École Supérieure de Chimie Organique et Minérale

Production of biogas from different organic materials is a most interesting source of renewable energy. The biomethane potential (BMP) of these materials has to be determined to get insight in design parameters for anaerobic digesters. Although several norms and guidelines for BMP tests exist, inter-laboratory tests regularly show high variability of BMPs for the same substrate. A workshop was held in June 2015, in Leysin, Switzerland, with over 40 attendees from 30 laboratories around the world, to agree on common solutions to the conundrum of inconsistent BMP test results. This paper presents the consensus of the intense roundtable discussions and cross-comparison of methodologies used in respective laboratories. Compulsory elements for the validation of BMP results were defined. They include the minimal number of replicates, the request to carry out blank and positive control assays, a criterion for the test duration, details on BMP calculation, and last but not least criteria for rejection of the BMP tests. Finally, recommendations on items that strongly influence the outcome of BMP tests such as inoculum characteristics, substrate preparation, test setup, and data analysis are presented to increase the probability of obtaining validated and reproducible results.

iron - organomagnesium compounds - alkenyl halides - alkenylation - cross-coupling reaction - Z- or E-alkenes

Carbon-carbon cross-coupling reactions are among the most important processes in organic chemistry, and Suzuki-Miyaura reactions are among the most widely used protocols for the formation of carbon-carbon bonds. These reactions are generally catalyzed by soluble palladium complexes with various ligands. However, the use of toxic organic solvents remains a scientific challenge and an aspect of economical and ecological relevance. This Review will summarize various recently developed significant methods by which the Suzuki-Miyaura coupling was conducted in aqueous media, and analyzes if they are "real green" protocols.

Glucosinolates are a large group of plant secondary metabolites with nutritional effects, and are mainly found in cruciferous plants. After ingestion, glucosinolates could be partially absorbed in their intact form through the gastrointestinal mucosa. However, the largest fraction is metabolized in the gut lumen. When cruciferous are consumed without processing, myrosinase enzyme present in these plants hydrolyzes the glucosinolates in the proximal part of the gastrointestinal tract to various metabolites, such as isothiocyanates, nitriles, oxazolidine-2-thiones, and indole-3-carbinols. When cruciferous are cooked before consumption, myrosinase is inactivated and glucosinolates transit to the colon where they are hydrolyzed by the intestinal microbiota. Numerous factors, such as storage time, temperature, and atmosphere packaging, along with inactivation processes of myrosinase are influencing the bioavailability of glucosinolates and their breakdown products. This review paper summarizes the assimilation, absorption, and elimination of these molecules, as well as the impact of processing on their bioavailability.

Any old iron: Two efficient iron-catalyzed cross-coupling reactions between aryl Grignard reagents and alkyl bromides were developed that are suitable for large-scale applications. The first procedure uses iron acetylacetonate and involves a cooperative effect between the two ligands N,N,N′,N′-tetramethylethylenediamine (TMEDA) and hexamethylenetetraamine (HMTA), while the second procedure uses [(FeCl3)2(tmeda)3] as catalyst. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2007/z700742_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Biobased production of furfural has been known for decades. Nevertheless, bioeconomy and circular economy concepts is much more recent and has motivated a regain of interest of dedicated research to improve production modes and expand potential uses. Accordingly, this review paper aims essentially at outlining recent breakthroughs obtained in the field of furfural production from sugars and polysaccharides feedstocks. The review discusses advances obtained in major production pathways recently explored splitting in the following categories: (i) non-catalytic routes like use of critical solvents or hot water pretreatment, (ii) use of various homogeneous catalysts like mineral or organic acids, metal salts or ionic liquids, (iii) feedstock dehydration making use of various solid acid catalysts; (iv) feedstock dehydration making use of supported catalysts, (v) other heterogeneous catalytic routes. The paper also briefly overviews current understanding of furfural chemical synthesis and its underpinning mechanism as well as safety issues pertaining to the substance. Eventually, some remaining research topics are put in perspective for further optimization of biobased furfural production.

At -40°C aryl iodides that contain other functional groups can be selectively converted into Grignard reagents, which react with electrophiles such as benzaldehyde in the usual manner [Eq. (a)]. Aryl bromides and iodides that are immobilized as esters on a Wang resin behave analogously.

Atmospheric oxygen was used for the first time as an oxidant in metal-catalyzed homocoupling of Grignard reagents. These manganese- or iron-catalyzed reactions are efficient, cheap, and eco-friendly. They are applicable to the large-scale synthesis of symmetrical conjugated compounds.

Encapsulation of bioactive materials and drugs using the emulsion electrospinning method.

Iron-catalyzed homo-coupling of simple and functionalized arylmagnesium reagents is described. The reaction is highly chemoselective (CN, COOEt and NO(2) groups are tolerated). The procedure was used to perform intramolecular couplings. This cyclization reaction is the key step of the total synthesis of the N-methylcrinasiadine.

Lignin nanomaterials have emerged as a promising alternative to fossil-based chemicals and products for some potential added-value applications, which benefits from their structural diversity and biodegradability. This review elucidates a perspective in recent research on nanolignins and their nanocomposites. It summarizes the different nanolignin preparation methods, emphasizing anti-solvent precipitation, self-assembly and interfacial crosslinking. Also described are the preparation of various nanocomposites by the chemical modification of nanolignin and compounds with inorganic materials or polymers. Additionally, advances in numerous potential high-value applications, such as use in food packaging, biomedical, chemical engineering and biorefineries, are described.

The application of strong electric fields in gases, water and organic liquids has been studied for several years, because of its importance in electrical transmission processes and its practical applications in biology, chemistry, and electrochemistry. More recently, electrical discharges have been investigated and are being developed in water for enhancing the extraction of biocompounds from different raw materials. This paper reviews the current status of research on the application of high voltage electrical discharges for promoting cell disruption in aqueous suspension of biological materials, with particular emphasis on application to biocompounds extraction.

The South American plant Stevia rebaudiana Bertoni is a great source of noncaloric sweeteners (steviol glycosides), mainly concentrated in its leaves, but also has important antioxidant compounds (vitamin C, polyphenols, chlorophylls, and carotenoids) and other important macro- and micronutrients such as folic acid and all of the essential amino acids except tryptophan. Traditionally, conventional methods have been used to recover nutritionally valuable compounds from plant food matrices. However, nowadays, the need for obtaining greener, sustainable, and viable processes has led both food industries and food scientists to develop new processes in full correspondence with the green extraction concept. This review focuses on some of the most promising nonconventional and emerging technologies, which may constitute a potential alternative to conventional methods or even could be combined to obtain a synergistic effect, thus reducing extraction time as well as solvent consumption and avoiding the use of toxic solvents.

The first iron-catalyzed cross-coupling reaction between alkenyl Grignard reagents and n- or s-alkyl bromides is described. The reaction is stereoselective and takes place in the presence of 5 mol % of [Fe(acac)3/TMEDA/HMTA] (1:2:1) under very mild conditions (THF, 0 degrees C, 45 min).

Abstract Numerous products, such as polymers, chemicals or pharmaceuticals and ultra-pure metals, which often do not actually contain chlorine, are produced using either chlorine or its derivatives. They are essential in all industrial sectors and in our daily lives. New chlorine production units have adopted the membrane electrolytic process, but the century-old diaphragm and mercury processes retain their high-performance characteristics when appropriately modernised and improved.

The most important model catalytic reaction to test the catalytic activity of metal nanoparticles is the reduction of 4-nitrophenol to 4-aminophenol by sodium borohydride as it can be precisely monitored by UV–vis spectroscopy with high accuracy. This work presents the catalytic reduction of 4-nitrophenol (4-Nip) to 4-aminophenol (4-Amp) in the presence of Pd nanoparticles and sodium borohydride as reductants in water. We first evaluate the kinetics using classical pseudo first-order kinetics. We report the effects of different initial 4-Nip and NaBH4 concentrations, reaction temperatures, and mass of Pd nanoparticles used for catalytic reduction. The thermodynamic parameters (activation energy, enthalpy, and entropy) were also determined. Results show that the kinetics are highly dependent on the reactant ratio and that pseudo first-order simplification is not always fit to describe the kinetics of the reaction. Assuming that all steps of this reaction proceed only on the surface of Pd nanoparticles, we applied a Langmuir−Hinshelwood model to describe the kinetics of the reaction. Experimental data of the decay rate of 4-nitrophenol were successfully fitted to the theoretical values obtained from the Langmuir–Hinshelwood model and all thermodynamic parameters, the true rate constant k, as well as the adsorption constants of 4-Nip, and BH4− (K4-Nip and KBH4−) were determined for each temperature.

Nicht zum alten Eisen: Zwei effiziente eisenkatalysierte Kreuzkupplungen von Aryl-Grignard-Reagentien mit Alkylbromiden eignen sich für die Anwendung im großen Maßstab. Das erste Verfahren nutzt Eisenacetylacetonat und einen kooperativen Effekt der Liganden N,N,N′,N′-Tetramethylethylendiamin (TMEDA) und Hexamethylentetraamin (HMTA), im zweiten dient [(FeCl3)2(tmeda)3] als Katalysator. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2001/2007/z700742_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

A rationale of reaction metrics for green chemistry is presented, along with relationships between them. Starting from the definition of mass intensity, it is easy to find the mathematical formula giving the reaction metrics, such as the E-factor, versus the parameters of a reaction sequence: yields of each step, atom economy, excess of reactants, mass of auxiliaries and possibly their retrieval. For a complex mixed linear and convergent sequence, such a rationale could be expressed with a mathematical formula as simple as eqn (24). Based on experimental data, the application of such a methodology was proved to be useful to quantify the influence of each parameter of a chemical process on the environmental impact.

Brewers’ spent grains constitute a valuable byproduct of the beer industry. They are characterized by a rich nutritional composition consisting of around 70% lignocellulosic fibrous material, 20% proteins, 10% lipids, in addition to vitamins, minerals, amino acids, and phenolic compounds. These spent grains are produced in large amounts all through the year, are cheap, and lack economically feasible applications. Nowadays, 70% of these spent grains are used as animal feed, 10% are used for biogas production, and the remaining 20% are disposed in landfills. Due to the aforementioned facts, alternative uses of the brewers’ spent grains are highly sought-after. In fact, this nutrient-rich industrial by-product makes it a very good candidate for valorization through biotechnological processing, particularly microbial fermentation. After applying the needed pretreatments, using brewers’ spent grains as a substrate in submerged and solid-state fermentation of different microorganisms leads to the production of various value-added compounds such as organic acids, amino acids, volatile fatty acids, enzymes, vitamins, second-generation biofuels and other products.

Olefin oxidation with molecular oxygen, promoted by a transition metal catalyst and a thiophenol, involved C=C bond cleavage into the corresponding carbonyl derivatives. This new reaction proceeds under one atmosphere of oxygen, at room temperature, in the presence of an excess of thiophenol and a catalyst such as MnL(2) 3a or VClL(2) 3c. It was applied to aromatic and aliphatic olefins, as well as to functionalized or unfunctionalized acyclic compounds, providing the corresponding ketones and aldehydes in up to 98% yield. The synthetic interest of this catalytic oxidation was illustrated by a one-step preparation of the fragrance (-)-4-acetyl-1-methylcyclohexene 7e in 73% isolated yield. The C=C bond cleavage probably results from a catalyzed decomposition of the beta-hydroperoxysulfide intermediate 12 that is formed by the radical addition of thiophenol to the olefin in the presence of oxygen. Although an excess of the thiophenol was used, it was transformed into the disulfide which could then be reduced without purification in 83% overall yield, thereby allowing for recycling. In addition, the C=C bond cleavage under oxygen could be promoted by catalytic quantities of the thiyl radical, generated by photolysis of the disulfide; thus, in the presence of 0.1 equiv of bis(4-chlorophenyl) disulfide 4b and 5% of the manganese complex 3a, trans-methylstilbene 1b gave, under radiation, benzaldehyde 6a and acetophenone 7a in up to 95% yield. This new reaction offers an alternative to the classical C=C bond cleavage procedures, and further developments in the fields of bioinorganic and environmental chemistry are likely.