Synthesis of substituted diphenylamines and carbazoles: phototransformation products of diclofenac

The formation of stable and potentially hazardous compounds as a result of photochemical transformation of pharmaceutical substances in the aquatic environment implies a demand for standard compounds within environmental analysis. The major phototransformation products of diclofenac are comprised of substituted diphenylamines and carbazoles. Substituted diphenylamines were synthesized by Ullmann condensation reactions between anilines and halobenzenes. Monochlorocarbazoles were obtained from palladium-catalyzed intramolecular coupling reactions of monochlorinated diphenylamines, photocyclization of dichlorinated diphenylamines or by direct chlorination of carbazole. The availability of synthetic photoproducts of diclofenac is of critical importance for further studies on the environmental fate as well as the ecotoxicological effects of the drug in the environment.     

Synthesis of carboxylic dithiocarbamic anhydride and substituted thiourea derivatives in water

The use of water as a solvent has sometimes benefits such as improving reactivities and selectivities, simplifying work-up procedures, and environmentally benign. Many carboxylic dithiocarbamic anhydride products are valuable building blocks in heterocycles and natural products. Here we present a simple one-pot synthesis of carboxylic dithiocarbamic anhydride by condensation of amines, carbon disulfide, acyl halide, or acetic anhydride in water. We obtained a variety of biologically important acyl dithiocarbamate derivatives in 82–93% yields in 10–30 min. This procedure can be used for the synthesis of thioureas from dithiocarbamates. Here, the sequential, one-pot three-component reaction of amines, carbon disulfide, and isothiocyanates provides unsymmetrical substituted thioureas in 81–91% yields.     

Applications of steroid drugs entrapped in cyclodextrins

Environmental Chemistry Letters - Steroids are abundant in living organisms and are responsible for various biological functions. They are good candidates for inclusion complexes formation with...     

Remediation technologies using cyclodextrins: an overview

Nowadays, the human activity and the modern way of life are responsible for the increase of the environmental pollution. Industrial processes generate a variety of molecules that may pollute air, water, and soils due to negative impacts for ecosystems and humans. The development of innovative remediation technologies has thus emerged as a significant environmental priority. Within this scope, supramolecular chemistry, which is a recent discipline, could provide solutions. In particular, cyclodextrins (CDs) are a family of cyclic oligosaccharides having a low-polarity cavity in which organic compounds of appropriate shape and size can form inclusion complexes. This unique property makes them suitable for application in environmental protection. Here, we review the use of cyclodextrins and cyclodextrin derivatives in remediation technologies. Accordingly, the present review shows the advantages of using CDs in soil, groundwater, wastewater, and atmosphere remediation. Resulting processes are highly versatile, since the complexing ability of CD is applicable to a wide range of pollutants. They may also been referred to green processes, according to the CD innocuity. Moreover, as inclusion phenomena correspond to reversible equilibriums, a major trend in the CD environmental application field is to develop methods, which combine supramolecular chemistry and irreversible processes, as advanced oxidation or biodegradation. Such processes might lead to a complete remediation of pollutants and eventually to the CD recycling.     

Encapsulation in cyclodextrins to widen the applications of essential oils

Environmental Chemistry Letters - There is a growing interest for aromatic and biological properties of essential oils as alternatives to synthetic chemicals and drugs. However, essential oils and...     

A review on thermal analyses of cyclodextrins and cyclodextrin complexes

Environmental Chemistry Letters - Cyclodextrins are valuable natural or synthetically modified cyclic oligosaccharides that are widely used for ameliorating properties of biologically active...     

环糊精和表面活性剂对土壤中2-硝基联苯的解吸行为的影响

研究了3种羟丙基环糊精(HP-α-CD、HP-β-CD、HP-γ-CD)和2种非离子表面活性剂(Tween 80,Triton X-100)对土壤中2-硝基联苯的解吸行为的影响。通过比较摩尔增溶比率(MSR)的大小,确定了这5种添加剂对2-硝基联苯增溶能力由强到弱的顺序为:Tween 80,Triton X-100,HP-β-CD,HP-γ-CD,HP-α-CD。在5种添加剂中,HP-β-CD对促进土壤中2-硝基联苯的解吸最有效,且促进作用与其用量成正比。HP-α-CD对解吸过程没有明显的促进作用。Tween 80和Triton X-100由于易吸附于土壤中的特性,在低用量时对2-硝基联苯的解吸产生了负作用,只有用量足够大时才表现出明显的促进作用。     

Professor Casu’s contribution to cyclodextrins,the remarkable cage-shaped molecules: a review

Cyclodextrins are cage-shaped molecules having the remarkable ability to trap smaller compounds, and have thus led to applications in many disciplines such as medicine to increase the bioavailability of hydrophobic drugs. This historical review summarizes the outstanding contribution of the late Professor Benito Casu to cyclodextrin research and, more generally, to the chemistry and biochemistry of linear and cyclic oligosaccharides, polysaccharides, glycosaminoglycans, and heparin. Professor Casu was the first to elucidate the structure and conformations of cyclodextrins by infrared spectroscopy and proton nuclear magnetic resonance (NMR). In particular, he showed that trapped compounds induced a shift of H peaks in NMR due to the shielding effect of cyclodextrins. He also demonstrated that the d-glucopyranose cyclodextrin units are in the C-1 chair conformation by analyzing α-cyclodextrin by NMR in dimethylsulfoxide-d₆.

     

Accumulation,root-shoot translocation and phytotoxicity of substituted polycyclic aromatic hydrocarbons in wheat

Environmental Chemistry Letters - While pollution of the environment by polycyclic aromatic hydrocarbons has been rather well studied, the fate of substituted polycyclic aromatic hydrocarbons in...     

低浓度下4个取代苯污染物与硝酸铅的混合对发光菌的联合毒性

多种污染物混合特别是低浓度下的混合对生物的联合毒性是生态毒理学研究的热点之一。选择了3类污染物苯酚、间甲基苯酚、苯胺、对硝基苯胺、硝酸铅,采用美国微板光度计测定了它们对发光菌青海弧菌．Q67（Vibrio-qinghaiensissp-Q67）的单一及联合毒性。应用非线性拟合技术模拟了这5种物质及其混合物的剂量．效应曲线,硝酸铅可用Logit模型模拟,其它4个物质能用Weibull模型准确描述,所有拟合相关系数在0．98以上,均方根误差在O．02以下。根据纯物质的EC50值,获得这5个物质的毒性强弱顺序：硝酸铅〉对硝基苯胺〉间甲基苯酚〉苯酚〉苯胺。混合实验设计了各物质在EC50、EC1、无观察效应浓度（noobserved effectcon centration,NOEC）比例的混合。用浓度加和（doseaddition,DA）和独立作用模型（independentaction,IA）对混合物毒性进行预测。IA基本准确预测了这5个物质在各自EC50混合的毒性。DA与队模型都稍微过高地预测了以EC。及NOEC浓度比例混合的联合毒性,但都在毒理学实验容许的范围之内。这5个物质以NOEC混合时对测试生物Q67没有产生明显毒性,但是还不能判定这些物质在此浓度下混合是安全的。污染物在各自的NOEC浓度下混合是否对其它生物有潜在的威胁还需更多毒理学实验支持。     

低浓度下4个取代苯污染物与硝酸铅的混合对发光菌的联合毒性

多种污染物混合特别是低浓度下的混合对生物的联合毒性是生态毒理学研究的热点之一。选择了3类污染物苯酚、间甲基苯酚、苯胺、对硝基苯胺、硝酸铅,采用美国微板光度计测定了它们对发光菌青海弧菌-Q67(Vibrio-qinghaiensis sp.-Q67)的单一及联合毒性。应用非线性拟合技术模拟了这5种物质及其混合物的剂量-效应曲线,硝酸铅可用Logit模型模拟,其它4个物质能用Weibull模型准确描述,所有拟合相关系数在0.98以上,均方根误差在0.02以下。根据纯物质的EC50值,获得这5个物质的毒性强弱顺序:硝酸铅〉对硝基苯胺间甲基苯酚苯酚苯胺。混合实验设计了各物质在EC50、EC1、无观察效应浓度(no observed effect concentration,NOEC)比例的混合。用浓度加和(dose addition,DA)和独立作用模型(independent action,IA)对混合物毒性进行预测。IA基本准确预测了这5个物质在各自EC50混合的毒性。DA与IA模型都稍微过高地预测了以EC1及NOEC浓度比例混合的联合毒性,但都在毒理学实验容许的范围之内。这5个物质以NOEC混合时对测试生物Q67没有产生明显毒性,但是还不能判定这些物质在此浓度下混合是安全的。污染物在各自的NOEC浓度下混合是否对其它生物有潜在的威胁还需更多毒理学实验支持。     

粉煤灰合成分子筛的研究进展

粉煤灰是煤燃烧后的固体废弃物,其高附加值利用是国内外关注的一个方向.目前粉煤灰合成分子筛研究热点主要集中在改进实验合成方法和降低合成成本.此文综述了由粉煤灰合成分子筛的国内外进展,阐述并比较了目前由粉煤灰合成方法的优缺点并指明了未来的研究方向.同时探讨了粉煤灰分子筛在土壤治理、废水处理、空气净化等方面的应用前景.因此利用粉煤灰合成具有高附加值分子筛产品是粉煤灰综合利用的一个发展趋势.     

Synthesis of activated carbon from food waste

Environmental Chemistry Letters - Activated carbon is a material for many adsorption applications, combining low-cost and high-quality properties. Many sources of activated carbon have...     

Synthesis and medicinal properties of plant-derived vilangin

This article reports for the first time the antibacterial, antifungal, antioxidant and anticancer activities of vilangin synthesised from embelin isolated from Embelia ribes berries. E. ribes is widely used as traditional herbal medicine in India. E. ribes is used as appetiser, carminative, anthelmintic, alexiteric, laxative and alterative. This plant is also used to treat tumour, ascites, bronchitis, mental diseases, dyspnoea, heart diseases, urinary discharges, jaundice, hemicrania, and worms in wounds. Here the major compound, embelin, was isolated from the fruits of E. ribes. Vilangin was synthesised by condensation of embelin with formaldehyde in acetic acid solution. The biological activity of vilangin is unknown so far. Hence, we studied antibacterial, antifungal, antioxidant and anticancer activities of vilangin. The minimum inhibitory concentration value of vilangin was 62.5 μg/mL against Staphylococcus epidermidis and Salmonella typhimurium. The radical scavenging activity was maximum at 1,000 μg/mL. Ferric reducing antioxidant power assay of vilangin showed a twofold higher value compared to the standard. Vilangin showed 61.95 % of cytotoxic activity in vitro against A549 lung adenocarcinoma cancer cell line at a dose of 500 μg/mL with half-maximal inhibitory concentration (IC₅₀) of 400 μg/mL. Vilangin can thus be further tested as a new drug.     

靛蓝的微生物合成研究新进展

靛蓝是一种广泛应用于印染、医药等行业的有机色素,利用微生物法合成靛蓝已引起国内外学者的广泛关注.本文综述了微生物法合成靛蓝的研究进展及动态.靛蓝的微生物合成可归纳为3个阶段:野生型微生物催化合成、基因工程菌全细胞催化转化及代谢工程调控转化.多数芳烃降解菌及其编码酶均具备催化吲哚合成靛蓝的能力,采用定向进化、宏基因组技术以及两相体系等对已知酶资源进行深尺度研究,将为靛蓝生物合成过程注入新的活力.同时,靛蓝合成过程中产生的羟基吲哚及靛蓝衍生物是新型药物及化工中间体,也具有较大的研究价值.然而,由于靛蓝合成过程涉及的中间产物及副产物间转化关系及合成脉络仍不明晰,靛蓝产率低,因此将分子生物学及代谢工程手段融入到靛蓝合成机理及产业化应用的探索将成为该方向的研究重点.     

城市复合生态系统能值整合分析研究方法论

系统阐述了城市复合生态系统能值分析的基本概念原理与方法步骤,总结了城市可持续发展综合能值评价指标体系。在此基础上,从能值转换率的积累和统一、多尺度研究的整合与尺度推绎、城市功能流分析与空间结构分析的整合、能值成本价值论与使用(市场)价值论的整合等方面,讨论了能值研究方法在城市生态系统研究中的应用前景和发展方向。     

全基因合成方法学研究

通过基因全合成实现基因的分子改造和人工组建正成为一种实验室常规手段,因此,建立一种能够在相对低廉和短时间内准确和高效地设计和合成长片段基因的方法十分重要.本研究报道了一种重复性好、错误率低、低成本和简便的基因设计和全合成方法.此方法包含经DNA2.0软件的序列优化,Gene2Oligo软件的寡核苷酸设计,覆盖全长基因双链的寡核苷酸的组合和引物介导下的全基因的合成等步骤.运用此方法,对3个不同长度的基因(分别为653bp,1309bp和1498bp)成功地进行了密码子优化和一步全合成.其中的amyFF在大肠杆菌中表达量提高了12倍.图2参18     

电化学沉积法制备ZIF-8及其对四环素的吸附

ZIF-8的常用合成方法包括水/溶剂热法、机械研磨法、微波辅助法和超声法等.本实验采用"绿色"、批量、快速的电化学沉积法制备ZIF-8,同时研究导电盐十二烷基三甲基溴化铵(DTAB)质量浓度对ZIF-8形貌及其吸附降解四环素性能的影响.研究结果显示,当2-甲基咪唑(2-MI)与DTAB质量浓度比为10∶3时制得的ZIF-8对四环素吸附效果最好,可达到340.8 mg·g~(-1),其吸附过程符合伪二级动力学模型和Langmuir等温线模型.根据Langmuir等温线模型,计算Gibss自由能变(ΔG~00)、焓变(ΔH~00)和熵变(ΔS~00),说明吸附过程为吸热、趋于无序的自发过程,并且是一个以物理吸附为主的物理化学吸附.本文利用金属有机骨架材料的光催化性能,实现了紫外光照射下ZIF-8对四环素的光催化降解.同时,通过3次循环实验,对ZIF-8的重复利用性进行了探究,其吸附量分别为175.44、165.83、139.19 mg·g~(-1),结果表明ZIF-8具有良好的重复利用性.探讨了不同pH对吸附效果的影响,当4pH8时,其吸附效果最佳,而当pH 4或pH8时都会使其吸附效果变差.通过对ZIF-8进行PXRD、TGA、BET、FTIR、Zeta电位等表征,提出ZIF-8对四环素的吸附机理包括但不限于静电相互作用、氢键作用以及π-π堆积作用. ZIF-8在吸附去除水体中的四环素方面具有很大的应用潜力,同时ZIF-8可利用紫外光照射进行再生,表现出其优越的可持续循环利用性.