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A more sustainable and efficient protocol for the photocatalytic α-amino arylation promoted by fac-Ir(ppy)3 was developed. Three noteworthy results were achieved: i) the replacement of toxic medium DMA with the greener solvents NBP and NHP, and the concurrent improvement of the process efficiency by lowering both the amine and the base amount; ii) the development of a recycling protocol for both the sustainable solvent NHP and the commercially available costly photocatalyst fac-Ir(ppy)3, achieving environmental and economic benefits. This approach to the photocatalyst recovery avoids very demanding catalyst structural modifications; iii) the protocol in green solvents proved to be scalable up to 10 mmol of limiting reagent, maintaining excellent performance also lowering the photocatalyst loading down to 0.05 mol%. This is the first example of photocatalytic α-arylation of amines promoted by such a low amount of catalyst. Lastly, the versatility of this approach was demonstrated by extending the use of the green solvent NBP to another photoredox process.

Developing greener synthesis processes is an inescapable necessity to transform the industrial landscape, mainly in the pharmaceutical sector, into a long-term, sustainable reality. In this context, the renaissance of peptides as medical treatments, and the enforcement of more stringent sustainability requirements by regulatory agencies, pushed chemists toward the introduction of sustainable processes to prepare highly pure, active pharmaceutical ingredients (APIs). Innovative upstream (synthesis) and downstream (purification) methodologies have been developed during the last 5 years with the introduction and optimization of several technologies in solid-phase peptide synthesis (SPPS), liquid-phase peptide synthesis (LPPS), chemoenzymatic peptide synthesis (CEPS), and chromatographic procedures. These innovations are also moving toward the introduction of continuous processes that represent one of the most important targets for iterative processes. This overview discusses the most recent efforts in making peptide chemistry greener. The extensive studies that were carried out on green solvents, reaction conditions, auxiliary reagents and purification technologies in the peptide segment can be useful to other fields of organic synthesis

In recent years, several steps forward have been made toward a more sustainable approach for the extraction of bioactive compounds from plant materials based on the application of green extraction principles. It is currently recognized that waste and by-products deriving from agriculture and food industries still contain a wide array of high value-added substances, which can be re-used to obtain new products with various applications in the food, supplement, pharmaceutical, and cosmetic industries. Anthocyanins are a class of these valuable metabolites; they confer the red, violet, and blue color to fruits and vegetables, and scientific evidence has accumulated over the last few decades to support their beneficial effects on human health, in great part deriving from their powerful antioxidant capacity. This review provides a general overview of the most recent green procedures that have been applied for the recovery of anthocyanins from plant-derived wastes and by-products. The most widely used green solvents and the main sustainable techniques utilized for recovering this class of flavonoids from various matrices are discussed, together with the variables that mainly impact the extraction yield.

In recent years, there has been increasing interest in green extraction methods and green solvents due to their many advantages. In this study, the effects of an ultrasonic extraction method and deep eutectic solvents (DESs) on the extraction of different bioactive substances from bee pollen were investigated. In this regard, the effects of process variables such as the molar ratio of the DES (1, 1.5, and 2), sonication time (15, 30, and 45 min), and ultrasonic power (90, 135 and 180 W) on total individual amino acids, total individual organic acids, and total individual phenolic compounds were investigated by response surface methodology (RSM). The optimal conditions were found to be a molar ratio of 2, sonication time of 45 min, and ultrasonic power of 180 W (R2 = 0.84). Extracts obtained via the maceration method using ethanol as a solvent were evaluated as the control group. Compared with the control group, the total individual amino acid and total individual organic acid values were higher using DESs. In addition, compounds such as myricetin, kaempferol, and quercetin were extracted at higher concentrations using DESs compared to controls. The results obtained in antimicrobial activity tests showed that the DES groups had broad-spectrum antibacterial effects against all bacterial samples, without exception. However, in yeast-like fungus samples, this inhibition effect was negligibly low. This study is the first to evaluate the impact of DESs on the extraction of bioactive substances from bee pollen. The obtained results show that this innovative and green extraction technique/solvent (ultrasonic extraction/DES) can be used successfully to obtain important bioactive compounds from bee pollen.

Because of industrialization and modernization, phenomenal changes have taken place in almost all spheres of life. Consequently, the consumption of energy resources and the cases of environmental hazards have risen to an unprecedentedly high level. A development model with due consideration to nature and an efficient utilization of energy sources has become the need of the hour, in order to ensure a sustainable balance between the environmental and technological needs. Recent studies have identified the suitability of ionic liquids (ILs), often labeled as ‘green solvents’, in the efficient utilization of energy resources and activities such as bio-extraction, pollution control, CO2 capture, waste management etc. in an environmentally friendly manner. The advent of magnetic ionic liquids (MILs) and deep eutectic solvents (DESs) have opened possibilities for a circular economic approach in this filed. This review intends to analyze the environmental and energy wise consumption of a wide variety of ionic liquids and their potential towards future.

Polymer membranes have attracted interest in many areas, such as desalination, water treatment, gas separation, and energy storage and generation. Membrane fabrication requires large amounts of solvents for polymer dissolution. These solvents often show toxicity and need to be replaced by greener solvents to avoid adverse effects on human health and increase sustainability of the production processes. The need to use non-toxic compounds is increasing with the strong growth of the global membrane market. This review focuses on green solvents and green materials to prepare polymer-based membranes for the steadily increasing range of applications. Membrane fabrication techniques, choice of emerging green solvents, economic evaluation, and application areas will be comprehensively and critically reviewed. This review provides important selection guidelines for greener solvents for chemists, chemical engineers, and material scientists, focusing on organic chemicals and polymer processing. Furthermore, a simple cost analysis for a typical green solvent is provided, and its impact on the membrane fabrication cost is discussed. This journal is

Dimethyl isosorbide (DMI) is a well-known bio-based green replacement for conventional dipolar solvents such as dimethyl sulfoxide and dimethylformamide. The synthesis of DMI mainly relies on the etherification of the bio-based platform chemical isosorbide in the presence of basic or acid catalysts and by employing different alkylating agents. Among them, dimethyl carbonate (DMC) is considered one of the most promising for its good biodegradability and low toxicity. In this work, we report on a comprehensive investigation on high yielding methylation of isosorbide via DMC chemistry promoted by nitrogen organocatalyst N-methyl pyrrolidine (NMPy). Reaction conditions were optimized and then efficiently applied for the methylation of isosorbide epimers, isoidide and isomannide, and for some preliminary scale-up tests (up to 10 grams of isosorbide). The purification of DMI from the reaction mixture was achieved by both column chromatography and distillation at reduced pressure. NMPy demonstrated to be an excellent catalyst also for the one-pot conversion of D-sorbitol into DMI. Furthermore, for the first time, all seven methyl and methoxycarbonyl intermediates observed in the etherification of isosorbide were synthetised, isolated and fully characterised. This has provided an insight on the concurrent reaction pathways leading to DMI and on the role played by NMPy in the methylation of isosorbide. Finally, the reaction mechanisms for the methylation, methoxycarbonylation and decarboxylation promoted by NMPy partaking in the conversion of isosorbide into DMI via DMC chemistry have been proposed.

The need to develop alternative methods or to use “green” solvents constitutes an essential strategy under the emerging field of green chemistry, particularly in the development of new synthetic strategies in the field of pharmaceutic industry. We report an eco-friendly method of synthesis of poly(2-ethyl-2-oxazoline)-palmitoylate (PEtOz-PA) using Er(OTf)3 as Lewis’s acid catalyst in 2-MeTHF. The novel biomolecule derivative was characterized to confirm palmitoyl group substitution and employed for the formulation, characterization, and antioxidant activity evaluation of curcumin-loaded polymeric micelles.

Recently, glycerol has been exploited in a number of industrial applications, thanks to its high availability, its low cost and, overall, its peculiar properties which fit well with the green chemistry principles. In this work, the ability of glycerol to solubilize high molecular weight polymers and to allow the formation of glycerol-based semi-interpenetrating polymer networks, called “gly-semi-IPNs”, has been investigated. Compared to water, glycerol deeply affects the structural properties of the biopolymers, especially with reference to their chain flexibility. Among the polysaccharides, dextran methacrylate (DexMA) and gellan gum (Ge) were selected. Glycerol solutions of both polysaccharides and their mixtures, as well as a DexMA network (obtained by cross-linking in glycerol and in the presence of a photoinitiator), were rheologically characterized to assess the role of the solvent on the chain conformation and on the mechanical properties of the networks. Interestingly, glycerol was found to deeply influence the mechanical, morphological and optical properties of the formed hydrogels, as well as to improve the cross-linking kinetic of DexMA. Furthermore, glycerol leads to more homogeneous mixtures of the two polysaccharides than those observed in aqueous buffers. As such, novel gly-semi-IPNs, with enhanced formulation and mechanical properties, were prepared and characterized.

A formal C−H carboxylation of unactivated arenes using CO2 in green solvents is described. The present strategy combines a sterically controlled Ir‐catalyzed C−H borylation followed by a Cu‐catalyzed carboxylation of the in situ generated organoboronates. The reaction is highly regioselective for the C−H carboxylation of 1,3‐disubstituted and 1,2,3‐trisubstituted benzenes, 1,2‐ or 1,4‐symmetrically substituted benzenes, fluorinated benzenes and different heterocycles. The developed methodology was applied to the late‐stage C−H carboxylation of commercial drugs and ligands., Late‐stage carboxylation: Regioselective C−H carboxylation of unactivated arenes is now possible. C−H carboxylation can be realized in green solvents and can be used for the late‐stage carboxylation of practically valuable molecules.

Supported liquid membranes (SLMs) containing novel green solvents are proposed as a sustainable alternative separation process in the recovery of biomolecules. In this work, succinic acid has been successfully extracted from model fermentation broths through a stripping phase-facilitated transport mechanism with four different green supported liquid membranes: two eutectic solvents (DL-menthol:OctA and N4444Cl:OctA), the bio-based solvent eucalyptol and the ionic liquid [C4pyrr][Tf2N]. A permeability activity-based model that takes into account for the first time solute-phase affinities has been developed using the quantum chemical COSMO-RS method; the model corrects the mass transfer driving force and allows extraction predictions beyond the concentration equilibrium. The best recovery has been achieved experimentally for the eucalyptol-based SLM (concentration factor of 1.4) using an alkaline aqueous solution (0.5 M NaOH) as the stripping phase. A countercurrent cascade extraction process design is proposed, and a graphical method to determine the stage number, interstage concentrations as well as mass transfer area requirements is presented. This new tool, the Permeability Activity-Based Linear Operation (PABLO) method, will substantially enhance the process design of SLMs technology for the biorefinery industry., This work was funded by the CONICYT PFCHA/DOCTORADO BECAS CHILE/2017 – 72180306. P. Gorgojo acknowledges the Spanish Ministry of Economy and Competitiveness and the European Social Fund through the Ramon y Cajal programme (RYC2019-027060-I/AEI/10.13039/501100011033). M. González-Miquel acknowledges Madrid Government (Comunidad de Madrid-Spain) for funding through the Multiannual Agreement with Universidad Politécnica de Madrid under the Excellence Programme for University Professors, in the context of the V PRICIT (Regional Programme of Research and Technological Innovation).

The previous biodiesel purification by Solvent-Aided Crystallization (SAC) using 1-butanol as assisting agent and parameters for SAC were optimized such as coolant temperature, cooling time and stirring speed. Meanwhile, 2-Methyltetrahydrofuran (2-MeTHF) was selected as an alternative to previous organic solvents for this study. In this context, it is used to replace solvent 1-butanol from a conducted previous study. This study also focuses on the technological improvements in the purification of biodiesel via SAC as well as to produce an even higher purity of biodiesel. Experimental works on the transesterification process to produce crude biodiesel were performed and SAC was carried out to purify the crude biodiesel. The crude biodiesel content was analyzed by using Gas Chromatography–Mass Spectrometry (GC-MS) and Differential Scanning Calorimetry (DSC) to measure the composition of Fatty Acid Methyl Esters (FAME) present. The optimum value to yield the highest purity of FAME for parameters coolant temperature, cooling time, and stirring speed is −4 °C, 10 min and 210 rpm, respectively. It can be concluded that the assisting solvent 2-MeTHF has a significant effect on the process parameters to produce purified biodiesel according to the standard requirement.

Tobacco cultivation and industrialization are characterized by the production of trillions of pre-harvest and post-harvest waste biomasses each year with the resulting negative effects on the environment. The leaves of blunt, pre-harvest waste, could be further used to obtain bioactive metabolites, i.e., polyphenols and alkaloids, for its potential cosmetic use. This study was conducted to obtain bio-compounds from pre-harvest tobacco leaf waste (var. Virginia) by applying conventional and green solvents (NaDES). Leaves and ground leaf waste were characterized based on their microscopic features. Conventional solvents, such as water, acetone, ethanol, and non-conventional solvents, such as Natural Deep Eutectic Solvents (NaDES), i.e., sucrose:lactic acid (LAS), frutose:glucose:sucrose (FGS), lactic acid:sucrose:water (SALA), choline chloride:urea (CU), and citric acid: propylene glycol (CAP) were used for bioactive extraction from tobacco waste powder. CU, FGS, and acetone/ethanol had similar behavior for the best extraction of alkaloids (6.37–11.23 mg ACE/g tobacco powder). LAS, FGS, SALA, and CU were more effective in phenolic compound extraction than conventional solvents (18.13–21.98 mg AGE/g tobacco powder). Because of this, LAS and SALA could be used to obtain phenolic-enriched extracts with lower alkaloid content rather than CU and FGS. Extracts of the powder obtained with conventional solvent or CU showed a high level of sugars (47 mg/g tobacco powder) The ABTS antioxidant capacity of tobacco leaf powder was higher in the extracts obtained with CU, FGS, and acetone (SC50 1.6–5 µg GAE/mL) while H2O2 scavenging activity was better in the extracts obtained with LAS, CAP and SALA (SC50 3.8–8.7 µg GAE/mL). Due to the biocompatibility of the NaDES with the components of tobacco leaf waste, the opportunity to apply these extracts directly in antioxidant formulations, such as cosmetics, phytotherapic, and other formulations of topic use seems promising. Furthermore, NaDES constituents, i.e., urea and organic acid can also have beneficial effects on the skin.

The solubility and involved energies of organic acids in green solvents are relevant to the design of sustainable biorefinery downstream processes. In this work, the solubility of two important bio-based organic acids such as succinic acid and fumaric acid, in water and four bio-based solvents (i.e., ethyl acetate, 1,8-cineole, cyclopentyl methyl ether, and 2-methyl tetrahydrofuran) were measured within a temperature range of [283 – 313] K. A gravimetric methodology was adopted, previously validated using the organic acid aqueous solubilities available in the literature. The reported data present an average estimated uncertainty of measurement, with a level of confidence of 95%, of 5.2·10-4 mol·mol−1. Experimental results were correlated with the van’t Hoff equation, and the Buchowski–Ksiazaczak λh model, where the root mean squared deviations were, This work was funded by the CONICYT PFCHA/DOCTORADO BECAS CHILE/2017 – 72180306. P. Gorgojo acknowledges her Ramón y Cajal fellowship RYC2019-027060-I funded by MICIN/AEI/10.13039/501100011033 and by “ESF Investing in your future”. M. González-Miquel also acknowledges Comunidad Autónoma de Madrid (Spain) for funding through “Programa de Excelencia para el Profesorado Universitario”.

In this review, the function of water and the increasing role of water as a green solvent and co-extractant based on its application in ancient times and the need of environmental thinking have been discussed. A brief summary of various extraction methods for natural products, the application of conventional and innovative processes, based on water and future insights and perspectives considering water as an eco-friendly crossroad in green extraction have been reported. Taking into account also the issue of wastewater, this paper calls for-more effective use of water as a finite resource.

Ultrasound-assisted extraction (UAE) and pressurized liquid extraction (PLE) techniques were evaluated and compared with conventional extraction for obtaining spent coffee ground oil (SCGO). The use of absolute ethanol (ET0) and hydrated ethanol (ET6) as solvents, two levels of SCG mass ratio:solvent, 1:4 (U4) and 1:15 (U15), and ultrasound powers of 0, 200, 400, and 600 W were tested. ET0 and U15 resulted in higher extraction yields of SCGO (YSCGO, 82%). A positive effect of sonication on YSCGO was observed only for condition U4. UAE resulted in defatted solids (DS) with higher apparent density values, corroborating the increase in the amount of smaller diameter particles due to sonication. The micrographs showed changes in the surfaces of the solids from the UAE and PLE, although the crystalline structures of the DS were not altered. UAE and PLE, compared to conventional extraction, did not allow significant gains in terms of YSCGO and, consequently, in the number of contact stages in an extractor configured in cross-currents.

Functional polymers featuring good processability in non-halogenated, benzene-free green solvents are highly desired due to health and environmental concerns. Herein, a series of novel D-A type conjugated polymers, PBDT-IIDs, are designed and successfully prepared by “green” functionalization of the polymers with highly hydrophilic, highly polar, highly flexible, and biocompatible oligoethylene glycol (OEG) side chains in order to improve the processability. These series polymers are named PBDT-IID2, PBDT-IID3, and PBDT-IID4, respectively, according to the number of oxygen atoms in the side chain. After confirmation by structural characterization, the basic properties of PBDT-IIDs are also investigated. With the increase in the OEG side chain length, the polymer PBDT-IID4 not only has good solubility in the halogen solvent chlorobenzene, but also exhibits excellent solubility in the green halogen-free solvent methyltetrahydrofuran (Me-THF). As a result, the green solvent Me-THF can also be applied to prepare PBDT-IIDs’ electrochromic active layers, except for chlorobenzene and toluene. The electrochromism of PBDT IIDs under both positive and negative voltages has a practical application potential. The several controllable switches between dark green and khaki (0–0.6 V) are expected to show great potential in the field of military camouflage. Furthermore, according to the principle of red, green, and blue (RGB) mixing, light blue-green in the reduced state (−1.6 V) can be used in the preparation of complementary ECDs to provide one of the three primary colors (green).

In this paper, genipin, an important natural crosslinker and anti-neurodegenerative compound, was extracted from unripe Genipa americana L., combining high-intensity ultrasound (HIUS) and natural deep eutectic solvents (NADESs). The extraction process conditions were evaluated step-by-step to reach the best genipin recovery. The obtained ready-to-use genipin-NADES extract was examined regarding its crosslinking properties and anti-neurodegenerative capacity. For the condictions tested, the highest genipin recovery was obtained using 40 % water and 60 % betaine:lactic acid NADES in molar ratio 1:3 (n/n) as the solvent, a solvent:feed ratio of 19 (w/w), and HIUS acoustic power of 14 ± 1 W. The HIUS-assisted extraction using NADES as solvent showed to be a promising and efficient green extraction technique to obtain genipin. The ready-to-use genipin-NADES extract presented crosslinking capacity and anticholinergic activity. These results indicate that genipin-NADES extract can be directly applied in hydrogels for drug delivery, films, tissue engineering, and others. Moreover, it can be used in food, supplements, and medicine to enhance their neuroprotective effect., M. I. L. Neves thanks CAPES (001) and CAPES/PRINT (88887.572039/2020-00) for her doctoral assistantships. M. A. A. Meireles thanks CNPq (309825/2020-2) for her productivity grant. B. Socas-Rodríguez thanks the Ministry of Science and Innovation (MICINN) for his Juan de la Cierva postdoctoral grant. The support from project PID2020-113050RB-I00 (MICINN, Spain) is acknowledged.

Solvent-resistant UV-cured supports consisting of a semi-interpenetrating network of polysulfone (PSf) and cross-linked poly-acrylate were successfully synthesized for the first time using an alternative, non-reprotoxic, and biodegradable solvent. Tamisolve® NxG is a high-boiling, dipolar aprotic solvent with solubility parameters similar to those of dimethylformamide (DMF) and N-methyl-2-pyrrolidone (NMP), making it an eco-friendly alternative. The support membranes, prepared via UV-curing followed by non-solvent-induced phase inversion, can serve as a universal solvent-resistant support for the synthesis of a broad set of membranes, for which the selective layer can be deposited from any solvent. Parameters such as UV irradiation time and intensity, as well as the concentrations of PSf, penta-acrylate, and photo-initiator in the casting solution were varied to obtain such supports. The characteristics of the resulting supports were investigated in terms of separation performance, hydrophobicity, porosity, degree of acrylate conversion, and pure water flux. The resulting membranes showed improved chemical resistance in solvents such as ethyl acetate, NMP, tetrahydrofuran (THF), and toluene. Solvent-resistant supports with different pore sizes were synthesized and used for the preparation of thin film composite (TFC) membranes to demonstrate their potential. Promising separation performances with Rose Bengal (RB) rejections up to 98% and water permeances up to 1.5 L m-2 h-1 bar-1 were reached with these TFC-membranes carrying a polyamide top layer synthesized via interfacial polymerization. ispartof: MEMBRANES vol:12 issue:1 ispartof: location:Switzerland status: published

Phenolic compounds isolated from plant biomass consist of bioactive components showing a wide range of benefits for humans, including antioxidant, antimicrobial or anti-inflammatory effects. This paper presents the potential value of black alder (Alnus glutinosa (L.) Gaertn. (Betulaceae)) bark for the production of biologically active substances, despite its current use as a low value fuel source. Most of the extraction methods employ neat organic solvents to obtain extracts with a high antioxidant potential from biomass. The aim of this work is to show the advantages and disadvantages of the extraction process by taking into account the principles of ‘green chemistry’ and replacing the organic solvents with ‘green’ solvent water. Using the advantages of accelerated solvent extraction (ASE), it has been shown that the use of deionized water has the prospect of replacing organic solvents. In the case of the one-step water extraction, the total polyphenol content (TPC) varies from 0.55 to 0.62 Gallic acid equivalent (GAE) g/g in the extracts, depending on the temperature, whereas with the result of the sequential extraction with the organic solvents, the TPC content of the 40% (v:v) ethanol extracts ranges from 0.39 to 0.61 GAE g/g, depending on the temperature. The influence of the total polyphenol content and the total proanthocyanidin content on the antioxidant activity is shown. The antioxidant activity (IC50, mg/L) of the extracts obtained with the organic solvents in the (2,2-diphenyl-1-picrylhydrazyl) DPPH• test varies from 4.05 to 9.58, depending on the temperature in the range of 70–150 °C, respectively, while the results obtained with the deionized water showed promising results in the range of 6.33–7.36 in the temperature range of 70–150 °C, respectively. The extraction with the deionized water showed that approximately 90% of the substances in the extracts obtained with the organic solvents by sequential extraction are possible to obtain as deionized water extracts.

In this work, the effect of different production techniques was evaluated on the physical and antioxidant properties of bio-based packaging intended to prevent the premature oxidation of packaged foods. Spent coffee ground extract, rich in antioxidant molecules, obtained through high pressure and temperature extraction, was loaded on zein polymeric matrices. The techniques adopted in this work are particularly suitable due to their mild conditions to produce active packaging completely based on natural compounds: electrospinning, solvent casting, and spin coating. The novelty of this work lay in the investigation of the dependance of the properties of active packaging on the adopted production techniques; the results clearly indicated a strong dependence of the features of the films obtained by different production processes. Indeed, spin coated samples exhibited the best oxygen barrier properties, while a higher tensile strength was obtained for the casted samples, and the fastest release of active compounds was provided by electrospun mats. The films produced with different methods had different physical properties and the release of extract bioactive compounds can be tunable by varying the production technique, dependent on the variable to be considered. The products developed offer an alternative to traditional packaging solutions, being more eco-sustainable and promoting waste valorization.

Cost management and toxic waste generation are two key issues that must be addressed before the commercialization of perovskite optoelectronic devices. We report a groundbreaking strategy for eco-friendly and cost-effective fabrication of highly efficient perovskite solar cells. This strategy involves the usage of a high volatility co-solvent, which dilutes perovskite precursors to a lower concentration (1.4 M) solution. More than 70% of toxic waste and material cost can be reduced. Mechanistic insights reveal ultra-rapid evaporation of the co-solvent together with beneficial alteration of the precursor colloidal chemistry upon dilution with co-solvent, which in-situ studies and theoretical simulations confirm. The co-solvent tuned precursor colloidal properties also contribute to the enhancement of the stability of precursor solution, which extends its processing window thus minimizing the waste. This strategy is universally successful across different perovskite compositions, and scales from small devices to large-scale modules using industrial spin-coating, potentially easing the lab-to-fab translation of perovskite technologies., A universal strategy is reported for formation of very low concentration of perovskite precursor inks that yields high-efficiency photovoltaics while substantially reducing toxic waste generation, fabrication cost and process complexity, thus taking a step closer towards commercialization.

In this work, for the first time, porous Matrimid® 5218 membranes were prepared by employing a combination of vapour induced phase separation (VIPS) and non-solvent induced phase separation (NIPS) technique. N-methyl-2-pyrrolidone (NMP) and Rhodiasolv® Polarclean were used as a traditional and new green solvent, respectively, for the preparation of the membranes. Ternary phase diagrams with both solvents were preliminary carried out. The exposure time to humidity and the effect of polymer concentration on membrane morphology and properties were evaluated. The resulting membranes were fully characterized in terms of morphology, shrinkage propensity, thickness, porosity, mechanical properties, pore size, contact angle and water permeability.

International audience; Dipolar and aprotic solvents are often required in acid‐catalyzed reactions, however, many of them are listed in solvent selection guides as not‐recommended due to their toxicity or explosivity. A catalytically functionalized ionic liquid, namely a sulfone‐containing imidazolium‐based Brønsted acid ionic liquid, was synthesized. It alleviates the detrimental effect of classical dipolar aprotic solvents because this ionic liquid integrates the function of a dipolar aprotic solvent able to stabilize carbocation intermediates and the activating effect of a strong Brønsted acid on electrophiles. The use of this tailor‐made ionic liquid was exemplified in some transformation reactions of indoles, which proceeded with high yield and selectivity using a green and an industrially acceptable solvent, butyl acetate. The recyclability of the ionic liquid catalyst was also demonstrated.

Environmental protection and climate change are current issues at the heart of global economic growth. The awareness of the real risks connected with industrial membrane production sector has been the push towards the search of new, more sustainable, sol vents and raw materials . In this context, dihydrolevoglucosenone (Cyrene(TM)) comes as a green biosolvent derived from waste cellulose, with enormous potentiality, which could offer the possibility to re-design manufacturing processes from the origin. The increasing interest devoted to Cyrene(TM) has its basis in the similarity with many physi cal-chemical properties of highly toxic organic solvents normally used for fabrication membranes (such as N-Methyl-2-pyrrolidone, N,N-Dimethylformamide and N,N-dimethy l acetamide). In fact, Cyrene(TM) is presented as a polar aprotic organic solvent, comple tely miscible with water, and with a relatively high boiling point (227 °C). Herein, Cyrene(TM) was employed for the preparation of polyethersulfone (PES) and pol y(vinylidene fluoride) (PVDF) membranes via phase inversion [2]. By preparing PES/C yrene(TM) and PVDF/Cyrene(TM) casting solutions, without the use of any additive, and b y working at room temperature, microfiltration and ultrafiltration membranes were obta ined. Non-solvent induced phase separation (NIPS) and its combination with vapour-in duced phase separation (VIPS) were adopted as preparation procedure. PES and PVDF membranes were characterized in terms of thickness, porosity, pore size, contact angl e and pure water permeability. The morphology was also assessed. For PVDF membra nes, additional differential scanning calorimetry and Fourier transform infrared spectros copy analysis were performed. The obtained results evidenced as, by varying the exposure time to controlled humid a ir and temperature during the VIPS-NIPS process, membranes with different morpholo gy and properties can be prepared, demonstrating the applicability of Cyrene(TM) for a more sustainable membrane fabrication.

The enantioseparation of syn- and anti-3,5-disubstituted hydantoins 5a–i was investigated on three immobilized polysaccharide-based columns (CHIRAL ART Amylose-SA, CHIRAL ART Cellulose-SB, CHIRAL ART Cellulose-SC) by high performance liquid chromatography (HPLC) using n-hexane/2-PrOH (90/10, v/v) or 100% dimethyl carbonate (DMC) as mobile phases, respectively, and by supercritical fluid chromatography (SFC) using CO2/alcohol (MeOH, EtOH, 2-PrOH; 80/20, v/v) as a mobile phase. The chromatographic parameters, such as separation and resolution factors, have indicated that Amylose-SA is more suitable for enantioseparation of the most analyzed syn- and anti-3,5-disubstituted hydantoins than Celullose-SB and Cellulose-SC in both HPLC and SFC modalities. All three tested columns showed better enantiorecognition ability toward anti-hydantoins compared to syn-hydantoins, both in HPLC and SFC modes. We have demonstrated that environmentally friendly solvent DMC can be efficiently used as the mobile phase in HPLC mode for enantioseparation of hydantoins on the immobilized polysaccharide-based chiral stationary phases.

Converting agriculture and forestry lignocellulosic residues into high value-added liquid fuels (ethanol, butanol, etc.), chemicals (levulinic acid, furfural, etc.), and materials (aerogel, bioresin, etc.) via a bio-refinery process is an important way to utilize biomass energy resources. However, because of the dense and complex supermolecular structure of lignocelluloses, it is difficult for enzymes and chemical reagents to efficiently depolymerize lignocelluloses. Strikingly, the compact structure of lignocelluloses could be effectively decomposed with a proper pretreatment technology, followed by efficient separation of cellulose, hemicellulose and lignin, which improves the conversion and utilization efficiency of lignocelluloses. Based on a review of traditional pretreatment methods, this study focuses on the discussion of pretreatment process with recyclable and non-toxic/low-toxic green solvents, such as polar aprotic solvents, ionic liquids, and deep eutectic solvents, and provides an outlook of the industrial application prospects of solvent pretreatment.

Graphical abstract, Highlights • Ultrasonic-assisted extraction of fucoxanthin from S. fusiforme was investigated. • Ethyl lactate, limonene, and vegetable oils were compared for effective extraction. • The extraction conditions were optimized by single-factor and response surface tests. • The second-order kinetic model was fit to describe the dynamic extraction process., The development of green and sustainable extraction technologies for various naturally active biomaterials is gaining increasing attention due to their environmentally friendly advantages. In this work, the ultrasonic-assisted extraction of fucoxanthin from edible brown algae Sargassum fusiforme using different green solvents was presented. Ethyl lactate, limonene, soybean oil, and sunflower oil were used in place of traditional organic solvents. Ethyl lactate showed similar performance to organic solvents, whereas limonene and vegetable oil exhibited higher selectivity for fucoxanthin. Moreover, the effects of various extraction factors, including liquid/solid ratio, extraction time, extraction temperature, as well as amplitude were studied. The optimal conditions were optimized as follows: liquid/solid ratio, 40 mL/g; extraction time, 27 min; extraction temperature, 75 ℃; amplitude, 53%; and solvent, ethyl lactate. Optimal model of second-order kinetic parameters (rate constant, equilibrium concentration, and initial extraction rate) was successfully developed for describing the dynamic ultrasonic extraction process under different operating conditions.

It is imminent to explore new types of starting materials for natural deep eutectic solvents (NADESs). Herein, a series of natural aromatic organic acids as the hydrogen bond donor (HBD) and coumarin as the model hydrogen bond acceptor (HBA) were used to design and prepare NADESs. They are characterized by nuclear magnetic resonance (NMR) and attenuated total reflection flourier transformed infrared spectroscopy (ATR-FTIR), supported by quantum chemistry (QC) calculations. The liquid phase of the mixture is attributed to the non-ideal behavior of both components at most of the ratios. In addition, — ${\rm \Delta }E$ presented the energy dynamic equilibrium of eutectic systems. Using solid–liquid phase diagrams and mean interaction energies obtained by the conductor like screening model for real solvent model (COSMO-RS), the predicting formability of DESs can be achieved by choosing the proper HBAs and HBDs. Finally, five green solvents, including mandelic acid-coumarin, salicylic acid-coumarin, benzoic acid-coumarin, hydroxybenzoic acid-coumarin, and cinnamic acid-coumarin, were obtained. Thus, the aromatic organic acid studied in this work is vital for the development of novel green eutectic systems.

Chemoenzymatic oxidations involving the CAL-B/H2O2 system was developed in a sugar derived Natural Deep Eutectic Solvent (NaDES) composed by a mixture of glucose, fructose and sucrose. Good to excellent conversions of substrates like cyclooctene, limonene, oleic acid and stilbene to their corresponding epoxides, cyclohexanone to its corresponding lactone and 2-phenylacetophenone to its corresponding ester, demonstrate the viability of the sugar NaDES as a reaction medium for epoxidation and Baeyer-Villiger oxidation.

Resumen del trabajo presentado al 2nd International Meeting on Deep Eutectic Systems, celebrado online del 15 al 17 de junio de 2021.

Natural deep eutectic solvent (NaDES) is generally considered as a greener alternative to fossil solvent, with great potential in various areas. In the present work, 25 different NaDESs were screened for the extraction of puerarin (PUE) and its two natural derivatives from Radix Pueraria (RP). As the main isoflavone in RP, PUE has a wide range of biological activities. However, its application is restricted due to its poor solubility in water and low oral bioavailability. In this study, the extraction of PUE with NaDESs showed significant advantages compared with traditional solvents. While using L-Pro-Maa (L-proline-malic acid) under optimal conditions, the optimized yields of PUE, 3-MPR and PRX were 98.7 mg/g, 16.3 mg/g and 9.9 mg/g, respectively, which were 2.2-, 2.9- and 3.4-fold higher than that of water. Furthermore, the oral bioavailability of PUE in NaDES extracts was comparatively investigated in rats with HPLC-MS technique. Pharmacokinetic analysis revealed that the relative bioavailability of PUE in L-Pro-Maa extract is 323%. The result indicated that NaDES is not only a sustainable ionic liquid with higher extraction efficiency, but also an enhancer of oral bioavailability of specific natural products.

International audience; Rice bran (RB) corresponds to the outer layers of whole grain rice and contains several phenolic compounds (PCs) that make it an interesting functional food ingredient. PC richness is enhanced in pigmented RB varieties and requires effective ways of extraction of these compounds. Therefore, we investigated conventional and deep eutectic solvents (DES) extraction methods to recover a wide array of PCs from red and black RB. The RB were extracted with ethanol/water (60:40, v/v) and two DES (choline chloride/1.2-propanediol/water, 1:1:1 and choline chloride/lactic acid, 1:10, mole ratios), based on Generally Recognized as Safe (GRAS) components. Besides the quantification of the most typical phenolic acids of cereals, nontargeted metabolomic approaches were applied to PCs profiling in the extracts. Globally, metabolomics revealed 89 PCs belonging to flavonoids (52%), phenolic acids (33%), other polyphenols (8%), lignans (6%) and stilbenes (1%) classes. All extracts, whatever the solvents, were highly concentrated in the main phenolic acids found in cereals (37–66 mg/100 g in black RB extracts vs. 6–20 mg/100 g in red RB extracts). However, the PC profile was highly dependent on the extraction solvent and specific PCs were extracted using the acidic DES. The PC-enriched DES extracts demonstrated interesting DPPH scavenging activity, which makes them candidates for novel antioxidant formulations.

Lignans are plant phenols derived from phenylpropanoids. They play a significant role in plant defense and have features that make them appealing for pharmaceutical applications. Lignans can be obtained by plant in vitro cultures; their production by adventitious and hairy roots of Linum species seems to be a promising alternative to chemical synthesis. In the context of large-scale production, it is necessary to optimize their extraction from plants tissue by choosing the more suitable solvent and extraction procedure, paying attention to the use of green media and methods. With the aim to select the best conditions for the extraction of two interesting lignans (justicidin B and 6-methoxypodophyllotoxin) from Linum tissues, different green solvents and the method of ultrasound-assisted extraction were tested. The results showed that ethyl methyl ketone and dimethyl carbonate were the best media to extract justicidin B and 6-methoxypodophyllotoxin, respectively, in terms of purity and recovery. Moreover, we showed that ultrasound-assisted extraction presents different advantages compared to conventional methods. Finally, the optimal experimental conditions to extract justicidin B from L. austriacum hairy roots using methyl ethyl ketone were also determined by the response surface method. The models obtained are reliable and accurate to estimate the purity and recovery of justicidin B.

The potential of using the bio-based solvent 2-methyloxolane, also known as 2-methyltetrahydrofuran or 2-MeTHF, as an alternative to petroleum solvents such as hexane, was investigated for the extraction of volatile compounds from hop cones (Humulus lupulus L.). Lab scale extractions were coupled with in silico prediction of solutes solubility to assess the technical potential of this bio-based solvent. The predictive approach was performed using the simulation software COSMO-RS (conductor like screening model for real solvants) and showed that the 2-methyloxolane is as good as or better than hexane to solubilize the majority of aromas from hop cones. The experimental results indicated that the highest aroma yield was obtained with 2-methyloxolane with 20.2% while n-hexane was only able to extract 17.9%. The characterization of aromas extracted by the two solvents showed a similar composition, where lupulone was the main component followed by humulone. No selectivity of the solvents was observed for any of the major analytes. Finally, a sensory analysis was performed on the extracts, showing that both concretes using 2-methyloxolane and hexane have similar olfactory profiles. The results indicate that 2-methyloxolane could be a promising bio-based extraction solvent for hexane substitution.

Deep eutectic solvents (DESs) are emerging green solvents with very unique characteristics. Their contribution to atmospheric pollution is negligible, and they can be &ldquo, designed&rdquo, for desired properties. In this study, the feasibility of applying DESs (Reline, Ethaline, or Glyceline) as absorbents in absorption refrigeration cycles was investigated. The sophisticated cubic-plus-association (CPA) equation of state, considering the strong intermolecular interactions of such complex systems, was used to estimate the thermodynamic properties. At a fixed set of base case operating conditions, the coefficients of performance were calculated to be 0.705, 0.713, and 0.716 for Reline/water, Ethaline/water, and Glyceline/water systems, respectively, while the corresponding mass flow rate ratios were 33.73, 11.53, and 16.06, respectively. Furthermore, the optimum operating conditions of each system were estimated. To verify the feasibility, results were compared to literature systems, including LiBr/water and various ionic liquid/water systems. The results indicate that DES/water working fluids have the potential to be used in such cycles. Since DESs have the characteristic to be tuned (designed) to desired properties, including their solvent power and their enthalpies of absorption, much further research needs to be done to propose new DESs with higher energy efficiencies.

The search for sustainable alternatives for use in chemical synthesis and catalysis has found an ally in non-conventional energy sources and widely available green solvents. The use of glycerol, an abundant natural solvent, as an excellent "sacrificial" hydrogen source for the copper-catalyzed microwave (MW)-promoted transfer hydrogenation of nitrobenzene to aniline has been investigated in this work. Copper nanoparticles (CuNPs) were prepared in glycerol and the efficacy of the glycerol layer in mediating the interaction between the metal active sites has been examined using HRTEM analyses. Its high polarity, low vapor pressure, long relaxation time, and high acoustic impedance mean that excellent results were also obtained when the reaction media was subjected to ultrasound (US) and MW irradiation. US has been shown to play an important role in the process via its ability to enhance CuNPs dispersion, favor mechanical depassivation and increase catalytic active surface area, while MW irradiation shortened the reaction time from some hours to a few minutes. These synergistic combinations promoted the exhaustive reduction of nitrobenzene to aniline and facilitated the scale-up of the protocol for its optimized use in industrial MW reactors. ispartof: FRONTIERS IN CHEMISTRY vol:8 ispartof: location:Switzerland status: published

International Transaction Journal of Engineering, Management, & Applied Sciences & Technologies, 11, 1, 11A01N: 1-6

Organic solvents are required to carry out most organic transformations, which cause environmental pollution because of their low volatility. Glycerol, a side product obtained from biodiesel production, has emerged as a friendly solvent due to its advantageous properties. In this paper, an efficient procedure for the synthesis of flavones and chromones, using heteropolyacids as recyclable catalyst and glycerol as the solvent, is presented. The use of heteropolyacids as catalysts allows for excellent yields, easy separation and recovery, low environmental impact, and low cost. Glycerol can also be readily recovered and used over again. In addition, the presented method provides other advantages such as the low formation of waste and the replacement of corrosive mineral acids. Fil: Colombo Migliorero, María Belén. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina Fil: Palermo, Valeria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina Fil: Alarcón Durango, Edwin Alexis. Universidad de Antioquia; Colombia Fil: Holguín, Aída Luz Villa. Universidad de Antioquia; Colombia Fil: Vazquez, Patricia Graciela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina Fil: Sathicq, Angel Gabriel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina Fil: Romanelli, Gustavo Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Ciencias Aplicadas "Dr. Jorge J. Ronco". Universidad Nacional de la Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Ciencias Aplicadas; Argentina

A vortex-assisted liquid-liquid microextraction, based on a natural hydrophobic deep eutectic solvent made from the monoterpene thymol and octanoic fatty acid, was employed for the analysis of 11 phthalate esters and one adipate in kombucha (a tea-based fermented beverage). Separation and determination were performed using an ultra-high performance liquid chromatography (UHPLC) system coupled to a single quadrupole mass spectrometer. Confirmatory analyses were carried out through UHPLC tandem mass spectrometry. The full method was validated in terms of matrix effect, matrix-matched calibration, sensitivity, recovery, limits of detection and quantification and repeatability. Satisfactory determination coefficients for quadratic calibration curves (≥0.9938), recovery values (67–120%) and limits of detection (0.07–5.45 µg/L) were obtained. Analysis of 26 kombucha samples reported concentrations for dibutyl phthalate and dimethyl phthalate in the range between the limit of quantification (LOQ) and 16.18 ± 1.14 µg/L, although these phthalates were also detected under the LOQ in some of the analyzed samples. Only one of the samples bottled in plastic containers (7) did not present residues while only five of the 19 samples in glass bottles contained any plasticizer. However, the highest concentration was found in a kombucha bottled in food-grade glass. This work represents the first application in which phthalates and adipates are analyzed in kombuchas.

Peptide bond forming reactions are fundamental to the synthesis of peptides and peptidomimetics. Unfortunately, the chemistry of the peptide bond rouses much concern in terms of economic cost, environmental impact, and production of wastes, especially toxic organic solvents. In a Green Chemistry perspective, we reconsidered the use of unprotected N-carboxy anhydrides (NCAs) of standard α-amino acids under minimal liquid-assisted grinding (LAG) conditions. NCAs are very attractive in peptide synthesis for their simplicity and atom economy. Indeed, the molecular bulk of these N-protected/C-activated bidentate reactants remains with the newly formed peptide. However, the NCAs are prone to polymerization, a formidable obstacle to the development of mechanochemical conditions. Nevertheless, polymerization can be prevented by operating under controlled basic conditions. In this work, we describe peptide bond forming reactions from NCAs and amino partners by LAG in amalgam with nanocrystalline hydroxyapatite (HAp) powder as a bio-compatible, reusable inorganic base. The experiments supported the combination of HAp and the green solvent γ-valerolactone, and highlighted the importance of NCAs’ purity and crystallinity, as studied by NMR, SEM, and XRD. The efficacy of the procedure was assessed by the synthesis of the 13-mer cytotoxic peptide PTP7.

Levodopa is an amino acid commonly used in the treatment of Parkinson’s disease found in several plants, such as Mucuna pruriens. The extraction of levodopa from biomass has been achieved using methanol, ethanol:water mixtures in presence of ascorbic acid, chloroform in alkaline media, and acetonitrile. Aiming at finding more sustainable solvents and develop efficient extraction processes, in this work, aqueous solutions of carboxylic acids (acetic, propionic, citric, glycolic, and lactic acid) and (poly)alcohols (ethanol, ethylene glycol and glycerol) were studied for the extraction of levodopa from Mucuna pruriens seeds. An initial screening with aqueous solutions of these compounds (at 50 wt%) was conducted at 50 °C, with an extraction time of 90 min at a solid/liquid (biomass/solvent) ratio of 1:10. Based on these results, citric acid aqueous solutions were identified as the best solvent, and an experimental design was carried out to optimize the temperature (T), solid/liquid ratio (S:L) and concentration of acid (wt.%), with the following optimal extraction conditions found: T = 60 °C, S:L = 1:7 and concentration of acid at 58 wt%. Under these optimal conditions, an extraction efficiency of 9.2 ± 0.1 wt% of levodopa was achieved. The recovery of levodopa from the acidic aqueous solution was achieved using an ion exchange column, allowing the recovery of approximately 84% of levodopa. The solvent was shown to be reusable in three successive extraction cycles, with no significant losses in the extraction efficiency of levodopa. The results here obtained show that citric acid aqueous solutions can lead to the effective extraction of levodopa from seeds of Mucuna pruriens, serving as basis for the development of more effective and environmentally friendly processes to recover natural products with therapeutic properties.

Pigments from microalgae and cyanobacteria have attracted great interest for industrial applications due to their bioactive potential and their natural product attributes. These pigments are usually sold as extracts, to overcome purification costs. The extraction of these compounds is based on cell disruption methodologies and chemical solubility of compounds. Different cell disruption methodologies have been used for pigment extraction, such as sonication, homogenization, high-pressure, CO2 supercritical fluid extraction, enzymatic extraction, and some other promising extraction methodologies such as ohmic heating and electric pulse technologies. The biggest constrain on pigment bioprocessing comes from the installation and operation costs; thus, fundamental and applied research are still needed to overcome such constrains and give the microalgae and cyanobacteria industry an opportunity in the world market. In this review, the main extraction methodologies will be discussed, taking into account the advantages and disadvantages for each kind of pigment, type of organism, cost, and final market., Foundation for Science and Technology (FCT, Portugal) under the auspices of Operational Program Human Capital (POCH), supported by the European Social Fund and Portuguese funds (MECTES); as well as by the national funds through FCT within the scope of UIDB/04423/2020, UIDP/04423/2020 and UIDB/04469/2020, info:eu-repo/semantics/publishedVersion

Battery separator membranes for lithium-ion batteries have been developed based on poly(vinylidene fluoride), PVDF, and using the “green solvent” - N,N’-dimethylpropyleneurea (DMPU). This separator presents a porous microstructure with a degree of porosity of 20% and pore size below 1 µm, showing excellent mechanical properties. Further, its ionic conductivity, tortuosity and MacMullin number values are 0.1 mS.cm-1, 4 and 82, respectively. This PVDF separator membrane was evaluated in Li/C–LiFePO4 half-cells with electrolyte solution showing good cyclability and rate capability, with a discharge value after 50 cycles of 56 mAh.g-1 at C, corresponding to 50% of the capacity retention. Its electrochemical performance soaked in ionic liquid presents a discharge capacity of 45 mAh.g -1 at C/5-rate and capacity retention of 60 %, respectively. Thus, this separator is an appropriate candidate for environmentally friendlier and safer lithium-ion batteries., This work was supported by the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Funding UID/FIS/04650/2013. The authors thank FEDER funds through the COMPETE 2020 Programme and National Funds through FCT under the projects PTDC/CTM-ENE/5387/2014 and UID/CTM/50025/2013 and grants SFRH/BD/90313/2012 (A.G.), and SFRH/BPD/112547/2015 (C.M.C.). The authors acknowledge funding by the Spanish Ministry of Economy and Competitiveness (MINECO) through the project MAT2016-76039- C4-3-R (AEI/FEDER, UE) and from the Basque Government Industry Department under the ELKARTEK program., info:eu-repo/semantics/publishedVersion

Despite the enormous potential shown by recent biorefineries, the current bioeconomy still encounters multifaceted challenges. To develop a sustainable biorefinery in the future, multidisciplinary research will be essential to tackle technical difficulties. Herein, we leveraged a known plant genetic engineering approach that results in aldehyde-rich lignin via down-regulation of cinnamyl alcohol dehydrogenase (CAD) and disruption of monolignol biosynthesis. We also report on renewable deep eutectic solvents (DESs) synthesized from phenolic aldehydes that can be obtained from CAD mutant biomass. The transgenic Arabidopsis thaliana CAD mutant was pretreated with the DESs and showed a twofold increase in the yield of fermentable sugars compared with wild type (WT) upon enzymatic saccharification. Integrated use of low-recalcitrance engineered biomass, characterized by its aldehyde-type lignin subunits, in combination with a DES-based pretreatment, was found to be an effective approach for producing a high yield of sugars typically used for cellulosic biofuels and biobased chemicals. This study demonstrates that integration of renewable DES with plant genetic engineering is a promising strategy in developing a closed-loop process.

The aim of this work consisted of investigating the influence of the pressure applied with high pressure homogenizer with Microfluidizer® technology (2500, 5000, 7500, 10000, 12500 y 15000 psi) on the droplet size distribution and physical stability of O/W emulsions formulated with thyme essential oil and an alkyl poly pentoside as an emulsifier. In addition, the number of passes (1 or 2 cycles) through the homogenizer is also studied. In order to study the quality of emulsions, techniques such as laser diffraction and multiple light scattering have been used together. It has been shown that, in general, for thyme essential oil emulsions stored at 4ºC, the lower the pressure applied and the number of passes through the homogenizer the better the physical stability being the main mechanisms of destabilization the creaming and the so-called oiling off. This work contributes to the development of ecological emulsions with the added value of that they have antimicrobial properties which is very interesting in industries such as food, cosmetics or agrochemical El objetivo de este trabajo ha consistido en investigar cómo influye la presión aplicada en homogeneizador de alta presión con tecnología Microfluidizer® (2500, 5000, 7500, 10000, 12500 y 15000 psi) sobre la distribución de tamaños de gota y estabilidad física de una emulsión O/W formulada con aceite esencial de tomillo y un alquil polipentósido como emulsionante. Adicionalmente se estudia la influencia del número de pasadas (1 y 2) a través del homogeneizador. Para estudiar la calidad de las emulsiones se han utilizado conjuntamente técnicas como la difracción láser y el multiple light scattering. Se ha demostrado que, en general, para las emulsiones de aceite esencial de tomillo almacenadas en frío, a una temperatura de 4ºC, cuanto menor es la presión aplicada y el número de pasadas a través del homogeneizador mejor es la estabilidad física de las mismas siendo los principales mecanismos de desestabilización el cremado y el conocido como oiling off. Este trabajo contribuye al desarrollo de emulsiones ecológicas que tienen además el valor añadido de poseer propiedades antimicrobianas, propiedades de gran interés en industrias como la alimentaria, la cosmética o la agroquímica. Spanish Ministerio de Economía y Competitividad-CTQ2015-70700 European Commission (FEDER Programme)

Background Green organic solvents such as lactate esters have broad industrial applications and favorable environmental profiles. Thus, manufacturing and use of these biodegradable solvents from renewable feedstocks help benefit the environment. However, to date, the direct microbial biosynthesis of lactate esters from fermentable sugars has not yet been demonstrated. Results In this study, we present a microbial conversion platform for direct biosynthesis of lactate esters from fermentable sugars. First, we designed a pyruvate-to-lactate ester module, consisting of a lactate dehydrogenase (ldhA) to convert pyruvate to lactate, a propionate CoA-transferase (pct) to convert lactate to lactyl-CoA, and an alcohol acyltransferase (AAT) to condense lactyl-CoA and alcohol(s) to make lactate ester(s). By generating a library of five pyruvate-to-lactate ester modules with divergent AATs, we screened for the best module(s) capable of producing a wide range of linear, branched, and aromatic lactate esters with an external alcohol supply. By co-introducing a pyruvate-to-lactate ester module and an alcohol (i.e., ethanol, isobutanol) module into a modular Escherichia coli (chassis) cell, we demonstrated for the first time the microbial biosynthesis of ethyl and isobutyl lactate esters directly from glucose. In an attempt to enhance ethyl lactate production as a proof-of-study, we re-modularized the pathway into (1) the upstream module to generate the ethanol and lactate precursors and (2) the downstream module to generate lactyl-CoA and condense it with ethanol to produce the target ethyl lactate. By manipulating the metabolic fluxes of the upstream and downstream modules through plasmid copy numbers, promoters, ribosome binding sites, and environmental perturbation, we were able to probe and alleviate the metabolic bottlenecks by improving ethyl lactate production by 4.96-fold. We found that AAT is the most rate-limiting step in biosynthesis of lactate esters likely due to its low activity and specificity toward the non-natural substrate lactyl-CoA and alcohols. Conclusions We have successfully established the biosynthesis pathway of lactate esters from fermentable sugars and demonstrated for the first time the direct fermentative production of lactate esters from glucose using an E. coli modular cell. This study defines a cornerstone for the microbial production of lactate esters as green solvents from renewable resources with novel industrial applications.

Graphical abstract, Highlights • Natural ternary deep eutectic solvents deconstructed corn straw without pollution. • Ultrasound and microwave enhanced the deconstruction by deep eutectic solvent. • Ultrasound/microwave sequential pretreatment increased cellulose content by 76.08%. • The removal of lignin was 46.44% under mild pretreatment conditions. • The mechanism of deconstruction of corn straw was proposed., Mild and effective pretreatments are essential to deconstruct lignocellulosic biomass so as to reuse cellulose content for value-added products. In this study, sequential multimode-ultrasound and microwave with natural ternary deep eutectic solvent (NATDES) pretreatments were used to deconstruct corn straw and optimized factors such as NATDES, ultrasonic, and microwave parameters. Results indicated that the ultrasound-NATDES or microwave-NATDES pretreatment could remove 37.86% and 52.36% lignin, respectively. When using sequential multimode-ultrasound and microwave assisted NATDES pretreatment, the delignification efficiency increased to 61.50%, and the cellulose content increased from 34.70% to 76.08%. In addition, the delignification of sequential multimode-ultrasound and microwave assisted NATDES pretreatment (under the mild conditions of microwave heating at 60 °C and 60 min) increased to 57.39%, and the cellulose content increased to 59.98%, too. This highlighted the effect of the combined ultrasound and microwave technology. Finally, the microstructural changes of mercury intrusion porosimeters, scanning electron microscopy, thermogravimetric, X-ray diffraction and Fourier transform mid-infrared spectroscopy were conducted to confirm the effectiveness of this method to deconstruct corn straw. A mechanism of the deconstruction of corn straw biomass in NATDES with the assistance of the sequential multimode-ultrasound and microwave heating was proposed. This research could open a window for future use of biomass energy by deconstructing lignocellulosic biomasses using environmentally friendly pretreatment methods.