Green chemistry

绿色化学
  • 文章类型: Journal Article
    来自绿色资源的材料拥有低碳足迹,形成材料科学循环经济方法的基础。因此,在这项研究中,用丙二醇(PG)对废聚对苯二甲酸乙二醇酯(PET)进行解聚,和随后与生物基马来酸酐(MA)缩聚产生的不饱和聚酯树脂(b-UPR)。生物衍生的丙烯酰改性的牛皮纸木质素(KfL-A)在b-UPR基质中用作乙烯基反应性填料,以创建b-UPR/KfL-A复合材料。KfL-A和b-UPR的结构表征涉及FTIR和NMR技术的使用。通过拉伸强度评估了新制备的复合材料的机械性能,维氏显微硬度,和动态力学测试。向刚性b-UPR基质中添加KfL-A增强了材料的柔韧性,导致较少的刚性和坚硬的材料,同时保持复合韧性。例如,掺入10wt.b-UPR中%的KfL-A导致硬度降低17%,拉伸强度降低48%,和20%的韧性降低。通过掺入64wt。%的可再生和回收原材料。类似制备的b-UPR/KfL复合材料显示出结构不均匀性和更好的机械性能。透射(TEM)和扫描(SEM)电子显微镜揭示了复合材料的机械和结构性能与KfL-A添加程度之间的适当关系。UL94V可燃性等级证实了阻燃性随KfL-A的添加成比例地增加。一旦沉积在垃圾填埋场,这些复合材料预计比PET更容易分解,减少对环境的危害,促进塑料循环的可持续性。
    Materials from green resources boast a low carbon footprint, forming the foundation of the circular economy approach in materials science. Thus, in this study, waste poly(ethylene terephthalate) (PET) was subjected to depolymerization using propylene glycol (PG), and subsequent polycondensation with bio-based maleic anhydride (MA) produced unsaturated polyester resin (b-UPR). Bio-derived acryloyl-modified Kraft lignin (KfL-A) served as a vinyl reactive filler in the b-UPR matrix to create b-UPR/KfL-A composites. The structural characterization of KfL-A and b-UPR involved the use of FTIR and NMR techniques. The mechanical properties of the newly fabricated composites were assessed through tensile strength, Vickers microhardness, and dynamic mechanical tests. The addition of KfL-A to the rigid b-UPR matrix enhanced material flexibility, resulting in less stiff and hard materials while preserving composite toughness. For instance, incorporating 10 wt% of KfL-A in b-UPR led to a 17% reduction in hardness, a 48% decrease in tensile strength, and a 20% reduction in toughness. Positive environmental impact was achieved by incorporation of 64 wt% of renewable and recycled raw material. Analogously prepared b-UPR/KfL composites showed structural inhomogeneity and somewhat better mechanical properties. Transmission (TEM) and scanning (SEM) electron microscopies revealed a suitable relationship between mechanical and structural properties of composites in relation to the extent of KfL-A addition. The UL94V flammability rating confirmed that flame resistance increased proportionally with the KfL-A addition. Once deposited in a landfill, these composites are expected to disintegrate more easily than PET, causing less harm to the environment and contributing to sustainability in the plastics cycle.
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  • 文章类型: Journal Article
    报道了一种用于荧光3-卤代-4H-色烯-4-酮衍生物的通用合成策略。该方法涉及通过有效且可持续的氧化体系进行烯胺酮的氧化α-卤化。Oxone®与KCl结合使用,KBr,或KI能够制备3-氯-,3-溴-,或3-碘-4H-chromen-4-one在良好到优异的产量,具有很大的功能组耐受性,该方案适用于克级合成。对所提出的4H-chromen-4-one的光物理性质的分析显示,在紫外线区域吸收,在紫色至青色区域荧光发射,斯托克斯位移相对较大。在解决方案中,所有化合物都呈现双重荧光发射,无论溶剂如何,分配给部分芳香化的分子内电荷转移机制,考虑到色酮支架中存在假芳香环,并且不存在取代基电子特征对光学行为的影响。
    A versatile synthesis strategy for fluorescent 3-halo-4H-chromen-4-one derivatives is reported. The method involves the oxidative α-halogenation of enaminones performed by an efficient and sustainable oxidation system. The use of Oxone® in combination with KCl, KBr, or KI enables the preparation of 3-chloro-, 3-bromo-, or 3-iodo-4H-chromen-4-one in good to excellent yields, with great functional group tolerance where the protocol is amenable to gram-scale synthesis. The analysis of the photophysical properties of the presented 4H-chromen-4-one showed absorption in the UV region and fluorescence emission in the violet-to-cyan region with a relatively large Stokes shift. In solution, all compounds present a dual fluorescence emission, regardless of the solvent, assigned to a partially aromatised intramolecular charge transfer mechanism, considering the presence of a pseudo-aromatic ring in the chromone scaffold and the absence of the influence of substituent electronic features in optical behaviour.
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  • 文章类型: Journal Article
    在过去的一个世纪里,大量的研究集中在开发缓蚀剂,特别关注绿色“植物基”缓蚀剂。在各种类型的抑制剂中,多酚由于其有利的特性而成为有前途的候选者,其中包括便宜,可生物降解,可再生,and,最重要的是,对环境和人类都是安全的。它们作为可持续腐蚀抑制剂的性能鼓励了许多电化学实验以及理论,机械学,和计算研究,许多论文报道抑制效率超过85%。在这次审查中,关于抑制各种类型的多酚的大多数文献贡献,他们的自然提取技术,以及它们作为“绿色”金属缓蚀剂的应用被彻底描述和讨论,重点是它们的制备,抑制机制,和性能。根据文献综述,可以得出结论,多酚具有非常有希望的潜力被用作绿色和强大的腐蚀抑制剂;因此,进一步调查,实验或计算,仍然需要实现更高的抑制效率,达到≈100%。
    Over the past century, a substantial amount of research focused on developing corrosion inhibitors, with a special focus on green \"plant-based\" corrosion inhibitors. Among the various types of inhibitors, polyphenols emerged as a promising candidate due to their advantageous characteristics, which include being inexpensive, biodegradable, renewable, and, most importantly, safe for both the environment and humans. Their performance as sustainable corrosion inhibitors have encouraged many electrochemical experiments as well as theoretical, mechanistic, and computational studies, with many papers reporting inhibition efficiencies of over 85%. In this review, the majority of literature contributions on the inhibition of various types of polyphenols, their natural extraction techniques, and their applications as \"greener\" corrosion inhibitors for metals are thoroughly described and discussed with a focus on their preparation, inhibition mechanism, and performance. Based on the reviewed literature, it can be concluded that polyphenols have a very promising potential to be used as both green and powerful corrosion inhibitors; therefore, further investigations, experimental or computational, are still required to realize higher inhibition efficiencies reaching up to ≈ 100%.
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  • 文章类型: Journal Article
    生物催化具有实现绿色化学的潜力。需要新的酶固定化方法来提高酶的稳定性,产品净化,以及不同酶在相同反应条件下的相容性。脱氧核糖核酸(DNA)在超分子支架中脱颖而出,简单的Watson-Crick碱基配对规则可用于合理设计级联中每个单独酶周围的独特纳米级环境。先前已经报道了DNA纳米结构上酶活性和稳定性的增强,但从来没有在工业相关的化学合成或反应条件的背景下。这里,作者表明DNA可以增强半乳糖氧化酶突变体的活性和稳定性,可用于从木质素生产生物塑料的级联。该酶在无细胞提取物中增强,据他们所知,以前没有发现DNA上的任何酶。这是重要的,因为粗生物催化反应成本有效得多。这为通过调节单个酶的特性进一步研究多酶级联打开了大门。
    Biocatalysis has the potential to enable green chemistry. New methods of enzyme immobilisation will be required to improve enzyme stability, product purification, and compatibility of different enzymes in the same reaction conditions. Deoxyribonucleic acid (DNA) stands out among supramolecular scaffolds, as simple Watson-Crick base-pairing rules can be used to rationally design a unique nanoscale environment around each individual enzyme in a cascade. Enhancements of enzyme activity and stability on DNA nanostructures have previously been reported, but never in the context of industrially relevant chemical syntheses or reaction conditions. Here, the authors show DNA can enhance the activity and stability of a galactose oxidase mutant, which could be used in a cascade to produce bioplastics from lignin. The enzyme was enhanced in the cell-free extract, which to their knowledge has not been shown before for any enzymes on DNA. This is significant because crude biocatalytic reactions are vastly more cost-effective. This opens the door to further work on multienzyme cascades by tuning the properties of individual enzymes.
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  • 文章类型: Journal Article
    Although the concepts underpinning green chemistry have evolved over the past 30 years, the practice of green chemistry must move beyond the environmental and human health-related roots of green chemistry towards a more systems-based, life cycle-informed, and interdisciplinary practice of chemistry. To make a transition from green to sustainable chemistry, one must learn to think at a systems level; otherwise green chemistry-inspired solutions are unlikely to be sustainable. This perspective provides a brief description of why the current situation needs to change and is followed by how life cycle thinking helps chemists avoid significant systems-level impacts. The transition from batch to continuous flow processing and novel approaches to isolation and purification provide a case for interdisciplinary collaboration. Finally, an example of end-of-useful-life considerations makes the case that systems and life cycle thinking from an interdisciplinary perspective needs to inform the design of new chemical entities and their associated processes.
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  • 文章类型: Journal Article
    Due to the negative effects of emerging contaminants on the environment, that can potentially induce deleterious effects in aquatic and human life, this paper focuses on the removal from the water of Furosemide, through the adsorption process. Indeed, only a few papers are available in the literature about the Furosemide adsorption and, chitosan films are thus proposed for this purpose as safe, sustainable, and recyclable adsorbent materials. In the present work, the effects on the adsorption process of several experimental parameters such as the pH values, ionic strength, amount of adsorbent/pollutant, and temperature values were investigated. The kinetics models, isotherms of adsorption, and the thermodynamic parameters were studied showing that the Furosemide physisorption occurred on the heterogeneous Chitosan surface, endothermically (ΔH° = +31.27 ± 3.40 kJ mol-1) and spontaneously (ΔS° = +150.00 ± 10.00 J mol-1 K-1), following a pseudo-second-order kinetic model. The 90% of the pollutant was adsorbed in 2 h, with a maximum adsorption capacity of 3.5 mg × g-1. Despite these relatively low adsorption capacities, experiments of desorption were performed and 100% of adsorbed Furosemide was recovered by using concentrated NaCl solutions, proposing a low-cost and green approach, with respect to the previous literature relative to the Furosemide adsorption, fundamental for the pollutant recovery and adsorbent reuse.
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  • 文章类型: Journal Article
    This paper describes a sustainability index (SI) as a quantitative measure of \"sustainability\" applicable to synthesis plans based on the provenance of input materials and energy sources and the fate of output waste products. The index is computed as the root-mean-square average of the following four parameters: mass fraction of valorized inputs (F VI ), mass fraction of valorized outputs (F VO ), mass fraction of valorized target product (F VP ), and input enthalpic energy fraction arising from renewable energy sources (F RE ). Valorized input materials originate from renewable, recycled, or reclaimed sources. Valorized output materials are destined for recycling or reclaiming so that they may be used in the same or other chemical processes. Valorized target product refers to that portion of the target product that is actually used for its intended purpose. Renewable energy sources are defined as originating from hydroelectric, wind, solar, geothermal, and biomass sources. The computation of SI is illustrated for 22 synthesis plans of the high commodity flavour ingredient vanillin from biofermentation, chemical synthesis, and solvent extraction processes. In addition, these plans are compared and ranked according to Borda count and poset (partially ordered set) pairwise dominance analyses using the following attributes: process mass intensity (PMI), sacrificial reagent (SR) consumption, input enthalpic energy (IEE) consumption, Rowan solvent greenness index (RSGI), and sustainability index (SI).
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  • 文章类型: Journal Article
    近年来,可持续化学概念和方法的进步及其应用已成为设计的核心部分,合成,和制造化学品。可持续化学不仅利用绿色化学的原理,但也扩大到纳入经济,社会,和环境方面。这进一步阐明了结合生命周期评估/思想,包括原材料生产,制造,processing,以及使用和处置阶段,允许对化学品对环境和人类健康的影响进行全面评估。本文件概述了为可持续合成被确定为现有关注化学品替代品的化学品制定初步框架的方法。该框架与有机磷酸酯的案例研究同时引入,这些有机磷酸酯被选作溴化阻燃剂(BFR)的潜在替代品。该框架旨在将现有的绿色化学知识应用于替代品的合成,随着其纳入生命周期评估,最终开发了与其前身相比更全面的可持续化学实体。
    In recent years, the advancement of sustainable chemistry concepts and approaches along with their demonstrated application has become a central part of the design, synthesis, and manufacture of a chemical. Sustainable chemistry not only utilizes the principles of green chemistry, but also expands to incorporate economic, societal, and environmental aspects. This is further elucidated by the incorporation of life cycle assessment/thinking to include the raw material production, manufacture, processing, and use and disposal stages, allowing for a comprehensive evaluation of the environmental and human health impacts attributed to a chemical. This contribution outlines an approach for the development of a preliminary framework for the sustainable synthesis of a chemical that is identified as an alternative for an existing chemical of concern. The framework is introduced concurrently with a case study for organophosphates that are selected as potential replacements for brominated flame retardants (BFRs). This framework is designed to apply existing knowledge of green chemistry to the synthesis of alternatives, along with its integration into Life Cycle Assessment culminating in the development of a more overall sustainable chemical entity when compared to its predecessor.
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  • 文章类型: Journal Article
    对于两种羧酸的酮基脱羧的反应机理,β-酮酸在许多实验和理论研究中被认为是关键的中间体。α-位的氢原子是底物通过遵循该机理反应的必不可少的必要条件。然而,使用叔羧酸的分离观察结果与它不一致,并且在本文中重新讨论和讨论这些。用新戊酸获得的实验结果表明,该底物不会发生酮脱羧。相反,它在其他反应中被消耗,如分解成异丁烯,一氧化碳,和水(逆-Koch反应)。此外,羧酸异构化或失去碳原子,将叔羧酸转化为带有α-质子原子的羧酸。因此,后者适于通过β-酮酸途径反应。第二基板,2,2,5,5-四甲基己二酸,通过遵循相同的反Koch途径进行反应。主要产物是单羧酸2,2,5-三甲基-4-己烯酸(及其双键异构体),可能进一步转化为环烯酮或内酯。酮脱羧产物,观察到痕量的2,2,5,5-四甲基环戊酮(<0.2%产率)。因此,可以得出结论,观察到的实验结果进一步支持了通过β-酮酸中间体进行酮基脱羧的拟议机理。
    For the reaction mechanism of the ketonic decarboxylation of two carboxylic acids, a β-keto acid is favored as key intermediate in many experimental and theoretical studies. Hydrogen atoms in the α-position are an indispensable requirement for the substrates to react by following this mechanism. However, isolated observations with tertiary carboxylic acids are not consistent with it and these are revisited and discussed herein. The experimental results obtained with pivalic acid indicate that the ketonic decarboxylation does not occur with this substrate. Instead, it is consumed in alternative reactions such as disintegration into isobutene, carbon monoxide, and water (retro-Koch reaction). In addition, the carboxylic acid is isomerized or loses carbon atoms, which converts the tertiary carboxylic acid into carboxylic acids bearing α-proton atoms. Hence, the latter are suitable to react through the β-keto acid pathway. A second substrate, 2,2,5,5-tetramethyladipic acid, reacted by following the same retro-Koch pathway. The primary product was the monocarboxylic acid 2,2,5-trimethyl-4-hexenoic acid (and its double bond isomer), which might be further transformed into a cyclic enone or a lactone. The ketonic decarboxylation product, 2,2,5,5-tetramethylcyclopentanone was observed in traces (<0.2 % yield). Therefore, it can be concluded that the observed experimental results further support the proposed mechanism for the ketonic decarboxylation via the β-keto acid intermediate.
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  • 文章类型: Journal Article
    In the context of recycling metal to embrace the sustainability challenge, this work proposes a geochemically-analogous process of metal recovery through mechanochemistry for the first time, to avoid the limitations of on-going methods and to establish an innovative technology philosophy. This work systematically investigates this geochemically-analogous process, to keep it green and to generalize it further. Copper recovery from waste printed circuit boards (WPCBs), a typical copper-rich waste, is chosen as a case study in this work. Nearly 98% of the copper in the WPCBs can be recycled in the optimized conditions and 82.3% of the sulfur can be reused, by means of the process. Based on the experimental result, this paper purports a closed-loop route of copper recovery which follows the green chemistry principles (high yield, high atom economy and no secondary pollution). This route can be generalized into other second-hand resources that are rich in copper. Some other metals (e.g. lead) that are commonly present as corresponding sulfides in nature can be taken into consideration in this geochemically-analogous process as well.
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