ChemCatChem最新文献

{"title":"Orthogonal Valorization of 5-Hydroxymethylfurfural Using Self-Sufficient Heterogeneous Biocatalysts Composed of Two Co-Immobilized Dehydrogenases","authors":"Jakub F. Kornecki,&nbsp;Eleftheria Diamanti,&nbsp;André Pick,&nbsp;Prof. Fernando López-Gallego","doi":"10.1002/cctc.202500734","DOIUrl":"10.1002/cctc.202500734","url":null,"abstract":"<p>5-Hydroxymethyl furfural (HMF) is a key molecule in biorefineries, but its conversion into valuable products faces technological challenges. Biocatalysis offers a sustainable solution, yet high cofactor costs and poor enzyme recyclability hinder industrial implementation. In this work, we develop a self-sufficient heterogeneous biocatalyst (ssHB) composed of two NADH-dependent dehydrogenases co-immobilized with NADH on porous supports. This system enables redox disproportionation of HMF, yielding both 2,5-bis(hydroxymethyl)furan (BHMF) and 5-hydroxymethyl-2-furancarboxylic acid (HMFCA). The reaction relies on NADH/NAD⁺ hydride transport, transferring hydrogen between HMF molecules. Volumetric productivities of 0.75–1.5 g L⁻¹ h⁻¹ and an 80% overall yield (40% per product) were achieved using boronic acid–functionalized supports. The system maintained the same yield over two cycles without additional cofactor, demonstrating efficient cofactor recycling with total turnover numbers (TTN_NADH) of 100–160, around 5 times higher than using exogenous cofactor. This work highlights the potential of self-sufficient heterogeneous biocatalysts to enhance cofactor efficiency and reduce process costs, paving the way for more sustainable biocatalytic valorization of HMF.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 17","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144998649","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}

{"title":"DFT Insights into Mg-Modified Support Effects in Hydrodesulfurization: Mo─O Bond Weakening and Sulfur Vacancy Formation","authors":"Peng Zheng,&nbsp;Zitao Zhu,&nbsp;Jiayi Xiao,&nbsp;Jiyuan Fan,&nbsp;Xilong Wang","doi":"10.1002/cctc.202500529","DOIUrl":"10.1002/cctc.202500529","url":null,"abstract":"<p>In this research, the theoretical investigations were conducted to discuss the impact of Mg-modification on the TiO₂/Al₂O₃ supported catalysts for regulating the MoO₃ precursor and the MoS₂ active phase in hydrodesulfurization (HDS). First, the DFT results verified that the Mg-modification could effectively modulate the d-band center of Mo in the MoO₃ precursor. Specifically, on Al₂O₃ (100) and Mg-Al₂O₃ (100) surfaces, the d-band centers of Mo atoms were calculated to be −1.25 eV and −0.04 eV, respectively. This significant shift in d-band center directly affected the adsorption of pre-sulfiding agents, thereby improving the sulfidation process. The COHP results also indicated that the Mo─O bond strength could be weakened after the addition of magnesium, clarifying that the incorporation of magnesium was favorable for the transformation process to the MoS₂ nanoclusters from MoO₃. Additionally, the phase diagrams of sulfur vacancy formation revealed that Mg-modification indeed had a significant impact on the sulfur vacancy formation processes, particularly on the Al₂O₃ (100) surface where the effect was most pronounced. This study presented a synthesized strategy for MoS₂-based catalysts with controllable sulfur vacancy concentration and helped establish rational design principles for future HDS catalysts.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 17","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-07-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144998650","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}

{"title":"Advances in Ligand-Driven Pd-Catalyzed C─H Functionalizations: Recent Insights and Updates","authors":"Jesús Moradell,&nbsp;Cosmina Bohan,&nbsp;Dr. Alexandra Pop,&nbsp;Dr. Esteban P. Urriolabeitia","doi":"10.1002/cctc.202500664","DOIUrl":"10.1002/cctc.202500664","url":null,"abstract":"<p>The activation of C─H bonds mediated by transition metals has become an essential tool for synthetic chemists, enabling more efficient, selective, and sustainable processes. This progress has been driven by the elimination of precursor prefunctionalization, shortening and reducing the cost of syntheses. However, challenges remain in this methodology, both in terms of activity and selectivity. The introduction of DG to achieve maximum selectivity represents the core of this issue, as it fails to overcome the problem of prefunctionalization, and reaction control remains dependent on substrate design. Recently, we have witnessed a revolution in this field, as activity and selectivity of new processes are no longer controlled by the substrate but by the catalyst. It is the design of the catalyst itself—particularly the ligands—that determines whether the reaction occurs, its rate, and selectivity. This review analyzes the crucial role of ligands in Pd-catalyzed C─H functionalizations in the period from 2022 to the present, focusing on five types of ligands:(i) mono-<i>N</i>-protected amino acids (MPAAs); (ii) pyridones; (iii) pyridines, related <i>N</i>-heterocycles; (iv) thioacids; (v) phosphines and NHCs. For each category, its role, how the reaction is accelerated, and the origin of its selectivity is analyzed.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 15","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202500664","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145135200","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}

{"title":"DFT Study of Halide-Free Mechanism of the CO2 Cycloaddition onto Epoxide by [PW11O39{Zn(H2O)}]5−: Evidences for the Formation of Hydrogencarbonate Intermediates","authors":"Jingjing Ren,&nbsp;Prof. Franck Launay,&nbsp;Dr. Richard Villanneau,&nbsp;Prof. Hélène Gérard","doi":"10.1002/cctc.202500312","DOIUrl":"10.1002/cctc.202500312","url":null,"abstract":"<p>The intertwined experimental and theoretical study of the reaction of CO₂ with styrene oxide in the presence of the tetraoctylammonium salt of [PW₁₁O₃₉Zn^II(H₂O)]⁵⁻ evidences the carbonic anhydrase-like role of the polyoxometalate center in catalyzing the reaction. We computationally propose a reaction pathway involving the transient formation of an HCO₃⁻ moiety involved in the stepwise conversion of the epoxide into a cyclic carbonate. These calculations enabled us to improve the catalytic reactivity of these polyoxometalates by introducing HCO₃⁻ as a co-catalyst in the cycloaddition reactions of CO₂ on a variety of epoxides.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 15","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202500312","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145135806","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}

{"title":"Oxidative Dehydrogenation of Ethylbenzene over Iron-Based Catalysts: Challenges, Prospects, and Future Trends","authors":"Johnatan de Oliveira Soares,&nbsp;Felipe Fernandes Barbosa,&nbsp;Tiago Pinheiro Braga","doi":"10.1002/cctc.202500224","DOIUrl":"10.1002/cctc.202500224","url":null,"abstract":"<p>The production of styrene (ST) by the petrochemical industry has traditionally relied on the ethylbenzenedehydrogenation (EB) reaction, using iron-based catalysts. Estimates suggest that in 2025, the production of EB and ST will surpass 36 and 41 million tons, respectively. In this manner, the major aspects that led to the present stage of EB and ST production were described, discussing historical aspects, alternatives to produce these solvents, its characteristics, types of oxidants, and properties of iron-based catalysts. Noteworthy advancements in this field include the utilization of CO₂ as a soft oxidant and the employment of innovative catalysts derived from green synthesis methods. On the other hand, as an alternative to the fossil source for EB production, the utilization of lignin from biomass emerges as a promising eco-friendly approach. The potential for implementing the ODH reaction in alternative reactors gives rise to questions regarding the necessity for industry to adapt to current climate needs. Furthermore, certain aspects of the mechanism have been called into question, as some fundamental points remain to be fully consolidated. These include the extent of the participation of CO₂ in the reactivation of the active sites and the origin of the deposited coke.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 15","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://chemistry-europe.onlinelibrary.wiley.com/doi/epdf/10.1002/cctc.202500224","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145135805","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}

{"title":"Non-Covalent Organocascade Catalysis: Michael–Mannich Synergy for Enantioselective Building of Aza-Spirocycles","authors":"Ram N Yadav,&nbsp;Luciana C. Schmidt,&nbsp;Ashok Kumar Srivastava,&nbsp;Md. Firoj Hossain","doi":"10.1002/cctc.202500460","DOIUrl":"10.1002/cctc.202500460","url":null,"abstract":"<p>The Michael–Mannich reaction has evolved into a cornerstone of synthetic organic chemistry, enabling the rapid and efficient building of architecturally complex molecular frameworks, particularly spirocyclic scaffolds. These distinctive structures, featuring rigid, fused-ring systems, exhibit remarkable conformational properties and biological relevance, rendering them highly sought-after motifs in pharmaceutical and natural product synthesis. Despite significant advances, the enantioselective construction of spiro-quaternary centers remains a formidable challenge, demanding innovative catalytic strategies. Central to this pursuit is the activation of achiral substrates and precise stereocontrol, historically achieved through transition metal catalysis, biocatalysis, and organocatalysis. Among these, organocatalysis has redefined asymmetric synthesis by harnessing enantiomerically pure organic catalysts to mediate highly stereocontrolled transformations. Notably, non-covalent organocatalysis—driven by finely tuned hydrogen bonding and other weak intermolecular forces—has emerged as a powerful platform to transcend the inherent limitations of metal- and enzyme-based systems. This review spotlights recent breakthroughs in non-covalent organocascade catalysis, emphasizing the strategic Michael–Mannich synergy for the enantioselective building of aza-spirocycles. By emulating enzymatic activation and control mechanisms, researchers have unlocked unprecedented levels of enantio- and diastereoselectivity, charting transformative pathways for constructing architecturally complex, biologically potent spirocyclic molecules. This burgeoning approach not only expands the frontier of asymmetric catalysis but also sets the stage for next-generation innovations in complex molecule synthesis.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 15","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145135807","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}

{"title":"Probing Protease-Mediated Decrease of Albumin-Catalyzed Kemp Elimination: Potential Application as Biosensors","authors":"Shikha Shikha,&nbsp;Priyanka Priyanka,&nbsp;Ekta Shandilya,&nbsp;Subhabrata Maiti","doi":"10.1002/cctc.202500815","DOIUrl":"10.1002/cctc.202500815","url":null,"abstract":"<p>Proteases function as “molecular scissors” to govern signaling pathways by modulating the levels of specific proteins. Herein, we report the ability of three different serine proteases – trypsin (Tr), chymotrypsin (ChT), and Proteinase K (PrK) in decreasing serum albumin-catalyzed Kemp elimination (KE) reaction in simple aqueous buffered media and complex body fluids, namely – urine and blood serum. We find with increasing albumin cleavage rate by proteases, the KE reactivity decreases and the order of KE reaction decreasing trend is: PrK &gt; Tr &gt; ChT. We demonstrate the utilization of this method in sensing albumin and trypsin in urine sample, important for diagnosing Kidney function and pancreatitis. Additionally, we report the albumin-catalyzed KE reactivity in complex environments like blood serum. In this case, the presence of additional Gamma globulin (GGB) shows a lesser effect in ChT-mediated decrease of albumin-catalyzed KE-reactivity, resulting a significant decrease in KE reactivity ratio of Tr/ChT and PrK/ChT. Understanding protease-specific functional alteration in a multiprotein environment can be utilized as an important tool not only for pathological purpose, but also in the designing of synthetic biochemical networks in complex biological media.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 17","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144997912","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}

{"title":"Zeolitic Imidazolate Framework-Derived Ru/RuO2–Co3O4 Catalyst for Methanol Oxidation Reaction in Alkaline Media","authors":"Salma A. Khanam,&nbsp;Donguk Kim,&nbsp;Young-Bin Park,&nbsp;Amit Das,&nbsp;Kangkan Sarmah,&nbsp;Ankur K. Guha,&nbsp;Kusum K. Bania","doi":"10.1002/cctc.202500505","DOIUrl":"10.1002/cctc.202500505","url":null,"abstract":"<p>The present study explores the possibility of a hybrid nanostructure of ruthenium (Ru) and cobalt oxide (Co₃O₄) for effective methanol oxidation reaction (MOR) in alkaline media. The spherical Ru/RuO₂ nanoparticle, uniformly dispersed in zeolitic Co₃O₄ derived from its ZIF-67 precursor, showed significant activity in MOR process. The duly characterized material exhibited a maximum current density of 131 mAcm⁻² with an onset potential of ∼1.07 V vs RHE (reversible hydrogen electrode). Under the electrocatalytic condition, the material exhibited stability up to 500 cycles of 12 h without substantial loss in current density. A comparative study showed that incorporation of Ru/RuO₂ into zeolitic spinel Co₃O₄ altered the activity in the MOR process. The catalyst had a good methanol (CH₃OH) concentration tolerance up to 2.5 M in alkaline media. A diffusion-controlled MOR process was indicated by the linear dependency of the current density against the square root of the scan rate. It was predicted that the temperature influenced the MOR process, and the apparent activation energy, <i>E</i>_a(app), calculated from the Arrhenius plot, was 27.45 kJmol⁻¹. The mechanism of the MOR was studied by using the density functional theory (DFT) calculation, and it was supported experimentally through the FTIR (Fourier transform infrared) and Raman analysis. DFT suggested for the engagement of both cobalt (Co) and Ruthenium (Ru) in the catalytic cycle. FTIR study showed that Ru nanoparticles get poisoned through CO (carbon monoxide) adsorption after 100 cycles and retard the activity after 12 h. On the other hand, the Raman study predicted that the Co₃O₄ surface gets hydroxylated, forming ─CoOOH (cobalt oxyhydroxide) species that participated in the deprotonation of CH₃OH with the assistance of Ru/RuO₂ nanoparticles.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 17","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144997913","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}

{"title":"Visible-Light-Driven Photocatalytic Glycerol Oxidation to Value-Added and Highly Selective Glyceric/Lactic Acid","authors":"Mukta Kulkarni-Sambhare,&nbsp;Kranti N Salgaonkar,&nbsp;Avishek Saha,&nbsp;Chinnakonda S Gopinath","doi":"10.1002/cctc.202500641","DOIUrl":"10.1002/cctc.202500641","url":null,"abstract":"<p>Achieving economical and sustainable artificial photosynthesis (APS) in direct sunlight for liquid fuel production with high efficiency remains an important challenge. A major obstacle in the photoelectrochemical (PEC) oxidation of organic compounds is attaining high selectivity with the desired product(s). This study introduces a novel strategy by integrating BiVO₄ quantum dots (BVQDs), structurally and electronically, into the nanopores of commercial TiO₂ (BVT for BVQDs integrated in pores of TiO₂) to improve solar-driven photocatalysis. The band gap of the BVT photoanode decreases to 2.53 eV as compared to pure TiO₂ (3.2 eV), which enhances visible light absorption and charge separation. BVT with Pt as a co-catalyst acts as an APS system, which selectively oxidizes glycerol into lactic acid (100% selectivity at 1 mM glycerol) and glyceric acid (98% selectivity at 100 mM), while simultaneously generating green hydrogen. Selectivity of the product can be further controlled by anaerobic or aerobic conditions as well as the length of the reaction time. Direct integration of BVQDs into TiO₂ mesopores significantly enhances charge separation as well as utilization at redox sites. Current work provides key insights into optimizing photocatalytic conditions for highly selective value-added chemical production, which highlights the sustainability and efficacy of TiO₂-based semiconductors with quantum dot integration.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 17","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144999144","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}

{"title":"Stereocontrolled 1,3-Nitrogen Migration Catalyzed by Artificial Metalloenzymes Bearing Stereogenic Metal Centers","authors":"Dr. Qingqing Chen,&nbsp;Jinmeng Yu,&nbsp;Senmiao Li,&nbsp;Chang Wang,&nbsp;Prof. Peng Zheng,&nbsp;Prof. Hui-Jie Pan","doi":"10.1002/cctc.202500901","DOIUrl":"10.1002/cctc.202500901","url":null,"abstract":"<p>Octahedral complexes with linear tetradentate ligands are effective catalysts for various chemical transformations, with the <i>cis</i>-α geometry typically being the active form. These complexes possess stereogenic metal centers, adopting either Λ- or Δ-configurations. We hypothesized that embedding these complexes within the chiral environment of protein scaffolds could yield artificial metalloenzymes (ArMs) with both an enantioenriched metal center and a chiral catalytic pocket. This combination could potentially act synergistically, enhancing catalytic reactivity and selectivity, thereby producing more powerful and tunable catalysts compared to the complexes alone. In this study, we designed two cofactors featuring octahedral Fe complexes: <b>cofactor 1</b>, which, due to its rigid chiral backbone, exclusively forms the Δ-configuration, and <b>cofactor 2</b>, which forms a racemic mixture. Using biotin-streptavidin technology, we developed ArMs based on these cofactors and evaluated them in a 1,3-nitrogen migration reaction to produce chiral α-amino acids. Both ArMs exhibited protein mutant-dependent reactivity and selectivity, with <b>cofactor 1</b> demonstrating notable synergistic or conflicting effects between the protein scaffold and the metal-centered configuration. This work highlights the potential of developing ArMs with stereogenic metal centers for highly selective catalysis.</p>","PeriodicalId":141,"journal":{"name":"ChemCatChem","volume":"17 16","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144905444","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}