ACS Organic & Inorganic Au最新文献_第2页

Solvent-Controlled Reaction Productivity and Mechanistic Pathways in the Multicomponent Synthesis of 2-Amino-3-cyano-4H-pyrans 多组分合成2-氨基-3-氰基- 4h -吡喃的溶剂控制反应率和机理途径

IF 5.2

ACS Organic & Inorganic Au Pub Date : 2026-10-07 Epub Date: 2026-07-15 DOI: 10.1021/acsorginorgau.6c00059

Jhonathan Renner Nunes dos Santos, Luciana Machado Ramos, Juliana Gonzaga de Morais Lima, Saulo T. A. Passos, Aline Lima de Oliveira, Fabricio Machado, Brenno A. D. Neto

{"title":"Solvent-Controlled Reaction Productivity and Mechanistic Pathways in the Multicomponent Synthesis of 2-Amino-3-cyano-4H-pyrans","authors":"Jhonathan Renner Nunes dos Santos, Luciana Machado Ramos, Juliana Gonzaga de Morais Lima, Saulo T. A. Passos, Aline Lima de Oliveira, Fabricio Machado, Brenno A. D. Neto","doi":"10.1021/acsorginorgau.6c00059","DOIUrl":"https://doi.org/10.1021/acsorginorgau.6c00059","url":null,"abstract":"In this work, we present a detailed mechanistic and solvent-effectstudy of the multicomponent synthesis of 2-amino-3-cyano-4H-pyran (ACP) derivatives catalyzed by a water-solubleimidazolium-functionalized polymer (PEI.IL)─a synthetic enzyme(synzyme). Rather than focusing solely on synthetic scope, this studydissects how solvent properties and reaction equilibria govern reactionproductivity and pathway selection in this multicomponent transformation.Solvent effects were quantitatively analyzed using the Kamlet-Abboud-Taftmodel, revealing that hydrogen-bond acidity (α), hydrogen-bondbasicity (β), and dipolarity/polarizability (π*) playdistinct and competing roles at different stages of the reaction.Control experiments, combined with systematic variation of reactionconditions, demonstrate that product formation proceeds predominantlythrough a pathway initiated by the reversible condensation betweenbenzaldehyde and malononitrile, followed by enol-mediated a new C–Cbond formation. Reaction productivity was treated as a thermodynamicallyoriented descriptor, allowing correlations between solvent effects,keto–enol equilibria, and overall efficiency to be established.The methodology affords a series of ACP derivatives ingood to excellent yields under optimized conditions, with the catalystremaining recyclable over multiple cycles without loss of activity.By integrating solvent-effect analysis, equilibrium considerations,and mechanistic control experiments, this work provides an experimentallygrounded framework for understanding and optimizing multicomponentreactions beyond conventional yield-based approaches.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 5","pages":"654–674"},"PeriodicalIF":5.2,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149124784","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

Aqueous-Phase Peptide Synthesis via Stepwise Amino Acid Elongation Catalyzed by Aqualigase 水合酶催化氨基酸分步延伸合成水相多肽

IF 5.2

ACS Organic & Inorganic Au Pub Date : 2026-10-07 Epub Date: 2026-08-26 DOI: 10.1021/acsorginorgau.6c00067

Xin Yan, Zihan Lin, Ruyi Chen, Luobin Huang, Lige Tong, Bei Gao, Lujia Zhang

{"title":"Aqueous-Phase Peptide Synthesis via Stepwise Amino Acid Elongation Catalyzed by Aqualigase","authors":"Xin Yan, Zihan Lin, Ruyi Chen, Luobin Huang, Lige Tong, Bei Gao, Lujia Zhang","doi":"10.1021/acsorginorgau.6c00067","DOIUrl":"https://doi.org/10.1021/acsorginorgau.6c00067","url":null,"abstract":"Peptides have broad applications in fields such as food,medicine,and functional materials. Conventional solid-phase peptide synthesis(SPPS) constructs diverse peptide sequences through stepwise aminoacid elongation but relies on stoichiometric coupling reagents andorganic solvents, thereby generating considerable chemical waste.Aqualigase, an engineered subtilisin, offers a green alternative thatdirectly condenses free carboxylic acids and amines in pure aqueousmedia. However, whether this system can support stepwise elongationusing amino acids as building blocks remains unclear. Here, usingthe Aqualigase-catalyzed ligation of Ala-Ala-Pro-Phe and Ala-Phe asa model reaction, hydrogen-bond analysis revealed that a stable interactionbetween the P1′ residue of the acyl acceptor and Asn155 inthe substrate-binding pocket is critical for effective binding ofthe acyl acceptor. Guided by this finding, we demonstrated that Aqualigaseligates peptides ranging from dipeptides to pentapeptides with aminoacids as acyl acceptors, expanding its catalytic mode from peptide-fragmentligation to fragment-amino acid ligation. RMSF analysis further revealedpronounced flexibility in the loops surrounding the catalytic pocket,particularly residues 95 to 106 and 155 to 164, providing a structuralbasis for substrate accommodation. Substrate scope analysis showedthat, under Aqualigase catalysis, amino acids are more broadly compatibleas acyl acceptors than as acyl donors, supporting an N-to-C-terminalstepwise elongation strategy. Using this approach, the functionaltripeptide Gly-Leu-Phe was synthesized in pure aqueous media throughsequential amino acid elongation. This study establishes an engineeredsubtilisin-catalyzed strategy for stepwise peptide synthesis in pureaqueous media, providing a green route for flexible peptide construction.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 5","pages":"687–696"},"PeriodicalIF":5.2,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149124842","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

Multifunctional UiO-66 MOFs in Photocatalytic and Electrocatalytic Nitrogen Reduction: A New Horizon in Green Ammonia Synthesis 光催化和电催化氮还原的多功能UiO-66 MOFs：绿色合成氨的新领域

IF 5.2

ACS Organic & Inorganic Au Pub Date : 2026-10-07 Epub Date: 2026-08-10 DOI: 10.1021/acsorginorgau.6c00042

Arup Anurup Dash, Priyanka Priyadarshini, Diptirani Behera, Kulamani Parida

{"title":"Multifunctional UiO-66 MOFs in Photocatalytic and Electrocatalytic Nitrogen Reduction: A New Horizon in Green Ammonia Synthesis","authors":"Arup Anurup Dash, Priyanka Priyadarshini, Diptirani Behera, Kulamani Parida","doi":"10.1021/acsorginorgau.6c00042","DOIUrl":"https://doi.org/10.1021/acsorginorgau.6c00042","url":null,"abstract":"The conventional production of ammonia (NH3) rests onthe energy-intensive Haber process, driving the scientific communityto search for sustainable catalysts capable of reducing the inertN≡N bond under ambient conditions. Among the various porousmaterials examined for the nitrogen reduction reaction (NRR), UiO-66,a Zr-based MOF, stands out owing to its exceptional robustness, highBET surface area, tunable porosity and strong Lewis acidity at theZr4+ nodes, making it a highly versatile platform for bothphotocatalytic and electrocatalytic NH3 production. Thisreview aims to deliver a comprehensive overview of UiO-66-based materialsfor photocatalytic (P-NRR) and electrocatalytic (E-NRR) nitrogen reduction,while providing a detailed account of the key parameters governingNRR, including its thermodynamics and kinetics, the challenges ofactivating the inert N≡N bond, and competing hydrogen evolutionreaction (HER). Several synthesis methods for UiO-66 are criticallydiscussed with respect to how each approach influences material properties,including crystallinity, surface area, stability, and porosity. Targetedmodification strategies, such as metal doping, linker functionalization,defect engineering, and composite formation, are systematically explored,each aimed at introducing suitable active sites and establishing afavorable environment for N2 adsorption and activationacross both photocatalytic and electrocatalytic systems. P-NRR andE-NRR performances are critically analyzed, with due considerationgiven to NH3 detection methods, including colorimetricassays, ion chromatography, and 1H NMR spectroscopy, whichare essential for reliable quantification. Finally, current challengesand future directions are outlined to guide the rational design ofefficient, selective, and robust UiO-66-based catalysts for sustainableNH3 synthesis.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 5","pages":"512–538"},"PeriodicalIF":5.2,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149093637","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

Programmable Leaving Group Controlled Skeletal Editing of Pyrroles into Pyridines via Sulfenylcarbenes 可编程的离开基团控制的骨架编辑吡咯到吡啶通过磺酰基羰基

IF 5.2

ACS Organic & Inorganic Au Pub Date : 2026-10-07 Epub Date: 2026-08-07 DOI: 10.1021/acsorginorgau.6c00077

Upasana Chatterjee, Prakash Kafle, Shuhei Yasuda, Indrajeet Sharma

引用次数: 0

Facile Pd(II)-Catalyzed Ortho C(sp2)–H Alkenylation of 2′-Methyl Biaryl-2-Amines with Bulky Internal Alkynes Enabled by Steric Effects: From Alkenylation to Orthogonal Polycyclic Aromatics 空间效应使2′-甲基双芳基-2胺与大体积内炔的邻位C(sp2) -H烯化：从烯化到正交多环芳烃

IF 5.2

ACS Organic & Inorganic Au Pub Date : 2026-10-07 Epub Date: 2026-09-02 DOI: 10.1021/acsorginorgau.6c00062

Guganchandar Vedarethinam, Pei-Lin Chen, Yun-Ming Li, Shih-Ching Chuang

引用次数: 0

Structured HTE Data and Integrated Bayesian Optimization Accelerate Scalable Amidation Process Development 结构化HTE数据和集成贝叶斯优化加速可扩展的改进过程开发

IF 5.2

ACS Organic & Inorganic Au Pub Date : 2026-10-07 Epub Date: 2026-08-17 DOI: 10.1021/acsorginorgau.6c00051

Jason M. Stevens, Dung L. Golden, Nikki Dare, Shubhangi Aggarwal, David Del Valle, Stacey DiSomma, Michael Eng, Ariel Furman, Lauren Grant, Diane Hendrix, Bilal Hoblos, Jiajie Huo, Mikalai Malashchonak, Ketleine Miller, Emily Mumford, Cheng Peng, Lingxiang Lu, Donggeon Nam, Frederick Roberts, Victor Rosso, Eric Saurer, Sushant Singh, Dmitriy Snetkov, Anton Terekh, Alexander E. Waked, Michael Williams, Chengmin Zhang

{"title":"Structured HTE Data and Integrated Bayesian Optimization Accelerate Scalable Amidation Process Development","authors":"Jason M. Stevens, Dung L. Golden, Nikki Dare, Shubhangi Aggarwal, David Del Valle, Stacey DiSomma, Michael Eng, Ariel Furman, Lauren Grant, Diane Hendrix, Bilal Hoblos, Jiajie Huo, Mikalai Malashchonak, Ketleine Miller, Emily Mumford, Cheng Peng, Lingxiang Lu, Donggeon Nam, Frederick Roberts, Victor Rosso, Eric Saurer, Sushant Singh, Dmitriy Snetkov, Anton Terekh, Alexander E. Waked, Michael Williams, Chengmin Zhang","doi":"10.1021/acsorginorgau.6c00051","DOIUrl":"https://doi.org/10.1021/acsorginorgau.6c00051","url":null,"abstract":"We describe the evolutionof our early hit-identification workflowfor reagent-mediated amidation reactions in support of commercialroute development. Over the past decade, our strategy progressed frombroad, exhaustive high-throughput experimentation (HTE) with limiteddata maturity to a modern, enterprise-scale digital platform thatembeds data science tools directly into the experimental workflow.By tailoring Katalyst D2D─a commercial electronic laboratorynotebook (ELN) for HTE developed by ACD/Laboratories─we establisheda structured, machine-readable data architecture and enabled seamlessintegration with the EDBO+ Bayesian optimization engine. Retrospectiveanalysis of historical amidation data sets showed that, despite screeningmore than 60 reagents, only a small subset consistently translatedto commercial processes. This insight motivated a streamlined workflowin which chemists begin with a focused survey of six reaction conditionsrooted in empirical performance and commercial precedent, followedby Bayesian optimization within the ELN to identify optimal reagent/base/solventcombinations. This study highlights how treating reaction data asa digital asset─FAIR, interoperable, and directly linked tooptimization tools─accelerates the transition from reactionscreening to robust process development.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 5","pages":"624–635"},"PeriodicalIF":5.2,"publicationDate":"2026-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149124619","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

A Terbium(III) Luminescent Probe for Quantifying Bicarbonate Levels in Ocean Water 一种用于定量海水中碳酸氢盐含量的铽（III）发光探针

IF 5.2

ACS Organic & Inorganic Au Pub Date : 2026-10-07 Epub Date: 2026-07-31 DOI: 10.1021/acsorginorgau.6c00044

Thibaut L. M. Martinon, Avisikta Sinha, Tristen E. Garner, Taylor Hatch, Logan Olson, Alexander Sunne, Katie L. Peterson, Valérie C. Pierre

引用次数: 0

Planar Chirality Directs Enantiospecific Diastereoselectivity in Isocyanide-Based Multicomponent Reactions 平面手性指导异氰化物多组分反应的对映体非对映选择性

IF 5.2

ACS Organic & Inorganic Au Pub Date : 2026-08-05 Epub Date: 2026-05-26 DOI: 10.1021/acsorginorgau.6c00034

Michael Kapsalis, Michael Fragkiadakis, Iakovos Konstantaras, Konstantinos G. Froudas, Taxiarchis Stergiannakos, Rongyu Sun, Erica Benedetti, Constantinos G. Neochoritis

引用次数: 0

Gallylene-Mediated C–C Bond Activation of Diphenylcyclopropenone and Chalcogen Atom Insertion into a Ga–C Bond 二苯基环丙烯介导的C-C键活化及硫原子插入Ga-C键。

IF 5.2

ACS Organic & Inorganic Au Pub Date : 2026-08-05 Epub Date: 2026-07-14 DOI: 10.1021/acsorginorgau.6c00053

Nijito Mukai, Sota Iwasaki, Takuya Kodama, Mamoru Tobisu

引用次数: 0

A Low-Potential π-Extended Viologen Electron Donor Results in Increased H2 Production by CpI [FeFe]-Hydrogenase 低电位π扩展紫素电子给体导致CpI [FeFe]-氢化酶产氢量增加

IF 5.2

ACS Organic & Inorganic Au Pub Date : 2026-08-05 Epub Date: 2026-01-20 DOI: 10.1021/acsorginorgau.5c00106

Nils Ostermann, Sophie Webb, Andrea Do Nascimento Henriques, Ross D. Milton

{"title":"A Low-Potential π-Extended Viologen Electron Donor Results in Increased H2 Production by CpI [FeFe]-Hydrogenase","authors":"Nils Ostermann, Sophie Webb, Andrea Do Nascimento Henriques, Ross D. Milton","doi":"10.1021/acsorginorgau.5c00106","DOIUrl":"https://doi.org/10.1021/acsorginorgau.5c00106","url":null,"abstract":"[FeFe]-hydrogenases are known for their exceptional dihydrogenproduction activity, which opens a pathway to green hydrogen formation.To achieve the high turnover numbers found in natural environments,researchers aim to mimic biological electron donors using artificialelectron delivery systems. In this sense, the use of an externallyapplied electrochemical potential is of particular interest, for whichredox mediators often have to be included to effectively shuttle electronsbetween the electrode and the enzyme. The class of viologens, withmethylviologen being the most prominent example, has been shown toperform efficient electron transfer. However, the reduced forms ofsuch viologens are restricted in terms of stability and accessibilityof the more reduced, low-potential species. Herein, we report theelectrochemical and spectroscopic characterization of a viologen-basedderivative, which is capable of storing two electrons at a low potentialof −0.75 V vs. SHE. In combination with the[FeFe]-hydrogenase CpI, an activity of up to 10,480μmolH2 mg–1CpI min–1 (molar activity of 11,179 μmolH2 μmol–1CpI s–1) could be achieved, which is 10 times greaterthan the commonly used dithionite-driven methylviologen assay underthe same conditions.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 4","pages":"398–405"},"PeriodicalIF":5.2,"publicationDate":"2026-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148693677","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