ACS Organic & Inorganic Au最新文献

{"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":"Modeling 2D van der Waals Materials with Homonuclear Bonds of Main Group Cations","authors":"Peng Yan,&nbsp;Anthony A. Casale,&nbsp;Joseph W. Bennett","doi":"10.1021/acsorginorgau.5c00096","DOIUrl":"10.1021/acsorginorgau.5c00096","url":null,"abstract":"<p>We survey a rangeof 2D van der Waals (vdW) layered materials thatcontain homonuclear bonds of main group elements, specifically Ga–Ga,In–In, Si–Si, Ge–Ge, and P–P, using first-principlesdensity functional theory (DFT) methods. The covalent bonding andgeometries present in these materials can stabilize oxidation statesthat differ from those found in conventional semiconductors composedof main group elements, such as Si, InP, and GaAs. Since 2D vdW materialsdid not gain widespread use until recently, many have been excludedfrom the first-principles test sets developed over a decade prior,where the focus was on determining the accuracy of potentials usedin different modeling methods. In this study, we benchmark the setby exploring a range of modeling methods that include GGA and meta-GGAexchange-correlation functionals commonly used in first-principlesDFT methods, as well as exact exchange introduced using HSE06 andPBE0. We investigate their effects on the ground-state structure,electronic band structure, and computational cost and report on thisbenchmarking data. Our test set of 2D vdW materials contains multiplestructural types that span binary, ternary, and quaternary compositions,including ferroic ground states. We found that the vdW-corrected GGAis capable of accurately capturing lattice constants (within ±2%relative to available experimental data) across various 2D vdW materialsin our test set, with relatively low computational cost and turn-keycompatibility with the open-source code Quantum Espresso. Additionally,vdW-corrected GGA can reliably identify stable ferroelectric and ferromagneticground states, can be used to determine trends in electronic bandstructure, and serve as a starting point for predicting more accurateband gaps. The predicted electronic band structure and correspondingprojected density of states (PDOS) are crucial for establishing theconnection between microscopic properties and atomic or molecularorbitals, which can, in turn, be used to predict novel functional2D vdW materials.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"104–118"},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143507","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":"More than Catalyst Recycling: Tuning Synthetic Photocatalytic Processes via Heterogenization on Silica and Alumina","authors":"Zacharias Amara,&nbsp;Pierre Zimberlin,&nbsp;Augustin Pirenam Atakpa,&nbsp;Yahya Al Ayi,&nbsp;Maxime Lancel","doi":"10.1021/acsorginorgau.5c00088","DOIUrl":"10.1021/acsorginorgau.5c00088","url":null,"abstract":"<p>The heterogenizationof homogeneous photocatalysts on inert supportssuch as silica and alumina offers more than improved recyclability.Unlike semiconducting supports such as titanium dioxide, which canalter the photocatalyst behavior through electron injection, insulatingoxides preserve the intrinsic photophysical and redox properties ofthe molecular species. However, such heterogenization is an opportunityto completely modify the physicochemical properties of the surroundingenvironment, thereby influencing excited-state properties and enhancingreactivity and stability as well as compatibility with green solventsand flow systems. In addition, advanced support design introducesfurther potential for selectivity or reactivity with gas, althoughthese remain largely underexplored. While silica is widely used dueto its tunability and surface area, alumina offers complementary propertiesbut remains less developed. This review highlights the early stage,yet rapidly evolving landscape of heterogenized photocatalysts onsilica and alumina, emphasizing the emerging functionalities thatextend well beyond catalyst recovery.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"8–22"},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143515","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":"Novel Nitroxide-Substituted Hydrazone Switch: Experimental and Theoretical Insights into Photoswitching Behavior","authors":"Lucie Kotásková,&nbsp;Ivan Nemec,&nbsp;Radovan Herchel,&nbsp;Vinicius T. Santana,&nbsp;Petr Neugebauer","doi":"10.1021/acsorginorgau.5c00068","DOIUrl":"10.1021/acsorginorgau.5c00068","url":null,"abstract":"<p>Hydrazones are a versatile class of molecular switcheswith dualresponsiveness to both light and pH. To investigate their switchingproperties, we incorporated a nitroxide moiety, enabling analysisby not only conventional techniques such as ¹H NMR andUV–vis spectroscopy but also EPR spectroscopy, which providesvaluable insights into structure and dynamics. A novel nitroxide-substitutedhydrazone switch (<strong>2</strong>) was synthesized and fully characterized.However, initial experiments using ¹H NMR and UV–visrevealed restricted photoisomerization of <strong>2</strong>. Theoreticalstudies employing DFT and TD-DFT methods revealed the presence ofthe D₁ excited state related to π → π*electron transfer of the nitroxide moiety, and D₂ excitedstate related to π → π* electron transfer withinthe hydrazone moiety. The latter excitation results in weakening ofthe C<span></span>N bond and enables the rotation around the hydrazonebond; however, the internal conversion D₂ → D₁ process is most likely responsible for the quenching of photoisomerizationin <strong>2</strong>. Additionally, pH-induced switching was monitoredusing UV–vis and EPR spectroscopy, revealing that strong acidssuch as trifluoroacetic acid had no significant effect on the paramagneticcenter.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"64–75"},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143505","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":"Rotational Behavior in Piano Stool Ru(II) Complexes with Bulky-Substituted Cyclopentadienyl Ligands","authors":"Naoki Ito,&nbsp;Toshio Nishino,&nbsp;Jérôme Cuny,&nbsp;Shohei Katao,&nbsp;Kazuma Yasuhara,&nbsp;Gwénaël Rapenne","doi":"10.1021/acsorginorgau.5c00100","DOIUrl":"10.1021/acsorginorgau.5c00100","url":null,"abstract":"<p>In this study, wedesigned and synthesized a series ofnovel pianostool ruthenium complexes featuring bulky substituents on the cyclopentadienyl(Cp) ligand to investigate how the substituent structure affects rotationalbehavior around the Cp–Ru bond. Substituents, including <em>m</em>-xylyl, mesityl, and 9-anthracenyl groups, were introducedto create steric hindrance with the tripodal ligand to increase therotational barrier. NMR spectroscopy revealed that the Cp–Rubond in the complex with the <em>m</em>-xylyl group rotatedfaster than the NMR time scale, whereas complexes bearing mesityland 9-anthracenyl groups exhibited slower rotation. Variable-temperatureNMR measurements and line shape fitting analysis showed that the activationfree energy (Δ<em>G</em>^⧧) requiredfor the Cp ligand rotation by overcoming the steric hindrance betweenthe substituent and tripodal ligand was significantly higher for themesityl (69.5 kJ mol^–1) and 9-anthracenyl (67.8kJ mol^–1) complexes compared to the previously reportedpentaphenyl Cp complex (18.9 kJ mol^–1). The resultsindicate that the activation enthalpy is the primary contributor tothe overall activation energy, suggesting that the bulky substituentsincrease the rotational barrier by occupying the spatial gap betweenthe pyrazole rings of the tripodal ligand. This is confirmed by theoreticalcalculations and the characterization of the minimum energy pathsand transition states for each species. These findings offer valuableguidance for the molecular design of STM-operable molecular motorsthat can function at or near ambient temperature instead of the typicalextremely low-temperature conditions necessary to suppress randommolecular motion caused by thermal excitation.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"139–148"},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143545","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 Access to Fluorinated Analogs of a Known Streptococcus pneumoniae Type 14 Glycotope","authors":"Maximilian Reindl,&nbsp;Andreas Baumann,&nbsp;Anja Hoffmann-Röder","doi":"10.1021/acsorginorgau.5c00108","DOIUrl":"10.1021/acsorginorgau.5c00108","url":null,"abstract":"<p>For the first time, we present fluorinated analogs of <em>Streptococcus pneumoniae</em> serotype 14 (SPn14)-specifictetrasaccharide antigens originating from the repeating unit {6)-[β-<span>d</span>-Gal<em>p</em>-(1→4)-]-β-<span>d</span>-Glc<em>p</em>NAc-(1→3)-β-<span>d</span>-Gal<em>p</em>-(1→4)-β-<span>d</span>-Glc<em>p</em>-(1→}_<em>n</em> of the capsule’s outer cell surface,featuring different strategic fluorination sites. These modified pneumococcaltetrasaccharides are also equipped with allyl groups at the reducingend to enable further functionalization. Key transformation stepsduring the synthesis of these target molecules included (1 + 1)-glycosylationsof fluorinated galactosyl donors as well as late fluorination steps,which were selectively performed on lactosyl building blocks. Thesubsequent central (2 + 2) couplings of the lactosyl donors with therespective lactosaminyl building blocks proceeded with good yields,enabling the synthesis of the desired target tetrasaccharide antigenanalogs in amounts sufficient for future biological investigationsfollowing a global deprotection protocol. A total of six novel F-analogsof the SPn14 glycotope were produced using the methods described herein.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"161–168"},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143529","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":"ACS Organic & Inorganic Au: The 2025 Rising Stars","authors":"Géraldine Masson","doi":"10.1021/acsorginorgau.5c00124","DOIUrl":"10.1021/acsorginorgau.5c00124","url":null,"abstract":"","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"1–7"},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143772","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":"[3 + 2] Cycloadditions of Tertiary Amine N‑Oxides and Azoarenes as a Route to Substituted 1,2,4-Triazolidines","authors":"Nicholas A. Frankos,&nbsp;Malavika S. Nair,&nbsp;Aiden M. Lane,&nbsp;Megan M. Glista,&nbsp;Joshua K. Graber,&nbsp;Abbigail E. F. Black,&nbsp;Trista G. L. X. Newman,&nbsp;Elias R. Griffin,&nbsp;Kiera M. Luca,&nbsp;Eric J. Chartier,&nbsp;David B. Heisler,&nbsp;Thomas D. Montgomery","doi":"10.1021/acsorginorgau.5c00098","DOIUrl":"10.1021/acsorginorgau.5c00098","url":null,"abstract":"<p>We have developed a synthesis of 29 novel 1,2,4-triazolidinesusingtertiary amine <em>N</em>-oxides and a wide range of substitutedazoarenes. Our method utilizes a base-mediated [3 + 2] cycloaddition,starting from either commercially available or easily accessible precursorsto generate triazolidines in yields up to 99%. Density functionaltheory calculations were performed in parallel to the experimentalwork to provide insights into the reactivity patterns and the overallmechanism. Finally, preliminary biological data are included on theantibacterial properties of these compounds.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"119–129"},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143770","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":"Silver-Catalyzed C(sp3)–H Functionalization","authors":"Masoud Sadeghi","doi":"10.1021/acsorginorgau.5c00104","DOIUrl":"10.1021/acsorginorgau.5c00104","url":null,"abstract":"<p>Silver catalysis has emerged as a versatile tool forC­(sp³)–H bond functionalization, offering uniqueopportunitiesto transform simple hydrocarbons into valuable products. Both activatedand unactivated C­(sp³)–H bonds have been investigatedin recent years. However, most studies have focused on activated bonds.In these protocols, in situ generation of nitrene intermediates hasdominated the field, enabling efficient and selective C­(sp³)–H bond transformations. These reports demonstrate that liganddesign, in addition to the nature of the silver catalyst, plays acrucial role in achieving chemo-, site-, and even stereoselectivity.During the past decade, silver-catalyzed functionalization has beenused for the conversion of C­(sp³)–H bonds into C–C,C–N, C–O, and C–X (X = halogen) bonds. Theseprotocols have shown that Ag­(I) combined with suitable oxidants canbe used as a powerful synthetic tool for the functionalization ofspecific C­(sp³)–H bonds into desired C–Zbonds. This review highlights the advances and limitations in silver-catalyzedC­(sp³)–H functionalization that have been reportedduring the past decade.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"23–40"},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143550","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":"Theoretical Screening of the Water Oxidation Electrocatalytic Cycle Promoted by Single-Site Macrocyclic Copper(II) Complexes: Unraveling the Role of the HPO2–4 Anion under Neutral Conditions","authors":"João Pedro C. S. Neves,&nbsp;Joel Leitão Nascimento,&nbsp;Bruno S. Sampaio,&nbsp;Roberto Rivelino,&nbsp;Tiago Vinicius Alves,&nbsp;Vitor H. Menezes da Silva","doi":"10.1021/acsorginorgau.5c00047","DOIUrl":"10.1021/acsorginorgau.5c00047","url":null,"abstract":"<p>Herein, a comprehensivetheoretical investigation of the electrocatalyticcycle related to water oxidation (WO) (i.e., the bottleneck of H₂ electrochemical production) catalyzed by a single-site copper­(II)complex bearing the 14-TMC ligand (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane)is presented. Density Functional Theory (DFT) calculations were carriedout to characterize two distinct single–electron transfer–waternucleophilic attack (SET-WNA) mechanisms that operate in the O–Obond formation in the electrocatalytic cycle. The electrochemicalreaction is initiated with the formation of a [Cu­(14-TMC)­(H₂O)]⁺² intermediate, followed by a proton-coupled electrontransfer (PCET) redox transformation. The first PCET is succeededby a SET or a second PCET, leading to the formation of [Cu­(14-TMC)­(OH)]⁺³ (⁴<strong>2</strong>) or [Cu­(14-TMC)­(O)]⁺² (⁴<strong>3</strong>), the starting reaction intermediatesfor the two SET-WNA mechanisms proposed. Notably, the presence ofHPO<span><span>^{<strong>2–</strong>}_{<strong>4</strong>}</span></span> plays a critical role in promoting the formationof the O–O bond formation. A proton transfer from water toHPO<span><span>^2–₄</span></span> facilitates the O–O bond formation involving [Cu­(14-TMC)­(OH)]⁺³ (⁴2) and [Cu­(14-TMC)­(O)]⁺² (⁴<strong>3</strong>) species. To reinforce the crucial role of HPO<span><span>^2–₄</span></span> underneutral conditions, in the absence of this anion, the overall reactionbarrier for O–O bond formation is ≈40 kcal/mol, whichrules out this reaction pathway at room temperature. Finally, successivePCET or SET steps involving [Cu­(14-TMC)­(HOOH)]⁺² or [Cu­(14-TMC)­(OOH)]⁺ intermediates result in the evolution of the O₂ and regeneration of the catalyst. The thermodynamic and kineticcomputational results show good agreement with previous experimentalelectrochemical data. Overall, based on these computational findings,we propose a new picture for the WO electrocatalytic cycle mediatedby macrocyclic Cu complexes bearing the 14-TCM ligand.</p>","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 1","pages":"53–63"},"PeriodicalIF":5.2,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146143579","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}