Pub Date : 2025-08-01Epub Date: 2024-05-24DOI: 10.1016/j.gresc.2024.05.005
Zhiqiang Hao , Zhongzhen Wang , Dajiang Huang , Xinlei Huangfu , Xuejing Yang , Junnian Wei , Wei Liu , Wen-Xiong Zhang
Compared with rare and expensive late-transition metals, rare-earth photocatalysts are much less investigated in synthetic chemistry, particularly concerning redox-inactive rare-earth metals. Herein, we describe a general strategy to realize the redox-inactive rare-earth photocatalysis by grafting a light-absorbing scaffold onto common ligands in rare-earth organometallics. Three guanidinate rare-earth complexes with photocatalytic functions were synthesized and found to exhibit higher catalytic efficiency than phenothiazine in the reductive homocoupling of benzyl bromides. These preliminary results illustrated that our “grafting” strategy could serve as a facile methodology for the construction of redox-inactive rare-earth photocatalysis systems.
{"title":"Harnessing redox-inactive rare-earth metals for photocatalytic reductive coupling of benzyl bromides","authors":"Zhiqiang Hao , Zhongzhen Wang , Dajiang Huang , Xinlei Huangfu , Xuejing Yang , Junnian Wei , Wei Liu , Wen-Xiong Zhang","doi":"10.1016/j.gresc.2024.05.005","DOIUrl":"10.1016/j.gresc.2024.05.005","url":null,"abstract":"<div><div>Compared with rare and expensive late-transition metals, rare-earth photocatalysts are much less investigated in synthetic chemistry, particularly concerning redox-inactive rare-earth metals. Herein, we describe a general strategy to realize the redox-inactive rare-earth photocatalysis by grafting a light-absorbing scaffold onto common ligands in rare-earth organometallics. Three guanidinate rare-earth complexes with photocatalytic functions were synthesized and found to exhibit higher catalytic efficiency than phenothiazine in the reductive homocoupling of benzyl bromides. These preliminary results illustrated that our “grafting” strategy could serve as a facile methodology for the construction of redox-inactive rare-earth photocatalysis systems.</div></div>","PeriodicalId":12794,"journal":{"name":"Green Synthesis and Catalysis","volume":"6 3","pages":"Pages 324-328"},"PeriodicalIF":0.0,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141134849","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-08-01Epub Date: 2024-05-18DOI: 10.1016/j.gresc.2024.05.004
Qingwei Song , Wenhao Wu , Weijie Chen, Hui Gao, Zhi Zhou, Zhongyi Zeng, Wei Yi
Taking advantage of facilely available α-chloroketones as C(sp3)-based electrophilic partners and oxidized alkyne equivalents, we here present a novel CpxRh(III)-catalyzed enantioselective C–H [4 + 2] annulation of sulfoximines under mild and redox-neutral conditions to access S-chiral 1,2-benzothiazines. It represents the first example of such C(sp3)-electrophiles enabling enantioselective C–H functionalization.
{"title":"α-Chloroketones enabled Rh(III)-catalyzed enantioselective C–H [4+2] annulation of sulfoximines under mild and redox-neutral conditions","authors":"Qingwei Song , Wenhao Wu , Weijie Chen, Hui Gao, Zhi Zhou, Zhongyi Zeng, Wei Yi","doi":"10.1016/j.gresc.2024.05.004","DOIUrl":"10.1016/j.gresc.2024.05.004","url":null,"abstract":"<div><div>Taking advantage of facilely available α-chloroketones as C(sp<sup>3</sup>)-based electrophilic partners and oxidized alkyne equivalents, we here present a novel Cp<sup>x</sup>Rh(III)-catalyzed enantioselective C–H [4 + 2] annulation of sulfoximines under mild and redox-neutral conditions to access <em>S</em>-chiral 1,2-benzothiazines. It represents the first example of such C(sp<sup>3</sup>)-electrophiles enabling enantioselective C–H functionalization.</div></div>","PeriodicalId":12794,"journal":{"name":"Green Synthesis and Catalysis","volume":"6 3","pages":"Pages 320-323"},"PeriodicalIF":0.0,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141140539","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Stereoselective chemical glycosylation reactions are pivotal for preparing manifold biologically and medically important compounds, while mechanisms of chemical glycosylation reactions remain obscure and largely speculative. Herein, we performed DFT calculations to delve into the multifaceted mechanistic details of glycosylation reactions, including the equilibria among reactive glycosyl triflate intermediates in solution, the stereoselectivity imparting protecting groups, solvent effects, base, and the anomeric effect. Our results provided theoretical corroboration to 2-OAc neighbouring group participation (NGP), the arming/disarming effect, the coordination theory of solvent effect on glycosylation stereochemistry, and the influence of solvent polarity on the reaction kinetics spanning the SN1-SN2 continuum. For the first time, the existence of putative contact-ion-pairs (CIP) of glycosyl oxocarbenium and triflate anion in organic solutions was theoretically confirmed with the identification of multiple ground state structures employing an implicit Solvation Model based on Density (SMD). Kinetics of nucleophilic attack of model glucosyl triflates by simple alcohol acceptors ethanol (EtOH) and trifluoroethanol (TFE), complexed with 2,4,6-tri-tert-butylpyrimidine (TTBP) were explored, revealing the essential role of the close accompanying base for rendering glycosidic bond formation thermodynamically favourable. Our work deepens the comprehension of the glycosylation mechanism, paving the way for the rational design and future advancement of efficient and environmentally friendly stereoselective glycosylation reactions.
{"title":"Unraveling chemical glycosylation: DFT insights into factors imparting stereoselectivity","authors":"Aoxin Guo , Yuan Xu , Zhenhua Jia , Teck-Peng Loh , Xue-Wei Liu","doi":"10.1016/j.gresc.2024.03.004","DOIUrl":"10.1016/j.gresc.2024.03.004","url":null,"abstract":"<div><div>Stereoselective chemical glycosylation reactions are pivotal for preparing manifold biologically and medically important compounds, while mechanisms of chemical glycosylation reactions remain obscure and largely speculative. Herein, we performed DFT calculations to delve into the multifaceted mechanistic details of glycosylation reactions, including the equilibria among reactive glycosyl triflate intermediates in solution, the stereoselectivity imparting protecting groups, solvent effects, base, and the anomeric effect. Our results provided theoretical corroboration to 2-OAc neighbouring group participation (NGP), the arming/disarming effect, the coordination theory of solvent effect on glycosylation stereochemistry, and the influence of solvent polarity on the reaction kinetics spanning the S<sub>N</sub>1-S<sub>N</sub>2 continuum. For the first time, the existence of putative contact-ion-pairs (CIP) of glycosyl oxocarbenium and triflate anion in organic solutions was theoretically confirmed with the identification of multiple ground state structures employing an implicit Solvation Model based on Density (SMD). Kinetics of nucleophilic attack of model glucosyl triflates by simple alcohol acceptors ethanol (EtOH) and trifluoroethanol (TFE), complexed with 2,4,6-tri-<em>tert</em>-butylpyrimidine (TTBP) were explored, revealing the essential role of the close accompanying base for rendering glycosidic bond formation thermodynamically favourable. Our work deepens the comprehension of the glycosylation mechanism, paving the way for the rational design and future advancement of efficient and environmentally friendly stereoselective glycosylation reactions.</div></div>","PeriodicalId":12794,"journal":{"name":"Green Synthesis and Catalysis","volume":"6 3","pages":"Pages 302-310"},"PeriodicalIF":0.0,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140148065","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-08-01Epub Date: 2024-04-25DOI: 10.1016/j.gresc.2024.04.002
Kangning Cao , Shutao Qi , Jianhui Li , Wenshao Ye , Junfeng Yang , Junliang Zhang , Fener Chen
Aza-Heck cyclization of alkene-tethered oxime esters has received considerable attention as an effective strategy for synthesizing 1-pyrroline derivatives. However, the achievement of tandem aza-Heck reaction with alkyl electrophiles remains a challenge. Herein, we report a palladium-catalyzed tandem aza-Heck reaction of alkene-tethered oxime esters with cyclopropanols. This catalytic system features mild conditions and broad substrate scopes, allowing the direct synthesis of structurally diverse 1-pyrroline derivatives in good yields.
{"title":"Palladium-catalyzed tandem aza-Heck reaction of alkene-tethered oxime esters with cyclopropanols","authors":"Kangning Cao , Shutao Qi , Jianhui Li , Wenshao Ye , Junfeng Yang , Junliang Zhang , Fener Chen","doi":"10.1016/j.gresc.2024.04.002","DOIUrl":"10.1016/j.gresc.2024.04.002","url":null,"abstract":"<div><div>Aza-Heck cyclization of alkene-tethered oxime esters has received considerable attention as an effective strategy for synthesizing 1-pyrroline derivatives. However, the achievement of tandem aza-Heck reaction with alkyl electrophiles remains a challenge. Herein, we report a palladium-catalyzed tandem aza-Heck reaction of alkene-tethered oxime esters with cyclopropanols. This catalytic system features mild conditions and broad substrate scopes, allowing the direct synthesis of structurally diverse 1-pyrroline derivatives in good yields.</div></div>","PeriodicalId":12794,"journal":{"name":"Green Synthesis and Catalysis","volume":"6 3","pages":"Pages 329-332"},"PeriodicalIF":0.0,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140772259","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-08-01Epub Date: 2024-02-10DOI: 10.1016/j.gresc.2024.02.001
Yu Zhang , Xinyu Han , Rongkai Wu , Jinxin Wang , Qiannan Li , Jingchuan Lin , Dingding Xia , Xin Hong , Shoubhik Das , Wei-Dong Zhang
Direct synthesis of olefins continues to attract stellar attention due to the high importance of olefins. In this context, due to the wide availability of ketones, the synthesis of olefins directly from ketones provides a straightforward route. Considering this, olefins synthesis from ketones via the formation of donor/donor type carbenes has been developed which leads to the efficient synthesis of versatile olefins by using a metal-free strategy. This approach features mild reaction conditions and exhibits a broad substrate scope when a biomass-derived solvent as a green reaction media is used. The practical utility of this approach has been demonstrated via late-stage modifications and even by scaling up to 20 g scale. At the end, mechanistic investigations and density functional theory studies clearly proved the formation of donor/donor carbenes, and examined the necessity of all the reagents and the effect of light in this system.
{"title":"Metal-free and visible-light-mediated method enables the synthesis of olefins from ketones","authors":"Yu Zhang , Xinyu Han , Rongkai Wu , Jinxin Wang , Qiannan Li , Jingchuan Lin , Dingding Xia , Xin Hong , Shoubhik Das , Wei-Dong Zhang","doi":"10.1016/j.gresc.2024.02.001","DOIUrl":"10.1016/j.gresc.2024.02.001","url":null,"abstract":"<div><div>Direct synthesis of olefins continues to attract stellar attention due to the high importance of olefins. In this context, due to the wide availability of ketones, the synthesis of olefins directly from ketones provides a straightforward route. Considering this, olefins synthesis from ketones <em>via</em> the formation of donor/donor type carbenes has been developed which leads to the efficient synthesis of versatile olefins by using a metal-free strategy. This approach features mild reaction conditions and exhibits a broad substrate scope when a biomass-derived solvent as a green reaction media is used. The practical utility of this approach has been demonstrated <em>via</em> late-stage modifications and even by scaling up to 20 g scale. At the end, mechanistic investigations and density functional theory studies clearly proved the formation of donor/donor carbenes, and examined the necessity of all the reagents and the effect of light in this system.</div></div>","PeriodicalId":12794,"journal":{"name":"Green Synthesis and Catalysis","volume":"6 3","pages":"Pages 275-281"},"PeriodicalIF":0.0,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139876892","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
2-(Furan-2-yl)-2-oxoacetic acid (2-FOA) is a critical building block for the C7 side chain of cefuroxime, a second-generation antibiotic. Traditional chemical synthesis of 2-FOA involves harsh conditions and toxic reagents, creating significant environmental challenges. Here, we developed an alternative biocatalytic approach to produce 2-FOA, beginning with the condensation of furfural and formaldehyde to form 2-furyl hydroxymethyl ketone (2-FHMK), followed by enzymatic oxidation to 2-FOA. To address the rate-limiting oxidation step, we engineered a galactose oxidase from Fusarium graminearum (FgGOase) through error-prone PCR and site-saturation mutagenesis. The optimal variant M 13 exhibited 46-fold and 102-fold enhancements in oxidation efficiency toward 2-FHMK and the intermediate aldehyde, respectively, compared to wild-type. Molecular dynamics simulations revealed that the introduced mutations improved substrate binding through increased hydrophobic interactions, along with enhanced hydration. The engineered variant M 13 was then integrated into a complete biocatalytic pathway, achieving 2-FOA production at a concentration of 14.6 g/L with 86.7% conversion. Our study addressed the inherent limitations of the FgGOase while demonstrating its potential as a model for developing efficient "through-oxidation" biocatalysts, offering a sustainable alternative biocatalytic approach to 2-FOA synthesis. It emphasised the potential of enzyme engineering in diversifying sustainable chemical processes. An artificial double-enzyme coupled biosystem was developed based on engineered galactose oxidase, achieving highly efficient biosynthesis of 2-FOA, a key precursor of cefuroxime.
{"title":"Engineering galactose oxidase for biocatalytic synthesis of 2-(furan-2-yl)-2-oxoacetic acid, a critical precursor of cefuroxime","authors":"Tong Zhang, Wei Hao, Yunju Zhang, Tengteng Qi, Kehao Yuan, Bin Wang, Ziyan Zhang, Liangqing Chen, Qinyuan Ma, Xiuzhen Gao","doi":"10.1016/j.gresc.2025.05.010","DOIUrl":"https://doi.org/10.1016/j.gresc.2025.05.010","url":null,"abstract":"2-(Furan-2-yl)-2-oxoacetic acid (2-FOA) is a critical building block for the C7 side chain of cefuroxime, a second-generation antibiotic. Traditional chemical synthesis of 2-FOA involves harsh conditions and toxic reagents, creating significant environmental challenges. Here, we developed an alternative biocatalytic approach to produce 2-FOA, beginning with the condensation of furfural and formaldehyde to form 2-furyl hydroxymethyl ketone (2-FHMK), followed by enzymatic oxidation to 2-FOA. To address the rate-limiting oxidation step, we engineered a galactose oxidase from Fusarium graminearum (FgGOase) through error-prone PCR and site-saturation mutagenesis. The optimal variant M 13 exhibited 46-fold and 102-fold enhancements in oxidation efficiency toward 2-FHMK and the intermediate aldehyde, respectively, compared to wild-type. Molecular dynamics simulations revealed that the introduced mutations improved substrate binding through increased hydrophobic interactions, along with enhanced hydration. The engineered variant M 13 was then integrated into a complete biocatalytic pathway, achieving 2-FOA production at a concentration of 14.6 g/L with 86.7% conversion. Our study addressed the inherent limitations of the FgGOase while demonstrating its potential as a model for developing efficient \"through-oxidation\" biocatalysts, offering a sustainable alternative biocatalytic approach to 2-FOA synthesis. It emphasised the potential of enzyme engineering in diversifying sustainable chemical processes. An artificial double-enzyme coupled biosystem was developed based on engineered galactose oxidase, achieving highly efficient biosynthesis of 2-FOA, a key precursor of cefuroxime.","PeriodicalId":12794,"journal":{"name":"Green Synthesis and Catalysis","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147333722","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-01Epub Date: 2024-04-29DOI: 10.1016/j.gresc.2024.04.003
Zhenguo Zhang , Mi Ren , Ming-Zhu Lu , Zhenhua Jia , Teck-Peng Loh
An unusual 1,3-addition products were obtained when amines were reacted with α,β-unsaturated aldehydes compounds in the presence of iodine and an oxidant. The versatile unsaturated α-amino acetals are highly useful amino acid derivatives and can be converted to a wide variety of synthetically useful building blocks. Various control experiments have shown that the reaction proceeded via a mechanism involving the formation of imine/enamine intermediates followed by a 1,2-amine group migration reaction.
{"title":"Carbonyl group-assisted 1,3-amine addition to α,β-unsaturated aldehydes","authors":"Zhenguo Zhang , Mi Ren , Ming-Zhu Lu , Zhenhua Jia , Teck-Peng Loh","doi":"10.1016/j.gresc.2024.04.003","DOIUrl":"10.1016/j.gresc.2024.04.003","url":null,"abstract":"<div><div>An unusual 1,3-addition products were obtained when amines were reacted with α,β-unsaturated aldehydes compounds in the presence of iodine and an oxidant. The versatile unsaturated α-amino acetals are highly useful amino acid derivatives and can be converted to a wide variety of synthetically useful building blocks. Various control experiments have shown that the reaction proceeded via a mechanism involving the formation of imine/enamine intermediates followed by a 1,2-amine group migration reaction.</div></div>","PeriodicalId":12794,"journal":{"name":"Green Synthesis and Catalysis","volume":"6 2","pages":"Pages 202-205"},"PeriodicalIF":0.0,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141936667","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-01Epub Date: 2024-09-23DOI: 10.1016/j.gresc.2024.09.005
Shadeera Rouf , Yaser E. Greish , Bart Van der Bruggen , Sulaiman Al-Zuhair
In the present work, a highly stable zirconium-based metal-organic framework (MOF), UiO66, and its derivative, UiO66-NH2, were tested as support materials to immobilize Formate dehydrogenase (FDH) for use in CO2 hydrogenation. Both physical adsorption and cross-linking approaches were tested for immobilization. Cross-linking with glutaraldehyde has been suggested to enhance the stability of the enzyme and reduce leaching, which is prone to physical attachment. The adsorption isotherm and kinetics were best described by Sips and pseudo-second-order models, respectively. The influences of the secondary structure of the protein on catalytic performance and formate production were studied. Immobilization of FDH resulted in a change in the secondary structure, with the α-helical content increased from 29.4 % of the free enzyme to 43 % after immobilization on UiO66 and 100 % after immobilization on UiO66-NH2. This structural change significantly enhanced the enzyme activity. At optimum conditions of pH 5.5 and 30 mM NaHCO3, the activity of immobilized FDH was 19.6 times higher than that of free FDH. Formate production was also enhanced using immobilized FDH on UiO66-NH2, where production was 2.4 times higher than that achieved using free FDH. Better stability and reusability were achieved by cross-linking with glutaraldehyde. The results of this work provide a novel insight into the changes in the secondary structure of FDH after immobilization and its positive effect on catalytic efficiency. These findings are expected to pave the way for the commercial applications of FDH for CO2 utilization.
{"title":"Enhancement of CO2 hydrogenation to formate using formate dehydrogenase immobilized on UiO66 and its derivatives","authors":"Shadeera Rouf , Yaser E. Greish , Bart Van der Bruggen , Sulaiman Al-Zuhair","doi":"10.1016/j.gresc.2024.09.005","DOIUrl":"10.1016/j.gresc.2024.09.005","url":null,"abstract":"<div><div>In the present work, a highly stable zirconium-based metal-organic framework (MOF), UiO66, and its derivative, UiO66-NH<sub>2</sub>, were tested as support materials to immobilize Formate dehydrogenase (FDH) for use in CO<sub>2</sub> hydrogenation. Both physical adsorption and cross-linking approaches were tested for immobilization. Cross-linking with glutaraldehyde has been suggested to enhance the stability of the enzyme and reduce leaching, which is prone to physical attachment. The adsorption isotherm and kinetics were best described by Sips and pseudo-second-order models, respectively. The influences of the secondary structure of the protein on catalytic performance and formate production were studied. Immobilization of FDH resulted in a change in the secondary structure, with the α-helical content increased from 29.4 % of the free enzyme to 43 % after immobilization on UiO66 and 100 % after immobilization on UiO66-NH<sub>2</sub>. This structural change significantly enhanced the enzyme activity. At optimum conditions of pH 5.5 and 30 mM NaHCO<sub>3</sub>, the activity of immobilized FDH was 19.6 times higher than that of free FDH. Formate production was also enhanced using immobilized FDH on UiO66-NH<sub>2</sub>, where production was 2.4 times higher than that achieved using free FDH. Better stability and reusability were achieved by cross-linking with glutaraldehyde. The results of this work provide a novel insight into the changes in the secondary structure of FDH after immobilization and its positive effect on catalytic efficiency. These findings are expected to pave the way for the commercial applications of FDH for CO<sub>2</sub> utilization.</div></div>","PeriodicalId":12794,"journal":{"name":"Green Synthesis and Catalysis","volume":"6 2","pages":"Pages 140-156"},"PeriodicalIF":0.0,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144535920","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-01Epub Date: 2024-02-05DOI: 10.1016/j.gresc.2024.01.006
Muhammad Zubair Mohsin , Ali Mohsin , Waqas Qamar Zaman , Xiaojuan Zhu , Xihua Zhao , Zain Abbas , Muhammad Hammad Hussain , Ali Shan , Salim-ur-Rehman , Muhammad Asif Nawaz , Rabia Omer , Yingping Zhuang , Meijin Guo , Jiaofang Huang
This study investigated a new approach for synthesizing Bacillus subtilis biofilm-supported Mn–Ce/zeolite catalysts for the degradation of gaseous toluene. Four different metal oxide nano-catalysts (ZMn, ZMnCe-10 %, ZMnCe-20 %, and ZMnCe-30 %) were synthesized with varying ratios of manganese (Mn) and cerium (Ce) on zeolite nanoparticles. TEM, SEM, XRD, BET, XPS, and EDX mapping were used to examine these four samples, as well as simple zeolite. Based on these analyses, the catalytic activity of the prepared samples ZMn, ZMnCe-10 %, ZMnCe-20 %, and ZMnCe-30 % for the complete oxidation of toluene and toluene intermediate products were tested with Non-thermal plasma (NTP) technology in a dielectric barrier discharge (DBD) reactor. Among all, ZMnCe-20 % showed the highest toluene degradation efficiency (89 %) at low concentrations (200 ppm) and humidity (>50 %). Later, highly efficient and hydrophobic nano-biocatalysts were prepared by combining B. subtilis biofilm wild-type (WT) and engineered B. subtilis biofilm EPS with ZMnCe-20 % catalyst. EPS is the main component found in biofilm matrix and plays a key role in influencing properties such as biofilm stability, electron transfer, surface roughness and hydrophobicity. Compared to WT B. subtilis biofilm, EPS overexpressed B. subtilis biofilm showed stronger growth and development on ZMnCe-20 % nanocatalyst. Moreover, the NTP system packed with ZMnCe-20 %/biofilm (EPS+) nano-biocatalyst exhibited the highest toluene degradation activity (99 %) with (83 %) CO2 selectivity, (up to 50 %) reduction in NOx concentration and complete ozone decomposition at (250 ppm) toluene concentrations and increased humidity (>90 %). High-energy electrons generated in the NTP system break the C–H and C–C bond between the rings of the toluene molecule, forming several byproducts which are later reacted with active radical species such as O, OH, and O3 and further converted into final degradation products (CO2 and H2O). The results demonstrated successful biofilm development and growth on the ZMnCe-20 % catalyst with advanced features such as superhydrophobicity, H2O resistance, improved surface roughness, and electron generation. In short, the study's approach combines bioengineering and material science to develop sustainable nano-biocatalysts for removing VOCs in industrial and environmental settings.
{"title":"Efficient toluene degradation using Bacillus subtilis biofilm-supported Mn–Ce/zeolite catalysts","authors":"Muhammad Zubair Mohsin , Ali Mohsin , Waqas Qamar Zaman , Xiaojuan Zhu , Xihua Zhao , Zain Abbas , Muhammad Hammad Hussain , Ali Shan , Salim-ur-Rehman , Muhammad Asif Nawaz , Rabia Omer , Yingping Zhuang , Meijin Guo , Jiaofang Huang","doi":"10.1016/j.gresc.2024.01.006","DOIUrl":"10.1016/j.gresc.2024.01.006","url":null,"abstract":"<div><div>This study investigated a new approach for synthesizing <em>Bacillus subtilis</em> biofilm-supported Mn–Ce/zeolite catalysts for the degradation of gaseous toluene. Four different metal oxide nano-catalysts (ZMn, ZMnCe-10 %, ZMnCe-20 %, and ZMnCe-30 %) were synthesized with varying ratios of manganese (Mn) and cerium (Ce) on zeolite nanoparticles. TEM, SEM, XRD, BET, XPS, and EDX mapping were used to examine these four samples, as well as simple zeolite. Based on these analyses, the catalytic activity of the prepared samples ZMn, ZMnCe-10 %, ZMnCe-20 %, and ZMnCe-30 % for the complete oxidation of toluene and toluene intermediate products were tested with Non-thermal plasma (NTP) technology in a dielectric barrier discharge (DBD) reactor. Among all, ZMnCe-20 % showed the highest toluene degradation efficiency (89 %) at low concentrations (200 ppm) and humidity (>50 %). Later, highly efficient and hydrophobic nano-biocatalysts were prepared by combining <em>B. subtilis</em> biofilm wild-type (WT) and engineered <em>B. subtilis</em> biofilm EPS with ZMnCe-20 % catalyst. EPS is the main component found in biofilm matrix and plays a key role in influencing properties such as biofilm stability, electron transfer, surface roughness and hydrophobicity. Compared to WT <em>B. subtilis</em> biofilm, EPS overexpressed <em>B. subtilis</em> biofilm showed stronger growth and development on ZMnCe-20 % nanocatalyst. Moreover, the NTP system packed with ZMnCe-20 %/biofilm (EPS+) nano-biocatalyst exhibited the highest toluene degradation activity (99 %) with (83 %) CO<sub>2</sub> selectivity, (up to 50 %) reduction in NOx concentration and complete ozone decomposition at (250 ppm) toluene concentrations and increased humidity (>90 %). High-energy electrons generated in the NTP system break the C–H and C–C bond between the rings of the toluene molecule, forming several byproducts which are later reacted with active radical species such as O<img>, OH<img>, and O<sub>3</sub> and further converted into final degradation products (CO<sub>2</sub> and H<sub>2</sub>O). The results demonstrated successful biofilm development and growth on the ZMnCe-20 % catalyst with advanced features such as superhydrophobicity, H<sub>2</sub>O resistance, improved surface roughness, and electron generation. In short, the study's approach combines bioengineering and material science to develop sustainable nano-biocatalysts for removing VOCs in industrial and environmental settings.</div></div>","PeriodicalId":12794,"journal":{"name":"Green Synthesis and Catalysis","volume":"6 2","pages":"Pages 128-139"},"PeriodicalIF":0.0,"publicationDate":"2025-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139772287","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-05-01Epub Date: 2023-11-30DOI: 10.1016/j.gresc.2023.11.007
Tao Ye , Na Lin , Jia-Huan Shen , Lichun Kong , Yang-Zi Liu , Quannan Wang , Wei-Ping Deng
A simple and highly efficient catalytic system for the selective aerobic oxidative ring-opening of substituted furans has been achieved using Fe(NO3)3·9H2O as a catalyst and air as an oxidant under mild conditions. A series of (Z)-1,4-enediones were obtained in good yields (up to 97 %) with excellent stereoselectivity (up to > 20:1 Z/E ratio). The present synthetic method exhibits perfect atom economy, wide substrate scope, and highly functionalized products allowing diverse transformations.
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