Electrochemical production and use of chlorinated oxidants for the treatment of wastewater contaminated by organic pollutants and disinfection

In the last years, an increasing attention has been devoted to the use of electrogenerated chlorinated oxidants for the treatment of wastewater polluted by recalcitrant organics and/or for the disinfection of water contaminated by pathogen microorganisms. In this review, more recent and relevant findings were presented and critically discussed. The main advantages and disadvantages of this technique were commented, including the potential formation of toxic chlorinated organic specie and of chlorate and perchlorate or the difficult selection of proper operative parameters, as well as the key points that should be addressed to enhance the use on an applicative scale.     

Electrochemical oxidation of organic pollutants for wastewater treatment

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Chemoenzymatic Cascades Combining Biocatalysis and Transition Metal Catalysis for Asymmetric Synthesis

The combination of catalytic methods provides multiple advantages in organic synthesis, allowing access to diverse organic molecules in a straightforward manner. Merging metal and enzyme catalysis is currently receiving great attention due to the possibility to assemble metal catalysis in C−C coupling, olefin metathesis, hydration and other reactions with the exquisite stereospecificity displayed by enzymes. Thus, this minireview is organized based on the action of the metal species (Pd, Ru, Au, Ir, Fe…) in combination with different enzymes. Special attention will be paid to the design of sequential processes and concurrent cascades, presenting solutions such as the use of surfactants or compartmentalization strategies for those cases where incompatibilities could hamper the overall process.     

New additions to the arsenal of biocatalysts for noncanonical amino acid synthesis

Noncanonical amino acids (ncAAs) merge the conformational behavior and native interactions of proteinogenic amino acids with nonnative chemical motifs and have proven invaluable in developing modern therapeutics. This blending of native and nonnative characteristics has resulted in essential drugs like nirmatrelvir, which comprises three ncAAs and is used to treat COVID-19. Enzymes are appearing prominently in recent syntheses of ncAAs, where they demonstrate impressive control over the stereocenters and functional groups found therein. Here we review recent efforts to expand the biocatalyst arsenal for synthesizing ncAAs with natural enzymes. We also discuss how new-to-nature enzymes can contribute to this effort by catalyzing reactions inspired by the vast repertoire of chemical catalysis and acting on substrates that would otherwise not be used in synthesizing ncAAs. Abiotic enzyme-catalyzed reactions exploit the selectivity afforded by a macromolecular catalyst to access molecules not available to natural enzymes and perhaps not even chemical catalysis.     

Recent update on use of ionic liquids for enzyme immobilization,activation, and catalysis: A partnership for sustainability

Recent literature survey suggested that, ionic liquid not only possesses potential as a green solvent, but also plays a significant role in enzyme immobilization, activation, stabilization, and catalysis. Furthermore, biocatalysis in ionic liquids (IL) may be a key sustainable solution for the next generation chemical processes, which requisite extensive research efforts to expand the knowledge horizons in this field. In view of this, the present review highlights the recent update of potential applications of IL in biocatalysis for (i) biomass pretreatment/hydrolysis, (ii) enzyme immobilization-activation, (iii) organic transformation, (iv) bioremediation, and (v) biosensing. Moreover, this review also addresses the challenging issues and future outlook of this research area for the industrial development in near future.     

Co-encapsulating Cofactor and Enzymes in Hydrogen-Bonded Organic Frameworks for Multienzyme Cascade Reactions with Cofactor Recycling

Use of hydrogen-bonded organic frameworks (HOFs) for enzyme immobilization faces challenges in the improvement of enzyme activity recovery and the assembly of cofactor-dependent multienzyme systems. Herein, we report a polyelectrolyte-assisted encapsulation approach (PAEA) that enables two cascades with four oxidoreductases and two nicotinamide adenine dinucleotide (phosphate) (NAD(P)H) cofactors co-encapsulated in BioHOF-1 with excellent cargo loading and over 100 % cascade activity. The key role of the polyelectrolyte is to coat enzymes and tether NAD(P)H, thus interacting with HOF monomers in place of enzymes, avoiding the destruction of enzymes by HOF monomers. The versatility and efficiency of PAEA are further illustrated by an HOF-101-based bio-nanoreactor. Moreover, the immobilization by PAEA makes enzymes and NAD(P)H display excellent stability and recyclability. This study has demonstrated a facile and versatile PAEA for fabricating cofactor-dependent multienzyme cascade nanoreactors with HOFs.     

Electrochemical oxidation of organic pollutants for the wastewater treatment: direct and indirect processes

In recent years, there has been increasing interest in finding innovative solutions for the efficient removal of contaminants from water, soil and air. The present tutorial review summarizes the results of an extensive selection of papers dealing with electrochemical oxidation, which is proposed as an alternative for treating polluted wastes. Both the direct and indirect approaches are considered, and the role of electrode materials is discussed together with that of other experimental parameters. Apart from discussing the possibility of removing selected contaminants from water using different anodes, efficiency rates for pollutant removal have been collected, the dependence of these rates on operational conditions advantages and disadvantages determining the further full-scale commercial application.     

Enzymatic Approach to and Odor Description of the Twelve Enantiomerically Pure Isomers of Pelargene®

Pelargene^® is a commercial fragrance sold as a mixture of three regioisomeric pyran derivatives ( 1 – 3 ). The enantiomers of each of the two possible diastereoisomers of 1 – 3 were prepared by means of a biocatalyzed approach, and the odor properties of the twelve isolated stereoisomers were evaluated.     

Review of the QuEChERS method for the analysis of organic pollutants: Persistent organic pollutants,polycyclic aromatic hydrocarbons,and pharmaceuticals

In multi-residue pesticide analysis, the quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction method has replaced less efficient traditional extraction methods due to its many advantages. In addition to pesticide analysis, this method has been widely used for the detection and analysis of pharmaceuticals, polycyclic aromatic hydrocarbons (PAHs), and several persistent organic pollutants (POPs), including dioxins, polychlorinated biphenyls, perfluoroalkyl substances, and brominated flame retardants in food, biological, and environmental matrices. The analysis of PAHs and POPs is challenging due to the properties of the target compounds and their low concentrations in complex matrices. This review summarizes previously reported the QuEChERS extraction approaches to the analysis of a wide range of analytes. The QuEChERS approaches, which include dispersive solid phase extraction (d-SPE), have generally been combined with either gas chromatography–mass spectrometry (GC–MS) or liquid chromatography–mass spectrometry (LC–MS) analysis. Further on, in recent years, GC and LC-tandem mass spectrometry has been utilized with the QuEChERS extraction due to its high selectivity, sensitivity, and specificity. This enables the extraction methods for target analytes to be modified through the selection of different extraction solvents, salt formulations, and buffers for salting-out partitioning and the selection of different d-SPE and SPE sorbents for the clean-up process. The most significant advantage of this method is that concentration steps are not required. This review aims to provide an up-to-date overview of information regarding the modification of extraction techniques based on target compounds and sample matrices.     

Very fast sorbent for organic dyes and pollutants

The increasing use of organic compounds endangering the environment encourages search for more efficient sorbents. While crude clay minerals are effective for the adsorption of cations, modified organoclays may adsorb negative and hydrophobic molecules. In this short communication, we present a very fast adsorbing organoclay based on montmorillonite with crystal violet pre-adsorbed up to neutralization of the negative charges. Sorption of erythrosin-B and 2,4,5-trichlorophenol to such organoclay reaches equilibrium in less than a minute, whereas with activated carbon, it took tens of minutes. The pseudo second-order kinetic coefficient for the process was at least two orders of magnitude smaller for the organoclay. Because sorption kinetics is an important factor in water purification, such fast sorbent might have broad environmental applications.     

Microarrayelectrodes for voltammetric and amperometric detection of organic pollutants

Disk and band shaped microarrayelectrodes (MAE) of gold and carbon have been developed. These electrodes can be used for electrochemical detection of different organic pollutants in organic and aqueous media. Differential pulse voltammetric, cyclic voltammetric and amperometric investigations at these MAE in stationary and flowing solutions with selected pesticides, polyaromatic hydrocarbons (PAH) and phenols have been carried out.     

Microarrayelectrodes for voltammetric and amperometric detection of organic pollutants

Disk and band shaped microarrayelectrodes (MAE) of gold and carbon have been developed. These electrodes can be used for electrochemical detection of different organic pollutants in organic and aqueous media. Differential pulse voltammetric, cyclic voltammetric and amperometric investigations at these MAE in stationary and flowing solutions with selected pesticides, polyaromatic hydrocarbons (PAH) and phenols have been carried out.     

Two-step enzymatic modification of solid-supported bergenin in aqueous and organic media

The natural flavonoid bergenin was directly immobilized onto carboxylic acid-functionalized controlled pore glass (carboxy-CPG) at 95% yield. Immobilized bergenin was brominated via chloroperoxidase in aqueous solution and then transesterified with vinyl butyrate in diisopropyl ether by subtilisin carslberg (SC) extracted into the organic solvent via ion-pairing. Enzymatic cleavage of 7-bromo-4-butyrylbergenin from carboxy-CPG (9.6% final yield) was accomplished using lipase B (LipB) in an aqueous/organic mixture (90/10 v/v of water/acetonitrile), demonstrating the feasibility of solid-phase biocatalysis of a natural product in aqueous and non-aqueous media.     

Catalytic electrochemical pre-treatment for the degradation of persistent organic pollutants

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Usage of coconut coir for sustainable production of high-valued carbon dots with discriminatory sensing aptitude toward metal ions

A novel, remunerative, green synthetic methodology without adding any kind of extra chemical reagent has been proposed for synthesizing highly fluorescent carbon dots (C-dots) by using waste coconut coir as the C source. The as-prepared C-dots possessed a quantum yield of 48% and displayed a high solubility rate in aqueous media. The fluorescence emission intensity of C-dots is found to be excitation dependent with high stability toward variation in the reaction medium. The bio-congenial performance of C-dots has been checked by employing quantitative multi-assay including fungus, plant, aquatic animals, and at the chromosomal level. It is notable that the antibacterial studies of as-prepared C-dots have presented appealing outcomes which advocated that C-dots prepared using coconut coir are biocompatible toward both Gram-positive and Gram-negative bacteria with no zone of inhibition in much higher concentration ranges. The as-prepared C-dots provided a simple sensing podium with high sensitivity and selectivity with a “turn-on and turn-off” fluorescence response for the detection of dual metal ions i.e. cadmium and copper ions in aqueous media with a detection limit of 0.18 nM and 0.28 nM, respectively. The practical utilities of the biocompatible C-dots have been checked over different water resources. The current work provided a simple, easy, bio-matched, harmless, rapid, and cost-effective sensory probe for wastewater remediation.     

基于色谱-质谱联用的新型有机污染物分析方法与技术

新型有机污染物是目前国内外关注的热点。在发现和分析新型有机污染物方面色谱-质谱联用技术发挥着至关重要的作用。本文对5类新型有机污染物(全氟化合物、药物、饮用水消毒副产物、农药转化产物和新农药、溴化阻燃剂)的主要色谱-质谱联用技术进行了介绍和评价,并对色谱-质谱联用的发展趋势进行了展望。     

Optimized cleanup methods of organic extracts for the determination of organic pollutants in biological samples

The analytical performances of various adsorbents used to clean up an organic extract of biological samples, particularly for the determination of polycyclic aromatic hydrocarbons (PAHs), polychlorobiphenyls (PCBs), both in mussel tissue and in krill samples, are critically compared. DDT and its degradation products, namely DDE and DDD, are also considered. Silica gel, alumina, aminopropyl-silica, cyanopropyl-silica, florisil, graphitized nonporous carbon and silica gel–alumina mixture (3:1) were used for column chromatography cleanup in combination with modified supercritical CO₂ as a mobile phase. Recovery and reproducibility were evaluated by analyzing standard solutions and standard reference materials containing various classes of pollutants. A silica gel–alumina mixture was found to be the most effective in the cleanup of organic extracts, allowing quantitative recoveries of all analytes to be obtained. Finally, the application of the optimized procedure to the determination of PCBs in Antarctic krill samples is presented.     

Fabricated metal zeolites as photocatalysts for the degradation of organic pollutants

Research on Chemical Intermediates - Zeolite frameworks provide an excellent host for metal ions like silver, gold, and copper. The modified zeolites were characterized using various spectroscopic...     

Biological technologies for the treatment of atmospheric pollutants

Most industrial activities emit atmospheric pollutants nowadays. Many of these activities are performed in stationary hotspots such as chemical industry facilities, wastewater and solid waste treatment plants. Other important stationary sources of gas pollutants include facilities for mining, intensive livestock farming and rendering. Volatile organic compounds (VOCs), odours and greenhouse gases are released from the above-mentioned sources, leading to issues related to global warming, health disorders and complaints to public administrations due to odour annoyance. When the release of atmospheric pollutants cannot be prevented, the sort of pollutants, their concentration and the flow rate of the waste gas emission must be characterised in order to select the most cost-effective treatment technology. Over the last decades, the use of biological technologies for the treatment of atmospheric pollutants has gradually increased due to their proven robustness, high cost-effectiveness and low environmental impact. The fundamentals of the most commonly implemented biological technologies in industrial applications (biofiltration, biotrickling filtration, bioscrubbing and activated sludge diffusion) are described in this work. The latest findings in the field of biological technologies for air pollution control are also presented and discussed.