Reaction Chemistry & Engineering最新文献

{"title":"Unveiling the dual-function applications of a magnetically retrievable chemically grafted Schiff base Cu-complex on graphene oxide for catalytic and antibacterial applications†","authors":"Himadri Priya Gogoi, Nilotpal Goswami and Pranjit Barman","doi":"10.1039/D4RE00211C","DOIUrl":"10.1039/D4RE00211C","url":null,"abstract":"<p >In the current work, a new Schiff base complex containing Cu(<small>II</small>) ions was covalently anchored in a stepwise manner onto graphene oxide nanosheets, followed by a combination with magnetic iron oxide, to form a potential catalyst for C–H functionalization of indoles on C-3 <em>via</em> a one-pot multicomponent reaction. Numerous methods were used to characterize the as-synthesized nanostructure (CuSB-GO/FO), including VSM, XRD, FT-IR, SEM, EDX, TEM, Raman spectroscopy, N<small>₂</small> adsorption–desorption measurement and ICP-AES techniques. The as-synthesized CuSB-GO/FO was evaluated as an effective and versatile catalyst for reactions of different indoles, malononitrile, and substituted benzaldehydes in ethanol/water at 35 °C, producing 3-substituted indoles. The key advantages of this catalytic system are its quick reaction time, high product yield, use of green solvents, and ease of separation. The catalytic efficiency of the nanocatalyst rose dramatically when the complex was covalently grafted onto the graphene oxide surface, which might be due to the chemical alteration of the graphene oxide sheets. The findings demonstrate that the synthesized nanocatalyst may be reused four times with great chemical stability and minimal reduction in its activity as a catalyst. In addition, Gram-positive and Gram-negative bacteria responded well to the synthesized nanostructure as an antibacterial agent.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 10","pages":" 2569-2583"},"PeriodicalIF":3.4,"publicationDate":"2024-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141573545","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":"Lipase-catalysed esterification in a reactive natural deep eutectic solvent leads to lauroylcholine chloride rather than glucose ester†","authors":"Alina Ramona Buzatu, Miguel Angel Soler, Ozge Ozkilinc, Sara Fortuna, Diana Maria Dreavă, Ioan Bîtcan, Paolo Giannozzi, Federico Fogolari, Lucia Gardossi, Francisc Peter, Anamaria Todea and Carmen Gabriela Boeriu","doi":"10.1039/D4RE00209A","DOIUrl":"10.1039/D4RE00209A","url":null,"abstract":"<p >Enzymatic esterification of glucose with lauric acid catalyzed by lipase B from <em>Candida antarctica</em> immobilized on acrylic resin (LAR) was investigated in hydrophilic reactive natural deep eutectic solvents (R-NADESs), composed of choline chloride (ChCl) as the hydrogen bond acceptor (HBA) and glucose (Glc) and water as hydrogen bond donors (HBDs) in different molar ratios. Surprisingly, no glucose esters were obtained, the only esterification product being lauroylcholine chloride, obtained in the ChCl : Glc : H<small>₂</small>O (2 : 1 : 1) ternary R-NADES. Molecular dynamic simulations clearly explained this unexpected selectivity, showing that the lipase-catalyzed synthesis of glucose lauryl esters is hindered by the manifold and strong interactions in the H-bond network and the formation of voluminous adducts of glucose with the chloride ion, which cannot access the alcohol catalytic subsite. The free choline chloride, not involved in the H-bond network of the ChCl : Glc : H<small>₂</small>O (2 : 1 : 1) R-NADES, did enter the CalB catalytic pocket and was converted to the corresponding lauroylcholine ester.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 10","pages":" 2623-2634"},"PeriodicalIF":3.4,"publicationDate":"2024-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/re/d4re00209a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141573547","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":"Biocatalysis in microfluidic systems: an experimental basis for data science†","authors":"John M. Woodley","doi":"10.1039/D3RE00703K","DOIUrl":"10.1039/D3RE00703K","url":null,"abstract":"<p >Biocatalysis using (recombinant) enzymes is gaining traction as a method for selective chemical catalysis, especially in the pharmaceutical industry. Flow systems, especially miniaturized microfluidic systems, have proven to be a useful method to test new enzyme reaction sequences and processes. In this brief article, it will be argued that microfluidics not only can be used for rapid testing of reaction processes, but also can be used nowadays for collection of process data, especially for parameters in relevant kinetic and stability models, and thereby to help with scale-up, which remains a major challenge for implementation of biocatalysis in many industries. The ability to quickly change conditions (such as temperature) in microfluidic devices makes them ideally suited to such scale-down studies, and can form the experimental basis for data science as a tool for future process development.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 8","pages":" 2028-2033"},"PeriodicalIF":3.4,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141573546","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":"Selective hydrogenation of CO2 to formic acid with higher yield in an aqueous medium with a nano-nickel-metal catalyst: reaction parameter optimization by response surface methodology (RSM)†","authors":"Rajeev Ranjan, Prakash Biswas and K. K. Pant","doi":"10.1039/D4RE00194J","DOIUrl":"10.1039/D4RE00194J","url":null,"abstract":"<p >A highly active mesoporous nano-nickel catalyst was synthesized by the sol–gel method for the selective conversion of CO<small>₂</small> to formic acid (FA) in an aqueous medium. In this study, CO<small>₂</small> hydrogenation reactions were performed in a high-pressure autoclave, and the experimental conditions were set by using the response surface methodology (RSM). The RSM analysis was done using a three-factor, one-response, and five-level central composite design (CCD) integrated with the desirability approach. Experiments revealed that under the optimized reaction conditions (200 °C, 60 bar), the obtained formic acid yield was significantly high (2245 μmol g<small>⁻¹</small> h<small>⁻¹</small>) with 100% catalyst selectivity. The obtained turnover number (TON) was ∼285, significantly higher in an aqueous medium and the presence of a non-noble nickel nano-metal catalyst. Mesoporous nano nickel particles (15–26 nm) facilitated the selective adsorption and splitting of hydrogen molecules to hydrogen radicals, which further reacted with the carbonate ions present in the reaction medium. Na<small>₂</small>CO<small>₃</small> acted as a promoter, which enhanced the CO<small>₂</small> adsorption and the formic acid yield. The catalyst recyclability was confirmed by performing the experiments five times and a constant yield of formic acid was found.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 10","pages":" 2635-2646"},"PeriodicalIF":3.4,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141577931","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":"Intelligent method for analysis of the active phase of hydrogenation catalysts: stripe phase identification of UC-S/SC-S†","authors":"Zhujun Wang, Ailin Cui and Song Bao","doi":"10.1039/D4RE00239C","DOIUrl":"10.1039/D4RE00239C","url":null,"abstract":"<p >In order to realize the intelligent recognition and statistics of hydrogenation catalyst image information, different from traditional methods, this paper presents a new method to judge the active phase by image recognition. Firstly, image enhancement and Gabor filtering are used for image preprocessing to suppress the background and obtain the region with strong contrast. The fringe of the hydrogenation catalyst was extracted using a morphological algorithm. Finally, the edge of the fringe was extracted using a Sobel operator to detect the end of the skeleton line, which realized segmentation and recognition of the hydrogenation catalyst image. This method extracts features through data analysis of a large number of image samples to improve the robustness of the method and reduce the errors caused by manual judgment. The experimental results show that the proposed method has high accuracy and is highly consistent with the traditional method of judging the active phase, which has practical engineering application value.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 10","pages":" 2647-2658"},"PeriodicalIF":3.4,"publicationDate":"2024-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141573548","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":"Experimental study on the leaching effect of different chelating agents on the constant metal ions of lignite","authors":"Dawei Chen, Jun Xie, Jingyi Zhang, Yi Wang and Faquan Wang","doi":"10.1039/D4RE00257A","DOIUrl":"10.1039/D4RE00257A","url":null,"abstract":"<p >Chelating agents can increase the porosity of coal by leaching metal ions from it. Therefore, selecting the most suitable chelating agent based on the characteristics of the coal type is crucial when applying chelating agents. In this study, lignite from southwest China was chosen as the sample. Four chelating agents, namely tetrasodium iminodisuccinate (IDS), diethylenetriaminepentaacetic acid (DTPA), tetrasodium aspartate diacetate (ASDA), and tetrasodium glutamate diacetate (GLDA), were evaluated for their impact on the leaching of constant metal ions (CMIs). The leaching effect of CMIs was characterized and analyzed using inductively coupled plasma, scanning electron microscopy, and Brunauer–Emmett–Teller measurements. The results indicated that the ASDA chelating agent was the most effective in leaching Ca<small>²⁺</small>, Mg<small>²⁺</small>, Fe<small>^2+/3+</small>, and Al<small>³⁺</small>. Under the optimal concentration condition of 2500 mg L<small>⁻¹</small>, the leaching effect of CMIs from different chelating agents could be ranked as: ASDA &gt; DTPA &gt; IDS &gt; GLDA. The contact angle of the ASDA chelating agent with the coal sample decreased from 48.2° at 1 s to 26.5° at 20 s. The metal minerals on the surface of the coal dissolved under the action of the ASDA chelating agent, and the micropores on the coal surface transitioned to mesopores and macropores. The pore volume of coal samples increased from 0.0254 cm<small>³</small> g<small>⁻¹</small> to 0.0276 cm<small>³</small> g<small>⁻¹</small>, and the pore size increased from 3.26 nm to 4.06 nm. As the pore size of the coal increased, the permeability also significantly increased.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 9","pages":" 2489-2504"},"PeriodicalIF":3.4,"publicationDate":"2024-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141573551","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":"Scalable preparation of macroporous collagen microgels by air bubble-induced breakup and ice templating†","authors":"Sushant Singh, Wing Yan Chu, Rojin Ostadsharif Memar, Andrew De Carlo, Teodor Veres and Axel Günther","doi":"10.1039/D3RE00595J","DOIUrl":"10.1039/D3RE00595J","url":null,"abstract":"<p >Collagen I, the most abundant protein of the extracellular matrix, has found widespread use in three-dimensional cell culture, and increasingly also in bioprinting and biofabrication applications. However, several limitations remain, such as the capacity to locally recapitulate the multiscale organization of collagen in native tissues. Bioprinting cellular collagen structures with high feature fidelity so far either requires a more rapidly gelling biopolymer to be added or an acellular collagen structure to be defined before the delivery of cells. Here, we report the flow synthesis of macroporous collagen microgels (MCMs) that serve as building blocks for granular bioinks. Obtained bioinks offer excellent printability, provide an avenue to faithfully recapitulate the multiscale collagen organization of native tissues, and overcome the aforementioned limitations. Viscous collagen solutions with concentrations as high as 10 mg ml<small>⁻¹</small> are consistently converted into droplets using a parallelized microfluidic device <em>via</em> air bubble induced droplet breakup into a continuous oil phase. MCMs are obtained by inducing gelation, oil removal, and washing, and incorporating internal pores of tunable size <em>via</em> ice templating at freezing rates between 0.1 and 10 °C min<small>⁻¹</small>. Independent control over the MCM diameter (175–250 μm) and porosity (58–76%) allows the extracellular matrix structure to be tailored to different tissue engineering applications. The wall structures within MCMs share similarities with the highly compacted and recapitulated collagen porosity in native tissues. This approach in the future can be used to 3D print more complicated biomimetic structures that require cell positioning during printing.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 10","pages":" 2584-2598"},"PeriodicalIF":3.4,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141530555","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":"A multiscale investigation of polypropylene glycol polymer upcycling to propionaldehyde via catalytic cracking on acid sites of mesoporous Y zeolites†","authors":"Abraham Martinez, Kanan Shikhaliyev, Xuemin Li, Jinyi Han, Kaustav Chaudhuri, Son-Jong Hwang, Jagoda M. Urban-Klaehn, Alexander Kuperman, Anne Gaffney, Jochen Lauterbach and Alexander Katz","doi":"10.1039/D4RE00001C","DOIUrl":"10.1039/D4RE00001C","url":null,"abstract":"<p >We investigate acid-catalyzed upcycling of PPG polymer, emphasizing crucial features on multiple length scales that span reaction engineering on macroscopic length scales down to zeolite catalyst design on the nanoscale. We modified a previously described semi-batch reactor configuration to minimize coking and enhance recovered selectivities by incorporating rapid quenching of reaction products (instead of slower quenching with a condenser, which facilitates sequential coupling reactions), and decreased the initial carrier-gas residence time in the bed consisting of mixed catalyst and PPG polymer, further reducing the deposition of solid residues in the used catalyst. Our results highlight the importance of tight interfacial contact between the catalyst surface and the initial PPG polymer reactant, which is achieved <em>via</em> a pretreatment that removes adsorbed water, for drastically increasing the propionaldehyde selectivity, particularly for the large surface-area mesoporous catalysts. Our best catalyst consisted of mesoporous Y zeolite synthesized at an alkalinity of 0.16 M and exhibited nearly the same high propionaldehyde selectivity of approximately 95% (86% propionaldehyde yield) for a PPG polymer with molecular weights of 425 and 2000 Daltons (Da), suggesting the absence of mass transport restrictions. We also deconvolute the catalyst attribute between extra-framework aluminum (Al<small>_EF</small>) content and mesopore external surface area that most sensitively controlled propionaldehyde selectivity. This was performed by synthetically incorporating Al<small>_EF</small> content into our optimum catalyst, at a high and low alumina dispersion. The high dispersion alumina catalyst consisted of a uniform 10 nm-thick alumina layer covering the interior pores of the mesoporous Y catalyst, whereas the low dispersion alumina catalyst had a completely phase-separated alumina phase, commensurate in size to the zeolite particles. Our results demonstrate that Al<small>_EF</small> content in the catalyst decreases propionaldehyde yield by increasing the amount of solid residues in the catalyst post reaction, and had a minor effect on the propionaldehyde selectivity. These results point to a Brønsted rather than Lewis acid-catalyzed mechanism of catalysis for PPG polymer upcycling to propionaldehyde. In summary, our study demonstrates the most sensitive controlling attribute of the zeolite catalyst for selective propionaldehyde synthesis is its mesoporosity (as reflected in the mesopore volume and surface area) and that the multiscale details of the catalyst and reactor design also have profound consequences in achieving high propionaldehyde selectivity and yield.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 9","pages":" 2469-2482"},"PeriodicalIF":3.4,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141504212","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":"Autonomous reaction self-optimization using in-line high-field NMR spectroscopy†","authors":"Nour El Sabbagh, Margherita Bazzoni, Yuliia Horbenko, Aurélie Bernard, Daniel Cortés-Borda, Patrick Giraudeau, François-Xavier Felpin and Jean-Nicolas Dumez","doi":"10.1039/D4RE00270A","DOIUrl":"10.1039/D4RE00270A","url":null,"abstract":"<p >Autonomous self-optimization in flow is a powerful approach to efficiently optimize chemical transformations in a high dimensional space. Self-optimizing flow reactors combine automated flow devices with feedback optimization algorithms, which are powered by process analytical technology. In this contribution, we introduce the concept of autonomous self-optimizing flow reactors guided by in-line high-field NMR spectroscopy. We designed an autonomous experimental setup, combining an automated flow reactor with a high-field NMR spectrometer and a feedback optimization algorithm. User-friendly interfaces were developed for straightforward input of experimental parameters and precise control of equipment. Using 1D <small>¹</small>H NMR spectroscopy with a solvent suppression method, we achieved accurate quantitative measurements. Self-optimization utilizing the Nelder–Mead algorithm to maximize either the yield or the throughput of a formal [3 + 3] cycloaddition was conducted through the fine-tuning of the residence time, stoichiometry, and catalyst loading as input variables. The integration of high-field NMR within autonomous flow systems promises enhanced precision and efficiency in chemical synthesis optimization, particularly for complex reaction mixtures, setting the stage for advances in chemical synthesis.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 10","pages":" 2599-2609"},"PeriodicalIF":3.4,"publicationDate":"2024-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141504213","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":"Efficient synthesis of glycerol carbonate over a commercially available 4A molecular sieve via an integrated vacuum reactive distillation process†","authors":"Jiayin Huang, Anwei Wang, Chunsheng Zhao, Yu Fan, Shanshan Cao, Zheng Tian and Weiyou Zhou","doi":"10.1039/D4RE00213J","DOIUrl":"10.1039/D4RE00213J","url":null,"abstract":"<p >Various heterogeneous catalysts have been investigated in the transesterification of glycerol with ethylene carbonate to glycerol carbonate in a batch reactor, and a commercially available 4A molecular sieve exhibited relatively high catalytic performance for its surface strong basic and acidic sites. Further, an integrated vacuum reactive distillation process was developed for the transesterification in the presence of the 4A molecular sieve. The produced ethylene glycol could be efficiently removed from the reaction system to overcome the equilibrium, and excellent glycerol conversion (99%) and glycerol carbonate selectivity (&gt;99%) were obtained under the optimal reaction conditions. The recycling and the scale-up experiments demonstrate the excellent practical potential of the present process, thus providing an efficient reaction process for the preparation of glycerol carbonate.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 9","pages":" 2452-2459"},"PeriodicalIF":3.4,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141504149","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}