Markus Hegelmann, Wilson Felipe Bohorquez, Johannes Luibl, Andreas Jess, Alvaro Orjuela, Mirza Cokoja
Vegetable oils (VOs) are an environmentally benign alternative and sustainable carbon feedstock for various industrially relevant compounds, e.g. the epoxidized products (EVOs). The commercial production of EVOs is a heterogeneous liquid-liquid reaction with low reaction rates and a limited epoxide selectivity. Furthermore, the separation of the EVOs from the reaction mixture is very intricate, limiting a large-scale applicability. In this work, we introduce surface-active imidazolium tungstate ionic liquids (SAILs) as sustainable catalysts for the epoxidation of VOs in water using hydrogen peroxide as green oxidant. Micelle formation and substrate uptake into the aqueous phase depend on the nature of the cation of the SAIL catalyst, studied by dynamic light scattering (DLS), transmission electron microscopy (TEM) and cryo-TEM at various concentrations and temperatures. Recycling studies demonstrate that the catalyst remains in the aqueous phase and can be recovered completely. The absence of catalyst and additive in the product phase is verified by inductively coupled plasma mass spectrometry (ICP-MS) and 31P-NMR spectroscopy.
植物油（VOs）是生产各种工业相关化合物（如环氧化产物（EVOs））的一种无害环境且可持续的碳原料。EVO 的商业化生产是一种异相液-液反应，反应速率低，环氧化物选择性有限。此外，从反应混合物中分离 EVO 的过程非常复杂，限制了大规模应用。在这项工作中，我们引入了表面活性咪唑鎓钨酸盐离子液体（SAILs）作为可持续催化剂，用于以过氧化氢为绿色氧化剂的 VOs 在水中的环氧化反应。在不同浓度和温度下，通过动态光散射（DLS）、透射电子显微镜（TEM）和低温透射电子显微镜（cryo-TEM）对 SAIL 催化剂中阳离子的性质进行了研究。回收研究表明，催化剂留在水相中，可以完全回收。电感耦合等离子体质谱法（ICP-MS）和 31P-NMR 光谱法验证了产品相中不存在催化剂和添加剂。
{"title":"Biphasic Phase-Transfer Catalysis: Epoxidation of Vegetable Oils by Surface Active Ionic Liquids in Water","authors":"Markus Hegelmann, Wilson Felipe Bohorquez, Johannes Luibl, Andreas Jess, Alvaro Orjuela, Mirza Cokoja","doi":"10.1039/d4re00215f","DOIUrl":"https://doi.org/10.1039/d4re00215f","url":null,"abstract":"Vegetable oils (VOs) are an environmentally benign alternative and sustainable carbon feedstock for various industrially relevant compounds, e.g. the epoxidized products (EVOs). The commercial production of EVOs is a heterogeneous liquid-liquid reaction with low reaction rates and a limited epoxide selectivity. Furthermore, the separation of the EVOs from the reaction mixture is very intricate, limiting a large-scale applicability. In this work, we introduce surface-active imidazolium tungstate ionic liquids (SAILs) as sustainable catalysts for the epoxidation of VOs in water using hydrogen peroxide as green oxidant. Micelle formation and substrate uptake into the aqueous phase depend on the nature of the cation of the SAIL catalyst, studied by dynamic light scattering (DLS), transmission electron microscopy (TEM) and cryo-TEM at various concentrations and temperatures. Recycling studies demonstrate that the catalyst remains in the aqueous phase and can be recovered completely. The absence of catalyst and additive in the product phase is verified by inductively coupled plasma mass spectrometry (ICP-MS) and 31P-NMR spectroscopy.","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141780952","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}
Haohui Yan, Yan Chen, Peiwen Liu, Weiping Zhu, Fang Zhao
Herein, we report a size scale-up method for the 3D curved circular microchannel reactor (3D-CCMR), based on a rule of keeping fluid velocity and residence time constant during sizing-up and validated via computational fluid dynamics simulation with mixing index as the key evaluation indicator. The energy dissipation rate was also investigated via simulaiton to evaluate the energy consumption during sizing-up. Then, a scaled-up microreactor (3D-CCMR-2), aiming at a throughput scale-up factor of 4, was manufactured, and it was demonstrated experimentally that the mass and heat transfer performance was not deterioated in 3D-CCMR-2 as compared to the orginal microreactor (3D-CCMR-1). Utimately, the continuous flow synthesis of the intermediate of anti AIDS drug zidovudine was performed in both 3D-CCMRs and an actual throughput scale-up factor of 4.0 was achieved. The work in this paper represents as the first key step for the scale-up of continuous flow synthesis of zidovudine, and the sizing-up strategy proposed in this paper could offer good guidelines for the size scale-up of microreactors.
{"title":"Reliable sizing-up of 3D curved circular microchannel reactor for continuous flow synthesis of zidovudine intermediate","authors":"Haohui Yan, Yan Chen, Peiwen Liu, Weiping Zhu, Fang Zhao","doi":"10.1039/d4re00200h","DOIUrl":"https://doi.org/10.1039/d4re00200h","url":null,"abstract":"Herein, we report a size scale-up method for the 3D curved circular microchannel reactor (3D-CCMR), based on a rule of keeping fluid velocity and residence time constant during sizing-up and validated via computational fluid dynamics simulation with mixing index as the key evaluation indicator. The energy dissipation rate was also investigated via simulaiton to evaluate the energy consumption during sizing-up. Then, a scaled-up microreactor (3D-CCMR-2), aiming at a throughput scale-up factor of 4, was manufactured, and it was demonstrated experimentally that the mass and heat transfer performance was not deterioated in 3D-CCMR-2 as compared to the orginal microreactor (3D-CCMR-1). Utimately, the continuous flow synthesis of the intermediate of anti AIDS drug zidovudine was performed in both 3D-CCMRs and an actual throughput scale-up factor of 4.0 was achieved. The work in this paper represents as the first key step for the scale-up of continuous flow synthesis of zidovudine, and the sizing-up strategy proposed in this paper could offer good guidelines for the size scale-up of microreactors.","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141780871","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}
1,4-butanediol (1,4-BDO) is a key ingredient in the polymer industry. When derived from renewable erythritol, it can pave the way for sustainable poly(butylene terephthalate), polyurethane and polyester manufacturing. Hydrodeoxygenation (HDO) of erythritol on Brønsted acidic metal-metal oxide catalysts can result in 1,4-BDO, among other alcohols. Selective synthesis of 1,4-BDO requires deep insights on the preference for the cleavage of the different C-O bonds and the energy landscape for the formation of other polyol intermediates. In this work, we used density functional theory (DFT) simulations to investigate HDO of erythritol and other polyol intermediates on an inverse Ir-ReOx catalyst, where rhenium oxide is dispersed on iridium. While Ir nanoparticles can drive HDO through dehydroxylation, a protonation and dehydration mechanism happening at the Ir-ReOx interface has greater kinetic relevance. We show the kinetic preference for secondary C-O cleavage in erythritol to explain the predominant formation of 1,2,4-butanetriol (1,2,4-BTO) during erythritol HDO. The kinetic preference for 1,4-BDO formation from the 1,2,4-BTO makes it the most prominent butanediol during erythritol HDO. C-O bond cleavage in 1,4-BDO has a high barrier making 1,4-BDO less reactive in a polyol mixture. This indicates potentially selectivity formation of 1,4-BDO, with a possibility of tuning reaction conditions and reaction time to maximise its yield. Our analyses reveal that C-O cleavage is not always the kinetically relevant step and it can be the hydrogenation that follows the C-O cleavage. Hence, reactions at high hydrogen pressure and lower temperatures might suit higher selectivity towards desired alcohols such as 1,4-BDO.
{"title":"Mechanistic insights into C-O Bond Cleavage in Erythritol During Hydrodeoxygenation on Ir-ReOx Catalyst","authors":"Ajin Rajan, Jithin John Varghese","doi":"10.1039/d4re00245h","DOIUrl":"https://doi.org/10.1039/d4re00245h","url":null,"abstract":"1,4-butanediol (1,4-BDO) is a key ingredient in the polymer industry. When derived from renewable erythritol, it can pave the way for sustainable poly(butylene terephthalate), polyurethane and polyester manufacturing. Hydrodeoxygenation (HDO) of erythritol on Brønsted acidic metal-metal oxide catalysts can result in 1,4-BDO, among other alcohols. Selective synthesis of 1,4-BDO requires deep insights on the preference for the cleavage of the different C-O bonds and the energy landscape for the formation of other polyol intermediates. In this work, we used density functional theory (DFT) simulations to investigate HDO of erythritol and other polyol intermediates on an inverse Ir-ReOx catalyst, where rhenium oxide is dispersed on iridium. While Ir nanoparticles can drive HDO through dehydroxylation, a protonation and dehydration mechanism happening at the Ir-ReOx interface has greater kinetic relevance. We show the kinetic preference for secondary C-O cleavage in erythritol to explain the predominant formation of 1,2,4-butanetriol (1,2,4-BTO) during erythritol HDO. The kinetic preference for 1,4-BDO formation from the 1,2,4-BTO makes it the most prominent butanediol during erythritol HDO. C-O bond cleavage in 1,4-BDO has a high barrier making 1,4-BDO less reactive in a polyol mixture. This indicates potentially selectivity formation of 1,4-BDO, with a possibility of tuning reaction conditions and reaction time to maximise its yield. Our analyses reveal that C-O cleavage is not always the kinetically relevant step and it can be the hydrogenation that follows the C-O cleavage. Hence, reactions at high hydrogen pressure and lower temperatures might suit higher selectivity towards desired alcohols such as 1,4-BDO.","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141780870","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}
Kwihwan Kobayashi, Jun Matuzawa, Hajime Kawanami, Nagatoshi Koumura
The development of multistep flow synthesis methods for fine chemicals and pharmaceuticals is desirable in terms of cost and energy efficiency. Methods for connecting the first and second flow reactions are essential for the development of multistep flow reactions; however, some reactions are incompatible with necessary solvents. Herein, we developed continuous-removal methods for polar co-solvents that negatively affect subsequent reactions. These sequential flow reactions facilitated the production of multicomponent compounds from simple starting materials. Furthermore, scaled-up experiments for the sequential flow reaction using reaction columns approximately 40 times larger than the original were successfully conducted, with a productivity of 16.1 g h-1. We believe that our continuous extraction method holds promise for various sequential flow reactions for the synthesis of fine chemicals and pharmaceuticals.
{"title":"Continuous-Inline Extraction of Polar Co-solvent During Sequential Flow Reactions","authors":"Kwihwan Kobayashi, Jun Matuzawa, Hajime Kawanami, Nagatoshi Koumura","doi":"10.1039/d4re00276h","DOIUrl":"https://doi.org/10.1039/d4re00276h","url":null,"abstract":"The development of multistep flow synthesis methods for fine chemicals and pharmaceuticals is desirable in terms of cost and energy efficiency. Methods for connecting the first and second flow reactions are essential for the development of multistep flow reactions; however, some reactions are incompatible with necessary solvents. Herein, we developed continuous-removal methods for polar co-solvents that negatively affect subsequent reactions. These sequential flow reactions facilitated the production of multicomponent compounds from simple starting materials. Furthermore, scaled-up experiments for the sequential flow reaction using reaction columns approximately 40 times larger than the original were successfully conducted, with a productivity of 16.1 g h-1. We believe that our continuous extraction method holds promise for various sequential flow reactions for the synthesis of fine chemicals and pharmaceuticals.","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141754065","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}
Xiangxue Zhang, Xinyi Chao, Nina Fei, Wenyao Chen, Gang Qian, Jing Zhang, De Chen, Xuezhi Duan, Xing-Gui Zhou, Weikang Yuan
The catalytic oxidation of CO over Cu-based catalysts has garnered significant interest due to their promising potential in addressing environmental pollution and enhancing industrial processes. Herein, we report a dual-stimuli strategy to boost the catalytic performance of CO oxidation via synergistically harnessing active Cu+ species with oxygen vacancies by engineering the grain boundary of Cu-Mn catalysts. The nanorod-like MnO2 with a tunnel structure was prepared by a hydrothermal method and employed as the catalyst support, where different amounts of Cu were further introduced via impregnation to obtain Cu/MnO2 catalysts. It is found that apart from the highly dispersed Cu species within MnO2 lattice to create lattice mismatch and distortion, some Cu are present as oxidized nanoparticles over MnO2 surface, thus sparking off increased dislocations and grain boundaries. A combination of characterizations demonstrates that the proportion of active Cu+ species decreases with the increasing amount of Cu, presenting an inverse relationship to the abundance of oxygen vacancies over catalyst surface. Correspondingly, both Cu+ species and oxygen vacancies are identified as the main active sites for the adsorption and activation of CO and O2, respectively. Therefore, a trade-off between the percentage of active Cu+ species and oxygen vacancies for the 15% Cu/MnO2 catalyst with a moderate Cu introduction contributes to its highest catalytic activity, with T50 and T90 reaching 66 °C and 89 °C, respectively. This investigation highlights the potential of synergistically harnessing active Cu+ species with oxygen vacancies via grain boundary engineering for enhanced catalytic performance in CO oxidation applications.
由于铜基催化剂在解决环境污染和改善工业过程方面具有广阔的潜力，因此其催化氧化一氧化碳的性能备受关注。在此，我们报告了一种双刺激策略，即通过对 Cu-Mn 催化剂的晶界进行工程设计，协同利用活性 Cu+ 物种和氧空位，从而提高 CO 氧化的催化性能。采用水热法制备了具有隧道结构的纳米棒状 MnO2 并将其用作催化剂载体，然后通过浸渍法引入不同量的 Cu 得到 Cu/MnO2 催化剂。研究发现，除了高度分散在 MnO2 晶格中的铜会造成晶格错配和畸变外，一些铜还会以氧化纳米颗粒的形式存在于 MnO2 表面，从而引发位错和晶界的增加。综合表征结果表明，活性 Cu+ 物种的比例随着 Cu 含量的增加而降低，与催化剂表面氧空位的丰度呈反比关系。相应地，Cu+ 物种和氧空位被确定为分别吸附和活化 CO 和 O2 的主要活性位点。因此，对于适度引入铜的 15% Cu/MnO2 催化剂来说，在活性 Cu+ 物种和氧空位比例之间进行权衡有助于提高其最高催化活性，T50 和 T90 分别达到 66 °C 和 89 °C。这项研究凸显了通过晶界工程协同利用活性 Cu+ 物种和氧空位来提高一氧化碳氧化应用催化性能的潜力。
{"title":"Engineering Grain Boundary and Surface Sites of Binary Cu-Mn Catalysts to Boost CO Oxidation","authors":"Xiangxue Zhang, Xinyi Chao, Nina Fei, Wenyao Chen, Gang Qian, Jing Zhang, De Chen, Xuezhi Duan, Xing-Gui Zhou, Weikang Yuan","doi":"10.1039/d4re00222a","DOIUrl":"https://doi.org/10.1039/d4re00222a","url":null,"abstract":"The catalytic oxidation of CO over Cu-based catalysts has garnered significant interest due to their promising potential in addressing environmental pollution and enhancing industrial processes. Herein, we report a dual-stimuli strategy to boost the catalytic performance of CO oxidation via synergistically harnessing active Cu+ species with oxygen vacancies by engineering the grain boundary of Cu-Mn catalysts. The nanorod-like MnO2 with a tunnel structure was prepared by a hydrothermal method and employed as the catalyst support, where different amounts of Cu were further introduced via impregnation to obtain Cu/MnO2 catalysts. It is found that apart from the highly dispersed Cu species within MnO2 lattice to create lattice mismatch and distortion, some Cu are present as oxidized nanoparticles over MnO2 surface, thus sparking off increased dislocations and grain boundaries. A combination of characterizations demonstrates that the proportion of active Cu+ species decreases with the increasing amount of Cu, presenting an inverse relationship to the abundance of oxygen vacancies over catalyst surface. Correspondingly, both Cu+ species and oxygen vacancies are identified as the main active sites for the adsorption and activation of CO and O2, respectively. Therefore, a trade-off between the percentage of active Cu+ species and oxygen vacancies for the 15% Cu/MnO2 catalyst with a moderate Cu introduction contributes to its highest catalytic activity, with T50 and T90 reaching 66 °C and 89 °C, respectively. This investigation highlights the potential of synergistically harnessing active Cu+ species with oxygen vacancies via grain boundary engineering for enhanced catalytic performance in CO oxidation applications.","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141745390","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}
Konstantza Atanassova Tonova, Svetlana Nikolova Zhivkova, Madlena Petkova Lazarova, Ahmad Mustafa
This study deals with hydrophobic phosphonium ionic liquids (ILs), phosphinate and neodecanoate, used in liquid–liquid extraction for the purpose of complex detoxification of lignocellulosic hydrolysates from inhibitors, but preserving the sugar content. The topic is considered from two aspects, theoretical one in which extraction from a model multicomponent solution composed of acids, furan, phenolics, and sugars is investigated, and practically by employing a real rice straw hydrolysate. Using the model solution in cross-current extraction mode, the main process parameters, pH and concentration of the ILs, are studied. The extraction mechanisms of acids (sulfuric, gallic, acetic and levulinic acids) and aldehydes (vanillin and furfural) are established. Extraction of the acids in both ILs proceeds by a competitive mechanism until the two reactive H-bonding sites located at the two oxygen atoms in the IL’s anion are occupied. In addition to H-bonding, extraction of the phenolic acid is substantially assisted by hydrophobic interactions, while the sulfuric acid is readily extracted by protonation of the IL’s anion. An above-stoichiometric extraction of acids by phosphonium phosphinate has been found, which occurs by acid–acid H-bonds between phenolic and organic acids. Co-extraction between phenolic acid and phenolic and furanic aldehydes is observed which is based on the H-bonds that exist in acidic media and the staking interactions of the aromatic rings. The extraction of real rice straw hydrolysate carried out in three runs reaches a high removal of organic acids (over 63%), furans (over 80%) and phenolic compounds (over 97%) in each run.
本研究涉及疏水性膦离子液体（ILs）、膦酸盐和新癸酸盐，用于液-液萃取，目的是对木质纤维素水解物进行复合解毒，去除抑制剂，同时保留糖分含量。本课题从两个方面进行了研究，一是理论方面，研究了从由酸、呋喃、酚类和糖组成的多组分模型溶液中萃取的方法；二是实际方面，采用了真正的稻草水解物。利用横流萃取模式下的模型溶液，研究了主要工艺参数、pH 值和离子交换树脂的浓度。确定了酸（硫酸、没食子酸、乙酸和乙酰丙酸）和醛（香兰素和糠醛）的萃取机理。酸在两种惰性离子中的萃取都是通过竞争机制进行的，直到位于惰性离子阴离子中两个氧原子上的两个活性 H 键位点被占据为止。除了 H 键作用外，疏水作用也对酚酸的萃取有很大帮助，而硫酸则很容易通过 IL 阴离子的质子化作用被萃取出来。研究发现，膦酸对酸的萃取超过了化学计量，这是通过酚酸和有机酸之间的酸-酸 H 键实现的。酚酸与酚醛和呋喃醛之间的共萃取是基于存在于酸性介质中的 H 键和芳香环的固定作用。对真正的稻草水解物进行了三次萃取，每次萃取的有机酸去除率（超过 63%）、呋喃去除率（超过 80%）和酚类化合物去除率（超过 97%）都很高。
{"title":"Extraction by ionic liquids for the case of detoxification of lignocellulosic hydrolysates","authors":"Konstantza Atanassova Tonova, Svetlana Nikolova Zhivkova, Madlena Petkova Lazarova, Ahmad Mustafa","doi":"10.1039/d4re00154k","DOIUrl":"https://doi.org/10.1039/d4re00154k","url":null,"abstract":"This study deals with hydrophobic phosphonium ionic liquids (ILs), phosphinate and neodecanoate, used in liquid–liquid extraction for the purpose of complex detoxification of lignocellulosic hydrolysates from inhibitors, but preserving the sugar content. The topic is considered from two aspects, theoretical one in which extraction from a model multicomponent solution composed of acids, furan, phenolics, and sugars is investigated, and practically by employing a real rice straw hydrolysate. Using the model solution in cross-current extraction mode, the main process parameters, pH and concentration of the ILs, are studied. The extraction mechanisms of acids (sulfuric, gallic, acetic and levulinic acids) and aldehydes (vanillin and furfural) are established. Extraction of the acids in both ILs proceeds by a competitive mechanism until the two reactive H-bonding sites located at the two oxygen atoms in the IL’s anion are occupied. In addition to H-bonding, extraction of the phenolic acid is substantially assisted by hydrophobic interactions, while the sulfuric acid is readily extracted by protonation of the IL’s anion. An above-stoichiometric extraction of acids by phosphonium phosphinate has been found, which occurs by acid–acid H-bonds between phenolic and organic acids. Co-extraction between phenolic acid and phenolic and furanic aldehydes is observed which is based on the H-bonds that exist in acidic media and the staking interactions of the aromatic rings. The extraction of real rice straw hydrolysate carried out in three runs reaches a high removal of organic acids (over 63%), furans (over 80%) and phenolic compounds (over 97%) in each run.","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141722384","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}
We would like to take this opportunity to thank all of Reaction Chemistry & Engineering's reviewers for helping to preserve quality and integrity in chemical science literature. We would also like to highlight the Outstanding Reviewers for Reaction Chemistry & Engineering in 2023.
{"title":"Outstanding Reviewers for Reaction Chemistry & Engineering in 2023","authors":"","doi":"10.1039/d4re90019g","DOIUrl":"https://doi.org/10.1039/d4re90019g","url":null,"abstract":"We would like to take this opportunity to thank all of <em>Reaction Chemistry & Engineering</em>'s reviewers for helping to preserve quality and integrity in chemical science literature. We would also like to highlight the Outstanding Reviewers for <em>Reaction Chemistry & Engineering</em> in 2023.","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141611885","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}
In the current work, a new Schiff base complex containing Cu(II) 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 via 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, N2 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.
{"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, Pranjit Barman","doi":"10.1039/d4re00211c","DOIUrl":"https://doi.org/10.1039/d4re00211c","url":null,"abstract":"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><sub>2</sub></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.","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":3.9,"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}
Alina Ramona Buzatu, Miguel Angel Soler, Özge Özkılınç, Sara Fortuna, Diana Maria Dreavă, Ioan Bitcan, Paolo Giannozzi, Federico Fogolari, Lucia Gardossi, Francisc Peter, Anamaria Todea, Carmen Gabriela Boeriu
Enzymatic esterification of glucose with lauric acid catalyzed by lipase B from Candida antarctica immobilized on acrylic resins (LAR) was investigated in hydrophilic reactive natural deep eutectic solvents (R-NADES), composed of choline chloride (ChCl) as hydrogen bond acceptor (HBA) and glucose (Glc) and water as hydrogen bond donors (HBD) in different molar ratios. Surprisingly, no glucose esters were obtained, the only esterification product being lauroylcholine chloride, obtained in the ChCl:Glc:H2O (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, that cannot access the alcohol catalytic subsite. The free choline chloride, not involved in the H-bond network of the ChCl:Glc:H2O (2:1:1) R-NADES, did enter the CalB catalytic pocket and was converted to the corresponding lauroylcholine ester.
研究人员在亲水活性天然深共晶溶剂（R-NADES）中研究了固定在丙烯酸树脂（LAR）上的南极念珠菌脂肪酶 B 催化的葡萄糖与月桂酸的酶促酯化反应，R-NADES 由不同摩尔比的氯化胆碱（ChCl）作为氢键受体（HBA），葡萄糖（Glc）和水作为氢键供体（HBD）组成。令人惊讶的是，在 ChCl:Glc:H2O (2:1:1) 三元 R-NADES 中没有得到葡萄糖酯，唯一的酯化产物是氯化月桂酰胆碱。分子动力学模拟清楚地解释了这种意想不到的选择性，表明脂肪酶催化的葡萄糖月桂基酯合成受到 H 键网络中多种强相互作用的阻碍，葡萄糖与氯离子形成大量加合物，无法进入醇催化位点。游离的氯化胆碱没有参与 ChCl:Glc:H2O (2:1:1) R-NADES 的氢键网络，但却进入了 CalB 催化袋，并转化为相应的月桂酰胆碱酯。
{"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, Özge Özkılınç, Sara Fortuna, Diana Maria Dreavă, Ioan Bitcan, Paolo Giannozzi, Federico Fogolari, Lucia Gardossi, Francisc Peter, Anamaria Todea, Carmen Gabriela Boeriu","doi":"10.1039/d4re00209a","DOIUrl":"https://doi.org/10.1039/d4re00209a","url":null,"abstract":"Enzymatic esterification of glucose with lauric acid catalyzed by lipase B from <em>Candida antarctica</em> immobilized on acrylic resins (LAR) was investigated in hydrophilic reactive natural deep eutectic solvents (R-NADES), composed of choline chloride (ChCl) as hydrogen bond acceptor (HBA) and glucose (Glc) and water as hydrogen bond donors (HBD) in different molar ratios. Surprisingly, no glucose esters were obtained, the only esterification product being lauroylcholine chloride, obtained in the ChCl:Glc:H<small><sub>2</sub></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, that cannot access the alcohol catalytic subsite. The free choline chloride, not involved in the H-bond network of the ChCl:Glc:H<small><sub>2</sub></small>O (2:1:1) R-NADES, did enter the CalB catalytic pocket and was converted to the corresponding lauroylcholine ester.","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","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":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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.
{"title":"Biocatalysis in microfluidic systems: an experimental basis for data science","authors":"John M. Woodley","doi":"10.1039/d3re00703k","DOIUrl":"https://doi.org/10.1039/d3re00703k","url":null,"abstract":"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.","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":null,"pages":null},"PeriodicalIF":3.9,"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}
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