Polysaccharides derived from natural sources applied to the development of chemically modified electrodes for environmental applications: A review

Potentially toxic organic and inorganic compounds have been released into the environment by different sources. Due to this detrimental problem, the modern analytical chemistry has increasingly acted in the interface of knowledge in terms of developing methods which are robust, efficient, sensitive, inexpensive, and aim at meeting green chemistry principles. From an electroanalytical standpoint, the application of polysaccharides derived from natural sources in the development of chemically modified electrodes has increased in the last decades. Chitosan, cellulose and other polysaccharides have been widely used in the development of modified electrodes due to their high mechanical strength, relatively low cost, and green features. Several studies have reported in the past few years that chemically modified electrodes elaborated with these polysaccharides usually present superior analytical properties as compared to the conventional electrodes. This review describes the general aspects of these polysaccharides, extraction sources, characterization methods, derivatives and crosslinking processes as well as a comprehensive overview of their several applications in the development of new sensors applied to environmental samples.     

Multicriteria Decision Analysis and Grouping of Analytical Procedures for Phthalates Determination in Disposable Baby Diapers

This study presents the application of one of the tools from the multicriteria decision analysis set (MCDA), the Technique for Order Preference by Similarity to Ideal Solution (TOPSIS). Selected green analytical chemistry metrics were used to rank analytical procedures for the phthalate determination in disposable baby diapers. Nine analytical procedures were assessed in order to find one that has the lowest environmental impact and the best analytical figures of merit. Nine different criteria, where weighting was based on the experts’ evaluation, were used in the procedures’ assessment. With the use of TOPSIS, an easy and straightforward technique, selection of the most appropriate procedure was made.     

Direct arylation and heterogeneous catalysis; ever the twain shall meet

The formation of aryl–aryl bonds and heteroaryl analogues is one of the most important C–C bond forming processes in organic chemistry. Recently, a methodology termed Direct Arylation (DA) has emerged as an attractive alternative to traditional cross-coupling reactions (Suzuki–Miyaura, Stille, Negishi, etc.). A parallel focus of the pharmaceutical and other chemical industries has been on the use heterogeneous catalysis as a favourable substitute for its homogeneous counterpart in cross-coupling reactions. Only very recently has heterogeneous catalysis been proposed and applied, to DA reactions. In this perspective, we consider the terms ‘heterogeneous’ and ‘homogeneous’ and the problems associated with their delineation in transition-metal catalysed reactions. We highlight the reports at the interface of DA and heterogeneous catalysis and we comment briefly on the methods used which attempt to classify reaction types as homo- or heterogeneous. In future work we recommend an emphasis be placed on kinetic methods which provide an excellent platform for analysis. In addition two analytical techniques are described which if developed to run in situ with DA reactions would illuminate our understanding of the catalysis. Overall, we provide an entry point, and bring together the mature, yet poorly-understood, subject of heterogeneous catalysis with the rapidly expanding area of DA, with a view towards the acceleration of catalyst design and the understanding of catalyst behaviour.     

Green chemistry and the evolution of flow analysis. A review

Flow analysis has achieved its majority as a well-established tool to solve analytical problems. Evolution of flow-based approaches has been analyzed by diverse points of view, including historical aspects, the commutation concept and the impact on analytical methodologies. In this overview, the evolution of flow analysis towards green analytical chemistry is demonstrated by comparing classical procedures implemented with different flow approaches. The potential to minimize reagent consumption and waste generation and the ability to implement processes unreliable in batch to replace toxic chemicals are also emphasized. Successful applications of greener approaches in flow analysis are also discussed, focusing on the last 10 years.     

绿色分析化学

绿色分析化学是把绿色化学的原理使用在新的分析方法和技术的设计方面,旨在减轻分析化学对环境的影响。无污染或少污染的绿色分析化学技术将是今后分析化学的一个发展方向。文中介绍了分析化学与环境的关系,绿色分析化学的特点及其方法的发展。     

Response surface design as a powerful tool for the development of environmentally benign HPLC methods for the determination of two antihypertensive combinations: Greenness assessment by two green analytical chemistry evaluation tools

Interest in implementing green chemistry principles in analytical chemistry has grown dramatically in the past few years. The solvents used have the major influence on the greenness of the method. Most conventional high‐performance liquid chromatography methods employed utilize solvents that are “hazardous for the environment”. In the present study, two‐factor three‐level response surface design was exploited to develop eco‐friendly chromatographic methods for two different mixtures. The first one was atorvastatin and amlodipine and the second one was amlodipine, perindopril, and indapamide. As it is nontoxic to the environment, ethanol was used as the organic modifier in the mobile phase. The separation of the first mixture was attained using phosphate buffer (pH 7)/ethanol (42:58 v/v), and the second mixture was fully resolved using phosphate buffer (pH 5)/ethanol (40:60 v/v). The use of high‐performance liquid chromatography allows excellent resolution in a short run time, hence, less waste was produced. The greenness of the developed methods was assessed by two evaluation tools, namely, National Environmental Methods Index and analytical eco‐scale, and found to be excellent green analytical methods. Moreover, the developed methods were compared with other reported methods regarding accuracy and greenness and were found to be perfect alternatives to reported methods for separation and quantification of the mixtures.     

Application of quantum dots as analytical tools in automated chemical analysis: A review

Colloidal semiconductor nanocrystals or quantum dots (QDs) are one of the most relevant developments in the fast-growing world of nanotechnology. Initially proposed as luminescent biological labels, they are finding new important fields of application in analytical chemistry, where their photoluminescent properties have been exploited in environmental monitoring, pharmaceutical and clinical analysis and food quality control. Despite the enormous variety of applications that have been developed, the automation of QDs-based analytical methodologies by resorting to automation tools such as continuous flow analysis and related techniques, which would allow to take advantage of particular features of the nanocrystals such as the versatile surface chemistry and ligand binding ability, the aptitude to generate reactive species, the possibility of encapsulation in different materials while retaining native luminescence providing the means for the implementation of renewable chemosensors or even the utilisation of more drastic and even stability impairing reaction conditions, is hitherto very limited. In this review, we provide insights into the analytical potential of quantum dots focusing on prospects of their utilisation in automated flow-based and flow-related approaches and the future outlook of QDs applications in chemical analysis.     

Multisyringe Flow Injection Potentialities for Hyphenation with Different Types of Separation Techniques

The advantages of combining flow techniques with separation techniques are noteworthy. Flow-based methods are excellent tools for automating analytical procedures owing to their speed of analysis, reagent and sample saving ability, versatility, and inexpensive equipment. However, flow-based methods alone do not allow the separation of several analytes in a mixture. On the other hand, separation techniques (viz., chromatographic separations, capillary electrophoresis), widely used in analytical research due to high selectivity, require more expensive instrumentation. Thus, the combination of both techniques achieved the required selectivity with a more versatile, automated and, in some cases, low-cost methodology.

Multisyringe flow injection evidences interesting features with the utilization of the aforementioned combination of methods. Its potential for hyphenation with different separation techniques have been recently explored and are depicted in the present paper.     

Single-drop microextraction technique for the determination of antibiotics in environmental water

Growing concerns related to antibiotic residues in environmental water have encouraged the development of rapid, sensitive, and accurate analytical methods. Single-drop microextraction has been recognized as an efficient approach for the isolation and preconcentration of several analytes from a complex sample matrix. Thus, single-drop microextraction techniques are cost-effective and less harmful to the environment, subscribing to green analytical chemistry principles. Herein, an overview and the current advances in single-drop microextraction for the determination of antibiotics in environmental water are presented were included. In particular, two main approaches used to perform single-drop microextraction (direct immersion-single-drop microextraction and headspace-single-drop microextraction) are reviewed. Furthermore, the impressive analytical features and future perspectives of single-drop microextraction are discussed in this review.     

绿色分析化学技术研究进展

绿色分析化学是受到广泛关注的一门前沿科学,它是把绿色化学的基本原理应用在新的分析方法和技术方面.对绿色分析样品前处理技术、绿色分析分离富集技术和绿色分析测试技术进行了综述.     

新创实验:废旧棉中纤维素的提取改性及水凝胶的制备

水凝胶作为一种有着广阔应用前景的高分子材料,是当今科学研究的热门领域,其制备方法相对简单,还将有机合成化学、高分子化学、无机配位化学和分析化学结合于一体,显示出进一步改编为教学实验的潜力。水凝胶自身环境友好的特点还十分贴合绿色化学的主题,便于在教学实验设计中引入相关内容。虽然绿色化学教育在当今的化学专业人才培养中的重要性与日俱增,但在实际推广中也遇到了一些困难,比如定性描述较多,概念模糊不清,很难激发学生兴趣;定量计算过于简单,只关注反应前后质量变化等。针对绿色化学的教学困境,我们在将水凝胶这一科研成果转化为教学实验外,还引入了最新的绿色化学半定量评价方法,引导学生在实验准备阶段运用新颖的半定量评价方法找寻绿色程度较高的水凝胶合成路线。最终以废旧棉为原料提取改性得到羧甲基纤维素钠,再以滴定法测定其取代度,然后采取金属离子交联方法制备出可视化水凝胶产品,并对其吸附性能进行了初步测试。     

Structural and adsorption behaviour of ZnO/aminated SWCNT-COOH for malachite green removal: face-centred central composite design

In this study, an effective adsorbent was synthesized to remove malachite green (MG), which is one of the toxic dyes. Firstly, single walled carbon nanotube with carboxylated acid (SWCNT-COOH) was functionalized with diethylenetriamine and a new nanocomposite was obtained using nano zinc oxide (ZnO) powder. The effects of pH (3–7), the amount of adsorbent (5–15 mg) and the initial concentration (10–50 mg L^–1) of the solution on the adsorption uptake were investigated. The optimal parameters that maximize the adsorption uptake according to the specified working range are found to be 4.63 for pH, 49.94 mg L^–1 for initial concentration, 5.25 mg for the adsorbent dose, and the maximum adsorption capacity has been found as 52.26 mg g^–1. The excellent fitting of the pseudo-second kinetic model with (R² = 0.9912) was fitted the experimental data. The Freundlich isotherm model gave a clue about the type of adsorption. Furthermore, thermodynamic results showed that adsorption process was endothermic.     

Green chemistry: Analytical and chromatography

Nowadays, the environment protection and the personal health and safety are given more consideration in the field of chemistry, thus resulting in an increased number of published researches about how to work according to green instructions, to follow up the recommendations of environmental agencies and to obtain better clean handling of chemistry. In this review, green chemistry definition, importance, principles, and some recent applications in the field of green chemistry were discussed. In addition, the review summarizes the evolution of green analytical chemistry (GAC) with its specific principles and how to make the analytical process more environmentally benign with special emphasis on recent applications of GAC. Moreover, the green chromatography, its methods, and some of its applications were outlined. Finally, different techniques available up till now for the assessment of greening of the methods were also presented.     

Meeting reports: International conference on chemometrics in analytical chemistry

In the field of analytical chemistry, chemometrics has been defined as 'the chemical discipline which uses mathematical and statistical methods to achieve the aim of analytical chemistry, namely the obtention, in the optimal way, of relevant information about material systems'. There has been a tremendous growth of interest in the role of chemometrics in analytical chemistry in recent years and this has been reflected in the number of symposia devoted to the subject. Two meetings, held in Europe in September 1982, covered different aspects of chemometrics and some of the more significant points discussed are summarized in the reports below.     

Cross-dehydrogenative N–N couplings

The relatively high electronegativity of nitrogen makes N–N bond forming cross-coupling reactions particularly difficult, especially in an intermolecular fashion. The challenge increases even further when considering the case of dehydrogenative N–N coupling reactions, which are advantageous in terms of step and atom economy, but introduce the problem of the oxidant in order to become thermodynamically feasible. Indeed, the oxidizing system must be designed to activate the target N–H bonds, while at the same time avoid undesired N–N homocoupling as well as C–N and C–C coupled side products. Thus, preciously few intermolecular hetero N–N cross-dehydrogenative couplings exist, in spite of the central importance of N–N bonds in organic chemistry. This review aims at analyzing these few rare cases and provides a perspective for future developments.

For more than a century, the dehydrogenative formation of N–N bonds has remained mostly confidential. Several cross-dehydrogenative N–N coupling methods have appeared recently, promising a soon to come broad applicability of the concept.     

Fabric Phase Sorptive Extraction: A Paradigm Shift Approach in Analytical and Bioanalytical Sample Preparation

Fabric phase sorptive extraction (FPSE) is an evolutionary sample preparation approach which was introduced in 2014, meeting all green analytical chemistry (GAC) requirements by implementing a natural or synthetic permeable and flexible fabric substrate to host a chemically coated sol–gel organic–inorganic hybrid sorbent in the form of an ultra-thin coating. This construction results in a versatile, fast, and sensitive micro-extraction device. The user-friendly FPSE membrane allows direct extraction of analytes with no sample modification, thus eliminating/minimizing the sample pre-treatment steps, which are not only time consuming, but are also considered the primary source of major analyte loss. Sol–gel sorbent-coated FPSE membranes possess high chemical, solvent, and thermal stability due to the strong covalent bonding between the fabric substrate and the sol–gel sorbent coating. Subsequent to the extraction on FPSE membrane, a wide range of organic solvents can be used in a small volume to exhaustively back-extract the analytes after FPSE process, leading to a high preconcentration factor. In most cases, no solvent evaporation and sample reconstitution are necessary. In addition to the extensive simplification of the sample preparation workflow, FPSE has also innovatively combined the extraction principle of two major, yet competing sample preparation techniques: solid phase extraction (SPE) with its characteristic exhaustive extraction, and solid phase microextraction (SPME) with its characteristic equilibrium driven extraction mechanism. Furthermore, FPSE has offered the most comprehensive cache of sorbent chemistry by successfully combining almost all of the sorbents traditionally used exclusively in either SPE or in SPME. FPSE is the first sample preparation technique to exploit the substrate surface chemistry that complements the overall selectivity and the extraction efficiency of the device. As such, FPSE indeed represents a paradigm shift approach in analytical/bioanalytical sample preparation. Furthermore, an FPSE membrane can be used as an SPME fiber or as an SPE disk for sample preparation, owing to its special geometric advantage. So far, FPSE has overwhelmingly attracted the interest of the separation scientist community, and many analytical scientists have been developing new methodologies by implementing this cutting-edge technique for the extraction and determination of many analytes at their trace and ultra-trace level concentrations in environmental samples as well as in food, pharmaceutical, and biological samples. FPSE offers a total sample preparation solution by providing neutral, cation exchanger, anion exchanger, mixed mode cation exchanger, mixed mode anion exchanger, zwitterionic, and mixed mode zwitterionic sorbents to deal with any analyte regardless of its polarity, ionic state, or the sample matrix where it resides. Herein we present the theoretical background, synthesis, mechanisms of extraction and desorption, the types of sorbents, and the main applications of FPSE so far according to different sample categories, and to briefly show the progress, advantages, and the main principles of the proposed technique.     

Microwaves as “Co-Catalysts” or as Substitute for Catalysts in Organophosphorus Chemistry

The purpose of this review is to summarize the importance of microwave (MW) irradiation as a kind of catalyst in organophosphorus chemistry. Slow or reluctant reactions, such as the Diels-Alder cycloaddition or an inverse-Wittig type reaction, may be performed efficiently under MW irradiation. The direct esterification of phosphinic and phosphonic acids, which is practically impossible on conventional heating, may be realized under MW conditions. Ionic liquid additives may promote further esterifications. The opposite reaction, the hydrolysis of P-esters, has also relevance among the MW-assisted transformations. A typical case is when the catalysts are substituted by MWs, which is exemplified by the reduction of phosphine oxides, and by the Kabachnik–Fields condensation affording α-aminophosphonic derivatives. Finally, the Hirao P–C coupling reaction may serve as an example, when the catalyst may be simplified under MW conditions. All of the examples discussed fulfill the expectations of green chemistry.     

绿色分析化学技术进展

绿色分析化学技术是国际分析化学的前沿,受到广泛关注.绿色分析化学是把绿色化学的原理使用在新的分析方法和技术方面.目前的研究主要集中在环境友好的样品前处理技术(如微波消解、微波萃取、固相萃取、固相微萃取、超临界流体萃取等)和绿色分析测试技术(如X射线荧光分析法、近红外技术、毛细管电泳、顶空气相色谱等).文章对上述内容进行了综述.