Reaction Chemistry & Engineering最新文献

{"title":"Experimental monitoring and modeling of oxygen dynamics in laccase-catalyzed phenolic oxidation","authors":"Ernesto Gonzalez, Jorge Garcia-Montalvo, Elena Gallego-Rojo, Miguel Ladero and Juan M. Bolivar","doi":"10.1039/D5RE00450K","DOIUrl":"https://doi.org/10.1039/D5RE00450K","url":null,"abstract":"<p >Oxygen-dependent enzymes such as laccases play a central role in green oxidation processes, yet kinetic analyses often overlook the dynamic role of dissolved oxygen. In this study, we propose a useful methodology for the experimental monitoring and kinetic modeling of oxygen-consuming enzymatic reactions, demonstrated using the laccase-catalyzed oxidation of gallic acid and ferulic acid. The method integrates real-time monitoring of dissolved oxygen and substrate concentration with dynamic simulations accounting for oxygen mass transfer and bi-substrate kinetic models commonly used to describe laccase-catalyzed reactions. Experiments were conducted in both non-sparged and air-sparged systems to assess kinetic behavior under oxygen-limited and oxygen-sufficient conditions. The method yielded well-constrained kinetic constants for gallic acid and revealed a biphasic oxygen-uptake pattern for ferulic acid, arising from secondary oxidation of radical intermediates. Using Aspen Custom Modeler built-in non-linear regression and numerical integration algorithms, kinetic parameters were estimated by fitting them to complete time-course data, enabling accurate modeling of complex oxygen-dependent reactions. The proposed framework provides a practical tool for studying oxidase-catalyzed processes under conditions where dissolved-oxygen dynamics can be experimentally resolved, and supports more rational design of biocatalytic systems where oxygen availability governs the activity, selectivity and control of complex reaction networks.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 6","pages":" 1283-1294"},"PeriodicalIF":3.1,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148202872","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":"The promotional effect of gallium loading on the bifunctional Cu–Ga/γ-Al2O3 catalyst for CO2 hydrogenation to methanol and dimethyl ether at atmospheric pressure","authors":"Sezer Osmanaga, Yasemin Kaya, Isik Onal and Bahar Ipek","doi":"10.1039/D5RE00481K","DOIUrl":"https://doi.org/10.1039/D5RE00481K","url":null,"abstract":"<p >Hydrogenation of CO<small>₂</small> to methanol and dimethyl ether (DME) was investigated over gallium-promoted copper catalysts supported on γ-Al<small>₂</small>O<small>₃</small> (Cu–Ga/γ-Al<small>₂</small>O<small>₃</small>) at atmospheric pressure—conditions under which Ga-promoted Cu/γ-Al<small>₂</small>O<small>₃</small> catalysts have not been investigated before. Reaction parameters—including temperature, H<small>₂</small> : CO<small>₂</small> feed ratio, and gas hourly space velocity (GHSV)—were optimized prior to evaluating the effect of Ga loading. Catalysts with varying Ga loadings (5, 10, 12, and 15 wt%) were tested, with the 5 wt% Ga catalyst achieving the highest combined formation rate of methanol and DME at 246 μmol<small>_carbon</small> g<small>_cat</small><small>⁻¹</small> h<small>⁻¹</small> and a combined selectivity of 20.6% under optimal conditions (220 °C, 9 : 1 H<small>₂</small> : CO<small>₂</small>, GHSV = 30 000 mL g<small>_cat</small><small>⁻¹</small> h<small>⁻¹</small>), where the DME production rate was twofold that of the Ga-free catalyst. For comparison, a commercial Cu/ZnO/Al<small>₂</small>O<small>₃</small> catalyst was synthesized and showed a significantly lower methanol selectivity (7.2%) and formation rate (60 μmol g<small>_cat</small><small>⁻¹</small> h<small>⁻¹</small>) under identical operating conditions, with no DME production observed. The promotional effect of Ga was further explored using periodic density functional theory (DFT) calculations on a Cu<small>₄</small>/β-Ga<small>₂</small>O<small>₃</small>(001) model. Theoretical results suggest that CO<small>₂</small> hydrogenation proceeds primarily <em>via</em> a carboxyl intermediate, rather than through formate or CO pathways.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 4","pages":" 948-958"},"PeriodicalIF":3.1,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147626268","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":"Indirect hard modeling of low resolution benchtop NMR data for the kinetic fitting of a complex organic reaction","authors":"Niklas Sulzer, Christopher A. Hone and C. Oliver Kappe","doi":"10.1039/D5RE00436E","DOIUrl":"https://doi.org/10.1039/D5RE00436E","url":null,"abstract":"<p >Despite recent significant advances in hardware, software, and data analysis, low resolution benchtop NMR systems are still underutilized for the kinetic investigation of organic reactions. Moreover, their use has typically been restricted to monitoring a limited number of species with well-behaved peaks that were easily integrable. In this work, the chlorination reaction of 4-fluorothiophenol with <em>N</em>-chlorosuccinimide (NCS) was investigated by continuous in-line monitoring of five different reaction species through the utilization of a 43 MHz benchtop NMR instrument. The reaction was carried out under synthetically relevant conditions within different modes of operation, including re-circulating batch and single pass continuous flow modes. Quantitative concentration values could be obtained even when peaks overlapped through the use chemometric modeling, specifically indirect hard modeling (IHM). The reaction profiles were then fitted to obtain kinetic parameter estimates for a six step model structure. This study demonstrates that complex organic reaction kinetics can be explored using a low resolution NMR setup for quantitative monitoring.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 4","pages":" 922-931"},"PeriodicalIF":3.1,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/re/d5re00436e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147626266","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":"Deciphering alcohol dehydrogenase catalysis in glycerol-based deep eutectic solvents through experimental and computational insights","authors":"Ningning Zhang, Jan Philipp Bittner, Aaron Pfleger, Pablo Domínguez de María, Sven Jakobtorweihen, Irina Smirnova and Selin Kara","doi":"10.1039/D5RE00448A","DOIUrl":"https://doi.org/10.1039/D5RE00448A","url":null,"abstract":"<p >Designing enzyme-compatible deep eutectic solvents (DESs) may be challenging due to their compositional complexity and variable enzyme responses. For instance, glycerol is beneficial for enzyme catalysis, while choline chloride is detrimental. This study assesses, experimentally and computationally, the performance of horse liver alcohol dehydrogenase (HLADH) in two glycerol-based DESs: betaine–glycerol (Bet–Gly, choline–chloride-free) and choline acetate–glycerol (ChAc–Gly, only chloride-free). Bet–Gly enables superior HLADH stability and activity, while ChAc–Gly, despite improved thermostability, shows significantly lower activity. Molecular dynamics (MD) simulations revealed a critical solvation transition at ∼20 vol% water content, where water begins to dominate the enzyme's solvation shell, maximizing enzyme stability at 40–50 vol%. Hydrogen-bond analyses reveal that water preferentially fills internal cavities at low concentrations, while in excess, it disrupts the stabilizing glycerol shell. Free energy profiles, calculated with MD, demonstrate that Bet–Gly permits unimpeded substrate diffusion and optimal positioning near the catalytic zinc ion. In contrast, ChAc–Gly components infiltrate the active site, increasing energy barriers and impeding catalysis. These findings highlight the dual role of DES composition and hydration in modulating enzyme stability and function, offering design principles for future tailored biocatalytic environments in non-aqueous media.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 4","pages":" 874-887"},"PeriodicalIF":3.1,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147626261","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":"Continuous-flow asymmetric aldol reactions using sawdust-supported cross-linked l-proline catalysts","authors":"Hemanshu A. Patel, Sudhirkumar S. Katariya, Jagrut Barot, Kulsum Mondal and Hemant P. Soni","doi":"10.1039/D5RE00537J","DOIUrl":"https://doi.org/10.1039/D5RE00537J","url":null,"abstract":"<p >Cross-linked <small>L</small>-proline immobilized on polymaleated octadecene (PMHC18-<small>L</small>-pro-CL) was developed as a robust heterogeneous catalyst for asymmetric aldol reactions and evaluated under both batch and continuous-flow conditions. Although the polymer exhibited partial gelation in DMSO during batch operation, blending with sawdust generated a mechanically stable, permeable packed bed that enabled gravity-driven flow without external pumping, thereby functioning as a pump-optional catalytic evaluation platform. The optimized 50 : 50 sawdust/polymer bed afforded quantitative conversion, a 97 : 3 <em>syn</em> : <em>anti</em> ratio, and &gt;90% ee in a single 53 min residence time. Mass-normalized TON/TOF values were determined (TON = 3.4, TOF = 0.14 h<small>⁻¹</small> in batch; TON = 0.05, TOF = 0.05 h<small>⁻¹</small> under flow), and contextualized against representative heterogeneous proline catalysts. Axial-dispersion analysis indicated near-plug-flow behavior, consistent with the reproducible ee/dr across cycles and the absence of channeling. A preliminary multi-tubular reactor mode was developed to assess industrial feasibility, suggesting that the packed-bed concept can be scaled using multiple small-diameter tubes. Overall, this gravity-assisted sawdust-stabilized reactor provides a simple, low-energy, pump-optional platform for early-stage continuous-flow organocatalysis and offers mechanistic and engineering insights relevant to future scale-up.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 6","pages":" 1213-1227"},"PeriodicalIF":3.1,"publicationDate":"2025-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148202910","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":"Improving the univariate calibration approach with Bayesian modeling for IR reaction monitoring","authors":"Jiayu Zhang and Jason E. Hein","doi":"10.1039/D5RE00400D","DOIUrl":"https://doi.org/10.1039/D5RE00400D","url":null,"abstract":"<p >Infrared (IR) spectroscopy is a powerful tool for real-time reaction monitoring in chemical synthesis. For applications that require tracking concentration profiles of reactive species, univariate linear calibration models are commonly used to relate IR signals to analyte concentrations. Despite their simplicity, the accuracy of these models can be limited by spectral overlap and other effects that distort the linear relationship between concentration and signal. To address this limitation, chemometric models are often employed, typically without further examination of opportunities to improve univariate calibration performance itself. Here, we present a novel workflow based on Bayesian statistics to enhance univariate calibration for IR reaction monitoring. The central feature of this workflow is the use of three diagnostic Bayesian probabilistic models, combined with data-preprocessing selection, to screen for IR signals that can potentially improve univariate calibration performance when non-linear effects are present. We applied the workflow to a test reaction system and identified an IR signal in the fingerprint region, along with an uncommon preprocessing strategy, that reduced prediction error by more than 50% compared with the univariate model using the original preprocessing steps. Overall, our workflow aims to improve the usability of univariate calibration approaches and expand the toolbox available to chemists for IR monitoring of complex chemical processes.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 4","pages":" 903-909"},"PeriodicalIF":3.1,"publicationDate":"2025-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/re/d5re00400d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147626264","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":"Model based process optimization for nanoparticle precipitation","authors":"Andrea Gilch, Adeel Muneer, Jana Dienstbier and Lukas Pflug","doi":"10.1039/D5RE00333D","DOIUrl":"https://doi.org/10.1039/D5RE00333D","url":null,"abstract":"<p >This study introduces a derivative-based optimization framework for the controlled synthesis of nanoparticles, with a focus on achieving target particle size distributions <em>via</em> dynamic manipulation of reactant inflow during precipitation. The key novel aspects of our approach include coupling population balance equations (PBE)-which accounts for nucleation and growth phenomena-with a prior first-order reduction reaction formulated using the exact Method of Moments (eMoM), and implementing a discretize-then-optimize approach for efficient computation of parameter sensitivities, enabling effective optimization of the time-dependent inflow profile. The objective is to minimize the variance in particle size while ensuring a prescribed mean diameter. Numerical case studies explore the role of process constraints and regularization strategies in control performance. The following quantitative results highlight the effectiveness of our approach: first, the optimized time-varying inflow profiles significantly outperform constant-rate strategies. Within the size range <em>μ</em><small>_D</small> ± 0.1<em>μ</em><small>_D</small>, the optimal control yields nanoparticles with a purity exceeding 99%, compared with about 77% for the most effective constant control. Furthermore, the framework remains robust under variations in process parameters, sustaining performance despite limits on maximum inflow rate and total synthesis time. This framework offers a systematic and computationally tractable approach to optimizing transient operating conditions in nanoparticle synthesis, with strong potential for industrial application.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 5","pages":" 1108-1116"},"PeriodicalIF":3.1,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/re/d5re00333d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147872160","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":"A rapidly assembled ZnS–AB electrochemical sensor with enhanced performance for luteolin determination","authors":"Jiaoyang Xu, Qingtong Li, Haifei Yu, Wenrui Bi, Xinyue Niu, Rong Yuan, Nannan Huang, Chunjing Zhang and Haijun Pang","doi":"10.1039/D5RE00464K","DOIUrl":"https://doi.org/10.1039/D5RE00464K","url":null,"abstract":"<p >Luteolin (LU) exhibits notable antimicrobial, anti-inflammatory, and antioxidant activities by inhibiting inflammatory mediators and protecting cells from oxidative stress-induced damage. However, excessive LU intake may cause adverse health effects. In this work, a novel composite material, ZnS–AB, composed of zinc sulfide (ZnS) and acetylene black (AB), was successfully synthesized and applied for the efficient electrochemical detection of LU. The incorporation of AB effectively enhanced the conductivity of ZnS and promoted charge transfer, thereby improving the sensing performance of the ZnS–AB electrode. The sensor displayed a wide linear range of 0.0010–0.21, 0.21–3.7, and 3.7–28 μM with an ultralow detection limit of 0.0003 μM. It also exhibited excellent selectivity against common interfering species. Furthermore, the sensor was successfully applied to the determination of LU in <em>Lonicera japonica</em> and rat serum samples with satisfactory recovery rates, demonstrating low cost and strong potential for on-site rapid detection.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 4","pages":" 910-921"},"PeriodicalIF":3.1,"publicationDate":"2025-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147626265","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":"Silicon dioxide nanofluids with low-salinity brines for interfacial tension and wettability control in enhanced oil recovery","authors":"Junjie Hu, Cong Lu and Jianchun Guo","doi":"10.1039/D5RE00474H","DOIUrl":"https://doi.org/10.1039/D5RE00474H","url":null,"abstract":"<p >Residual oil recovery remains limited by high interfacial tension (IFT) and unfavorable wettability. This study aimed to evaluate a hybrid silicon dioxide (SiO<small>₂</small>) nanofluid–low-salinity water (LSW) system designed to reduce IFT, alter wettability, and enhance core-scale recovery efficiency. Twelve standardized core plugs (<em>n</em> = 6 sandstone, <em>n</em> = 6 carbonate) were tested using factorial flooding experiments. Treatments included baseline brine (5000 ppm NaCl), LSW (500–2000 ppm), SiO<small>₂</small>-only (0.01–0.05 wt%), and hybrid SiO<small>₂</small>–LSW. Interfacial tension was measured <em>via</em> pendant drop tensiometry, wettability was assessed <em>via</em> sessile drop/USBM index, and recovery was measured through core flooding to 98% water cut. Nanoparticle stability was evaluated using zeta potential and particle size distribution. Statistical analysis employed two-way ANOVA, regression, and Tukey <em>post hoc</em> tests (<em>p</em> &lt; 0.05). Sandstone cores exhibited higher porosity (21.3 ± 1.8%) than carbonate (16.7 ± 2.1%) and higher baseline recovery (28.7 ± 2.8% <em>vs.</em> 22.5 ± 3.1% original oil in place [OOIP]). Hybrid floods reduced IFT from 27.5 to 4.6 mN m<small>⁻¹</small> in sandstone and from 29.8 to 5.2 mN m<small>⁻¹</small> in carbonate, achieving &gt;75% reduction relative to brine. Contact angles decreased from 102° to 42° in sandstone and from 110° to 50° in carbonate, with USBM (U.S. Bureau of Mines) indices shifting from negative (oil-wet) to positive (water-wet). Incremental recovery reached 18.6% OOIP in sandstone and 14.1% in carbonate, both exceeding the 10% target. Permeability loss was minimal (&lt;2%), with stable nanoparticle retention (&lt;0.6 mg g<small>⁻¹</small> rock). Hybrid SiO<small>₂</small>–LSW flooding achieves field-relevant thresholds in IFT reduction, wettability alteration, and recovery efficiency, supporting scalable application in enhanced oil recovery.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 4","pages":" 888-902"},"PeriodicalIF":3.1,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147626262","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":"Comparative photochemical flow synthesis of ketenimines via Hg-lamp and UV-C LED irradiation","authors":"Adam Cruise, Rémy Broersma, Frouke van den Berg and Marcus Baumann","doi":"10.1039/D5RE00484E","DOIUrl":"https://doi.org/10.1039/D5RE00484E","url":null,"abstract":"<p >The use of novel UV-C LEDs emitting monochromatic light at 265 nm is reported for the continuous flow synthesis of ketenimines from isoxazoles. The resulting flow process is compared to the use of a traditional Hg-lamp showing that substantial improvements in reaction performance and efficiency are obtained demonstrating the value of these high-power UV-C LED modules (up to 40 W of input power).</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 3","pages":" 596-600"},"PeriodicalIF":3.1,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/re/d5re00484e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147335676","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}