Green Chemistry

绿色化学
  • 文章类型: Journal Article
    为探索木质素羟基与硼酸在碱性条件下的反应,我们通过密度泛函理论研究了使用水杨醇阴离子作为模型化合物形成阴离子硼酸二酯(ABDE)的三种拟议机理。ABDE具有很高的阻燃性,是木质素的潜在实际应用。发现钠阳离子的催化作用可增强水簇的去质子化。去质子化的产品,氢氧根阴离子,对关键步骤至关重要,这是硼酸分子的B-O键的裂解,在反应机制中。机理的能量曲线表明,木质素和硼酸之间的反应可以从木质素的羟甲基部分开始,因为对于上述关键步骤,其需要的能量比从木质素的苯酚部分更少。此外,氢氧根阴离子通过形成四羟基硼酸盐阴离子(TBA)与木质素中的羟甲基竞争形成B-O键,这需要非常高的活化能才能进一步反应成所需的产物ABDE。最佳条件是增强钠阳离子的催化作用,同时控制TBA的形成。
    For exploring the reaction between the hydroxyl groups of lignin and boric acid under the alkaline condition, we study three proposed mechanisms for the formation of the anionic borate diester (ABDE) using the salicyl alcohol anion as the model compound by the density functional theory. ABDE has high flame retardancy and is a potentially practical application of lignin. The catalysis of sodium cation is found to enhance the deprotonation of the water cluster. The deprotonated product, hydroxide anion, is essential to the critical step, which is the cleavage of B-O bonds of the boric acid molecule, in reaction mechanisms. The energy profiles of the mechanisms show that the reaction between lignin and boric acid may start from the hydroxymethyl moieties of lignin since it requires less energy for the aforementioned critical step than from the phenol moieties of lignin. Moreover, the hydroxide anions compete with the hydroxymethyl groups in lignin for the formation of B-O bonds by forming tetrahydroxyborate anion (TBA) which requires very high activation energies to further react to the desired product ABDE. The optimal condition is to enhance the catalytic effect of sodium cations and meanwhile to control the formation of TBA.
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  • 文章类型: Journal Article
    本工作涉及开发一种重新恢复钢残留物的方法,以创建基于氧化铁的阳光活性光催化剂。在低能耗设置中,在pH和温度的不同组合(50-90°C和3≥pH≤5)下,商用级钢质剩菜会被氧化。进一步探索了具有最高生产效率(产率>12%)和磁化率(χm=387×10-6m3/kg)的材料,并通过M2(Zn和Co)离子在氧化物结构内的扩散进行了改性。水热法创建ZnFe2O4,CoFe2O4和组合的Co-Zn铁氧体。(Co-Zn)Fe2O4的带隙为2.02eV,可以在阳光照射下激活。电子显微镜研究表明,(Co-Zn)Fe2O4由直径在400至700nm之间的颗粒组成,均匀尺寸,均匀分布,和良好的分散性。所开发的材料在来自纤维素提取的黑液的日光催化中的应用导致化学需氧量的降低(平均-15%)和在180分钟的反应后的生物降解性的提高(>0.57BOD/COD)。由于所提出的工艺采用直射太阳光,它为大规模水处理和化学升级应用开辟了可能性。
    The present work deals with developing a method for revalorizing steel residues to create sunlight-active photocatalysts based on iron oxides. Commercial-grade steel leftovers are oxidized under different combinations of pH and temperature (50-90 °C and 3 ≥ pH ≤ 5) in a low energy-intensive setup. The material with the highest production efficiency (yield > 12%) and magnetic susceptibility (χm = 387 × 10-6 m3/kg) was further explored and modified by diffusion of M2+ (Zn and Co) ions within the structure of the oxide using a hydrothermal method to create ZnFe2O4, CoFe2O4 and combined Co-Zn ferrite. (Co-Zn)Fe2O4 displayed a bandgap of 2.02 eV and can be activated under sunlight irradiation. Electron microscopy studies show that (Co-Zn)Fe2O4 consists of particles with diameters between 400 and 700 nm, homogeneous size, even distribution, and good dispersibility. Application of the developed materials in the sunlight catalysis of black liquors from cellulose extraction resulted in a reduction of the Chemical Oxygen Demand (- 15% on average) and an enhancement in biodegradability (> 0.57 BOD/COD) after 180 min of reaction. Since the presented process employs direct solar light, it opens the possibility to large-scale water treatment and chemical upgrading applications.
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  • 文章类型: Journal Article
    探索工业生产的当代替代品的需要推动了创新技术的发展,这些技术解决了与传统批量机械化学相关的关键限制。一种特别有前途的策略涉及将流动过程与机械化学相结合。该领域中的三种值得注意的技术是连续流动加热机械化学(ICHeM)中的单螺杆挤出(SSE)和双螺杆挤出(TSE)和冲击(感应)。这些技术超越了聚合物的工业生产,延伸到活性药物成分的合成,(纳米)材料的制造,以及通过生物质和废料的增值来提取高附加值产品。按照绿色化学的原则,与传统的溶剂热工艺相比,球磨工艺通常被认为更环保。事实上,球磨过程需要更少的溶剂,通过增加表面积和用机械化学能代替热能来提高反应速率和反应转化率,在其他人中。将特别注意产品的类型,反应物磨球的尺寸和反应条件,在2020-2022年期间应用筛选方法后选择60篇文章。本文旨在整理和分析将机械化学用于绿色化学应用的研究前沿。
    The need to explore contemporary alternatives for industrial production has driven the development of innovative techniques that address critical limitations linked to traditional batch mechanochemistry. One particularly promising strategy involves the integration of flow processes with mechanochemistry. Three noteworthy technologies in this domain are single-screw extrusion (SSE) and twin-screw extrusion (TSE) and Impact (Induction) in Continuous-flow Heated Mechanochemistry (ICHeM). These technologies go beyond the industrial production of polymers, extending to the synthesis of active pharmaceutical ingredients, the fabrication of (nano)materials, and the extraction of high-added value products through the valorisation of biomass and waste materials. In accordance with the principles of green chemistry, ball milling processes are generally considered greener compared to conventional solvothermal processes. In fact, ball milling processes require less solvent, enhance reaction rates and reaction conversion by increasing surface area and substituting thermal energy with mechanochemical energy, among others. Special attention will be given to the types of products, reactants, size of the milling balls and reaction conditions, selecting 60 articles after applying a screening methodology during the period 2020-2022. This paper aims to compile and analyze the cutting edge of research in utilizing mechanochemistry for green chemistry applications.
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  • 文章类型: Journal Article
    3D打印技术使科学家能够轻松制造电化学传感器。直到现在,这些传感器的设计采用了大量的材料,这增加了成本并降低了制造产量。在这项工作中,一种低成本的3D打印的滴上电化学传感器(3D-PES)是通过熔丝制造完全制造的,减少打印层的数量。采用炭黑/聚乳酸长丝,和设计和几个印刷参数进行了优化,以产生最大的电分析性能使用最少量的材料。打印速度和挤出宽度对3D-PES的电分析性能具有关键影响。在优化条件下,制造过程提供了极好的再现性(工作电极直径的RSD为1.3%),速度(<3分钟/单位),和成本(材料成本<0.01美元)。3D-PES已成功应用于苹果汁中根皮苷的测定。将3D-PES的分析性能与等效的商用滴下丝网印刷电极进行了比较,产生类似的精度和准确度,但灵敏度较低。然而,3D-PES提供了有趣的功能,如可回收性,生物降解性,低成本,以及在需要点附近制造的可能性,其中一些满足绿色化学的几个要求。这种具有成本效益的打印方法是制造一次性和便携式电分析设备的绿色和有前途的替代方案,不仅在现场食品分析中,而且在即时测试中也开辟了新的可能性。
    3D-printing technology allows scientist to fabricate easily electrochemical sensors. Until now, these sensors were designed employing a large amount of material, which increases the cost and decreases manufacturing throughput. In this work, a low-cost 3D-printed on-drop electrochemical sensor (3D-PES) was fully manufactured by fused filament fabrication, minimizing the number of printing layers. Carbon black/polylactic acid filament was employed, and the design and several printing parameters were optimized to yield the maximum electroanalytical performance using the minimal amount of material. Print speed and extrusion width showed a critical influence on the electroanalytical performance of 3D-PES. Under optimized conditions, the fabrication procedure offered excellent reproducibility (RSD 1.3% in working electrode diameter), speed (< 3 min/unit), and costs (< 0.01 $ in material cost). The 3D-PES was successfully applied to the determination of phloridzin in apple juice. The analytical performance of 3D-PES was compared with an equivalent commercial on-drop screen-printed electrode, yielding similar precision and accuracy but lower sensitivity. However, 3D-PES provides interesting features such as recyclability, biodegradability, low-cost, and the possibility of being manufactured near the point of need, some of which meets several demands of Green Chemistry. This cost-effective printing approach is a green and promising alternative for manufacturing disposable and portable electroanalytical devices, opening new possibilities not only in on-site food analysis but also in point-of-care testing.
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  • 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
    可可果实是多酚的丰富来源,包括类黄酮和酚酸,具有显著的健康益处。从可可果实的不同部位提取的这些生物活性化合物的准确鉴定和定量,比如豆荚,豆子,笔尖,还有可可贝壳,需要特定的处理条件和分析技术。这篇综述全面比较了用于鉴定和定量可可果实各个部分的多酚的提取工艺和分析技术。此外,它强调了这些方法对环境的影响,探索选择和利用提取的挑战和机遇,分析,和影响评估技术,同时考虑多酚的产量。该评论旨在全面概述当前的知识,这些知识可以指导那些寻求从可可果实的不同部分获得多酚的人的未来决策。
    The cacao fruit is a rich source of polyphenols, including flavonoids and phenolic acids, which possess significant health benefits. The accurate identification and quantification of these bioactive compounds extracted from different parts of the cacao fruit, such as pods, beans, nibs, and cacao shells, require specific treatment conditions and analytical techniques. This review presents a comprehensive comparison of extraction processes and analytical techniques used to identify and quantify polyphenols from various parts of the cacao fruit. Additionally, it highlights the environmental impact of these methods, exploring the challenges and opportunities in selecting and utilizing extraction, analytical, and impact assessment techniques, while considering polyphenols\' yield. The review aims to provide a thorough overview of the current knowledge that can guide future decisions for those seeking to obtain polyphenols from different parts of the cacao fruit.
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  • 文章类型: Journal Article
    关注水处理,提出提高光催化活性的新方法具有重要意义。由于光催化在几乎所有的化学制造过程中无处不在,光催化系统的发展对我们的环境具有重要意义。在这方面,三种不同量的共价有机框架装饰有钛(IV)氧化物纳米颗粒(TiO2/COF杂化物)在海藻酸盐-羧甲基纤维素(Alg-CMC)混合基质下制备,其中柠檬酸和氯化钙充当两个绿色交联键。基于这些生物纳米复合材料(bio-NC)珠的理化分析,Alg-CMC共混聚合物似乎是TiO2/COF杂化物差异的最佳候选者。COF不仅有助于增加TiO2纳米颗粒的分布,但是它降低了带隙能量。所得Alg-CMC/TiO2/COF(TiO2/COF=15:6)生物-NC珠在紫外光下表现出对甲基紫(MV)的有效光降解活性。获得的清除剂研究结果表明,超氧自由基和电子试剂在MV降解中起主要作用。进一步的研究证实,单氧添加和N-去甲基化可能是这些bio-NC珠分解MV的两个重要途径。
    Concerned about water treatment, it is of great importance to present new approaches for improving photocatalytic activity. Since photocatalysis is ubiquitous in almost all chemical manufacturing processes, the development of photocatalytic systems carries significance for our environment. In this regard, three different amounts of covalent organic frameworks decorated with titanium(IV) oxide nanoparticles (TiO2/COF hybrids) in Alginate-Carboxymethyl cellulose (Alg-CMC) blend matrix were prepared under ultrasound irradiation, which Citric acid and Calcium chloride acted as two green cross-linkages. Based on the physio-chemical analyses of these bio-nanocomposite (bio-NC) beads, the Alg-CMC blend polymer appeared to be the best candidate for a disparity of TiO2/COF hybrids. Not only did COF aid to increase the distribution of TiO2 nanoparticles, but it declined the bandgap energies. The resultant Alg-CMC/TiO2/COF (TiO2/COF = 15:6) bio-NC beads demonstrated efficient photodegradation activity towards Methyl violet (MV) under Ultraviolet light. The obtained results of scavenger studies indicated that superoxide radicals and electron agents played a major role in MV degradation. Further investigation confirmed that single oxygen addition and N-de-methylation could be two important pathways for the decomposition of MV by these bio-NC beads.
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  • 文章类型: Journal Article
    对皮肤病和伤口的精确治疗的要求,引起了人们对多功能聚合物复合材料的兴趣,能够模仿人体中的天然成分。此外,电活性复合膜传播内源性电刺激,促进细胞迁移及其在伤口部位的增殖,提出了更大的机会来升级传统的伤口贴片。在这项工作中,由氧化石墨烯制成的复合膜,Ag2O,PVA和壳聚糖被开发用于伤口愈合应用,通过溶液浇铸法。从物理化学分析中验证了纳米填料在聚合物基质中的均匀分散性。从AFM图像中注意到复合膜表面粗糙度的增加。还验证了聚合物复合材料的热稳定性和多孔性。膜的电导率值为0.16×10-4Scm-1。从MTT试验中,注意到膜是非细胞毒性的并且支持细胞粘附以及巨噬细胞(RAW264.7)细胞的细胞增殖。此外,复合膜还表现出<2%的非溶血活性,以及对大肠杆菌和金黄色葡萄球菌的优异抗菌活性。因此,获得的结果验证了所制备的复合膜可以被选为开发最先进的伤口敷料的创新候选人。
    The requirement for accurate treatments for skin diseases and wounds, generated a rising interest towards multifunctional polymer composites, that are capable of mimicking the natural compositions in human body. Also, electroactive composite films disseminate endogenous electrical stimulations that encourage cell migration and its proliferation at wound site, proposing greater opportunities in upgrading the conventional wound patches. In this work, the composite film made of graphene oxide, Ag2O, PVA and chitosan were developed for wound healing applications, by the solution casting method. The even dispersibility of nanofiller in polymeric matrix was validated from the physicochemical analyses. The increment in roughness of the composite film surface was noted from AFM images. The thermal stability and porous nature of the polymer composite were also verified. A conductivity value of 0.16 × 10-4 Scm-1 was obtained for the film. From MTT assay, it was noted that the films were non-cytotoxic and supported cell adhesion along with cell proliferation of macrophage (RAW 264.7) cells. Moreover, the composite film also demonstrated non-hemolytic activity of <2 %, as well as excellent antibacterial activity towards E. coli and S. aureus. Thus, the obtained results validated that the prepared composite film could be chosen as an innovative candidate for developing state-of-the-art wound dressings.
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  • 文章类型: Journal Article
    木质纤维素生物质在循环生物经济中具有有希望的作用,并且可用于产生用于绿色化学的有价值的分子。木质纤维素生物质,比如食物浪费,农业废弃物,木头,纸或纸板,相当于欧洲2020年产生的所有废物的15.7%,作为工业过程的二次原料具有很高的潜力。这篇综述首先介绍了工业木质纤维素废物的来源,就它们的组成而言,木质纤维素残留物的数量和类型。其次,详细介绍了木质纤维素废物转化可能获得的高附加值化学品,以及它们在食品工业中的应用潜力,生物医学,能源或化学部门,包括作为多酚的来源,酶,生物塑料前体或生物燃料。在第三部分,各种可用的转化处理,比如用超声波或热进行物理治疗,用酸或碱进行化学处理,用酶或微生物进行生物处理,被呈现。最后一部分讨论了使用木质纤维素废物的观点,以及降低转化成本是在循环经济和绿色化学方法中改善木质纤维素生物质使用的主要问题之一。因为它目前通常比石油基同行更昂贵。
    Lignocellulosic biomass has a promising role in a circular bioeconomy and may be used to produce valuable molecules for green chemistry. Lignocellulosic biomass, such as food waste, agricultural waste, wood, paper or cardboard, corresponded to 15.7% of all waste produced in Europe in 2020, and has a high potential as a secondary raw material for industrial processes. This review first presents industrial lignocellulosic waste sources, in terms of their composition, quantities and types of lignocellulosic residues. Secondly, the possible high added-value chemicals obtained from transformation of lignocellulosic waste are detailed, as well as their potential for applications in the food industry, biomedical, energy or chemistry sectors, including as sources of polyphenols, enzymes, bioplastic precursors or biofuels. In a third part, various available transformation treatments, such as physical treatments with ultrasound or heat, chemical treatments with acids or bases, and biological treatments with enzymes or microorganisms, are presented. The last part discusses the perspectives of the use of lignocellulosic waste and the fact that decreasing the cost of transformation is one of the major issues for improving the use of lignocellulosic biomass in a circular economy and green chemistry approach, since it is currently often more expensive than petroleum-based counterparts.
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  • 文章类型: Journal Article
    背景:果汁行业的废物副产品对于循环经济概念似乎很有价值,考虑到果皮几乎占水果总重量的一半。因此,从相关生物废弃物中回收这些非常有价值的成分已经成为一个非常有趣的研究课题。
    目的:本研究旨在开发一种基于统计实验设计方法的与疏水性深共晶溶剂(DES)集成的提取工艺。
    方法:使用均质器-辅助提取(HAE)从柠檬皮中回收富含柠檬烯(挥发性混合物的主要成分)的柑橘提取物。基于薄荷醇的低共熔混合物伴随着羧酸(甲酸,乙酸,和丙酸)。在以不同摩尔比(1/1、1/2和2/1)制备的溶剂中得到最高效率(就柠檬烯含量而言)的组合上继续优化。通过响应面法(RSM)的中心组合设计,对工艺参数进行了分析,以优化工艺。使用固相微萃取(SPME)技术,通过气相色谱-质谱法(GC-MS)定量D-柠檬烯产率。还通过体外生物活性测定(酚类含量和2,2-二苯基-1-吡啶酰肼[DPPH]自由基清除活性)评估了柠檬皮提取物的质量。
    结果:通过2mg固体/30mLDES实现了最大产量(每克新鲜样品3.80mg-柠檬烯),~53秒,和~8500转/分钟。统计上最有效的变量被确定为固体质量,然后是混合速度和提取时间的二次幂,p<0.0001。
    BACKGROUND: Waste by-products of the juice industry appear valuable for the circular economy concept, considering that the peel accounts for almost half of the total fruit weight. Therefore, the recovery of these highly valuable components from relevant biowaste has become a very interesting research topic.
    OBJECTIVE: The current study aims to develop an extraction process integrated with hydrophobic deep eutectic solvent (DES) based on statistical experimental design approach.
    METHODS: Homogenizer-assissted extraction (HAE) was used to recover the citrus extract rich in limonene (the main component of the volatile mixture) from lemon peels. Menthol-based deep eutectic mixtures were accompanied by carboxylic acids (formic, acetic, and propionic acids). Optimization continued on the combination that gave the highest efficiency (in terms of limonene content) among the solvents prepared at different molar ratios (1/1, 1/2, and 2/1). Process parameters were analyzed to optimize the process through central composite design with response surface method (RSM). D-Limonene yield was quantified with gas chromatography-mass spectrometry (GC-MS) with solid-phase microextraction (SPME) technique. The quality of the lemon peel extracts was also evaluated with respect to in vitro bioactivity assays (phenolic content and 2,2-diphenyl-1-picrylhydrazyl [DPPH] free radical scavenging activity).
    RESULTS: The maximum yield (3.80 mg-limonene per g fresh sample) was achieved by 2 mg solid/30 mL DES, ~53 sec, and ~8500 rpm. Statistically most effective variable was identified as solid mass, followed by second powers of mixing speed and extraction time at p < 0.0001.
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