ChemPlusChem最新文献

{"title":"Synergistic Role of Co⁰ and Lewis Basic Sites for Transfer Hydrogenation of Substituted Nitroarenes by In Situ Hydrogen Generation.","authors":"Anitya Sharma, Dhanmani Ramchiary, Devendra Sharma, Sahil Kumar, Venkata Krishnan","doi":"10.1002/cplu.70233","DOIUrl":"10.1002/cplu.70233","url":null,"abstract":"<p><p>Designing green and efficient methods for synthesizing anilines remains a key challenge in synthetic organic chemistry. Hydrogenation of nitro compounds is one of the most significant and widely employed method for producing functionalized anilines. Consequently, designing catalytic systems capable of hydrogenating nitroarenes under environmentally benign and mild reaction conditions remains a challenge. In this regard, a highly efficient CoAl catalyst has been designed for the hydrogenation of nitroarenes to corresponding amines. Various structural, compositional, and morphological characterizations were done to understand the catalyst's structural and surface properties. The as-synthesized catalyst exhibits excellent activity for the transfer hydrogenation of 1-chloro-4-nitrobenzene to 4-chloroaniline, achieving 98% yield at 60 °C within 1.5 h in ethanol. The developed protocol demonstrated excellent activity for wide range of substituted nitroarenes. Structure-activity relationships of CoAl show that basic sites play a crucial role in the transfer hydrogenation. Furthermore, mechanistic investigations reveal that transfer hydrogenation occurs predominantly via a hydroxylamine-mediated pathway. Moreover, the catalyst maintains good catalytic activity up to four consecutive cycles. This method eliminates the need for high-pressure H₂, offering a safe strategy for aromatic amine synthesis. The work demonstrates the potential of earth-abundant, non-noble-metal-based heterogeneous catalysts for hydrogenation reactions under environmentally benign conditions.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":"91 9","pages":"e70233"},"PeriodicalIF":3.1,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13526516/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148860464","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploring the Interaction of Flavonoids Baicalein and Scutellarein With Human Serum Albumin: Spectroscopic and Computational Study.","authors":"Vanda Boršová, Miriama Malček Šimunková, Marek Štekláč","doi":"10.1002/cplu.70234","DOIUrl":"10.1002/cplu.70234","url":null,"abstract":"<p><p>This study explores the interaction of human serum albumin (HSA) with two flavonoids (FLs), baicalein and scutellarein, and in situ formed Cu(II)-FL complexes using fluorescence spectroscopy, molecular docking, and molecular dynamics simulations. Fluorescence quenching experiments show diminished fluorescence intensity indicating that all compounds effectively bind to HSA, with free scutellarein exhibiting slightly higher affinity. Cu(II) coordination reduces quenching efficiency; however, the binding processes remain thermodynamically favorable. UV-Vis spectroscopy confirmed well-defined ground-state HSA-flavonoid complexes with minor indications of subtle protein conformational adjustments. A novel composite scoring function integrating effective free energies and thermodynamic stability was used to compute theoretical free energies. The results are in agreement with experimental results, showing that all ligands preferentially bound in Sudlow site I, while baicalein also samples site III. Per-residue energy decomposition indicates that Cu(II) complexes are stabilized by electrostatic interactions further from the intrinsic fluorophore Trp²¹⁴. Clustering analysis reveals distinct conformational landscapes, with baicalein favoring a few dominant states, whereas scutellarein adopts a more fragmented ensemble. Overall, HSA effectively accommodates both free and Cu(II)-complexed flavonoids, with metal coordination subtly modulating binding preferences and conformational dynamics.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":"91 9","pages":"e70234"},"PeriodicalIF":3.1,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13539296/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148878722","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Structure and Catalytic Performance of Aluminum-Based Ozone Catalysts Prepared by a Direct Mixing Method","authors":"Can Xu,&nbsp;Xin Zhao,&nbsp;Sheng Chen,&nbsp;Chunli Wan,&nbsp;Aijuan Zhou,&nbsp;Xiejin Mao,&nbsp;Yutong Duan,&nbsp;Changyong Wu","doi":"10.1002/cplu.70221","DOIUrl":"https://doi.org/10.1002/cplu.70221","url":null,"abstract":"<p>Ozonation catalysis has attracted considerable attention for the treatment of refractory organic wastewater due to its efficient generation of reactive oxygen species (ROS). However, conventional catalyst preparation methods often suffer from drawbacks such as the production of metal-containing waste effluents. In this study, flash calcined alumina (FCA) was employed as a support to synthesize four ozonation catalysts (γ-Al, Cu-Al, Fe-Al, and Ce-Al) via a direct solid-state mixing method with CuO, Fe₂O₃, and CeO₂. The structural properties and oxalic acid degradation performance of these catalysts were systematically investigated. The catalytic activity followed the order: Cu-Al &gt; Ce-Al &gt; Fe-Al &gt;&gt; γ-Al, with Cu-Al achieving a degradation efficiency of 90%. The superior performance of Cu-Al is attributed to the optimal dispersion of CuO on the support, along with the efficient Cu²⁺/Cu⁺ redox cycle that promotes continuous ·OH generation. In contrast, the Ce⁴⁺/Ce³⁺ redox pair exhibits higher reversibility than Fe³⁺/Fe²⁺, resulting in better catalytic activity of Ce-Al. Moreover, FCA mixing method eliminates repeated calcination steps and avoids the generation of metal-containing waste, while significantly reducing energy consumption, cost, and carbon emissions.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":"91 9","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148811120","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"First Synthesis of Multi-Stimuli Responsive PMOEP Microgels: Phosphorus-Based Platform for Controlled Drug Delivery","authors":"Yasemin Samav,&nbsp;Cansel Tuncer","doi":"10.1002/cplu.70232","DOIUrl":"https://doi.org/10.1002/cplu.70232","url":null,"abstract":"<p>In this study, novel phosphorus-containing and pH-responsive poly[2-(methacryloyloxy)ethyl phosphate] (PMOEP) microgels were successfully synthesized for the first time via emulsion polymerization using a PBzDMA-<i>b</i>-PMEMA diblock copolymer steric stabilizer. Their performance was systematically compared with poly[2-(diethylamino)ethyl methacrylate] (PDEA) microgels cross-linked with multifunctional phosphorus agents (DMEP, TMEP) and EGDMA. Dynamic light scattering (DLS) analysis demonstrated that while EGDMA-cross-linked PDEA microgels exhibited a volumetric swelling capacity of 3330%, PMOEP microgels reached a significantly lower swelling ratio of 594% under identical conditions. Electrokinetic and DLS measurements revealed high colloidal stability across pH 3–12. The electrophoretic mobility (<i>μ</i>_e) remained consistently negative, shifting from −1.20 × 10⁻⁸ m²V⁻¹s⁻¹ at pH 3.3 to a maximum magnitude of −2.49 × 10⁻⁸ m²V⁻¹s⁻¹ at pH 11.2, providing a robust evaluation of surface charge without model-dependent conversions for swollen soft structures. Furthermore, PMOEP microgels displayed multi-stimuli responsiveness to pH, temperature, and salt concentration. Evaluated using Ibuprofen as a model drug under physiological conditions (pH 7.4, 37 °C), in vitro release showed a biphasic sustained profile, reaching 100% cumulative release over 113 h. These findings demonstrate that potentially biocompatible, phosphonic acid-functionalized microgels represent a versatile platform for advanced controlled drug delivery systems.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":"91 9","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148811119","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Thermodynamic Evaluation of Micellization of an Azepanium Ionic Liquid-Based Surfactant in Water and Organic Solvent–Water Media","authors":"Supriya Pradeep Whaval,&nbsp;Amit Kumar Tiwari","doi":"10.1002/cplu.70235","DOIUrl":"https://doi.org/10.1002/cplu.70235","url":null,"abstract":"<p>A novel azepanium ionic liquid-based surfactant, 1-(2-hexadecyloxy-2-oxoethyl)-1-methylazepanium bromide (Azp-ILBS; C₂₅H₅₀NO₂Br), was successfully obtained and structurally characterized using ¹H, ¹³C NMR, FT-IR, HRMS, and CHNS elemental analysis. The critical micelle concentration (<i>cmc</i>) was evaluated via electrical conductivity measurements. Thermodynamic investigations of micellization were conducted in various water–organic solvent mixtures (ethylene glycol (EG), ethanol (Et-OH), 1,4-dioxane (DO), and N,N-dimethylformamide (DMF)) at temperatures of 303, 313, and 323 K. The influence of solvent composition and temperature on micellization behavior was systematically examined. Results indicated that <i>cmc</i> values increased from 0.328 to 0.614 mM with rising temperature from 303 to 323 K and from 0.328 to 0.761 mM with increasing solvent content of EG from 10% to 30%. All solvents showed similar trends: higher temperature and lower polarity delayed micellization, requiring higher surfactant concentrations. Degree of ionization (<i>α</i>) showed a similar trend, although a U-shaped pattern was observed specifically in the water–ethanol system. The Gibbs free energy of surfactant tail transfer (Δ<i>G</i>°_m _trans) values revealed the hydrophobic surfactant tail transfer into the micelle core from the surrounding medium as the Δ<i>G</i>°_m _trans value shifts from positive to negative on increasing temperature, affirming the role of hydrophobic interactions. Overall, the micelle formation phenomenon was observed to be spontaneous and exothermic, with entropy and enthalpy contributions varying depending on temperature and solvent environment. Notably, (Δ<i>H</i>–Δ<i>S</i>) compensation analysis shows that Azp-ILBS micellization becomes more enthalpy-driven as temperature increases. The negative Δ<i>H</i>°*_m values reflects the micelle formation is an exothermic process at zero entropy. The calculated compensation temperatures (<i>T</i>_c) at experimental temperatures 303, 313, and 323 K are 295.9, 296.15, and 301.75 K, respectively. These values are thermodynamically in a plausible range, showing a mild transition near 313 K, likely attributed to subtle variations in solute–solvent interactions or reorganization of surfactant structure.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":"91 9","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148811227","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Efficient Electrocatalytic Ethanol Oxidation Using Lanthanum Nickel Oxide Nanoparticles Anchored on Graphite Surface","authors":"Supriya Rana,&nbsp;Krishna K. Yadav,&nbsp;Kritika Sood,&nbsp;Sushma Kumai,&nbsp;Sapna Devi,&nbsp;Tanya Jamwal,&nbsp;Surinder K. Mehta,&nbsp;Menaka Jha","doi":"10.1002/cplu.70226","DOIUrl":"https://doi.org/10.1002/cplu.70226","url":null,"abstract":"<p>Ethanol oxidation reaction (EOR) using non-precious metal oxide-based nanostructures is important in the current energy landscape. However, the sluggish kinetics is one of the major bottleneck for EOR. Therefore, this work deals with the synthesis of lanthanum nickel oxide (LNO) via a facile coprecipitation method. The microstructural study confirms the formation of nanoparticles of size 40–70 nm. Furthermore, LNO NPs were deposited onto the graphite surface to evaluate their oxygen evolution reaction (OER) and EOR in an alkaline media. OER study shows an overpotential of 410 mV compared to graphite (740 mV). However, during EOR, the cyclic voltammetry (CV) shows the forward and backward oxidation peaks at 1.51 V, and the potential required to reach 10 mA/cm² decreases to 1.41 V with a high current density of ~80 mA/cm² at 2 V in the presence of ethanol in comparison to OER electrolysis in bare KOH (1.69 V). A significant reduction of ~280 mV in the required potential is observed compared to catalysis in bare KOH. The integration of LNO NPs with the graphite surface results in enhanced ethanol oxidation activity due to improved charge transport and interfacial synergy. Further, the catalytic insights have been discussed in detail using ECSA, EIS, and contact angle measurements.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":"91 9","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148811226","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrocatalytic HER Activity by Mono Terpyridyl Copper Complex in Homogeneous Aqueous Medium and After Immobilization on Electrode Surface Through Graphene Oxide","authors":"Md. Adnan Khan,&nbsp;Subhendu Naskar","doi":"10.1002/cplu.70230","DOIUrl":"https://doi.org/10.1002/cplu.70230","url":null,"abstract":"<p>The present work describes electrochemical proton reduction by a mononuclear Cu(II) complex of formula [CuL] (where L = <i>4′-</i>(<i>4-</i><i>fluorophenyl</i>)<i>-2</i>,<i>2′:6′</i>,<i>2″-terpyridine</i>). Single crystal X ray diffraction exhibited the CuN₃O₂ core structure of the metal complex with a hydroxide and a perchlorate ancillary ligand connected to the copper center forming a square pyramidal geometry. The complex exudes a moderately high TON_HER/TOF_HER of 22 and ~205 s⁻¹ by peak current method with a moderate F.E of ~52%. The TON_HER/TOF_HER of the immobilized electrocatalysts on glassy carbon (GC) as (GO+1) [GO = Graphene oxide] and (GO + 1 + Nafion) was calculated to be 1.09 × 10⁶/304 s⁻¹ and 3.12 × 10⁶/868 s⁻¹ with a F.E of 86% and 93% respectively. A ligand-based electrochemical hydrogen evolution reaction (HER) was observed. The catalytic cycle was proposed after analyzing the intermediates through mass spectroscopy and density function theory. The heterogeneized electrocatalysts were drop casted on GC electrode using water and with or without Nafion. A overpotential of 407 mV and 514 mV at an onset potential of −0.55 V and −0.65 V versus normal hydrogen electrode (NHE) was observed for HER. Gas analysis was done after CPE at −1.6 V versus NHE for 3600 s through gas chromatography.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":"91 8","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148783966","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tailoring Biowaste-Derived Activated Hydrochar With Multifunctionality Toward Antibiotic Adsorption, CO2 Capture, and Energy Storage","authors":"Şeyda Karadirek,&nbsp;Nergiz Kanmaz,&nbsp;Özlem Tuna,&nbsp;Hatice Hande Mert,&nbsp;Mehmet Selçuk Mert","doi":"10.1002/cplu.70227","DOIUrl":"https://doi.org/10.1002/cplu.70227","url":null,"abstract":"<p>This work investigates the potential of hydrochar (HC) produced from date seeds (DS) as a multifunctional material. Two adsorbents were synthesized by the hydrothermal route: HC and phosphoric acid-activated hydrochar (AHC). Their performances were assessed for levofloxacin (Lvx) removal, CO₂ uptake, and as stabilizers in palmitic acid (PA)-based composite phase change materials (PCMs). The maximum adsorption capacity of HC and AHC for Lvx was found to be 18.05 and 41.94 mg/g, respectively, at 25 °C and an initial concentration of 10 mg/L, due to the larger surface area, increased active sites, and lower binding energy, supported by Brunauer–Emmett–Teller analysis (BET), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS). Kinetic data were well described by Elovich and intraparticle diffusion models, while Langmuir and Temkin isotherms gave the best equilibrium fits. The adsorption showed a spontaneous and exothermic behavior. CO₂ capture measurements demonstrated the superior efficiency of AHC (1.53 mmol/g) compared to HC (0.32 mmol/g). Both HC and AHC were utilized to obtain shape-stabilized PCMs, where PA/AHC exhibited higher latent heat storage and thermal stability relative to PA/HC. Overall, the findings highlight activated HC as a versatile material that can simultaneously address antibiotic pollution, CO₂ mitigation, and energy storage challenges.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":"91 8","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/cplu.70227","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148784627","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Cobalt Oxide/Nickel Cobalt Sulfide/Poly(1,8-diaminonaphthalene) Electrochemical Sensor-Based Therapeutic Monitoring of Primaquine in Urine to Combat Low Treatment Adherence in Vivax Malaria Therapy","authors":"Faith Muthoni Wangui,&nbsp;Darko Kwabena Adu,&nbsp;John Alake,&nbsp;Malachie Monyele Tembo,&nbsp;Rajshekhar Karpoormath","doi":"10.1002/cplu.70225","DOIUrl":"https://doi.org/10.1002/cplu.70225","url":null,"abstract":"<p>Patients’ compliance with primaquine treatment is low due to the long 14-day duration of primaquine and the toxic side effects, including acute hemolytic anemia. This study aimed to develop a cobalt oxide/nickel cobalt sulfide/poly(1,8-diaminonaphthalene) (Co₃O₄@NiCo₂S₄@poly(1,8-DAN))-based electrochemical sensor for monitoring primaquine in urine to combat low adherence. The Co₃O₄@NiCo₂S₄@poly(1,8-DAN) nanocomposite was synthesized using hydrothermal and oxidative polymerization and characterized using high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR). Differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy were used to study the electrochemical properties of the nanocomposite. A 5 μL aliquot of Co₃O₄@NiCo₂S₄@poly(1,8-DAN) was drop-casted onto the glassy carbon electrode, and DPV was used to evaluate the electrochemical sensor’s performance. A linear calibration response was established over primaquine’s concentration range of 10–50 µM. The study found a detection limit of 2.51 nM with a linear concentration range of 10–50 µM. Real sample analysis in urine demonstrated recovery ranges of 98.3%–101.1%. This study reports, for the first time, the synthesis of the Co₃O₄@NiCo₂S₄@poly(1,8-DAN) ternary nanocomposite and its application for the detection of primaquine.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":"91 8","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148783970","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mechanistic Insights Into the Formaldehyde Dehydrogenase-Catalyzed Reduction of Formate: A Quantum Chemical Study","authors":"Baoyan Liu,&nbsp;Yingying Jiang,&nbsp;Hao Su,&nbsp;Xiang Sheng","doi":"10.1002/cplu.70231","DOIUrl":"https://doi.org/10.1002/cplu.70231","url":null,"abstract":"<p>The multienzyme cascade conversion of CO₂ to methanol is a promising route for sustainable chemical synthesis, yet the reduction of formate to formaldehyde remains its major bottleneck. Here, we use quantum chemical calculations to elucidate the catalytic mechanism of formaldehyde dehydrogenase from <i>Burkholderia multivorans</i> (<i>Bm</i>FaldDH). The lowest-energy pathway initiates with formate activation via a proton-relay network involving His52, Ser49, and the NADH ribose, followed by a concerted yet asynchronous proton-hydride transfer to yield methanediol with a barrier of 16.0 kcal mol⁻¹. Interestingly, calculations show that subsequent dehydration of methanediol to formaldehyde is more favorable in solution than within the active site, with barriers of 16.2 and 24.0 kcal mol⁻¹, respectively. This lower barrier in solution is mediated by a water-cluster model in which three water molecules facilitate proton relay, and two stabilize the methanediol. Furthermore, binding energy calculations indicate that methanediol has a relatively weak binding affinity for <i>Bm</i>FaldDH, suggesting that it readily dissociates into solution. Overall, this study demonstrates that the limited efficiency of <i>Bm</i>FaldDH in catalyzing formate reduction stems from its incompetence to catalyze methanediol dehydration within its active pocket. These findings provide a mechanistic insight for engineering efficient enzymes for the formate-to-formaldehyde conversion.</p>","PeriodicalId":148,"journal":{"name":"ChemPlusChem","volume":"91 8","pages":""},"PeriodicalIF":3.1,"publicationDate":"2026-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148784626","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}