Green Chemistry最新文献

{"title":"A comparative molecular dynamics approach guides the tailoring of glycosyltransferases to meet synthetic applications†","authors":"","doi":"10.1039/d4gc01508h","DOIUrl":"10.1039/d4gc01508h","url":null,"abstract":"<div><p>The properties of natural products can be significantly influenced by glycosylation, emphasizing the key role of glycosyltransferases (GTs) in this process. The pursuit of tailored GT catalysts to meet the demands of the glycosylation industry aligns with the principles of green chemistry. However, steering GT engineering towards the desired direction often requires substantial effort. Herein, we employ a comparative molecular dynamics approach to guide the engineering of GTs to alter their catalytic performances. Through comparing the structural flexibility and site-saturation mutagenesis of two GTs BarGT-1 with narrow substrate scope and BarGT-3 with wide substrate scope, the identified substitution K321P in C-loop 5 of BarGT-1 greatly expanded the substrate scope towards diverse pharmaceutically valuable substrates, thereby the catalytic efficiencies were remarkably improved (<em>e.g.</em>, 52- and 244-fold for 4′- and 6-hydroxyflavone, <em>k</em>_cat/<em>K</em>_M). Further, phylogenetic analysis demonstrated that lysine was a highly conserved residue in the GTs within BarGT-1 branch, and its key roles in regulating the substrate scope were validated through site-saturation mutagenesis in two novel GTs, BsyGT (K321F) and BgoGT (K322W). Moreover, the corresponding substitutions G325R/D in C-loop 5 of BarGT-3 also served as switches to regulate the substrate profile of BarGT-3. Finally, through the utilization of BarGT-1 and K321P, we successfully regulated the synthesis of valuable liquiritigenin glycosides with minor effort. The comparative molecular dynamics approach provides insights into the structural dynamics of GTs, optimizes enzymatic processes, and facilitates precise enzyme engineering, offering a directed synthetic paradigm to produce valuable glycosides.</p></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/gc/d4gc01508h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141739582","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Comparative environmental impact assessment of activated carbon electrodes for supercapacitors†","authors":"","doi":"10.1039/d4gc02700k","DOIUrl":"10.1039/d4gc02700k","url":null,"abstract":"<div><p>Activated carbon (AC) is considered as a potential material for electrodes in supercapacitors; however, its production process entails significant emissions to the environment. This study aims to assess the environmental impacts of manufacturing AC and electrodes for supercapacitors from waste materials, utilizing the life cycle assessment (LCA) principles. The process of producing AC involves raw material preparation, hydrothermal carbonization, and chemical activation processes, utilizing potassium hydroxide (KOH) as a chemical agent. The environmental impact of AC production and fabrication of AC electrodes was analyzed using the SimaPro software. A cradle-to-gate study was conducted to analyze the production of 1 kg of AC and one electrode from waste materials, including oil palm leaves, Sesbania, and filter cake, chosen based on the local availability in the study area. Life cycle data were compiled from the laboratory, ecoinvent database, and calculations based on the mass and energy balance. Using the ReCiPe midpoint (H) characterization method, potential environmental impacts were computed across eighteen categories. Sesbania AC exhibited the highest impact across fourteen out of eighteen categories for producing 1 kg of AC, with the largest impact observed in the marine ecotoxicity category due to the presence of KOH in the chemical activation process. For producing 1 farad (F) electrode, Sesbania showed the lowest environmental impact due to its high specific capacitance. Its environmental impacts of producing a 1 F electrode were unexpectedly lower than those of oil palm leaves because the predominant environmental impacts were from hydrothermal carbonization and pretreatment rather than KOH activation. Additionally, Sesbania exhibited significantly higher yields in hydrothermal carbonization, resulting in the use of relatively fewer materials and less energy, thereby leading to reduced impacts compared to other materials. The developed AC electrode showed excellent performance in several environmental impact categories, with AC production being the main contributor.</p></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141739581","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Towards the sustainable production of biomass-derived materials with smart functionality: a tutorial review","authors":"","doi":"10.1039/d4gc01771d","DOIUrl":"10.1039/d4gc01771d","url":null,"abstract":"<div><p>To meet the ever-increasing demand for the continuous development of human society and carbon neutralization, biomass has been demonstrated to be a pluripotent and powerful alternative. Regardless of the low cost, natural abundance, renewability, and biodegradability of biomass, the role of its unique (bio)chemical features in contributing to the on-demand regulatable structure and widely applicable versatility of the products has sparked growing interest. Besides, sustainable production from biomass to smart materials is believed to be one of the key strategies to achieve the global goals of carbon peaking and carbon neutrality. This review will focus on the green engineering of diverse biomass feedstocks for different applications, and the proposed outline is as follows: First, renewable biomass feedstocks of different hierarchies are introduced. Second, green preparations of biomass-derived materials are systematically categorized from the viewpoint of the structural orientation of the biomass, and the correlation between the biomass's structural features and the sustainability assessments of the preparation process is also discussed. Third, the applications in electrochemical energy storage, biomedical engineering, electronics, and sensing which feature their smart functionality were comprehensively summarized. Fourth, the advantages and the limitations of biomass-derived materials are qualitatively evaluated. Finally, future prospects and directions on the sustainable production of materials with smart functionality from biomass will be presented. We endeavor to offer comparative and balanced views, as well as insights into which biomass is particularly advantageous for specific intelligent applications.</p></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141745934","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Molecular origins of enhanced bioproduct properties by pretreatment of agricultural residues with deep eutectic solvents†","authors":"","doi":"10.1039/d4gc01877j","DOIUrl":"10.1039/d4gc01877j","url":null,"abstract":"<div><p>Pretreatment facilitates cost-effective operations on lignocellulosic biomass ranging from densification to deconstruction and bioproduct development. However, determining molecular-level mechanisms behind pretreatment and their effects has remained elusive. Here, we combine computational simulation and experiment to investigate the effects on wheat straw agricultural residue densification of an emerging pretreatment solvent, namely, a deep eutectic solvent (DES) consisting of choline chloride (ChCl) and oxalic acid (OA). <em>Ab initio</em> molecular dynamics indicates that dissociation of lignin from cellulose in lignin–carbohydrate complexes, which does not occur to a significant extent in aqueous solution, is favorable in the DES and occurs <em>via</em> cleavage of the guaiacyl : xylose ether bond linkage by OA. The ensuing hemicellulose removal exposes lignin to the DES which, molecular dynamics simulation indicates, leads to lignin expansion. The resulting changes in wheat straw fiber structure, lignin distribution, and functional group modifications upon DES treatment by scanning electron and fluorescence microscopy along with Fourier-transform infrared spectroscopy. The molecular expansion of lignin enhances inter-particle binding in wheat straw, leading to denser structures under pelletization. The resulting high mechanical stability and combustion properties make the wheat straw a suitable precursor of high-quality densified solids (<em>e.g.</em>, solid biofuel). Overall, we shed light on the molecular-level mechanisms involved in DES pretreatment for biomass densification, demonstrated here in the development of a solid biofuel. The approach here illuminates the rational design from first chemical principles of methods to convert lignocellulosic resources into advanced materials.</p></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/gc/d4gc01877j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141739583","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Selective C(sp3)–H bond aerobic oxidation enabled by a π-conjugated small molecule-oxygen charge transfer state†","authors":"","doi":"10.1039/d4gc02010c","DOIUrl":"10.1039/d4gc02010c","url":null,"abstract":"<div><p>Due to the high oxidation potential of arenes and alkenes, previous methods of benzylic and allylic C–H oxidation necessitated the use of strong oxidizing agents, metal catalysts, or free radical initiators (such as photocatalysts or hydrogen atom transfer reagents) to be effective. Herein, we employ oxygen to generate a triple-spin charge transfer state with π-conjugated compounds effectively accessing the triplet excited states of arenes, followed by energy transfer to form singlet oxygen facilitating C–H bond oxidation. Distinct from previous oxidations, it is the first time that a series of natural products and drug molecules (27 examples) are selectively oxidized without any catalysts or additives. The transformation can be implemented under sunlight to produce valuable unsaturated (aromatic) ketones and only water as waste, which meets every one of the 12 principles of green chemistry.</p></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141754101","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Guanidine hydrochloride (GuHCl)-catalysed microwave-mediated solvent- and metal-free synthesis of pyrimido[1,2-a]benzimidazole from aryl aldehyde and aryl methyl ketone†","authors":"","doi":"10.1039/d4gc01363h","DOIUrl":"10.1039/d4gc01363h","url":null,"abstract":"<div><p>A novel microwave-mediated synthesis method was developed for the rapid and eco-friendly production of pyrimido[1,2-<em>a</em>]benzimidazole in high yields utilizing simple and cost-effective starting materials. This reaction was facilitated by the green organocatalyst guanidine hydrochloride. This protocol offers a metal-free and organocatalysed technique to afford a library of highly fluorescent pyrimido[1,2-<em>a</em>]benzimidazole derivatives. Key features of this synthetic method include its broad compatibility with functional groups, operational simplicity, and scalability, making it a promising technique for various applications.</p></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141754104","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Metal-free decarboxylative C(sp3)–C(sp3) bond formation for the synthesis of unnatural amino acids and peptides via convergent paired electrolysis enabled radical–radical cross-coupling†","authors":"","doi":"10.1039/d4gc02848a","DOIUrl":"10.1039/d4gc02848a","url":null,"abstract":"<div><p>Herein, we present the first metal-free decarboxylative C(sp³)–C(sp³) cross-coupling of glycine derivatives with redox-active esters through highly atom and energy economical convergent paired electrolysis enabled radical–radical cross-coupling. Under mild and scalable conditions, various α-alkylated unnatural α-amino acids were prepared efficiently from readily available starting materials. The key point for the successful implementation of this strategy is minimizing the interelectrode distance to permit the rapid diffusion of radical species and outpace radical decomposition. Mechanistic investigations showed a radical–radical coupling pathway generated from anode and cathode simultaneously in the same electrolysis system. This novel protocol was successfully applied for the late-stage modification of pharmaceuticals, amino acids and peptides.</p></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141863996","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Path2Green: introducing 12 green extraction principles and a novel metric for assessing sustainability in biomass valorization","authors":"Leonardo M. de Souza Mesquita, Leticia S. Contieri, Francisca A. e Silva, Rafael Henrique Bagini, Felipe S. Bragagnolo, Monique M. Strieder, Filipe H. B. Sosa, Nicolas Schaeffer, Mara G. Freire, Sónia P. M. Ventura, João A. P. Coutinho, Maurício A. Rostagno","doi":"10.1039/d4gc02512a","DOIUrl":"https://doi.org/10.1039/d4gc02512a","url":null,"abstract":"We propose an innovative approach to address the pressing need for efficient and transparent evaluation techniques to assess extraction processes’ sustainability. In response to society's growing demand for natural products and the consequent surge in biomass exploration, a critical imperative arises to ensure that these processes are genuinely environmentally friendly. Extracting natural compounds has traditionally been regarded as a benign activity rooted in ancient practices. However, contemporary extraction methods can also significantly harm the environment if not carefully managed. Recognizing this, we developed a novel metric, <em>Path2Green</em>, tailored specifically and rooted in 12 new principles of a green extraction process. <em>Path2Green</em> seeks to provide a comprehensive framework beyond conventional metrics, offering a nuanced understanding of the environmental impact of extraction activities from biomass collection/production until the end of the process. By integrating factors such as resource depletion, energy consumption, waste generation, and biodiversity preservation, <em>Path2Green</em> aims to offer a holistic assessment of sustainability of an extraction approach. The significance of <em>Path2Green</em> lies in its ability to distill complex environmental data into a simple, accessible metric. This facilitates informed decision-making for stakeholders across industries, enabling them to prioritize greener extraction practices. Moreover, by setting clear benchmarks and standards, <em>Path2Green</em> incentivizes innovation and drives continuous improvement in sustainability efforts, being a new user-friendly methodology.","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.8,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141946924","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Extraction of collagen from bovine tannery solid waste preserving original conformation via radical initiation and hydrogen bond reformation†","authors":"","doi":"10.1039/d4gc02634a","DOIUrl":"10.1039/d4gc02634a","url":null,"abstract":"<div><p>Tannery solid waste (TSW) contains 70–90% collagen by weight. The rapid extraction of collagen while preserving its original and unique triple-helical conformation has proved challenging. In this paper, an ionic liquid-synergistic dissolution and regeneration (IL-SDR) method was developed based on a TBAH/DMSO/H₂O ternary (TDH) solvent for the rapid recovery of collagen from TSW under mild conditions. A solubility of 10.25% TSW and a collagen recovery yield of 51.2% were achieved in 30 minutes at room temperature. The original triplet helical conformation and the molecular weight of the collagen product were retained, confirmed <em>via</em> FT-IR, circular dichroism, and matrix-assisted laser desorption/ionization time-of-flight analysis. SEM was used to verify that dense and uniform pores could be formed within collagen by adjusting the DMSO content, and cytotoxicity and moisture retention tests demonstrated that the collagen produced <em>via</em> the IL-SDR process is comparable to natural collagen used in cosmetic and skincare applications. Moreover, the TDH solvent demonstrated excellent reproducibility across five cycles, achieving consistent solubility varying from 9.71% to 11.04%. EPR and ¹H NMR showed that the OH^– in TBAH induced the generation of DMSO˙ free radicals in the TDH solvent, and these radicals were indispensable for the dissolution of TSW. The DMSO content was positively correlated with the concentration of free radicals. A synergistic dissolution mechanism was proposed: DMSO˙ free radicals preferentially cleaved the terminal peptide chains, causing the collagen molecules to be exposed to DMSO. Subsequently, DMSO disrupted the original hydrogen bond network within the collagen molecules. Then, TBAH and DMSO formed hydrogen bonds with the collagen molecules, stabilizing the dissolved collagen and preventing the reformation of the hydrogen bond network between collagen molecules. This work provides an avenue for low-temperature and rapid dissolution of TSW, and reveals an in-depth, atypical dissolution mechanism for collagen-based materials during the IL-SDR process.</p></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141739615","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Green palladium and platinum recovery by microwave-assisted aluminum chloride solution†","authors":"","doi":"10.1039/d4gc02503b","DOIUrl":"10.1039/d4gc02503b","url":null,"abstract":"<div><p>Palladium and platinum are precious metals (PMs) used in industrial catalysis, and their green recycling is crucial but challenging. In this study, we aimed to create a novel leaching procedure for the environmentally friendly recovery of PMs using AlCl₃·6H₂O solution. We report here the use of a microwave-assisted AlCl₃·6H₂O solution to selectively recover Pd and Pt from spent catalysts. In a large-scale setting, our system can recover gram-scale Pd in a single batch. Electron paramagnetic resonance (EPR) and capture experiments revealed the hydroxyl radicals produced by proton dissociation and microwave coordination triggered the oxidative dissolution process. Microwave-assisted AlCl₃·6H₂O solution leaching and NaBH₄ reduction recovered high-purity Pd and Pt separately. In scale-up experiments, the dissolution performance of the microwave-assisted AlCl₃·6H₂O solution for Pd remained almost unchanged after seven cycles. Our approach uses around 1/50 and 1/20 of the energy and chemical inputs of the conventional hydrometallurgy process, respectively. Strong acids, poisonous cyanide, and volatile organic solvents were not used during the recovery process, enabling an efficient and sustainable PM recovery process and promoting an advanced oxidation process (AOPs) technology for secondary resource recycling.</p></div>","PeriodicalId":78,"journal":{"name":"Green Chemistry","volume":null,"pages":null},"PeriodicalIF":9.3,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141754102","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}