ChemCatChem最新文献_第2页

Quinuclidine-Catalyzed Electrochemical Minisci Acylation of N-Heteroarenes with Acylhydrazines

IF 3.8 3区化学

ChemCatChem Pub Date : 2024-12-03 DOI: 10.1002/cctc.202401642

Haonan Zhang, Dehui Wang, Prof. Kun Xu, Prof. Chengchu Zeng

引用次数: 0

Microkinetic Modelling of the Heterogeneously Catalyzed Hydrogenation of Glycolic Acid over Ru/C

IF 3.8 3区化学

ChemCatChem Pub Date : 2024-12-02 DOI: 10.1002/cctc.202400201

Florian M. Harth, Aleksa Kojčinović, Blaž Likozar, Roger Gläser, Matej Huš, Michael Goepel, Miha Grilc

{"title":"Microkinetic Modelling of the Heterogeneously Catalyzed Hydrogenation of Glycolic Acid over Ru/C","authors":"Florian M. Harth, Aleksa Kojčinović, Blaž Likozar, Roger Gläser, Matej Huš, Michael Goepel, Miha Grilc","doi":"10.1002/cctc.202400201","DOIUrl":"https://doi.org/10.1002/cctc.202400201","url":null,"abstract":"The heterogeneously catalyzed hydrogenation of biomass- or CO2-derived glycolic acid (GA) is a renewable pathway for obtaining the bulk chemical ethylene glycol (EG). In this study, the reaction network of the aqueous-phase hydrogenation of GA is investigated over a Ru/C catalyst. Beside this target reaction, both undesired parallel reactions (such as the hydrogenation of GA to acetic acid (AcA)) and unwanted consecutive reactions (such as over-hydrogenation) can occur. These reactions are experimentally assessed by employing different (possible) reaction intermediates and products (EG, AcA, glycolaldehyde, acetaldehyde, and ethanol) as reactants. The data for all individual reactions as well as the overall GA hydrogenation at different reaction temperatures (120–180 °C) is combined to propose a catalytic reaction pathway network and to develop a corresponding microkinetic model. The kinetic model describes the catalytic data in the range up to 150 °C, where EG is the main reaction product, with high accuracy. It is shown that selectivity for EG is highest at 120 °C (up to ca. 70%) and decreases strongly with increasing temperatures both due to the parallel reaction of GA into acetic acid (AcA), which has a significantly higher activation energy than the overall hydrogenation of GA into EG, and due to degradation of EG into ethanol and other volatile products. Temperatures exceeding 150 °C predominantly yield volatile products, suggesting low yields of EG or AcA at higher temperatures despite enhanced GA conversion.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 4","pages":""},"PeriodicalIF":3.8,"publicationDate":"2024-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202400201","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143438867","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Exploring Mechanistic Details and Catalyst Resilience in Electrocatalytic Water Oxidation With a Cu(II) Complex Bearing a Redox-Active Ligand

IF 3.8 3区化学

ChemCatChem Pub Date : 2024-11-30 DOI: 10.1002/cctc.202401357

Sachidulal Biswas, Srijan Narayan Chowdhury, Saikat Das, Suranjana Bose, Joyashish Debgupta, Satadal Paul, Achintesh N. Biswas

{"title":"Exploring Mechanistic Details and Catalyst Resilience in Electrocatalytic Water Oxidation With a Cu(II) Complex Bearing a Redox-Active Ligand","authors":"Sachidulal Biswas, Srijan Narayan Chowdhury, Saikat Das, Suranjana Bose, Joyashish Debgupta, Satadal Paul, Achintesh N. Biswas","doi":"10.1002/cctc.202401357","DOIUrl":"https://doi.org/10.1002/cctc.202401357","url":null,"abstract":"Herein, we report that a copper complex [Cu(dpaq)](ClO4) (1) (H-dpaq = 2-[bis(pyridin-2-ylmethyl)]amino-N-quinolin-8-yl-acetamide) acts as a molecular water oxidation catalyst (WOC) under strong basic condition. Complex 1 oxidizes water to dioxygen in 0.1 M phosphate buffer solution at pH 12.0, exhibiting a turnover frequency of 3.1 × 102 s−1 at a low overpotential (η) of ∼550 mV versus NHE at 1 mA cm−2. A turnover number of 4.0 can be obtained during controlled potential electrolysis (CPE) using 0.25 mM complex 1 at a potential of 1.5 V at pH 12.0 for 3 h. Postelectrolysis analysis, rinse tests, and chelating assays collectively support the homogeneous nature of the electrocatalyst. Mechanistic investigations and quantum chemical calculations reveal a pathway wherein two successive ligand-centered oxidations transform the catalyst into a Cu(II)(dpaq•)O•. intermediate. Absence of any metal centered oxidation renders the oxidized intermediate less electrophilic, resulting in the survival of the methylene groups present on the ligand backbone against oxidation. The formation of the O─O bond is proposed to proceed via two consecutive single electron transfers (SET) from incoming hydroxide ions to the formal CuIV–oxo species.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 4","pages":""},"PeriodicalIF":3.8,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143439162","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Recent Advances in Covalent Organic Framework for Selective Photocatalytic Reduction of CO2

IF 3.8 3区化学

ChemCatChem Pub Date : 2024-11-30 DOI: 10.1002/cctc.202401362

Dr. Shubham Avinash Deshmukh, Dr. Darpan Vijaykumar Bhuse, Dr. Selvaraj Suresh, Dr. Subodh Uttamrao Raut, Dr. Sharda Kondawar, Dr. Sujit Sarkar, Dr. Chandan Patel, Dr. Ganesh Agawane

{"title":"Recent Advances in Covalent Organic Framework for Selective Photocatalytic Reduction of CO2","authors":"Dr. Shubham Avinash Deshmukh, Dr. Darpan Vijaykumar Bhuse, Dr. Selvaraj Suresh, Dr. Subodh Uttamrao Raut, Dr. Sharda Kondawar, Dr. Sujit Sarkar, Dr. Chandan Patel, Dr. Ganesh Agawane","doi":"10.1002/cctc.202401362","DOIUrl":"https://doi.org/10.1002/cctc.202401362","url":null,"abstract":"Photocatalytic transformation of CO2 into clean fuels and chemicals is a promising solution to address both the energy dilemma and environmental issues. Recent years have seen several efforts to improve the effectiveness and selectivity of CO2 conversion by creating photocatalysts and reduction devices. An alternative to fossil fuels is urgently needed to address the rising energy demand and pollution. Porous heterogeneous catalysts are gaining popularity for carbon capture, with recent breakthroughs in design and application for CO2 conversion. Covalent organic frameworks (COFs) are porous crystalline polymeric materials made up of organic module units held together by strong covalent connections. COFs have numerous applications, including adsorption and separation, detection, catalysis, optoelectronic components, energy storage, and mass transport, due to their low density, massive specific surface area, superior thermal stability, developed pore structure, long-range sequence, good crystallinity, and excellent tunability of monomer units. In this review, we discuss the synthetic process, morphology, and linkage of COFs. We also elaborate the types of activations for CO2, that is, thermal, electrocatalytic, and photocatalytic activation. Finally, we discuss the application of COFs for conversion of CO2 to value added product (VAC).","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 4","pages":""},"PeriodicalIF":3.8,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143439173","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Process Understanding of Transamination Reaction in Chiral Pharmaceutical Intermediate Production Catalyzed by an Engineered Amine Transaminase

IF 3.8 3区化学

ChemCatChem Pub Date : 2024-11-30 DOI: 10.1002/cctc.202401405

Zeynep Perçin, Florian Kleinbeck, Paul Bubenheim, Thomas Ruch, Andreas Liese

{"title":"Process Understanding of Transamination Reaction in Chiral Pharmaceutical Intermediate Production Catalyzed by an Engineered Amine Transaminase","authors":"Zeynep Perçin, Florian Kleinbeck, Paul Bubenheim, Thomas Ruch, Andreas Liese","doi":"10.1002/cctc.202401405","DOIUrl":"https://doi.org/10.1002/cctc.202401405","url":null,"abstract":"Chiral amines are key building blocks for the synthesis of many active pharmaceutical ingredients (APIs). Biocatalytic routes offer significant advantages to provide sustainable access to such motifs on commercial scale, with sacubitril valsartan sodium hydrate as a recent example. In this study a deeper mechanistic and kinetic understanding of the central biocatalytic step in the synthesis of sacubitril valsartan sodium hydrate, applying the evolved transaminase CDX-043, was gained. The equilibrium of the transamination reaction was investigated in detail, and two kinetic models (ping-pong two-substrate kinetics and Michaelis–Menten double substrate kinetics) were established, considering substrate and product inhibition. The determined equilibrium constant indicates that the equilibrium lies strongly on the product side. The results of the kinetic studies demonstrate that the transaminase reaction is in conformity with the Michaelis–Menten double substrate kinetic model. Product inhibition was found to be more severe than substrate inhibition. The application of a plug flow reactor (PFR) was shown to be the preferred reactor setup to reduce the occurring inhibition.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 4","pages":""},"PeriodicalIF":3.8,"publicationDate":"2024-11-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143439172","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Molecular Aspects of the Mechanism of NH3-SCR on Tungsten-Loaded Ceria from Modulated Excitation DRIFTS 从调制激发 DRIFTS 看钨负载铈上 NH3-SCR 机制的分子方面

IF 3.8 3区化学

ChemCatChem Pub Date : 2024-11-28 DOI: 10.1002/cctc.202401839

Hiroe Kubota, Yucheng Qian, Shinya Mine, Takashi Toyao, Rob Jeremiah G. Nuguid, Filippo Buttignol, Davide Ferri, Ken-ichi Shimizu

{"title":"Molecular Aspects of the Mechanism of NH3-SCR on Tungsten-Loaded Ceria from Modulated Excitation DRIFTS","authors":"Hiroe Kubota, Yucheng Qian, Shinya Mine, Takashi Toyao, Rob Jeremiah G. Nuguid, Filippo Buttignol, Davide Ferri, Ken-ichi Shimizu","doi":"10.1002/cctc.202401839","DOIUrl":"https://doi.org/10.1002/cctc.202401839","url":null,"abstract":"Tungsten-loaded ceria is a potential alternative catalyst for the selective catalytic reduction of NOx by NH3 (NH3–SCR). In this work, we carried out operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments using concentration modulation excitation (ME) coupled with phase sensitive detection (PSD) analysis to study key transient adsorbates on a W(10 wt%)/CeO2 catalyst. During NO oxidation, NO2 produced by NO oxidation is adsorbed on the catalyst, and the adsorbed NO2 (NO2ad) undergoes disproportionation to yield NO+ and NO3−, accompanied by consumption of the bridged OH groups on the CeO2 surface. During NH3-SCR, NH3 adsorbed on a Ce4+ Lewis acid site (L-NH3) reacts with NO to yield Ce3+ site, N2, H2O, and H+ (Brønsted acid site). A portion of the initially adsorbed L-NH3 desorbs and subsequently re-adsorbs onto the newly created Brønsted acid site, generating what we term B-NH3. Consequently, the Ce3+ species undergoes oxidation, facilitated by O2 and H+, resulting in the regeneration of Ce4+ species as well as the formation of H2O. This oxidation process coincides with the depletion of the tentatively formed Brønsted acid site (B-NH3).","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 4","pages":""},"PeriodicalIF":3.8,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143438926","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

High-Throughput Screening of Co-Fe-Ni Electrocatalysts for High-Current-Density Water Electrolysis 高通量筛选用于高电流密度水电解的 Co-Fe-Ni 电催化剂

IF 3.8 3区化学

ChemCatChem Pub Date : 2024-11-28 DOI: 10.1002/cctc.202401749

Dr. Rajini P. Antony, Dr. Ridha Zerdoumi, Dr. Sascha Saddeler, Dr. Olga A. Krysiak, Dr. Lars Banko, Prof. Alfred Ludwig, Prof. Wolfgang Schuhmann

引用次数: 0

Progress in the Functionalization of Purines and Purine Nucleosides by Minisci Reactions Over the Past 50 Years

IF 3.8 3区化学

ChemCatChem Pub Date : 2024-11-28 DOI: 10.1002/cctc.202401550

Dr. Yangyan Li, Dr. Madiha Butt, Wenhu Bao, Ruoqian Xie, Prof. Gang Chen

{"title":"Progress in the Functionalization of Purines and Purine Nucleosides by Minisci Reactions Over the Past 50 Years","authors":"Dr. Yangyan Li, Dr. Madiha Butt, Wenhu Bao, Ruoqian Xie, Prof. Gang Chen","doi":"10.1002/cctc.202401550","DOIUrl":"https://doi.org/10.1002/cctc.202401550","url":null,"abstract":"Over the past decade, significant progress has been witnessed in the functionalization of purines and purine nucleosides via Minisci reactions. This review primarily focuses on the latest advancements in applying Minisci reactions to purine bases, while also including some notable early examples, with an emphasis on the late-stage functionalization of purine nucleosides. The Minisci reaction, a radical-based method, enables direct C─H functionalization of purines, facilitating the incorporation of a wide range of functional groups under mild conditions. Key developments discussed in this review include the regioselective functionalizations at the C6, C8, and C2 positions, which have greatly expanded the toolkit for nucleoside modification. Additionally, this review also explores mechanistic insights, as well as the role of catalysts and reaction conditions that enhance the selectivity and efficiency of these transformations. The progress in Minisci-type reactions offers valuable strategies for the synthesis of novel purine-based compounds with promising applications in drug discovery and development.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 4","pages":""},"PeriodicalIF":3.8,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143438927","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Engineering an Unspecific Peroxygenase From Thielavia terrestris for Specific Terminal Oxidation of Xylene Derivatives 从 Thielavia terrestris 中改造出一种非特异性过氧酶，用于二甲苯衍生物的特异性末端氧化

IF 3.8 3区化学

ChemCatChem Pub Date : 2024-11-28 DOI: 10.1002/cctc.202401752

Jian Wei, Ming-Yuan Lai, Hang-Cheng Li, Xin-Yi Lu, Jian-He Xu, Hui-Lei Yu

{"title":"Engineering an Unspecific Peroxygenase From Thielavia terrestris for Specific Terminal Oxidation of Xylene Derivatives","authors":"Jian Wei, Ming-Yuan Lai, Hang-Cheng Li, Xin-Yi Lu, Jian-He Xu, Hui-Lei Yu","doi":"10.1002/cctc.202401752","DOIUrl":"https://doi.org/10.1002/cctc.202401752","url":null,"abstract":"Xylene and its derivatives are bulk raw materials in the chemical industry, and their oxidation products, including p-toluic acid and terephthalic acid, are also crucial in the production of fine chemicals. Unspecific peroxygenases (UPOs) are heme-thiolate enzymes that are capable of oxidizing diverse organic compounds. In this study, a UPO from Thielavia terrestris (TteUPO) showed the ability to oxidize p-xylene to p-toluic acid with >99% chemoselectivity. To address the sensitivity of TteUPO to H2O2 during the reaction, a fusion protein of TteUPO and formate oxidase from Aspergillus oryzae (AoFOx) was constructed for in situ H2O2 regeneration. Additionally, site-directed saturation mutagenesis of TteUPO was performed, giving the mutant F63S/A155 V, which exhibited a 2.4-fold increase in the specific activity toward p-xylene compared with wild-type TteUPO. The engineered fusion protein TteUPOF63S/A155V-AoFOx achieved 3.8 mM p-toluic acid under 8 mM p-xylene loading, which is approximately 60-fold higher than previously reported p-toluic acid concentrations through bio-oxidation. It also showed the capability to convert other monocyclic and polycyclic aromatic hydrocarbons, indicating its potential for the high-value conversion of xylene and its derivatives.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 4","pages":""},"PeriodicalIF":3.8,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143438923","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Bioalkylation Strategies to Synthesize Allylated Tetrahydroisoquinolines by Using Norcoclaurine Synthase and O-Methyltransferases 利用去甲古柯碱合成酶和 O-甲基转移酶合成烯丙基化四氢异喹啉的生物烷基化战略

IF 3.8 3区化学

ChemCatChem Pub Date : 2024-11-28 DOI: 10.1002/cctc.202401668

Matthew T. Salinger, Prof. John M. Ward, Prof. Thomas S. Moody, Dr. Jack W. E. Jeffries, Prof. Helen C. Hailes

{"title":"Bioalkylation Strategies to Synthesize Allylated Tetrahydroisoquinolines by Using Norcoclaurine Synthase and O-Methyltransferases","authors":"Matthew T. Salinger, Prof. John M. Ward, Prof. Thomas S. Moody, Dr. Jack W. E. Jeffries, Prof. Helen C. Hailes","doi":"10.1002/cctc.202401668","DOIUrl":"https://doi.org/10.1002/cctc.202401668","url":null,"abstract":"O-Methyltransferase (O-MT)-mediated alkylations are of growing interest for the regioselective modification of bioactive motifs, although there are still few examples of applications with more structurally complex compounds. In this work, we have used O-MTs for the allylation of various catechol and tetrahydroisoquinoline substrates via a biocatalytic cascade involving additionally methionine adenosyltransferases (MATs) and a methylthioadenosine nucleosidase (MTAN). Furthermore, we have integrated norcoclaurine synthase into this cascade to stereoselectively generate (S)-THIQs in situ as both intermediates and products in the allylation cascade. Notably, a variation in the order in which NCS and MAT-MT-MTAN are added can significantly affect the regioselective outcome, enabling exquisite control of both stereochemistry and regiochemistry in the products. We also identified Ureaplasma urealyticum MAT as an effective enzyme for the formation of the S-adenosyl-S-allyl-L-homocysteine required as the cofactor for the O-MTs and established that the racemate rather than the single isomer of S-allyl-homocysteine can effectively be used in the cascades with MATs.","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 4","pages":""},"PeriodicalIF":3.8,"publicationDate":"2024-11-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202401668","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143438924","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0