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Sustainable Chemistry in France
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Sustainable Chemistry in France

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Green Chemistry".

Deadline for manuscript submissions: closed (31 May 2022) | Viewed by 34527

Special Issue Editors

Dr. Pascal Isnard

E-Mail Website
Guest Editor
Chairman of the Sustainable Chemistry Group at the French Chemical Society (SCF), ex-Sanofi, Paris, France
Interests: sustainable chemistry; industrial chemistry
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Jerome Guillard

E-Mail Website
Guest Editor
UMR 7285, Institut de Chimie des Milieux et Matériaux de Poitiers (IC2MP), Université de Poitiers, 86073 Poitiers, France
Interests: organic chemistry; medicinal chemistry; catalysis
Prof. Dr. Franck Launay

E-Mail Website
Guest Editor
UMR 7197, Laboratoire de Réactivité de Surface (LRS), Centre National de la Recherche Scientifique, Sorbonne Université, 75252 Paris, France
Interests: utilization of porous materials for the design of selective and stable catalysts; valorization of alkenes, CO2, and biomass; supported homogeneous catalysts (organocatalysts, metal complexes, polyoxometalates or even enzymes); supported heterogeneous catalysts (zero-valent metal/metal oxide colloids)
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Jean-Hugues Renault

E-Mail Website
Guest Editor
ICMR UMR 7312, Université de Reims Champagne-Ardenne, 51097 Reims, France
Interests: natural product chemistry; separative sciences; process engineering; computer assisted structure elucidation and chemoinformatics

Special Issue Information

Dear colleagues,

In the context of sustainable development, chemistry is of vital importance at two levels: the reduction in the environmental footprint of its own activity; and the ability to offer solutions capable of meeting the challenges of society. Sustainable chemistry is thus a reality which improves our everyday life. Many researchers are active in this domain searching for new products and processes, using less resources and energy and protecting human health and the environment. As described by Anastas and Warner in the 12 principles of Green Chemistry, this may be achieved in different ways, e.g., using renewable/bio-based resources, and/or new or improved technologies and processes.

The present Special Issue aims to review the work done in this field in French laboratories.

Dr. Pascal Isnard
Prof. Dr. Jerome Guillard
Prof. Dr. Franck Launay
Prof. Dr. Jean-Hugues Renault
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • sustainable chemistry
  • green chemistry
  • bio-based chemistry
  • renewable resources
  • process improvement
  • France

Published Papers (12 papers)

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Research

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15 pages, 8906 KiB  
Article
Mechanochemistry and Eco-Bases for Sustainable Michael Addition Reactions
by Yvette Lock Toy Ki, Armelle Garcia, Franck Pelissier, Tomasz K. Olszewski, Alicja Babst-Kostecka, Yves-Marie Legrand and Claude Grison
Molecules 2022, 27(10), 3306; https://doi.org/10.3390/molecules27103306 - 21 May 2022
Cited by 5 | Viewed by 1739
Abstract
The Michael addition reaction was revisited with a full focus on sustainability combined with efficiency, using mechanochemistry in mild conditions. First, the synthesis of cyclopentenone derivatives was chosen as a model reaction to find optimal conditions in mechanochemistry while using classical but weak [...] Read more.
The Michael addition reaction was revisited with a full focus on sustainability combined with efficiency, using mechanochemistry in mild conditions. First, the synthesis of cyclopentenone derivatives was chosen as a model reaction to find optimal conditions in mechanochemistry while using classical but weak bases. The reaction was efficient (84–95% yields), fast (2–6 h), solvent free, and required 0.1 equivalent of base. Aiming to reach greener conditions, classical bases were then replaced using new bio-sourced bases, called Eco-bases, that were easily prepared from plants and led to heterogeneous catalysts. The composition and structure of Eco-bases were characterized by MP-AES, XRPD, EBSD/EDS, HRTEM/EDX and ion chromatography. Interestingly, a high ratio of potassium was observed with the presence of K2Ca(CO3)2 for the most effective Eco-base. The new Eco-bases were used for the mechanical-assisted construction of functionalized alkenone derivatives. The versatility of the method has been successfully applied with good to excellent yields to different Michael donors and acceptors. Eco-bases were recycled and reused four times with the same performances. Combining Eco-bases and mechanochemistry in Michael addition reactions allowed reaching a maximum degree of sustainability (efficient, rapid, low catalyst loading, solvent-free reactions with bio-sourced catalysts) and participating in the development of mechanochemistry in sustainable chemistry. Full article
(This article belongs to the Special Issue Sustainable Chemistry in France)
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19 pages, 2890 KiB  
Article
Green and Effective Preparation of α-Hydroxyphosphonates by Ecocatalysis
by Pola Cybulska, Yves-Marie Legrand, Alicja Babst-Kostecka, Sébastien Diliberto, Anna Leśniewicz, Erwan Oliviero, Valérie Bert, Clotilde Boulanger, Claude Grison and Tomasz K. Olszewski
Molecules 2022, 27(10), 3075; https://doi.org/10.3390/molecules27103075 - 11 May 2022
Cited by 5 | Viewed by 2109
Abstract
A green and effective approach for the synthesis of structurally diversed α-hydroxyphosphonates via hydrophosphonylation of aldehydes under solventless conditions and promoted by biosourced catalysts, called ecocatalysts “Eco-MgZnOx” is presented. Ecocatalysts were prepared from Zn-hyperaccumulating plant species Arabidopsis halleri, with simple and benign [...] Read more.
A green and effective approach for the synthesis of structurally diversed α-hydroxyphosphonates via hydrophosphonylation of aldehydes under solventless conditions and promoted by biosourced catalysts, called ecocatalysts “Eco-MgZnOx” is presented. Ecocatalysts were prepared from Zn-hyperaccumulating plant species Arabidopsis halleri, with simple and benign thermal treatment of leaves rich in Zn, and without any further chemical treatment. The elemental composition and structure of Eco-MgZnOx were characterized by MP–AES, XRPD, HRTEM, and STEM–EDX techniques. These analyses revealed a natural richness in two unusual and valuable mixed zinc–magnesium and iron–magnesium oxides. The ecocatalysts were employed in this study to demonstrate their potential use in hydrophosphonylation of aldehydes, leading to various α-hydroxyphosphonate derivatives, which are critical building blocks in the modern chemical industry. Computational chemistry was performed to help discriminate the role of some of the constituents of the mixed oxide ecocatalysts. High conversions, broad substrate scope, mild reaction conditions, and easy purification of the final products together with simplicity of the preparation of the ecocatalysts are the major advantages of the presented protocol. Additionally, Eco-MgZnOx-P could be recovered and reused for up to five times. Full article
(This article belongs to the Special Issue Sustainable Chemistry in France)
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14 pages, 797 KiB  
Article
Unprecedented Biodegradable Cellulose-Derived Polyesters with Pendant Citronellol Moieties: From Monomer Synthesis to Enzymatic Degradation
by Aihemaiti Kayishaer, Sami Fadlallah, Louis M. M. Mouterde, Aurélien A. M. Peru, Yasmine Werghi, Fanny Brunois, Quentin Carboué, Michel Lopez and Florent Allais
Molecules 2021, 26(24), 7672; https://doi.org/10.3390/molecules26247672 - 18 Dec 2021
Cited by 11 | Viewed by 2560
Abstract
Levoglucosenone (LGO) is a cellulose-derived molecule that is present commercially on a multi-ton/year scale. Taking advantage of the α,β-conjugated ketone of LGO, a new citronellol-containing 5-membered lactone (HBO-citro) was synthesized through a one-pot two-step pathway involving oxa-Michael addition and Baeyer-Villiger oxidation. The solvent-free [...] Read more.
Levoglucosenone (LGO) is a cellulose-derived molecule that is present commercially on a multi-ton/year scale. Taking advantage of the α,β-conjugated ketone of LGO, a new citronellol-containing 5-membered lactone (HBO-citro) was synthesized through a one-pot two-step pathway involving oxa-Michael addition and Baeyer-Villiger oxidation. The solvent-free treatment of HBO-citro with NaBH4 at room temperature led to the full reduction of the lactone moiety which gave a novel fully renewable triol monomer having a citronellol side chain (Triol-citro). Noticeably, by simply changing the reducing agent, temperature and reaction duration, the partial reduction of HBO-citro can be achieved to yield a mixture of 5- and 6-membered Lactol-citro molecules. Triol-citro was chosen to prepare functional renewable polyesters having citronellol pendant chains via polycondensation reactions with diacyl chlorides having different chain lengths. Good thermal stability (Td5% up to 170 °C) and low glass transition temperatures (as low as −42 °C) were registered for the polyesters obtained. The polymers were then hydrolyzed using a commercial lipase from Thermomyces lanuginosus (Lipopan® 50 BG) to assess their biodegradability. A higher degradation profile was found for the polyesters prepared using co-monomers (acyl chlorides) having longer chain lengths. This is likely due to the decreased steric hindrance around the ester bonds which allowed enhanced accessibility of the enzyme. Full article
(This article belongs to the Special Issue Sustainable Chemistry in France)
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25 pages, 23408 KiB  
Article
Development of Sustainable Chemistry in Madagascar: Example of the Valuation of CNSL and the Use of Chromones as an Attractant for Mosquitoes
by Miarintsoa Michaele Ranarijaona, Ny Aina Harivony Rambala Rakotomena, Mbolatiana Tovo Andrianjafy, Fenia Diane Ramiharimanana, Lydia Clarisse Herinirina, Niry Hasinandrianina Ramarosandratana, Benoit Briou, Pauline Fajardie, Patrick Mavingui, Estelle Métay, Voahangy Vestalys Ramanandraibe and Marc Lemaire
Molecules 2021, 26(24), 7625; https://doi.org/10.3390/molecules26247625 - 16 Dec 2021
Cited by 3 | Viewed by 2274
Abstract
This article describes a part of the results obtained from the cooperation between the University of Lyon1 (France) and the University of Antananarivo (Madagascar). It shows (among others) that useful research can be carried out in developing countries of the tropics if their [...] Read more.
This article describes a part of the results obtained from the cooperation between the University of Lyon1 (France) and the University of Antananarivo (Madagascar). It shows (among others) that useful research can be carried out in developing countries of the tropics if their social, technical, and economic conditions are taken into account. The concepts and methods associated with so-called “green chemistry” are particularly appropriated for this purpose. To illustrate this approach, two examples are shown. The first deals with industrial ecology and concerns waste transformation from the production of cashew nut into an amphiphilic product, oxyacetic derivatives. This product was obtained with a high yield and in a single step reaction. It exhibited an important surfactant property similar to those of the main fossil-based ones but with a much lower ecological impact. The second talks about chemical ecology as an alternative to insecticides and used to control dangerous mosquito populations. New substituted chromones were synthesized and showed biological activities toward Aedes albopictus mosquito species. Strong repellent properties were recorded for some alkoxylated products if others had a significant attractant effect (Kairomone) depending on their stereochemistry and the length of the alkyl chain. Full article
(This article belongs to the Special Issue Sustainable Chemistry in France)
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17 pages, 2598 KiB  
Article
New Sustainable Synthetic Routes to Cyclic Oxyterpenes Using the Ecocatalyst Toolbox
by Camille Bihanic, Arthur Lasbleiz, Morgan Regnier, Eddy Petit, Pierre Le Blainvaux and Claude Grison
Molecules 2021, 26(23), 7194; https://doi.org/10.3390/molecules26237194 - 27 Nov 2021
Cited by 6 | Viewed by 2025
Abstract
Cyclic oxyterpenes are natural products that are mostly used as fragrances, flavours and drugs by the cosmetic, food and pharmaceutical industries. However, only a few cyclic oxyterpenes are accessible via chemical syntheses, which are far from being ecofriendly. We report here the synthesis [...] Read more.
Cyclic oxyterpenes are natural products that are mostly used as fragrances, flavours and drugs by the cosmetic, food and pharmaceutical industries. However, only a few cyclic oxyterpenes are accessible via chemical syntheses, which are far from being ecofriendly. We report here the synthesis of six cyclic oxyterpenes derived from ß-pinene while respecting the principles of green and sustainable chemistry. Only natural or biosourced catalysts were used in mild conditions that were optimised for each synthesis. A new generation of ecocatalysts, derived from Mn-rich water lettuce, was prepared via green processes, characterised by MP-AES, XRPD and TEM analyses, and tested in catalysis. The epoxidation of ß-pinene led to the platform molecule, ß-pinene oxide, with a good yield, illustrating the efficacy of the new generation of ecocatalysts. The opening ß-pinene oxide was investigated in green conditions and led to new and regioselective syntheses of myrtenol, 7-hydroxy-α-terpineol and perillyl alcohol. Successive oxidations of perillyl alcohol could be performed using no hazardous oxidant and were controlled using the new generation of ecocatalysts generating perillaldehyde and cuminaldehyde. Full article
(This article belongs to the Special Issue Sustainable Chemistry in France)
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7 pages, 1095 KiB  
Communication
Continuous Flow Synthesis of Propofol
by Romain Mougeot, Philippe Jubault, Julien Legros and Thomas Poisson
Molecules 2021, 26(23), 7183; https://doi.org/10.3390/molecules26237183 - 26 Nov 2021
Cited by 15 | Viewed by 5735
Abstract
Herein, we report a continuous flow process for the synthesis of 2,6-diisopropylphenol—also known as Propofol—a short-acting intravenous anesthesia, widely used in intensive care medicine to provide sedation and hypnosis. The synthesis is based on a two-step procedure: a double Friedel–Crafts alkylation followed by [...] Read more.
Herein, we report a continuous flow process for the synthesis of 2,6-diisopropylphenol—also known as Propofol—a short-acting intravenous anesthesia, widely used in intensive care medicine to provide sedation and hypnosis. The synthesis is based on a two-step procedure: a double Friedel–Crafts alkylation followed by a decarboxylation step, both under continuous flow. Full article
(This article belongs to the Special Issue Sustainable Chemistry in France)
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12 pages, 2088 KiB  
Article
Short Alternative Route for Nuclear Fuel Reprocessing Based on Organic Phase Self-Splitting
by Julie Durain, Damien Bourgeois, Murielle Bertrand and Daniel Meyer
Molecules 2021, 26(20), 6234; https://doi.org/10.3390/molecules26206234 - 15 Oct 2021
Cited by 2 | Viewed by 1666
Abstract
A more sustainable management of natural resources and the establishment of processes allowing a joint management of nuclear materials to avoid their diversion from their civilian use are two issues for the nuclear industry. Short alternatives to existing processes have therefore been proposed [...] Read more.
A more sustainable management of natural resources and the establishment of processes allowing a joint management of nuclear materials to avoid their diversion from their civilian use are two issues for the nuclear industry. Short alternatives to existing processes have therefore been proposed based on known systems available, tributylphosphate (TBP), for the separation of actinides by liquid/liquid extraction. Proof of concept of such alternative has been established on the uranium(VI)/thorium(IV) system. From an organic phase consisting of a mixture of TBP/n-dodecane loaded with uranium and thorium, two fluxes have been obtained: the first contains almost all of the thorium in the presence of uranium in a controlled ratio, the second contains surplus uranium. Two levers were selected to control the spontaneous separation of the organic phase: the addition of concentrated nitric acid, or the temperature variation. Best results have been obtained using a temperature drop in the liquid/liquid extraction process, and variations in process conditions have been studied. Final metal recovery and solvent recycling have also been demonstrated, opening the door for further process development. Full article
(This article belongs to the Special Issue Sustainable Chemistry in France)
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Review

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26 pages, 4026 KiB  
Review
Molybdenum, Vanadium, and Tungsten-Based Catalysts for Sustainable (ep)Oxidation
by Jana Pisk and Dominique Agustin
Molecules 2022, 27(18), 6011; https://doi.org/10.3390/molecules27186011 - 15 Sep 2022
Cited by 6 | Viewed by 2186
Abstract
This article gives an overview of the research activity of the LAC2 team at LCC developed at Castres in the field of sustainable chemistry with an emphasis on the collaboration with a research team from the University of Zagreb, Faculty of Science, Croatia. [...] Read more.
This article gives an overview of the research activity of the LAC2 team at LCC developed at Castres in the field of sustainable chemistry with an emphasis on the collaboration with a research team from the University of Zagreb, Faculty of Science, Croatia. The work is situated within the context of sustainable chemistry for the development of catalytic processes. Those processes imply molecular complexes containing oxido-molybdenum, -vanadium, -tungsten or simple polyoxometalates (POMs) as catalysts for organic solvent-free epoxidation. The studies considered first the influence of the nature of complexes (and related ligands) on the reactivity (assessing mechanisms through DFT calculations) with model substrates. From those model processes, the work has been enlarged to the valorization of biomass resources. A part concerns the activity on vanadium chemistry and the final part concerns the use of POMs as catalysts, from molecular to grafted catalysts, (ep)oxidizing substrates from fossil and biomass resources. Full article
(This article belongs to the Special Issue Sustainable Chemistry in France)
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24 pages, 4016 KiB  
Review
2,5-Furandicarboxylic Acid: An Intriguing Precursor for Monomer and Polymer Synthesis
by Adam Marshall, Bo Jiang, Régis M. Gauvin and Christophe M. Thomas
Molecules 2022, 27(13), 4071; https://doi.org/10.3390/molecules27134071 - 24 Jun 2022
Cited by 13 | Viewed by 4802
Abstract
The most versatile furanic building block for chemical and polymer applications is 2,5-furandicarboxylic acid. However, the classical 2,5-furandicarboxylic acid production methodology has been found to have significant drawbacks that hinder industrial-scale production. This review highlights new alternative methods to synthesize 2,5-furandicarboxylic acid that [...] Read more.
The most versatile furanic building block for chemical and polymer applications is 2,5-furandicarboxylic acid. However, the classical 2,5-furandicarboxylic acid production methodology has been found to have significant drawbacks that hinder industrial-scale production. This review highlights new alternative methods to synthesize 2,5-furandicarboxylic acid that are both more advantageous and attractive than conventional oxidation of 5-hydroxymethylfurfural. This review also focuses on the use of 2,5-furandicarboxylic acid as a polymer precursor and the various potential applications that arise from these furan-based materials. Full article
(This article belongs to the Special Issue Sustainable Chemistry in France)
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29 pages, 6935 KiB  
Review
Strengthening the Connection between Science, Society and Environment to Develop Future French and European Bioeconomies: Cutting-Edge Research of VAALBIO Team at UCCS
by Marcia Araque-Marin, Fabio Bellot Noronha, Mickäel Capron, Franck Dumeignil, Michèle Friend, Egon Heuson, Ivaldo Itabaiana, Jr., Louise Jalowiecki-Duhamel, Benjamin Katryniok, Axel Löfberg, Sébastien Paul and Robert Wojcieszak
Molecules 2022, 27(12), 3889; https://doi.org/10.3390/molecules27123889 - 17 Jun 2022
Cited by 3 | Viewed by 2116
Abstract
The development of the future French and European bioeconomies will involve developing new green chemical processes in which catalytic transformations are key. The VAALBIO team (valorization of alkanes and biomass) of the UCCS laboratory (Unité de Catalyse et Chimie du Solide) are working [...] Read more.
The development of the future French and European bioeconomies will involve developing new green chemical processes in which catalytic transformations are key. The VAALBIO team (valorization of alkanes and biomass) of the UCCS laboratory (Unité de Catalyse et Chimie du Solide) are working on various catalytic processes, either developing new catalysts and/or designing the whole catalytic processes. Our research is focused on both the fundamental and applied aspects of the processes. Through this review paper, we demonstrate the main topics developed by our team focusing mostly on oxygen- and hydrogen-related processes as well as on green hydrogen production and hybrid catalysis. The social impacts of the bioeconomy are also discussed applying the concept of the institutional compass. Full article
(This article belongs to the Special Issue Sustainable Chemistry in France)
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18 pages, 4635 KiB  
Review
A Landscape of Lignocellulosic Biopolymer Transformations into Valuable Molecules by Heterogeneous Catalysis in C’Durable Team at IRCELYON
by Laurent Djakovitch, Nadine Essayem, Marion Eternot and Franck Rataboul
Molecules 2021, 26(22), 6796; https://doi.org/10.3390/molecules26226796 - 10 Nov 2021
Cited by 2 | Viewed by 1823
Abstract
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 [...] Read more.
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. Full article
(This article belongs to the Special Issue Sustainable Chemistry in France)
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20 pages, 3262 KiB  
Review
Biomass Valorization Using Natural Deep Eutectic Solvents: What’s New in France?
by Laura Wils, Soukaina Hilali and Leslie Boudesocque-Delaye
Molecules 2021, 26(21), 6556; https://doi.org/10.3390/molecules26216556 - 29 Oct 2021
Cited by 25 | Viewed by 3891
Abstract
With the growing interest in more environmentally friendly solvents and processes, the introduction of Natural Deep Eutectic Solvents (NaDES) as low cost, non-toxic and biodegradable solvents represent a new opportunity for green and sustainable chemistry. Thanks to their remarkable advantages, NaDES are now [...] Read more.
With the growing interest in more environmentally friendly solvents and processes, the introduction of Natural Deep Eutectic Solvents (NaDES) as low cost, non-toxic and biodegradable solvents represent a new opportunity for green and sustainable chemistry. Thanks to their remarkable advantages, NaDES are now arousing growing interest in many fields of research such as food, health, cosmetics and biofuels. Around the world, NaDES are seen as a promising alternative to commonly used petrochemical solvents. The objective of this review is to draw up a panorama of the existing skills on NaDES in French laboratories and industries for the valuation of natural products. This review therefore focuses on current applications, skills and perspectives, in order to analyze the place of French research in the use of NaDES for the valorization of biomass since 2015. Full article
(This article belongs to the Special Issue Sustainable Chemistry in France)
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