Green chemistry

绿色化学
  • 文章类型: Journal Article
    将CO2电还原为多碳(C2+)产物(例如C2+醇)提供了一种有希望的CO2利用方式。使用强碱性电解质有利于生产C2+产物。然而,CO2可以与氢氧化物反应形成碳酸盐/碳酸氢盐,导致碳利用效率低、稳定性差。使用酸性电解液是解决问题的有效途径,但实现C2+产物的高选择性是一个挑战。在这里,我们报告了胺改性的铜纳米颗粒在酸性条件下表现出C2产物的高选择性和碳利用率。在酸性介质(pH=2)下,在正丁胺改性的Cu上,C2产物的法拉第效率(FE)达到81.8%,总电流密度为410mAcm-2。特别是C2+醇的FE为52.6%,高于在酸性条件下CO2电还原的报道。此外,C2+生产的单程碳效率高达60%。详细的研究表明,胺分子在表面的铜不仅可以促进形成,*CO的吸附和覆盖率,而且还提供了疏水环境,这导致在酸性条件下C2+醇的高选择性。
    Electroreduction of CO2 into multi-carbon (C2+) products (e.g. C2+ alcohols) offers a promising way for CO2 utilization. Use of strong alkaline electrolytes is favorable to producing C2+ products. However, CO2 can react with hydroxide to form carbonate/bicarbonate, which results in low carbon utilization efficiency and poor stability. Using acidic electrolyte is an efficient way to solve the problems, but it is a challenge to achieve high selectivity of C2+ products. Here we report that the amine modified copper nanoparticles exhibit high selectivity of C2+ products and carbon utilization at acidic condition. The Faradaic efficiency (FE) of C2+ products reach up to 81.8% at acidic media (pH=2) with a total current density of 410 mA cm-2 over n-butylamine modified Cu. Especially the FE of C2+ alcohols is 52.6%, which is higher than those reported for CO2 electroreduction at acidic condition. In addition, the single-pass carbon efficiency towards C2+ production reach up to 60%. Detailed studies demonstrate that the amine molecule on the surface of Cu cannot only enhance the formation, adsorption and coverage of *CO, but also provide a hydrophobic environment, which result in the high selectivity of C2+ alcohols at acidic condition.
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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
    已开发出一种高效,快速的用10%NaClO水溶液氧化卤化色胺的方案。这种反应的特点是操作简单,无金属条件,没有净化,和高产量。值得注意的是,得到的关键中间体适合用各种亲核试剂进一步官能化,包括胺,N-芳族杂环,吲哚和酚。整体转化表现出广泛的官能团耐受性,适用于复杂生物相关分子的后期官能化。
    An efficient and rapid protocol for the oxidative halogenation of tryptamines with 10 % aqueous NaClO has been developed. This reaction is featured by its operational simplicity, metal-free conditions, no purification, and high yield. Notably, the resulting key intermediates are suitable for further functionalization with various nucleophiles, including amines, N-aromatic heterocycles, indoles and phenols. The overall transformation exhibits broad functional-group tolerance and is applicable to the late-stage functionalization of complex biorelevant molecules.
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  • 文章类型: Journal Article
    在仪器分析之前,富含淀粉和富含蛋白质的谷物样品通常需要繁琐的样品制备步骤。本研究开发了一种小型化离心集成冷致相分离(CIPS)方法,以方便样品制备。一个小型离心管(2毫升)和一个低温离心机,两者都很容易接近,组成系统的基本组成部分。与需要逐步提取的常规样品制备方法不同,富集,净化,和离心,这种离心集成CIPS方法可以在低温离心机下通过一步组合方案进行.作为一项概念验证研究,从谷物中提取伏马菌素和曲霉毒素具有令人满意的回收率和富集因子。通过使用tSIM采集模式结合LC-HRMS产生了一种灵敏和选择性的定量方法,具有良好的线性(R2>0.998),准确度(82.9-106.5%),和精度(<13.4%)。这个策略很方便,低成本,可重复,易于半自动化,进一步扩大其他酸性真菌毒素的提取潜力。
    Starches-rich and protein-rich cereal samples commonly need tedious sample preparation steps before instrumental analysis. This study developed a miniaturized centrifugal integrated cold-induced phase separation (CIPS) method for convenient sample preparation. A small-sized centrifuge tube (2 mL) and a low-temperature centrifuge, both of which are easily accessible, make up the basic components of the system. Unlike conventional sample preparation methods that need a step-by-step extraction, enrichment, purification, and centrifugation, this centrifugal integrated CIPS method can be performed by a one-step combination protocol under a low-temperature centrifuge. As a proof-of-concept study, satisfactory recoveries and enrichment factors were demonstrated for the extraction of fumonisins and ochratoxins from cereals. A sensitive and selective quantification method was yielded by combining LC-HRMS using tSIM acquisition mode, with good linearity (R2 > 0.998), accuracy (82.9-106.5%), and precision (<13.4%). This strategy is convenient, low-cost, repeatable, and easy to semi-automate, further expanding the extraction potential for other acidic mycotoxins.
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  • 文章类型: Journal Article
    废水中的环烷酸(NAs)具有高毒性和难降解性,因此有必要对其进行处理。在有机污染物的非均相类Fenton高级氧化体系中,氧化剂和NAs的可及性不足极大地阻碍了反应效率。源自聚乙二醇(PEG)基深共晶溶剂的CO2响应相转移材料专门针对不混溶二元相系统。对NAs氧化降解过程进行了优化,包括催化剂的种类(PEG的分子量、DES的构成,和剂量。),温度,CO2的流速等。借助催化剂的荧光性质,亲水-疏水相互作用被目视监测和进一步研究。PEG-200/过硫酸钠/聚醚胺230(PEA230)的两亲性大大降低了过硫酸钠和NAs之间的水相/有机相转移屏障(高达84%),从而增加氧化速率。表面张力从35.364mN/m下降到28.595mN/m。为了控制反应速率,酰胺基的CO2响应结构起了重要作用。此外,还通过核磁共振探索了界面转移中间体和氧化途径,傅里叶变换红外光谱,表面张力,和自由基抑制实验。提出了CO2响应相转移催化剂催化NAs高级氧化的机理,弥补了有机污染物非均相化学氧化系统理论的不足。
    Treatment of naphthenic acids (NAs) in wastewater is necessary due to its high toxicity and difficult degradation. In the heterogeneous Fenton-like advanced oxidation of organic pollutant system, the insufficient accessibility of oxidizing agent and NAs greatly hamper the reaction efficiency. CO2-responsive phase transfer materials derived from polyethylene glycol (PEG)-based deep eutectic solvents were specific targeted at the immiscible-binary phase system. The NAs oxidative degradation process was optimized including the kinds of catalyst (Molecular weight of PEG, constitute of DESs, and dosage.), temperature, flow rate of CO2, et al. With the help of fluorescence properties of catalyst, the hydrophilic-hydrophobic interaction was visual-monitored and further studied. The amphipathic property of PEG-200/Sodium persulfate/Polyether amine 230 (PEA230) greatly reduced the aqueous/organic phase transfer barrier between sodium persulfate and NAs (up to 84 %), thus accreting oxidation rate. The surface tension decreased from 35.364 mN/m to 28.595 mN/m. To control the reaction rate, the CO2 respond structure of amido played an important role. In addition, the interfacial transfer intermediates and oxidation pathways were also explored by nuclear magnetic resonance, flourier transform infrared spectroscopy, surface tension, and radical inhibition experiments. The mechanism of advanced oxidation of NAs catalyzed by CO2-responsive phase transfer catalyst was proposed, which would made up for the deficiency of the system theory of heterogeneous chemical oxidation of organic pollutants.
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  • 文章类型: Journal Article
    研制了一种具有高吸附能力和可恢复性的磁性复合材料(Fe3O4@SiO2@PNIPAM-co-NHMA),用于富集和测定黄芩(SR)中的黄酮。开发了一种使用Fe3O4@SiO2@PNIPAM-co-NHMA吸收剂结合高效液相色谱(HPLC)的磁固相萃取(MSPE)技术,用于选择性富集和测定SR水提物中的生物活性黄酮,包括黄芩素,黄芩苷,Wogonoside和Wogonin.在优化的实验条件下,磁性吸附剂可以从SR中吸附高达77.0±0.98%-98.15±0.15%的四种代表性黄酮,洗脱率从55.10±0.25%到91.94±1.85%不等。检测限(LOD)和定量限(LOQ)分别为0.01-0.35μg/mL和0.03-0.98μg/mL,分别。此外,它在六次重复后仍然有效,证明了其作为富集中药中黄酮类化合物的可回收吸附剂的潜力。
    A magnetic composite (Fe3O4@SiO2@PNIPAM-co-NHMA) with high adsorption capacity and recoverability was developed for the enrichment and determination of flavonoids in Scutellaria Radix (SR). A magnetic solid-phase extraction (MSPE) technique using Fe3O4@SiO2@PNIPAM-co-NHMA absorbent in combination with high-performance liquid chromatography (HPLC) was developed for selectively enrichment and determination of the biologically active flavonoids in the aqueous extract of SR, including baicalein, baicalin, wogonoside and wogonin. Under the optimized experimental conditions, the magnetic adsorbent could adsorb up to 77.0 ± 0.98 % - 98.15 ± 0.15 % of four representative flavonoids from SR, with elution rates varying from 55.10 ± 0.25 % to 91.94 ± 1.85 %. The limits of detection (LOD) and limits of quantitation (LOQ) were 0.01-0.35 μg/mL and 0.03-0.98 μg/mL, respectively. In addition, it remained effective after six replicates, demonstrating its potential as a recoverable adsorbent for enriching flavonoids in traditional Chinese medicine.
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  • 文章类型: Journal Article
    氮杂环化合物普遍存在于生物活性天然产物和药物中。然而,用于氮杂环合成的生物催化工具是有限的。在这里,我们报告发现香草醇氧化酶(VAOs)作为有效的生物催化剂,用于从各种4-羟基苯甲醛和氨基硫醇一锅法合成2-芳基噻唑啉。野生型生物催化剂具有广泛的4-羟基苯甲醛。虽然氨基硫醇的范围是有限的,它可以通过半理性蛋白质工程来改善,使用野生型VAO产生变体以产生先前不可接近的半胱氨酸衍生的生物活性2-芳基噻唑啉。受益于酶产物中的可衍生官能团,我们进一步对这些产品进行化学修饰,以扩大化学空间,为结构多样的2-芳基-噻唑啉衍生物的绿色和有效合成提供了一种新的化学酶策略,以促进其在药物发现和催化中的应用。
    Nitrogen heterocycles are commonly found in bioactive natural products and drugs. However, the biocatalytic tools for nitrogen heterocycle synthesis are limited. Herein, we report the discovery of vanillyl alcohol oxidases (VAOs) as efficient biocatalysts for the one-pot synthesis of 2-aryl thiazolines from various 4-hydroxybenzaldehydes and aminothiols. The wild-type biocatalyst features a broad scope of 4-hydroxybenzaldehydes. Though the scope of aminothiols is limited, it could be improved via semi-rational protein engineering, generating a variant to produce previously inaccessible cysteine-derived bioactive 2-aryl thiazolines using the wild-type VAO. Benefiting from the derivatizable functional groups in the enzymatic products, we further chemically modified these products to expand the chemical space, offering a new chemoenzymatic strategy for the green and efficient synthesis of structurally diverse 2-aryl-thiazoline derivatives to prompt their use in drug discovery and catalysis.
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  • 文章类型: Journal Article
    在这里,我们开发了一种通过铜催化吡啶反应合成中嗪的新方法,苯乙酮,和硝基烯烃在温和条件下以高产率。该反应涉及C-N和C-C键的形成以及具有高立体选择性和优异的官能团耐受性的新中氮化合物。
    Herein, we have developed a new approach for the synthesis of indolizine via Cu-catalyzed reaction of pyridine, acetophenone, and nitroolefin under mild conditions in high yields. This reaction involved the formation of C-N and C-C bonds and new indolizine compounds with high stereoselectivity and excellent functional group tolerance.
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  • 文章类型: Journal Article
    β-环糊精(β-CD),作为毛细管电泳(CE)中重要的伪固定相(PSP),经常面临因其有限的水溶性而产生的挑战,特别是当需要高浓度来解析复杂的分析物时。传统上,研究人员经常使用(有毒)有机溶剂来提高β-CD的溶解度,建立非水性毛细管电泳(NACE)的特定分离。然而,这种做法危害健康,违背绿色分析化学的原则。在这项研究中,我们演示了一种低共熔溶剂(DES),脯氨酸:尿素(PU),作为用于基于β-CD的CE分离的常规有机溶剂的有希望的替代品。DES对β-CD的溶解度高达30%,与在水相中1.8%的溶解度相比有显著改善。利用这种DES型分离介质,我们实现了由八种结构相似的萘甲酸衍生物组成的复杂分析物的同时基线分离。此外,我们对β-CD在水性CE缓冲液中的性能进行了系统比较,有机溶剂,和DES,突出了这种新型环保CE分离介质的优越性。
    β-cyclodextrin (β-CD), as an important pseudo-stationary phase (PSP) in capillary electrophoresis (CE), frequently confronts challenges stemming from its limited water solubility, particularly when high concentrations are required for resolving complex analytes. Traditionally, researchers often resort to the use of (toxic) organic solvents to enhance the solubility of β-CD, establishing non-aqueous capillary electrophoresis (NACE) for specific separations. However, such practices are hazardous to health and run counter to the principles of green analytical chemistry. In this study, we demonstrate a deep eutectic solvent (DES), Proline:Urea (PU), as a promising alternative to conventional organic solvents for β-CD-based CE separations. The DES exhibits a solubility of up to 30% for β-CD, a significant improvement compared to the 1.8% solubility in the aqueous phase. Utilizing this DES-type separation medium, we achieved simultaneous baseline separation of a complex analyte composed of eight structurally similar naphthoic acid derivatives. Furthermore, we conducted a systematic comparison of β-CD\'s performance in aqueous CE buffers, organic solvents, and DESs, highlighting the superiority of this novel and environmentally friendly CE separation medium.
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  • 文章类型: Journal Article
    藻类生物光伏(BPV)技术的成功商业化取决于多方面的方法,包括诸如开发具有成本效益和高导电性的阳极材料等因素。为了解决这个问题,我们开发了一种生产还原氧化石墨烯(rGO)的环境友好方法,使用浓缩小球藻sp。UMACC313悬浮液作为还原剂。随后将所产生的rGO涂布在碳纸(rGO-CP)上并用作BPV装置的阳极。因此,小球藻的最大功率密度增加了950%。UMACC258(0.210mWm-2)和神经球菌的781%。UMACC371(0.555mWm-2)与裸CP相比。通过有效去除氧官能团带来的改善的微藻对阳极的粘附和改善的rGO电导率可能是造成这种情况的原因。这项研究证明了减少微藻的GO如何提高藻类BPV产生生物电的效率。
    The successful commercialization of algal biophotovoltaics (BPV) technology hinges upon a multifaceted approach, encompassing factors such as the development of a cost-efficient and highly conductive anode material. To address this issue, we developed an environmentally benign method of producing reduced graphene oxide (rGO), using concentrated Chlorella sp. UMACC 313 suspensions as the reducing agent. The produced rGO was subsequently coated on the carbon paper (rGO-CP) and used as the BPV device\'s anode. As a result, maximum power density was increased by 950% for Chlorella sp. UMACC 258 (0.210 mW m-2) and 781% for Synechococcus sp. UMACC 371 (0.555 mW m-2) compared to bare CP. The improved microalgae adhesion to the anode and improved electrical conductivity of rGO brought on by the effective removal of oxygen functional groups may be the causes of this. This study has demonstrated how microalgal-reduced GO may improve the efficiency of algal BPV for producing bioelectricity.
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