4.5) and lung liningfluid simulant (Gamble’s solution, GS, pH ∼ 7.4). Damageto model membranes (red blood cell, RBC), an initiating event in ES-inducedtoxicity, was quantified by membranolytic assay. Pristine ES dustwas negligibly membranolytic. Incubation in ALF markedly increasedES membranolytic activity, correlating with partial degradation ofthe resin. A complete removal of the resin produced a dust with furtherenhanced activity, associated with the exposure of nearly free silanol(NFS) groups, a recognized molecular trigger of quartz toxicity. NFSwere detected by infrared spectroscopy after H/D isotopic exchange.ALF incubation also led to substantial release of transition metalions, which catalyzed the formation of hydroxyl and carboxyl radicals,detected by EPR spectroscopy. In contrast, GS exposure resulted inminimal membranolytic activity and low radical generation. Our findingssuggest that prolonged residence of ES dust in lung cellular environments,particularly lysosomes, promotes resin degradation, exposes reactivesilanols, and releases transition metal ions, thereby imparting bothmembranolytic and oxidative potential. This work provides new molecularinsight into ES dust toxicity, emphasizes the urgency of safer occupationalpractices, and paves the way to safe-by-design strategies for futurecomposite materials.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"76–87"},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143632","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}

{"title":"Aggregation Tendency, Cellular Uptake, and Viability Effects of Structurally Distinct Carbazole–Phthalocyanine Gold Nanoconjugates","authors":"Neval Sevinç Özdemir,&nbsp;Özlem İpsiz Öney,&nbsp;Hacer Yasemin Yenilmez,&nbsp;Nazlı Farajzadeh Öztürk,&nbsp;Zehra Altuntaş Bayır","doi":"10.1021/acsorginorgau.5c00107","DOIUrl":"10.1021/acsorginorgau.5c00107","url":null,"abstract":"<p>Phthalocyanine–gold nanoparticle (Pc–AuNP)conjugatescombine the unique properties of gold with the therapeutic potentialof phthalocyanines, offering a promising strategy for cancer therapy.Here, two novel carbazole-containing Pcs, axially disubstituted Si­(IV)and peripherally tetra-substituted Zn­(II) derivatives, were synthesizedand conjugated to gold nanoparticles of two core sizes (20 and 40nm). Characterization was performed using TEM and SEM techniques.Stability assays in complete medium showed a stronger aggregationtendency for SiPc–AuNPs than for ZnPc–AuNPs. Bright-fieldmicroscopy revealed that Pc–AuNPs induced detachment of A549lung adenocarcinoma cells but not HUVEC endothelial cells, highlightinga cell type–dependent effect. Despite this detachment, no significantloss of viability occurred at 72 h, underscoring the resilience ofA549 cells to membrane and cytoskeletal stress. Once internalized,both SiPc- and ZnPc-based nanoconjugates displayed similar cytoplasmicand perinuclear localization, suggesting uptake was dominated by theAuNP carrier. Preliminary MTT assays showed dye–particle interference,leading to use of the PrestoBlue assay, which avoids insoluble formazanartifacts. Viability analysis indicated that only <strong>Au40/SiPc</strong> transiently increased A549 reducing capacity at 24 h, likely dueto short-term ROS scavenging, which normalized by 72 h. Overall, thesefindings demonstrate how metal center, substitution geometry, andparticle size collectively affect aggregation, cellular interactions,and cytotoxic profiles, providing insights for optimizing Pc–AuNPsas nanophototherapeutic agents.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"149–160"},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143712","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}

{"title":"Fluorinated Solvents for Chemoselective Oxidations: A Strategy toward Synthetic Ideality in Natural Product Synthesis","authors":"Victor C. S. Santana,&nbsp;Lucas D. P. Gonçalves,&nbsp;Yasmin N. Salmazo,&nbsp;Julian C. S. Pavan,&nbsp;Deborah de A. Simoni,&nbsp;Vladimir C. G. Heleno,&nbsp;Emilio C. de Lucca, Jr.","doi":"10.1021/acsorginorgau.5c00121","DOIUrl":"10.1021/acsorginorgau.5c00121","url":null,"abstract":"<p>Late-stage catalytic oxidations of complex natural productshavebeen shown to exhibit dramatically improved chemoselectivity throughthe crucial use of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), evenin the presence of oxidatively sensitive groups, such as hydroxylsand diols. This strategy reduced the need for protecting groups, effectivelymimicking enzymatic pathways, and substantially enhancing syntheticideality in the preparation of <em>ent</em>-beyerane and <em>ent</em>-kaurane metabolites.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"47–52"},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143324","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}