Reaction Chemistry & Engineering最新文献

{"title":"Development of site- and stereoselective continuous flow deuterium labelling method for carbohydrates using high dispersion effect towards Ru/C of hydrogen flow†","authors":"Naoya Sakurada, Daiki Sasaki, Manato Ono, Tsuyoshi Yamada, Takashi Ikawa and Hironao Sajiki","doi":"10.1039/D5RE00026B","DOIUrl":"https://doi.org/10.1039/D5RE00026B","url":null,"abstract":"<p >A site- and stereoselective deuterium labelling method for carbohydrates has been developed using a Ru/C catalyst under continuous flow conditions. It has been demonstrated that enhancing the void fraction of the catalyst cartridge leads to improved incorporation, while maintaining high selectivity over 150 h. This scalable, sustainable approach has the potential to reduce energy use, waste and Ru consumption, thus broadening continuous flow applications in organic synthesis.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 4","pages":" 777-781"},"PeriodicalIF":3.4,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143698424","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 synergistic effect of a novel photocatalyst based on triazine with 2-aminoanthraquinone for the Beckmann rearrangement in batch and a simple hand-made continuous flow photocatalytic reactor†","authors":"Mona Hosseini-Sarvari and Mohammad Namjoo","doi":"10.1039/D4RE00612G","DOIUrl":"https://doi.org/10.1039/D4RE00612G","url":null,"abstract":"<p >The Beckmann rearrangement is a fundamental organic transformation that plays an indispensable role in the synthesis of various functionalized compounds. In recent years, the development of efficient and selective catalysts for this reaction has garnered significant attention. In this study, we investigate the synergetic effect of a novel triazine-based photocatalyst in combination with 2-aminoanthraquinone in the Beckmann rearrangement under visible light irradiation. The triazine-based photocatalyst by incorporating 2-aminoanthraquinone, with its unique structural properties and high photocatalytic activity, offers promising potential for enhancing the efficiency and selectivity of the Beckmann rearrangement. Furthermore, we provide insights into a simple, handmade, continuous-flow photocatalytic reactor system that allows us to perform large-scale Beckmann rearrangement in a shorter time with reasonable efficiency. Overall, this study highlights the synergetic effect of a novel triazine-based photocatalyst with 2-aminoanthraquinone in the Beckmann rearrangement, offering new avenues for synthesizing functionalized compounds with improved efficiency and selectivity.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 6","pages":" 1386-1398"},"PeriodicalIF":3.4,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148246","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":"Effect of organic linker substituents on properties of metal–organic frameworks: a review†","authors":"Viktoriia V. Torbina, Yulia A. Belik and Olga V. Vodyankina","doi":"10.1039/D4RE00570H","DOIUrl":"https://doi.org/10.1039/D4RE00570H","url":null,"abstract":"<p >Tuning the properties of solid materials through the directed change of their composition is the most desirable tool for researchers. Varying the electronic structure of metal–organic frameworks by introducing different functional groups into the organic linker is usually regarded as the “Holy Grail” of the synthesis of porous materials with given properties. However, despite having more obvious structure–property relationships in comparison with inorganic porous materials, the chemistry of metal–organic frameworks is more complex, and the presence of a substituent can affect not only the electronic properties but also the structure, stability, numbers of defect sites and coordinatively unsaturated atoms, formation of new adsorption sites, <em>etc.</em> All these changes can influence the field of application of the designed/prepared materials. In the present review, the effect of the substituent nature on a broad range of metal–organic framework characteristics is discussed. The benefits and drawbacks of functionalizing organic linkers in metal–organic frameworks for gas storage and separation as well as catalysis and photocatalysis are also considered.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 6","pages":" 1197-1215"},"PeriodicalIF":3.4,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148234","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":"Gas–liquid flow synthesis of Zn3N2-quantum dots†","authors":"Malin G. Lüdicke, Jonas Schramm, Martin Wichert and Ralph A. Sperling","doi":"10.1039/D4RE00548A","DOIUrl":"https://doi.org/10.1039/D4RE00548A","url":null,"abstract":"<p >Continuous process engineering leads production of fine chemicals to a new level of industrialisation. This study elaborates specifications, benefits and pitfalls for the biphasic, high-temperature synthesis of Zn<small>₃</small>N<small>₂</small> quantum dots, which are made from inexpensive and earth-abundant starting materials. A micro-flow tubular reactor equipped with inline/online process sensors and a product analysis device is used. All technical requirements are fulfilled for the corrosive gas and air-sensitive starting and product materials to create a safe pilot plant for reproducible nanoparticle synthesis. The process parameter window yields tunable fluorescent nanocrystals (506–710 nm, 4–10 nm) which broadly match in quality (FWHM: 99–186 nm, QY: 15–56%) with those made in a batch approach. The transfer to a continuous synthesis practice greatly improves throughput because time is reduced as the reaction scheme can be realised in a single process step. In addition, handling effort is minimised with inline reagent dilution and optical spectroscopy which allows product adaptation by tuning of the process parameters in real-time.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 6","pages":" 1291-1301"},"PeriodicalIF":3.4,"publicationDate":"2025-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/re/d4re00548a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148242","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":"Bridging molecular dynamics and process engineering to predict the chemical recyclability of polyurethane foams†","authors":"Christophe de Graaf, Jonas Cassimon, Attila Kovacs, Matthew Porters, Christophe M. L. Vande Velde, Philippe Nimmegeers, Ana V. Cunha and Pieter Billen","doi":"10.1039/D4RE00505H","DOIUrl":"https://doi.org/10.1039/D4RE00505H","url":null,"abstract":"<p >Polyurethanes are versatile materials, but their thermoset nature limits mechanical recycling as they do not melt under heating. However, chemical recycling by depolymerization does not yet provide complete circularity, given the highly diverse monomers and additives. Especially for rigid foams, with short and multifunctional polyols, the separation of depolymerization products is challenging. In this paper, we propose a strategy to screen the separation of these products <em>via</em> liquid–liquid extraction by comparing molecular dynamics simulations with experimental results performed on a synthesized model rigid foam depolymerised by hydrolysis. Bifunctional ethyleneoxide polyols with molecular weights of 200, 400, 600 and 1000 are used together with 4,4′-methylene dianiline (MDA). The tested solvent systems are acetonitrile/<em>n</em>-hexane, water/dichloroethane, water/ethyl acetate and water/<em>n</em>-octanol. Coarse-grained (CG) molecular dynamics simulations were used to model the large-scale morphological organization during solution-processing. Our results show a clear separation between the polyols and the depolymerised aromatic components, except for the acetonitrile/<em>n</em>-hexane solvent system, where all solutes dissolve in acetonitrile. Polyols preferentially migrate to the aqueous phase, while aromatic amines such as MDA favour the organic phase. The simulations reveal that larger polyols tend to accumulate at the interface, particularly in the water/dichloroethane and water/ethyl acetate systems. Experimental partition coefficients, consistent with simulation predictions within error margins reported for the Martini 3 forcefield, indicate a strong correlation between polyol molecular weight and phase behaviour. This separation is further influenced by solvent polarity, with water/<em>n</em>-octanol systems exhibiting 2–3 times more MDA aggregation than the other systems, as predicted by the analysis of radial distribution functions and density profiles. The combined approach of molecular dynamics and experimental validation offers a promising strategy for optimizing liquid–liquid extraction in polyurethane depolymerization, guiding future design-for-circularity processes.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 6","pages":" 1268-1279"},"PeriodicalIF":3.4,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148240","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":"Synergistic effect of graphitic carbon nitride in enhancing flame-retardant properties of polypropylene composites","authors":"Vinod Sharma, Shilpi Agarwal, Shailey Singhal, Shikha Wadhwa and Ashish Mathur","doi":"10.1039/D4RE00590B","DOIUrl":"https://doi.org/10.1039/D4RE00590B","url":null,"abstract":"<p >Conventional flame retardants based on polymeric materials demonstrate high flammability, producing huge amounts of smoke, toxic gases and melt drips upon burning, causing immense damage to living beings and the environment. The use of brominated organic compounds, although effective, is discouraged due to their adverse effects and ubiquitous nature. In the present study, an intumescent flame-retardant (IFR) system (g-CN@3P) is developed by compounding different amounts of g-CN as a synergist with piperazine pyrophosphate (3P) in polypropylene (PP). SEM and XPS clearly demonstrate the interaction between g-CN and 3P, leading to enhanced flame-retardant properties of 3P. An IFR containing just 1.5 g of g-CN passed the vertical burning test (UL-94) with V0 rating. High flame retardancy of the composite makes it suitable for use in applications where high flame resistance is crucial. The composition also achieved an increase in limiting oxygen index (LOI) of 21.3% compared to the composition without the g-CN synergist. Moreover, the peak heat release rate, total heat release and smoke optical density were also reduced appreciably by 62.6%, 42.6% and 17.6%, respectively. The optimum composition of PP/g-CN@3P improved the mechanical properties compared to PP/3P samples. This study emphasizes the potential of graphitic carbon nitride additives as an environmentally friendly alternative to brominated organic compounds, offering a sustainable approach to enhancing flame-retardant properties.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 6","pages":" 1280-1290"},"PeriodicalIF":3.4,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148241","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 synthesis of functionalized biaryl compounds via a benzyne intermediate†","authors":"Chaoming Liang, Weixia Lin, Zilong Lin, Runxiang Yu, Yuyan Kang, Xiangmin Sang, Maolin Sun, Yueyue Ma, Ruihua Cheng and Jinxing Ye","doi":"10.1039/D5RE00023H","DOIUrl":"https://doi.org/10.1039/D5RE00023H","url":null,"abstract":"<p >A continuous flow protocol for the preparation of benzyne was developed utilizing readily accessible 1-bromo-2-iodobenzene and <em>i</em>PrMgCl·LiCl. The halogen–magnesium exchange and subsequent elimination reactions were conducted at temperatures of 0 °C and 80 °C, respectively, resulting in the generation of a highly reactive benzyne intermediate within minutes. The <em>in situ</em> generated benzyne can be efficiently employed in the continuous flow synthesis of functionalized biaryl compounds, including a series of ligands commonly utilized in Buchwald–Hartwig cross-coupling reactions.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 6","pages":" 1359-1364"},"PeriodicalIF":3.4,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148229","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":"Hydride-mediated chemoselective C–H bond formation during benzoic acid hydrodeoxygenation on anatase TiO2†","authors":"Mikyung Hwang, Jeremy Hu, Michael J. Janik and Konstantinos Alexopoulos","doi":"10.1039/D4RE00561A","DOIUrl":"https://doi.org/10.1039/D4RE00561A","url":null,"abstract":"<p >The chemoselective hydrogenation of benzoic acid to aromatic products such as benzaldehyde, benzyl alcohol, toluene, and benzene is studied on anatase TiO<small>₂</small> (001) using density functional theory (DFT) and microkinetic modeling (MKM). Oxygen vacancy (O<small>_vac</small>) sites are more active for benzoic acid hydrogenation than fully oxidized surface regions, with a nearly 2.5 eV lower energy for the first C–H bond formation reaction to occur near O<small>_vac</small>. This favorable C–H bond formation mechanism on anatase TiO<small>₂</small> occurs between hydrides (H<small>⁻</small>) and monoanionic intermediates coadsorbed in O<small>_vac</small>. A steady-state microkinetic model is constructed using computed reaction energies and activation barriers to determine rates of product formation at different reaction temperatures. Product selectivities differ in distinct temperature ranges, caused by competition among reaction and product desorption steps. Sensitivity analysis shows which elementary steps significantly affect the overall benzoic acid hydrogenation activity and selectivity.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 6","pages":" 1244-1258"},"PeriodicalIF":3.4,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/re/d4re00561a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144148238","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":"Enantioselective synthesis of (R)-citronellal from geraniol with an immobilised copper alcohol oxidase and ene reductase†","authors":"Beatrice Tagliabue, Christian M. Heckmann, Rocio Villa, Sacha Grisel, Jean-Guy Berrin, Mickael Lafond, David Ribeaucourt and Caroline E. Paul","doi":"10.1039/D5RE00034C","DOIUrl":"10.1039/D5RE00034C","url":null,"abstract":"<p >(<em>R</em>)-Citronellal is one of the key chiral intermediates in the synthesis of the isomer (−)-menthol, one of the most commercialised terpenoid flavours worldwide. Enzymatic approaches could represent a less energy-demanding alternative for its synthesis, such as a previously reported bienzymatic cascade starting from inexpensive, commercially available geraniol. A copper radical oxidase (<em>Cgr</em>AlcOx) followed by a flavin-dependent ene reductase (OYE2) were used to obtain (<em>R</em>)-citronellal. Here, we used a metal-affinity immobilisation strategy on the His-tagged enzymes for the cascade and studied enzyme recovery and reusability as well as increased solvent tolerance. After screening a panel of resins for enzyme immobilisation and water-immiscible co-solvents, we successfully obtained 95% conversion to (<em>R</em>)-citronellal with 96.9% enantiomeric excess (ee) in a concurrent cascade after 7 h of reaction time, starting from 10 mM of geraniol.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 6","pages":" 1320-1325"},"PeriodicalIF":3.4,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11908116/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143646383","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":"State-of-the-art heterogeneous polymerization kinetic modelling processes and their applications","authors":"Shu-Cen Lai, Jie Jin and Zheng-Hong Luo","doi":"10.1039/D5RE00005J","DOIUrl":"https://doi.org/10.1039/D5RE00005J","url":null,"abstract":"<p >Heterogeneous polymerization systems have been widely used in large-scale industrial production. Utilizing kinetic simulations to effectively reveal the underlying mechanisms of complex heterogeneous systems is invaluable for both product design and process optimization. The aim of this study is to comprehensively review the recent research progress on the development of heterogeneous polymerization kinetic modelling. We first provide an overview of the kinetic modelling processes of heterogeneous polymerization systems, focusing on mass transfer models, phase-state treatment approaches, and numerical methods. Further, to illustrate the importance of heterogeneous polymerization kinetic modelling, we give examples of its utilization in three research domains, including understanding the kinetics and transfer features, enabling the performance-oriented polymer structure design and precise synthesis, and guiding reactor design, optimization, and scale-up. Finally, the challenges and perspectives of heterogeneous polymerization kinetic modelling are discussed for future development.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 5","pages":" 942-952"},"PeriodicalIF":3.4,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/re/d5re00005j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143888507","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}