A Landscape of Lignocellulosic Biopolymer Transformations into Valuable Molecules by Heterogeneous Catalysis in C'Durable Team at IRCELYON.

This review article highlights part of the research activity of the C'Durable team at IRCELYON in the field of sustainable chemistry. This review presents a landscape of the work performed on the valorization of lignocellulosic biopolymers. These studies intend to transform cellulose, hemicellulose and lignin into valuable molecules. The methodology usually consists in evaluating the behavior of the biopolymers in the absence of catalyst under various conditions (solvent, temperature), and then to assess the influence of a catalyst, most often a heterogeneous catalyst, on the reactivity. The most significant results obtained on the upgrading of cellulose and lignin, which have been mainly investigated in the team, will be presented with an opening on studies involving raw lignocellulose.

Green Synthesis of CeO2 Nanoparticles from the Abelmoschus esculentus Extract: Evaluation of Antioxidant, Anticancer, Antibacterial, and Wound-Healing Activities.

Metal oxide nanoparticles synthesized by the biological method represent the most recent research in nanotechnology. This study reports the rapid and ecofriendly approach for the synthesis of CeO2 nanoparticles mediated using the Abelmoschus esculentus extract. The medicinal plant extract acts as both a reducing and stabilizing agent. The characterization of CeO2 NPs was performed by scanning electron microscopy (SEM), X-ray diffraction (XRD), ultraviolet-visible spectroscopy (UV-Vis), and Fourier transform infrared spectroscopy (FTIR). The in vitro cytotoxicity of green synthesized CeO2 was assessed against cervical cancerous cells (HeLa). The exposure of CeO2 to HeLa cells at 10-125 µg/mL caused a loss in cellular viability against cervical cancerous cells in a dose-dependent manner. The antibacterial activity of the CeO2 was assessed against S. aureus and K. pneumonia. A significant improvement in wound-healing progression was observed when cerium oxide nanoparticles were incorporated into the chitosan hydrogel membrane as a wound dressing.

Recent advances in lignocellulose prior-fractionation for biomaterials, biochemicals, and bioenergy.

Due to over-consumption of fossil resources and environmental problems, lignocellulosic biomass as the most abundant and renewable materials is considered as the best candidate to produce biomaterials, biochemicals, and bioenergy, which is of strategic significance and meets the theme of Green Chemistry. Highly efficient and green fractionation of lignocellulose components significantly boosts the high-value utilization of lignocellulose and the biorefinery development. However, heterogeneity of lignocellulosic structure severely limited the lignocellulose fractionation. This paper offers the summary and perspective of the extensive investigation that aims to give insight into the lignocellulose prior-fractionation. Based on the role and structure of lignocellulose component in the plant cell wall, lignocellulose prior-fractionation can be divided into cellulose-first strategy, hemicelluloses-first strategy, and lignin-first strategy, which realizes the selective dissociation and transformation of a component in lignocellulose. Ultimately, the challenges and opportunities of lignocellulose prior-fractionation are proposed on account of the existing problems in the biorefining valorization.

Initiatives to broaden safety concerns in anaesthetic practice: The green operating room.

The health sector is a major contributor to climate change through its large carbon footprint. Hospitals are highly energy and resource intensive. Operating rooms (ORs) contribute to a major part of these emissions because of anaesthetic gases, energy-intensive equipment and waste. Besides initiatives aimed to mitigate hospitals' climate footprints, health care professionals need to be involved in this process by changing their professional and personal behaviours without compromising the quality of care. Education on metrics (greenhouse gases), concepts (life cycle) and strategies to reduce the health care footprint would help professionals to commit themselves to the issue. The 5R's rule (reduce, reuse, recycle, rethink and research) used to promote an environmentally friendly way of life can be applied to the medical field and especially to the operating room and anaesthesia. When applied in the ORs, these strategies help question the use of disposable devices, attires and packaging, as well as our professional and personal behaviour. Greening the ORs requires the engagement of all professionals as well as other departments (pharmacy, hygiene) and management. Economic and social co-benefits are expected from this process.

Genetic and metabolic engineering challenges of C1-gas fermenting acetogenic chassis organisms.

Unabated mining and utilisation of petroleum and petroleum resources and their conversion to essential fuels and chemicals have drastic environmental consequences, contributing to global warming and climate change. In addition, fossil fuels are finite resources, with a fast-approaching shortage. Accordingly, research efforts are increasingly focusing on developing sustainable alternatives for chemicals and fuels production. In this context, bioprocesses, relying on microorganisms, have gained particular interest. For example, acetogens use the Wood-Ljungdahl pathway to grow on single carbon C1-gases (CO2 and CO) as their sole carbon source and produce valuable products such as acetate or ethanol. These autotrophs can, therefore, be exploited for large-scale fermentation processes to produce industrially relevant chemicals from abundant greenhouse gases. In addition, genetic tools have recently been developed to improve these chassis organisms through synthetic biology approaches. This review will focus on the challenges of genetically and metabolically modifying acetogens. It will first discuss the physical and biochemical obstacles complicating successful DNA transfer in these organisms. Current genetic tools developed for several acetogens, crucial for strain engineering to consolidate and expand their catalogue of products, will then be described. Recent tool applications for metabolic engineering purposes to allow redirection of metabolic fluxes or production of non-native compounds will lastly be covered.

Preparation of value-added metal-organic frameworks for high-performance liquid chromatography. Towards green chromatographic columns.

This work applies the concepts of green chemistry, where polyethylene terephthalate (PET) bottles were used as the acid-dicarboxylic linker source for the synthesis of MIL-53(Al) metal organic frameworks (MOFs) and then used as a stationary phase for the separation of various solutes and compared with MIL-53(Al) synthesized from traditional terephthalic acid. Both synthesized MIL-53(Al) MOFs were characterized by scanning electron microscopy (SEM), FT-IR, X-ray diffraction (XRD), thermogravimetric analysis (TGA), and specific surface area analysis. Eight groups of standard analytes in addition to real samples were tested to evaluate the separation performance of the MIL-53(Al) packed columns in HPLC under various chromatographic conditions. Based on elution order of the studied compounds and the effects of mobile phase composition, the working mechanism was reversed phase mode in the presence of size-exclusion effects for large molecules, which exceeded the dynamic diameter of MIL-53(Al) (~7.6 Å). The effects of stationary phase sieving, mobile phase flow rate and composition, injected sample mass, and temperature were investigated relative to the chromatographic behavior of MIL-53(Al). MIL-53(Al) particle sieving before packing reduced peak broadening and significantly enhanced the chromatographic performance of the prepared columns up to 2.26 times relative to the number of theoretical plates. The MIL-53(Al) packed columns offered high-resolution separation for all studied mixtures with Rs >2 and good stability and long-term durability. At optimal conditions, the prepared columns exhibited efficiencies between 5600-63200 plates m-1. Higher efficiencies were observed for alkylbenzenes and polyaromatic hydrocarbons as the organic linker in the MIL-53(Al) structure, which improved retention and separation of aromatics through π-π interactions. Thermodynamic parameters including ΔH, ΔS, and ΔG for the transfer of analyte from the mobile phase to the MIL-53(Al) stationary phase were studied. Compared with previously cited MOFs packed columns, the present MIL-53(Al) columns gave comparable selectivity and much better efficiency for most of the studied chemicals at optimum conditions, indicating the feasibility of MIL-53(Al) as a stationary phase for HPLC applications.

Review on Green Synthesis of Silver Nanoparticles through Plants.

Nature has the potential to reduce metal salts to their relative nanoparticles. Traditionally, physical and chemical methods were used for the synthesis of nanoparticles but due to the use of toxic chemicals, non-ecofriendly methods and other harmful effects, green chemistry approaches are now employed for synthesizing nanoparticles which are basically the most cost effective, ecofriendly and non-hazardous methods. In this review, we aimed to evaluate and study the details of various mechanisms used for green synthesis of silver nanoparticles from plants, their size, shape and potential applications. A total of 150 articles comprising both research and review articles from 2009 to 2019 were selected and studied in detail to get in-depth knowledge about the synthesis of silver nanoparticles specifically through green chemistry approaches. Silver ions and their salts are well known for their antimicrobial properties and have been used in various medical and non-medical applications since the emergence of human civilization. Miscellaneous attempts have been made to synthesize nanoparticles using plants and such nanoparticles are more efficient and beneficial in terms of their antibacterial, antifungal, antioxidant, anti-biofilm and cytotoxic activities than nanoparticles synthesized through physical and chemical processes. Silver nanoparticles have been studied as an important research area due to their specific and tunable properties and their application in the field of biomedicine such as tissue and tumor imaging and drug delivery. These nanoparticles can be further investigated to find out their antimicrobial potential in cell lines and animal models.

Nitrilase: a promising biocatalyst in industrial applications for green chemistry.

Nitrilases are widely distributed in nature and are able to hydrolyze nitriles into their corresponding carboxylic acids and ammonia. In industry, nitrilases have been used as green biocatalysts for the production of high value-added products. To date, biocatalysts are considered to be important alternatives to chemical catalysts due to increasing environmental problems and resource scarcity. This review provides an overview of recent advances of nitrilases in aspects of distribution, enzyme screening, molecular structure and catalytic mechanism, protein engineering, and their potential applications in industry.

Designing for a green chemistry future.

The material basis of a sustainable society will depend on chemical products and processes that are designed following principles that make them conducive to life. Important inherent properties of molecules need to be considered from the earliest stage-the design stage-to address whether compounds and processes are depleting versus renewable, toxic versus benign, and persistent versus readily degradable. Products, feedstocks, and manufacturing processes will need to integrate the principles of green chemistry and green engineering under an expanded definition of performance that includes sustainability considerations. This transformation will require the best of the traditions of science and innovation coupled with new emerging systems thinking and systems design that begins at the molecular level and results in a positive impact on the global scale.

Deep eutectic solvents for biocatalytic transformations: focused lipase-catalyzed organic reactions.

Biocatalysis is a green and sustainable technology for which the ideal solvent should be nontoxic, biocompatible, biodegradable, and sustainable, in addition to supporting high enzyme activity and stability. Deep eutectic solvents (DESs), a novel class of green solvents, have recently emerged as excellent alternatives for use in various biocatalytic reactions and, in particular, in lipase-catalyzed reactions with enzymes. This review discusses the achievements that have been made so far in the use of DESs as reaction media for lipase-catalyzed reactions. In addition, the application of DESs in esterification, transesterification, and amidation reactions with isolated or immobilized biocatalysts, toward enabling the synthesis of biodiesels, sugar esters, phenolipids, and fatty acyl ethanolamides, is summarized, while advances in lipase-catalyzed chemoenzymatic epoxidation reactions, C-C bond-forming Aldol reactions, and hydrolysis reactions in DESs are also discussed. This review also summarize some remaining questions concerning the use of DESs, including the intriguing role of water as a cosolvent in biocatalytic reactions carried out in DESs, and the relationship between the nature of the DESs and their influence on the enzyme stability and activity at the molecular level.

Biosurfactant: A new frontier for greener technology and environmental sustainability.

Petroleum hydrocarbons, oil, heavy metals pollution is becoming additional severe problem due to the growing call for crude oil and crude oil products related products in several fields of application. Such pollution have fascinated much considerations and attractions as it leads to ecological damages in both marines, aquatic and terrestrial ecosystems. Thus, different techniques including chemical surfactants and complex technologies have been proposed for their clean up from the environment, which in turn has detrimental effects on the environment. As of late, biosurfactant compounds have added much deliberation since they are considered as a reasonable option and eco-accommodating materials for remediation technology. The present society is confronting a few difficulties of usage, authorizing ecological protection and environmental change for the next generations. Biosurfactants hold the special property of minimizing and reducing the interfacial tension of liquids. Such features endure biosurfactants to afford a major part in emulsification, de-emulsification, biodegradability, foam formation, washing performance, surface activity, and detergent formulation, which have potential applications in the diverse industrial set-up. Conversations on cost-effective technologies, renewable materials, novel synthesis, downstream, upstream, emerging characterization techniques, molecular, and genetical engineering are substantial to produce biosurfactant of quality and quantity. Therefore, greater attention is being paid to biosurfactant production by identifying their environmental, and biotechnological applications. Be that as it may, the extravagant cost drew in with biosurfactants biotechnological synthesis and recovery can hamper their application in those areas. Notwithstanding these costs, biosurfactants can be used as these parts shows outstandingly high benefits that can at present beat the expenses incurred in the initial purification and downstream processes. Biosurfactant production by microorganisms is relatively considered one of the crucial know-how for improvement, growth, advancement, and environmental sustainability of the 21st century. There is a developing conversation around environmental safety and the significant role that biosurfactants will progressively play soon, for instance, the use of renewable by-products as substrates, potential reduction, re-use and recycling of waste and waste products. The review confers the usefulness of biosurfactants in the removal of environmental contaminants and, consequently, expanding environmental safety and drive towards greener technology.

An overview of the Brazilian contributions to Green Analytical Chemistry.

Green Analytical Chemistry (GAC) is a research field that seeks for more sustainable analytical approaches to minimize the toxicity and amounts of wastes without hindering the analytical performance. This is a trend in Analytical Chemistry worldwide and because of the diversity of innovations on this subject, Brazil stands out as the third in the list of the main contributors to GAC, with ca. 11.2% of the published articles. Significant innovations and interesting applications in several fields have been presented and Brazil is continuously moving from Chemistry to Green Chemistry also in the Analytical Chemistry field. Selected contributions for sample preparation, spectro- and electroanalysis, separation techniques, chemometrics, and also procedures for point-of-care measurements are critically reviewed.

Recent progress in the industrial and biomedical applications of tragacanth gum: A review.

Natural polymers have distinct advantages over synthetic polymers because of their abundance, biocompatibility, and biodegradability. Tragacanth gum, an anionic polysaccharide, is a natural polymer which is derived from renewable sources. As a biomaterial, tragacanth gum has been used in industrial settings such as food packaging and water treatment, as well as in the biomedical field as drug carriers and for wound healing purposes. The present review provides an overview on the state-of-the-art in the field of tragacanth gum applications. The structure, properties, cytotoxicity, and degradability as well as the recent advances in industrial and biomedical applications of tragacanth gum are reviewed to offer a backdrop for future research.

Electrochemical Reduction of Carbon Dioxide to Value-Added Products: The Electrocatalyst and Microbial Electrosynthesis.

The electrochemical reduction of carbon dioxide (CO2 ) to value-added products obtains great attention and investigation worldwide in recent years. The commercialization of this green process relies on the progress of relating high-performance electrocatalysts and their feasibility with proper reactor design. The microbial electrosynthesis (MES) is an alternative route to reduce CO2 with electroactive bio-film electrode as catalyst. This review presents the research status and development of cathode catalysts, particularly focusing on the active sites and development tendency, for highly efficient electrochemical reduction CO2 from personal viewpoint. Some of our results are also presented to exhibit contributions. MES shows a similar process to the typical electrochemical reduction of CO2 . Their combination is an important trend, and the future research in this field is full of challenges and opportunities.

From biotechnology principles to functional and low-cost metallic bionanocatalysts.

Chemical, physical and mechanical methods of nanomaterial preparation are still regarded as mainstream methods, and the scientific community continues to search for new ways of nanomaterial preparation. The major objective of this review is to highlight the advantages of using green chemistry and bionanotechnology in the preparation of functional low-cost catalysts. Bionanotechnology employs biological principles and processes connected with bio-phase participation in both design and development of nano-structures and nano-materials, and the biosynthesis of metallic nanoparticles is becoming even more popular due to; (i) economic and ecologic effectiveness, (ii) simple one-step nanoparticle formation, stabilisation and biomass support and (iii) the possibility of bio-waste valorisation. Although it is quite difficult to determine the precise mechanisms in particular biosynthesis and research is performed with some risk in all trial and error experiments, there is also the incentive of understanding the exact mechanisms involved. This enables further optimisation of bionanoparticle preparation and increases their application potential. Moreover, it is very important in bionanotechnological procedures to ensure repeatability of the methods related to the recognised reaction mechanisms. This review, therefore, summarises the current state of nanoparticle biosynthesis. It then demonstrates the application of biosynthesised metallic nanoparticles in heterogeneous catalysis by identifying the many examples where bionanocatalysts have been successfully applied in model reactions. These describe the degradation of organic dyes, the reduction of aromatic nitro compounds, dehalogenation of chlorinated aromatic compounds, reduction of Cr(VI) and the synthesis of important commercial chemicals. To ensure sustainability, it is important to focus on nanomaterials that are capable of maintaining the important green chemistry principles directly from design inception to ultimate application.

Green recipes to quinoline: A review.

The quinoline core possesses a vast number of biological activities such as anticancer, antimalarial, antimicrobial, antifungal, antitubercular and antileishmanial. The conventional classical synthetic methods require the use of expensive and harsh conditions such as high temperature. Currently the scientific communities are searching new methodology to eliminate the use of chemicals, solvents and catalysts, which are hazardous to human health as well as to environment. This review provides a concise overview of new dimensions of green chemistry approaches in designing quinoline scaffold that would encourage the researchers towards green chemistry as well as future application of these greener, non-toxic, environment friendly methods in designing quinoline scaffold.

Bacterial laccases: promising biological green tools for industrial applications.

Multicopper oxidases (MCOs) are a pervasive family of enzymes that oxidize a wide range of phenolic and nonphenolic aromatic substrates, concomitantly with the reduction of dioxygen to water. MCOs are usually divided into two functional classes: metalloxidases and laccases. Given their broad substrate specificity and eco-friendliness (molecular oxygen from air as is used as the final electron acceptor and they only release water as byproduct), laccases are regarded as promising biological green tools for an array of applications. Among these laccases, those of bacterial origin have attracted research attention because of their notable advantages, including broad substrate spectrum, wide pH range, high thermostability, and tolerance to alkaline environments. This review aims to summarize the significant research efforts on the properties, mechanisms and structures, laccase-mediator systems, genetic engineering, immobilization, and biotechnological applications of the bacteria-source laccases and laccase-like enzymes, which principally include Bacillus laccases, actinomycetic laccases and some other species of bacterial laccases. In addition, these enzymes may offer tremendous potential for environmental and industrial applications.

Recent advances in the capillary electrophoresis analysis of antibiotics with capacitively coupled contactless conductivity detection.

This review describes briefly the high rate of counterfeiting of antimicrobial drugs with focus upon its immediate health consequences. The major part of this review encompasses accounts of the improvements achieved in the domain of miniaturization of capillary electrophoresis with capacitively coupled contactless conductivity detection (CE-C4D). The application of this principle into the development of portable devices as well as its application to counter the health-system-crippling phenomenon of counterfeit antibiotic formulations, are discussed in the context of developing countries.

Green Toxicology-Know Early About and Avoid Toxic Product Liabilities.

Toxicology uniquely among the life sciences relies largely on methods which are more than 40-years old. Over the last 3 decades with more or less success some additions to and few replacements in this toolbox took place, mainly as alternatives to animal testing. The acceptance of such new approaches faces the needs of formal validation and the conservative attitude toward change in safety assessments. Only recently, there is growing awareness that the same alternative methods, especially in silico and in vitro tools can also much earlier and before validation inform decision-taking in the product life cycle. As similar thoughts developed in the context of Green Chemistry, the term of Green Toxicology was coined to describe this change in approach. Here, the current developments in the alternative field, especially computational and more organo-typic cell cultures are reviewed, as they lend themselves to front-loaded chemical safety assessments. The initiatives of the Center for Alternatives to Animal Testing Green Toxicology Collaboration are presented. They aim first of all for forming a community to promote this concept and then for a cultural change in companies with the necessary training of chemists, product stewards and later regulators.