Green chemistry

绿色化学
  • 文章类型: Journal Article
    在这项研究中,制备了基于镁碱沸石的磁性固体酸纳米催化剂,并将其用作室温在水中绿色合成某些[1,3]-恶嗪衍生物的催化剂。合成的化合物在短的反应时间后以高至优异的产率获得,合成产物的结构通过光谱方法如:FT-IR,1HNMR和13CNMR。利用XRD对制备的磁性固体酸催化剂进行了表征,FT-IR,FE-SEM,EDX,元素映射,TGA和VSM分析方法。磁性催化剂具有易于分离的能力,这导致更好和更容易的回收。[1,3]-恶嗪衍生物的制备和合成在室温下在M-FER/TEPA/SO3H存在下进行。简单的工作,绿色溶剂(水),反应时间短,产品产率高,是所提出方法的一些优点。对合成化合物结构的对接计算证明了它们对乳腺癌细胞的药用特性。
    In this research, the magnetic solid acid nanocatalyst based on ferrierite has been prepared and used as catalyst for the green synthesis of some [1,3]-oxazine derivatives in water at room temperature. The synthesized compounds were obtained in high to excellent yields after short reaction times and the structure of synthesized products were investigated by spectroscopic methods such as: FT-IR, 1H NMR and 13C NMR. The prepared magnetic solid acid catalyst was characterized using XRD, FT-IR, FE-SEM, EDX, elemental mapping, TGA and VSM analysis methods. Magnetic catalyst has easy separation ability, which leads to better and easier recycling. The preparation and synthesis of [1,3]-oxazine derivatives were carried out at room temperature in the presence of M-FER/TEPA/SO3H. Easy workup, green solvent (water) and also short reaction times with high to excellent yield of products, are some of advantageous of presented method. Docking calculations on the structure of the synthesized compounds proved their medicinal properties against breast cancer cells.
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  • 文章类型: Journal Article
    这篇综述致力于液相色谱的可持续实践。HPLC和UHPLC方法对常规分析技术有重要贡献。因此,将经典的液相色谱方法转移到可持续的方法中对于实现可持续发展目标至关重要。在使液相色谱方法绿色化的其他原理中,用绿色溶剂代替流动相中的有机溶剂组分受到了极大的关注。这篇综述集中于选择最佳的替代绿色有机溶剂来代替流动相中的经典溶剂,快速转移到更可持续的正相或反相液相色谱。本综述的主要重点将是描述非绿色到绿色和白色色谱方法的转移,以提高分析化学中的可持续性最佳实践。绿色属性和绿色排名,除了17种有机溶剂对液相色谱的色谱适用性外,提到对快速选择合适的溶剂以将经典的HPLC或UHPLC方法转化为更可持续的方法的问题有清晰的见解。提出了一种简单的指南,以使液相色谱方法更具可持续性。
    This review is dedicated to sustainable practices in liquid chromatography. HPLC and UHPLC methods contribute significantly to routine analytical techniques. Therefore, the transfer of classical liquid chromatographic methods into sustainable ones is of utmost importance in moving toward sustainable development goals. Among other principles to render a liquid chromatographic method green, the substitution of the organic solvent component in the mobile phase with a greener one received great attention. This review concentrates on choosing the best alternative green organic solvent to replace the classical solvent in the mobile phase for easy, rapid transfer to a more sustainable normal phase or reversed-phase liquid chromatography. The main focus of this review will be on describing the transfer of non-green to green and white chromatographic methods in an effort to elevate sustainability best practices in analytical chemistry. The greenness properties and greenness ranking, in addition to the chromatographic suitability of seventeen organic solvents for liquid chromatography, are mentioned to have a clear insight into the issue of rapidly choosing the appropriate solvent to transfer a classical HPLC or UHPLC method into a more sustainable one. A simple guide is proposed for making the liquid chromatographic method more sustainable.
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  • 文章类型: Journal Article
    杏仁树是世界上栽培最多的坚果树。生产杏仁会产生大量的副产品,其中大部分未使用。在这里,这项研究旨在开发一种绿色化学方法来鉴定和提取潜在有价值的化合物从杏仁副产品。最初,用10种不同的天然深共晶溶剂(NADES)进行筛选。乳酸/甘油的混合物,摩尔比为1:1(1:50植物材料与NADES(w/v),水含量为20%v/v)被确定为儿茶素的最佳提取溶剂,咖啡酰奎宁酸,和浓缩的杏仁壳中的单宁。随后,通过使用小型化提取技术的实验设计(DoE)协议对方法进行了优化,微波辅助萃取(MAE),与所选的NADES一起使用。发现最佳条件为70°C,辐照时间为15分钟。通过实验确认了由DoE确定的最佳提取条件,并与文献中已经建立的方法进行了比较。在这些条件下,代谢物的提取量高2.4倍,根据总峰面积的增加,而不是使用的既定文献方法。此外,通过应用多参数分析绿色度量(AGREE)和绿色分析过程指数(GAPI)度量,可以得出结论,所开发的方法比已建立的文献方法更绿色,因为它包括绿色分析化学的各种原理。
    Almond trees are the most cultivated nut tree in the world. The production of almonds generates large amounts of by-products, much of which goes unused. Herein, this study aimed to develop a green chemistry approach to identify and extract potentially valuable compounds from almond by-products. Initially, a screening was performed with 10 different Natural Deep Eutectic Solvents (NADESs). The mixture lactic acid/glycerol, with a molar ratio 1:1 (1:50 plant material to NADES (w/v) with 20% v/v of water) was identified as the best extraction solvent for catechin, caffeoylquinic acid, and condensed tannins in almond hulls. Subsequently, a method was optimized by a Design of Experiment (DoE) protocol using a miniaturized extraction technique, Microwave-Assisted Extraction (MAE), in conjunction with the chosen NADESs. The optimal conditions were found to be 70 °C with 15 min irradiation time. The optimal extraction conditions determined by the DoE were confirmed experimentally and compared to methods already established in the literature. With these conditions, the extraction of metabolites was 2.4 times higher, according to the increase in total peak area, than the established literature methods used. Additionally, by applying the multiparameter Analytical Greenness Metric (AGREE) and Green Analytical Process Index (GAPI) metrics, it was possible to conclude that the developed method was greener than the established literature methods as it includes various principles of green analytical chemistry.
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  • 文章类型: Journal Article
    产生的污水污泥(SS)的不断增加的体积给处置带来了挑战,鉴于其对环境和人类健康的潜在危害。本研究探索了SS管理的可持续解决方案,重点是能源回收。采用CO2辅助热解,我们将SS转化为可燃气体(H2和CO;合成气)。在CO2条件下SS的单级热解表明,在温度≥520℃时,CO2通过与挥发性物质(VM)的气相反应(GPR)提高了可燃气体的产量(尤其是CO)。具体来说,CO2部分氧化了从SS释放的VM,并同时还原为CO。为了提高温度≤520℃时的合成气产量,使用了具有额外热能和Ni/Al2O3催化剂的多级热解装置。这些配置显著增加了易燃气体的产量,特别是CO,温度≤520℃。的确,SS的催化热解中的可燃气体产率从N2条件下的200.3mmol增加到CO2条件下的219.2mmol,表示与CO2条件下的单级热解(50.0mmol)相比增加4.4倍。通过整合水煤气变换反应,二氧化碳辅助催化热解产生的可燃气体预计有可能产生40.4亿美元的收入。这些发现强调了在SS热解中使用CO2作为处理SS并使其成为有价值的能源的可持续且有效的方法的有效性。
    The escalating volume of sewage sludge (SS) generated poses challenges in disposal, given its potential harm to the environment and human health. This study explored sustainable solutions for SS management with a focus on energy recovery. Employing CO2-assisted pyrolysis, we converted SS into flammable gases (H2 and CO; syngas). Single-stage pyrolysis of SS in a CO2 conditions demonstrated that CO2 enhances flammable gas production (especially CO) through gas phase reactions (GPRs) with volatile matter (VM) at temperatures ≥ 520 ˚C. Specifically, the CO2 partially oxidized the VM released from SS and concurrently underwent reduction into CO. To enhance the syngas production at temperatures ≤ 520 ˚C, multi-stage pyrolysis setup with additional heat energy and a Ni/Al2O3 catalyst were utilized. These configurations significantly increased flammable gas production, particularly CO, at temperatures ≤ 520 ˚C. Indeed, the flammable gas yield in the catalytic pyrolysis of SS increased from 200.3 mmol under N2 conditions to 219.2 mmol under CO2 conditions, representing a 4.4-fold increase compared to single-stage pyrolysis under CO2 conditions (50.0 mmol). By integrating a water-gas-shift reaction, the flammable gases produced from CO2-assisted catalytic pyrolysis were expected to have the potential to generate revenue of US$4.04 billion. These findings highlight the effectiveness of employing CO2 in SS pyrolysis as a sustainable and effective approach for treating and valorising SS into valuable energy resources.
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  • 文章类型: Journal Article
    通过利用羟基自由基作为化学引发剂,超声波辐射具有选择性氧化水相中非挥发性有机底物的潜力。这里,通过从光解和辐射化学中收集见解来构建羟基自由基引发的乙二醛氧化的机理描述,以解释氧化产物的产率和动力学趋势。本文报道的机理描述和动力学测量表明,与来自C-C裂解的那些产物相比,通过改变超声频率增加羟基自由基的形成速率增加乙二醛消耗速率和对C2酸产物的选择性两者。在酸性条件下,乙二醛的消耗也发生得更快,对C2酸的选择性更高。这有利于羧酸酯中间体质子化为其反应性较低的酸性形式。利用这样的pH和频率效应对于通过与羟基自由基和氧化产物(特别是过氧化氢和超氧化物)的副反应来减轻产物降解是至关重要的。这些发现证明了超声作为醛官能团选择性氧化为羧酸的驱动器的潜力,为生物质衍生的平台分子提供了一条可持续的途径。
    Ultrasonic irradiation holds potential for the selective oxidation of non-volatile organic substrates in the aqueous phase by harnessing hydroxyl radicals as chemical initiators. Here, a mechanistic description of hydroxyl radical-initiated glyoxal oxidation is constructed by gleaning insights from photolysis and radiation chemistry to explain the yields and kinetic trends for oxidation products. The mechanistic description and kinetic measurements reported herein reveal that increasing the formation rate of hydroxyl radicals by changing the ultrasound frequency increases both the rates of glyoxal consumption and the selectivity towards C2 acid products over those from C-C cleavage. Glyoxal consumption also occurs more rapidly and with greater selectivity towards C2 acids under acidic conditions, which favor the protonation of carboxylate intermediates into their less reactive acidic forms. Leveraging such pH and frequency effects is crucial to mitigating product degradation by secondary reactions with hydroxyl radicals and oxidation products (specifically hydrogen peroxide and superoxide). These findings demonstrate the potential of ultrasound as a driver for the selective oxidation of aldehyde functions to carboxylic acids, offering a sustainable route for valorizing biomass-derived platform molecules.
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  • 文章类型: Journal Article
    锂-硫电池是锂离子电池的有希望的替代品,因为它们可以潜在地提供显著增加的容量和能量密度。不断增长的全球电池市场表明,对具有成本效益的电池电极材料的需求将持续存在。来自废物的材料可以同时解决当今的两个最大挑战,即,废物管理和开发可持续材料的要求。在这项研究中,我们详细介绍了蓝鲨的明胶和虾的甲壳质的碳化,这两种产品目前都被认为是海鲜行业的废弃副产品。所得碳的化学和物理性质通过结构表征技术的结果的相关性进行比较,包括电子成像,X射线衍射,拉曼光谱和氮气吸附。我们研究了所得碳作为用于锂硫电池的硫承载电极材料的应用。通过全面的电化学表征,我们证明了增值的多孔碳,源自海洋废物是锂硫电池的有前途的电极材料。当以C/5的速率恒电流循环500次循环时,两个样品均表现出令人印象深刻的容量保持。这项研究强调了将废物作为电池材料生产的可持续饲料的重要性。
    Lithium-sulfur batteries are a promising alternative to lithium-ion batteries as they can potentially offer significantly increased capacities and energy densities. The ever-increasing global battery market demonstrates that there will be an ongoing demand for cost effective battery electrode materials. Materials derived from waste products can simultaneously address two of the greatest challenges of today, i.e., waste management and the requirement to develop sustainable materials. In this study, we detail the carbonisation of gelatin from blue shark and chitin from prawns, both of which are currently considered as waste biproducts of the seafood industry. The chemical and physical properties of the resulting carbons are compared through a correlation of results from structural characterisation techniques, including electron imaging, X-ray diffraction, Raman spectroscopy and nitrogen gas adsorption. We investigated the application of the resulting carbons as sulfur-hosting electrode materials for use in lithium-sulfur batteries. Through comprehensive electrochemical characterisation, we demonstrate that value added porous carbons, derived from marine waste are promising electrode materials for lithium-sulfur batteries. Both samples demonstrated impressive capacity retention when galvanostatically cycled at a rate of C/5 for 500 cycles. This study highlights the importance of looking towards waste products as sustainable feeds for battery material production.
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  • 文章类型: Journal Article
    高对映异构体过量(ee)的手性化学品的不对称合成对制药工业至关重要,但是经典的化学通常需要多步反应,恶劣的条件,和昂贵的手性配体,并且有时遭受不令人满意的对映选择性。酶催化是一种更绿色、对映体选择性更强的替代方案,和级联生物转化与多步骤反应可以在一个锅中进行,以避免昂贵的中间分离和减少废物产生。酶促级联转化的最有吸引力的应用之一是以高产率和ee将容易获得的简单外消旋底物转化为有价值的功能化手性化学品。这里,我们回顾了建立这种级联生物转化的三种一般策略,包括对映会聚反应,动态动力学分辨率,以及手性的破坏和重新安装。使用外消旋底物如外消旋环氧化物的级联转化的例子,酒精,羟基酸,等。生产手性氨基醇,羟基酸,胺和氨基酸。产品浓度,ee,和产量,可扩展性,对这些酶促级联的底物范围进行了严格的审查。为了进一步提高级联的效率和实际适用性,使用最新的基于微流体的超高通量筛选和人工智能指导的定向进化来增强关键酶的催化活性的酶工程可能是有用的方法。
    Asymmetric synthesis of chiral chemicals in high enantiomeric excess (ee) is pivotal to the pharmaceutical industry, but classic chemistry usually requires multi-step reactions, harsh conditions, and expensive chiral ligands, and sometimes suffers from unsatisfactory enantioselectivity. Enzymatic catalysis is a much greener and more enantioselective alternative, and cascade biotransformations with multi-step reactions can be performed in one pot to avoid costly intermediate isolation and minimise waste generation. One of the most attractive applications of enzymatic cascade transformations is to convert easily available simple racemic substrates into valuable functionalised chiral chemicals in high yields and ee. Here, we review the three general strategies to build up such cascade biotransformations, including enantioconvergent reaction, dynamic kinetic resolution, and destruction-and-reinstallation of chirality. Examples of cascade transformations using racemic substrates such as racemic epoxides, alcohols, hydroxy acids, etc. to produce the chiral amino alcohols, hydroxy acids, amines and amino acids are given. The product concentration, ee, and yield, scalability, and substrate scope of these enzymatic cascades are critically reviewed. To further improve the efficiency and practical applicability of the cascades, enzyme engineering to enhance catalytic activities of the key enzymes using the latest microfluidics-based ultrahigh-throughput screening and artificial intelligence-guided directed evolution could be useful approaches.
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  • 文章类型: Journal Article
    介绍了一种设计用于兽药残留分析中样品制备的快速在线微体积流通透析探针。这项研究解决了对减少化学废物和试剂使用的高效绿色样品制备方法的需求。透析探头与液相色谱和质谱(LC-MS)系统集成,促进自动化,高通量分析。透析方法利用每个样品的最小试剂体积,与传统的样品制备技术相比,显著减少了溶剂废物的产生。将几种兽药掺入组织匀浆中并进行分析以验证探针的功效。对于该性能评估,获得>97%的诊断灵敏度和>95%的特异性。结果表明有效去除细胞碎片和颗粒,确保样品的完整性和防止仪器堵塞。自动透析探针对多种分析物的回收率在27%至77%之间,确认其简化兽药残留分析的潜力,同时坚持绿色化学原则。该方法突出了环境影响和运营效率的实质性改进,在监管和研究应用中提出了传统样品制备方法的可行替代方案。
    A rapid and online microvolume flow-through dialysis probe designed for sample preparation in the analysis of veterinary drug residues is introduced. This study addresses the need for efficient and green sample preparation methods that reduce chemical waste and reagent use. The dialysis probe integrates with liquid chromatography and mass spectrometry (LC-MS) systems, facilitating automated, high-throughput analysis. The dialysis method utilizes minimal reagent volumes per sample, significantly reducing the generation of solvent waste compared to traditional sample preparation techniques. Several veterinary drugs were spiked into tissue homogenates and analyzed to validate the probe\'s efficacy. A diagnostic sensitivity of >97% and specificity of >95% were obtained for this performance evaluation. The results demonstrated the effective removal of cellular debris and particulates, ensuring sample integrity and preventing instrument clogging. The automated dialysis probe yielded recovery rates between 27 and 77% for multiple analytes, confirming its potential to streamline veterinary drug residue analysis, while adhering to green chemistry principles. The approach highlights substantial improvements in both environmental impact and operational efficiency, presenting a viable alternative to conventional sample preparation methods in regulatory and research applications.
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  • 文章类型: Journal Article
    阿替洛尔,目前世界上最畅销的五大治疗心绞痛和高血压的药物之一,为了降低心脏病发作后的死亡风险,在当前的合成方法中面临挑战,以解决低效率和环境问题。这种药物的传统合成涉及产生大量废物和其他需要处理的副产品的过程。这项研究提出了一种基于一罐DES的可持续方案,用于合成阿替洛尔。使用DES可以在不需要额外的碱或催化剂的情况下进行整个过程。在短的反应时间内,在温和的条件下,避免色谱纯化。阿替洛尔的总收率为95%。成功证明了该工艺到克级生产的可扩展性,强调其在工业应用中的潜力。最后,“绿色”评价,使用FirstPassCHEM21MetricsToolkit执行,强调了原子经济方面的优势,反应质量效率,与现有方法相比,基于DES的合成的整体过程质量强度。
    Atenolol, one of the top five best-selling drugs in the world today used to treat angina and hypertension, and to reduce the risk of death after a heart attack, faces challenges in current synthetic methods to address inefficiencies and environmental concerns. The traditional synthesis of this drug involves a process that generates a large amount of waste and other by-products that need disposal. This study presents a one-pot DES-based sustainable protocol for synthesizing atenolol. The use of the DES allowed the entire process to be conducted with no need for additional bases or catalysts, in short reaction times, under mild conditions, and avoiding chromatographic purification. The overall yield of atenolol was 95%. The scalability of the process to gram-scale production was successfully demonstrated, emphasizing its potential in industrial applications. Finally, the \'greenness\' evaluation, performed using the First Pass CHEM21 Metrics Toolkit, highlighted the superiority in terms of the atom economy, the reaction mass efficiency, and the overall process mass intensity of the DES-based synthesis compared with the already existing methods.
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  • 文章类型: Journal Article
    在这项研究中,我们分析了使用无机铁化合物生产纳米颗粒的潜在用途。我们使用以下铁前体FeCl3×6H2O,FeCl2×4H2O,Fe(NO3)3×9H2O,Fe2(SO4)3×H2O,FeSO4×7H2O,无水FeCl3。发现干草莓中多酚和类黄酮的含量及其在DPPH和FRAP中的抗氧化活性分别为346.81µMTE/1g和331.71µMTE/1g,分别,与绿茶提取物相似。使用TEM技术制作的显微图像允许分离一些尺寸从几十纳米到几微米的纳米颗粒。所有样品中的电动电势的值是负的并且范围从-21,300mV至-11,183mV。XRF分析证实在浓度为0.01mol/dm3的样品中存在0.13%至0.92%的铁。FT-IR光谱分析显示了纳米颗粒的特征带。在量热测量中,在暴露于电磁场的任何测试中都没有观察到温度升高。总之,使用草莓干叶子和花萼的提取物作为试剂,我们可以获得尺寸取决于前体浓度的铁纳米颗粒。
    In this study, we analysed the potential use of dried strawberry leaves and calyces for the production of nanoparticles using inorganic iron compounds. We used the following iron precursors FeCl3 × 6H2O, FeCl2 × 4H2O, Fe(NO3)3 × 9H2O, Fe2(SO4)3 × H2O, FeSO4 × 7H2O, FeCl3 anhydrous. It was discovered that the content of polyphenols and flavonoids in dried strawberries and their antioxidant activity in DPPH and FRAP were 346.81 µM TE/1 g and 331.71 µM TE/1 g, respectively, and were similar to these of green tea extracts. Microimages made using TEM techniques allowed for the isolation of a few nanoparticles with dimensions ranging from tens of nanometres to several micrometres. The value of the electrokinetic potential in all samples was negative and ranged from -21,300 mV to -11,183 mV. XRF analyses confirmed the presence of iron ranging from 0.13% to 0.92% in the samples with a concentration of 0.01 mol/dm3. FT-IR spectra analyses showed bands characteristic of nanoparticles. In calorimetric measurements, no increase in temperature was observed in any of the tests during exposure to the electromagnetic field. In summary, using the extract from dried strawberry leaves and calyxes as a reagent, we can obtain iron nanoparticles with sizes dependent on the concentration of the precursor.
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