Suchergebnisse

The Diels–Alder reaction is a prototypical example of a thermally allowed [4 + 2] cycloaddition with good control over the regio- and stereochemical outcomes. Therefore, Diels–Alder reactions in which adjacent stereocenters are generated at the two ends of the newly formed single bonds imply two different possible stereochemical outcomes. In cases where the dienophile has a single electron-withdrawing substituent, the outcome can often be predicted by applying the known "endo rule". Furthermore, the use of chiral eutectic solvents in asymmetric synthesis has become a novel tool to maintain sustainability in organic synthesis. In the present work, a set of recyclable and sustainable bio-based deep eutectic solvents (DESs) was designed using hydrogen bond acceptors (HBAs) with a chiral center. These compounds were used in their racemic and enantiomerically enriched forms to prepare DESs with lactic acid (LA), glycerol (Gly), and ethylene glycol, which act as hydrogen bond donors (HBDs) in the corresponding eutectic mixture. These DESs were used as solvents to study the reaction between cyclopentadiene and ethyl acrylate or butyl acrylate in typical [4 + 2] cycloadditions. The best yields and endo-selectivity were achieved using LA as the HBD in the eutectic mixtures. The results and adduct ratios obtained show that these DESs were able to improve both reaction yields and selectivity when compared to those observed in organic solvents or ionic liquids. Moreover, the reaction products (adducts) were easily recovered with diethyl ether from the reaction mixture, where they appeared as an upper layer. ; The authors are grateful to the DBA center for providing the research facilities and equipment. DBA is a certified agent TECNIO in the category of technology developers from the Government of Catalonia. The authors would like to thank the Catalan Government for the quality accreditation given to the Agricultural Biotechnology and Bioeconomy Unit (2017 SGR 828). This work has been partially funded by the Spanish government grant (PID2019-110735RB-C21-MINECO/ FEDER) and Catalan government grant (2017 SGR 828).

Using the basic principle of construction between a hydrogen bond acceptor (HBA) and a hydrogen bond donor (HBD), four bio-based deep eutectic solvents (DESs) were prepared in a 1:2 molar ratio of HBA:HBD. 2,3-Dihydroxypropyl-1-triethylammonium chloride ([C9H22N+O2]Cl婨 ) was synthesized from raw glycerol and used as an HBA. Lactic acid, urea, pure glycerol, and ethylene glycol were selected as HBD. Attempts to prepare DESs, using citric acid and benzoic acid as HBDs, were unsuccessful. All these DESs were characterized using FTIR and NMR techniques. Besides, physicochemical parameters such as pH, viscosity, density, and melting point were determined. The behavior of these DES to fractionate olive pomace was studied. Lignin recovery yields spanned between 27% and 39% (w/w) of the available lignin in olive pomace. The best DES, in terms of lignin yield ([C9H22N+O2]Cl婨 -lactic acid), was selected to perform a scale-up lignin extraction using 40 g of olive pomace. Lignin recovery on the multigram scale was similar to the mg scale (38% w/w). Similarly, for the holocellulose-rich fractions, recovery yields were 34% and 45% for mg and multi-gram scale, respectively. Finally, this DES was used to fractionate four fruit pruning samples. These results show that our novel DESs are alternative approaches to the ionic liquid:triethylammonium hydrogen sulfate and the widely used DES: choline chloride:lactic acid (1:10 molar ratio) for biomass processing ; This work has been partially funded by the Spanish government (CTQ2015-70982-C3-1-R (MINECO/FEDER).

The compound 2,5-di(hydroxymethyl)furan (DHMF) is a high-value chemical block that can be synthesized from 5-hydroxymethylfurfural (HMF), a platform chemical that results from the dehydration of biomass-derived carbohydrates. In this work, the HMF biotransformation capability of different Fusarium species was evaluated, and F. striatum was selected to produce DHMF. The effects of the inoculum size, glucose concentration and pH of the media over DHMF production were evaluated by a 23 factorial design. A substrate feeding approach was found suitable to overcome the toxicity effect of HMF towards the cells when added at high concentrations (>75 mM). The process was successfully scaled-up at bioreactor scale (1.3 L working volume) with excellent DHMF production yields (95%) and selectivity (98%). DHMF was purified from the reaction media with high recovery and purity by organic solvent extraction with ethyl acetate. ; This work was partially supported by the Spanish government (PID2019-110735RB-C21, MICIN/FEDER) and the Catalan Government (FI_B1_00135).

The preparation of compounds of interest from biomass-derived 5-hydroxymethylfurfural (HMF) has attracted considerable attention. One such compound is 2,5-diformylfuran (DFF), obtained through oxidation of the hydroxyl group of HMF. Herein, we describe for the first time the whole-cell oxidation of HMF to DFF by Fusarium culmorum EAN 51. Although the chemocatalytic transformation of HMF into DFF has been widely studied, biocatalytic processes have been scarcely reported and are limited to enzymatic synthesis using the combination of several enzymes. The whole-cell transformation of HMF into DFF is preferable thanks to the inherent presence of the different enzymes, significantly reducing the cost of the process. F. culmorum showed a high capability to reduce to 2,5-di(hydroxymethyl)furan (DHMF) and oxidize to DFF the substrate with high yields depending on the nitrogen source and the concentration of peptone and glucose in the media, which highly affected the redox capability of this strain. After careful optimization of the concentration of both nutrients through response surface methodology, 50 mM HMF were transformed into DFF with a high yield (92%) and selectivity (94%). These results open a new line of investigation in the sustainable production of DFF from renewable biobased resources. ; This work was partially supported by the Spanish Government (PID2019-110735RB-C21, MICIN/FEDER) and the Catalan Government (FI_B1_00135).

Here we studied the modification of fibres derived from the fruit juice industry to prepare new value-added ingredients. These by-products are usually composted or used as animal feed. In this regard, fibres from apple, peach, and citrus fruit were enzymatically treated to improve their functional properties, with the aim to use them as food ingredients. Several enzymes were selected to modify various parts of the polymers present in the fibres. The effect of the treatments was assessed by comparing the water-holding capacity (WHC) and swelling water capacity (SWC) of the modified and raw fibres. FTIR spectrometry was also used to monitor changes in fibre structure. After the enzymatic modifications, some of these fibres not only showed an increase in WHC and SWC compared with the starting material but also greater viscosity. ; We acknowledge funding from Spanish Government (MINECO grant number: RTC-2015-3652-5) and Catalan Government, 2014 SGR 1296 Agricultural Biotechnology research group.

Here we authenticated single-varietal peach purees and pear juices on the basis of primary metabolite and phenolic compound analysis by Proton Nuclear Magnetic Resonance (1H-NMR) and Ultra Performance Liquid Chromatography coupled to Photodiode Array and Tandem Mass Spectrometry (UPLC-PDA-MS/MS), respectively. After suitable preprocessing, the 1H-NMR and chromatographic data were evaluated by principal component analysis (PCA). The PCA combining data from primary metabolites and phenolic compounds allowed the separation of the clusters in all cases, allowing discrimination of processed and unprocessed peach purees, both separately and pooled. The PCA of primary metabolites allowed the cluster separation of purees of distinct peach varieties but not between processed and non-processed purees. The PCA of phenolic compounds allowed better cluster separation than of primary metabolites. For pear juices, both PCA approaches allowed satisfactory discrimination of Alejandrina, Conference, and Blanquilla cultivars. These approaches may help to better control cultivar authenticity in fruit products. It could therefore contribute to the development of a process to achieve products characterized by a quality characteristic of a given cultivar. ; This research was funded by the Catalan Government, grant number [2017 SGR 828].

Since solvents of petroleum origin are now strictly regulated worldwide, there is a growing demand for using greener, bio-based and renewable solvents for extraction, purification and formulation of natural and food products. The ideal alternative solvents are non-volatile organic compounds (VOCs) that have high dissolving power and flash point, together with low toxicity and less environmental impact. They should be obtained from renewable resources at a reasonable price and be easy to recycle. Based on the principles of Green Chemistry and Green Engineering, vegetable oils could become an ideal alternative solvent to extract compounds for purification, enrichment, or even pollution remediation. This review presents an overview of vegetable oils as solvents enriched with various bioactive compounds from natural resources, as well as the relationship between dissolving power of non-polar and polar bioactive components with the function of fatty acids and/or lipid classes in vegetable oils, and other minor components. A focus on simulation of solvent-solute interactions and a discussion of polar paradox theory propose a mechanism explaining the phenomena of dissolving polar and non-polar bioactive components in vegetable oils as green solvents with variable polarity. ; Edinson Yara Varón thanks to fellowship funding (No. TECSPR14-2-0029) from the People Programme (Marie Curie Actions) of the Seventh Framework Programme of the European Union (FP7/2007-2013) under REA grant agreement No. 600388 (TECNIOspring programme), and from the Agency for Business Competitiveness of the Government of Catalonia, ACCIÓ. Ying Li would like to thank the National Natural Science Foundation of China (Grant 31701633) and the Fundamental Research Funds for the Central Universities (Grant 17817028), as well as special funds from "SanWu Talent 2014" and sixth "100-Talent" Programs.

Furfural (FF) and 5-hydroxymethylfurfural (HMF) are furan derivatives commonly generated during the pretreatment of lignocellulosic biomass and often considered among the most inhibitory compounds towards the sugar fermenting strains due to their acute toxicity and high concentrations. The present study describes the simultaneous detoxification and fermentation of lignocellulosic hydrolysates containing high concentrations of FF and HMF by a co-culture of a novel Fusarium striatum strain and a xylose consuming Saccharomyces cerevisiae strain. The process demonstrates a superior performance than those previously described in the literature, as FF and HMF were efficiently transformed into their less toxic added-value alcohol derivatives by F. striatum with high yields (99% and 86%, respectively) and the higher detoxification rates reported (0.56 g/L/h and 0.13 g/L/h, respectively). There was no sugar consumption by the filamentous fungus during the detoxification process, rendering it available for ethanol fermentation by S. cerevisiae, which started immediately after the detoxification of the inhibitors. Ethanol productivities were significantly higher when increasing the inoculum size of F. striatum, confirming its potential for the detoxification of the lignocellulosic hydrolysate. High ethanol yields (0.4 g/g) and productivities (0.46 g/L/h) were obtained in a bench-scale bioreactor (1.5 L) in the presence of 3.5 g/L HMF and 2.5 g/L FF, a concentration of furan derivatives that completely inhibited the fermentation process in the absence of F. striatum. The presented process allows access to lignocellulosic materials and pretreatment methods that result in high concentrations of FF and HMF that are currently not feasible, representing a significant advance for the lignocellulosic ethanol industry. ; This work was partially supported by the Spanish Government (PID2019-110735RB-C21, MICIN/FEDER) and the Catalan Government (FI_B1_00135). The support of the BIOPRO2 Strategic Research Center (Grant Agreement No. 4105-00020B) is gratefully acknowledged.

Nine monoamides were synthesized from carboxylic acids (C8-C18) and crude glycerol. The final monoamides were the result of a rearrangement of the acyl chain during the final hydrogenation process. The purity of the final compounds was determined by spectroscopic and mass spectrometry (MS) techniques. The thermophysical properties of solid monoamides were investigated to determine their capability to act as phase change materials (PCM) in thermal energy storage. Thermophysical properties were determined with a di erential scanning calorimeter (DSC). The melting temperatures of the analyzed material ranged from 62.2 C to 116.4 C. The analyzed enthalpy of these monoamides ranged from 25.8 kJ/kg to 149.7 kJ/kg. Enthalpy values are analyzed considering the carbon chain and the formation of hydrogen bonds. ; This work was partially funded by the Ministerio de Ciencia, Innovación y Universidades de España (grants: MINECO/FEDER CTQ2015-70982-C3-1-R and MINECO/FEDER RTI2018-093849-B-C31). This work is partially supported by ICREA under the ICREA Academia programme. Acknowledgments: R.C.-G. and L.F.C. would like to thank the Catalan Government for the quality accreditation given to their research groups (grants 2017 SGR 828 and GREiA 2017 SGR 1537, respectively). DBA and GREiA are certified agent TECNIO in the category of technology developers from the Government of Catalonia.

Pesticide remains contained in agrochemical packagingwaste are a source of uncontrolled risk for human health; they are also a quality feedstock for the plastic recycling industry.Many governments have recently started to establish laws and regulations to develop systems for recovering and recycling the polymeric packages used for pesticides. There is also a demand in having a procedure to control the suitability of the pesticide packages to be reused.We have developed a two-step operation process to assess the pesticide residues in agricultural containers made of a variety of polymeric matrices. The procedure is based on an extraction with a solvent mixture followed by UPLC-MS/MS determination. Solvents for neutral pesticides were selected considering the Hildebrand solubility (δ) of solvents and polymers togetherwith those estimated for the pesticides. The proposed technique is effective in recovering imbibed pesticides in polymeric matrices. Also, a simplified extraction procedure has been tested to become a routine method for these wastes. We have found that in many cases a significant amount of pesticides remain into the polymeric matrix, even after a standardized cleaning; the impact of releasing these hazardous compounds into the environment is to be of further consideration. ; The authors gratefully acknowledge generous support from the European Commission, SCT Programme MED, 2G-MED09-15, 2013, for the AgroChePack Project. The authors also want to thank to the professors Demetres Briassoulis and Miltiadis Hiskakis of Agricultural University of Athens, Greece, for providing the pesticide containers of Visaltia farmers.

"Formerly known as Journal of Molecular Catalysis A: Chemical" ; The thermal properties of various alkyl threo-9, 10-dihydroxystearates (DHSEs) prepared from non-edible fat were studied. Non-edible animal fat was hydrolyzed in a 93% yield with R. oryzae resting cells. Crude unsaturated fatty acids were recovered from the matter liquor resulting from a crystallization performed to achieve the saturated fatty acids. These unsaturated free fatty acids were epoxidized with 30% H2O2 using immobilized Candida antarctica Lipase-B (CAL-B) as biocatalyst. The epoxy ring was cleaved with hot water in the presence of tert-butanol (t-BuOH). Pure threo-9, 10-dihydroxystearic acid (DHSA) from animal fat was recovered by crystallization (51% yield). Subsequently, DHSA was esterified in alpha-limonene using biocatalysts yielding twelve DHSEs (58-90% yield). Differential scanning calorimetry (DSC) analysis of these esters revealed potential latent heats ranging from 136.83 kJ kg−1 to 234.22 kJ kg−1 and melting temperatures from 52.45 ◦C to 76.88 ◦C. Finally, the compounds with enthalpies above 200 kJ kg−1 were subjected to 100 and 1000 thermal cycles. These experiments showed that these products present good thermal reliability. ; GREA and DBA are certified agents TECNIO in the category of technology developers from the Government of Catalonia. We thanks to Subproductos Cárnicos Echevarria y Asociados S.L (Cervera, Spain) for supplying the non-edible fat. Moreover, the research leading to these results has received funding from the European Commission Seventh Framework Programme (FP/2007-2013) under grant agreement no PIRSES-GA-2013-610692 (INNOSTORAGE) and from the European Union's Horizon 2020 research and innovation program under grant agreement no 657466 (INPATH-TES). The authors would like to thank the Catalan Government for the quality accreditation given to their research groups GREA (2014 SGR 123) and Agricultural Biotechnology Research Group (2014 SGR 1296). This work has been partially funded by the Spanish government (CTQ2015-70982-C3-1-R (MINECO/FEDER) and ENE2015-64117-C5-1-R (MINECO/FEDER). Aran Solé would like to thank Ministerio de Economía y Competitividad de España for Grant Juan de la Cierva, FJCI-2015-25741.

A set of compounds from non-edible fat waste was prepared and their thermal behavior was studied. The fat was hydrolyzed and crystallized in a simple and robust process to yield palmitic acid-stearic acid (PA-SA) mixtures. The PA-SA mass ratios determined by GC-FID (gas chromatography-flame ionization detection) were similar to those reported for eutectic mixtures of PCMs (phase change materials). DSC (differential scanning calorimetry) results indicated that the melting and solidification temperatures were around 55 °C and 52 °C and the latent heat of the crystallized fractions measured was around 180 kJ kg−1. The thermal cycling reliability of the eutectic mixtures was also tested during 1000 melting/freezing cycles. The loss in melting and solidification enthalpies was below 14% in all mixtures showing a promising behavior for PCM applications. Additionally, the unsaturated fatty acids were recovered and transformed to threo-9,10-dihydroxystearic acid (DHSA) and some of their inorganic salts, which were analyzed by FT-IR (Fourier transform-infrared spectroscopy) and tested for the first time using the DSC technique. ; GREA and DBA are certified agents TECNIO in the category of technology developers from the Government of Catalonia. We thanks to Subproductos Cárnicos Echevarria y Asociados S.L (Cervera, Spain) for supplying the non-edible fat. Moreover, the research leading to these results has received funding from the European Commission Seventh Framework Programme (FP/2007–2013) under grant agreement no. PIRSES-GA-2013-610692 (INNOSTORAGE) and from the European Union's Horizon 2020 research and innovation program under grant agreement no. 657466 (INPATH-TES). The authors would like to thank the Catalan Government for the quality accreditation given to their research groups GREA (2014 SGR 123), Agricultural Biotechnology Research Group (2014 SGR 1296) and DIOPMA (2014 SGR 1543). This work has been partially funded by the Spanish government (CTQ2015-70982-C3-1-R (MINECO/FEDER), ENE2015-64117-C5-1-R (MINECO/FEDER) and ENE2015-64117-C5-2-R (MINECO/FEDER)). Dr Camila Barreneche would like to thank Ministerio de Economia y Competitividad de España for her grant Juan de la Cierva FJCI-2014-22886. Aran Solé would like to thank Ministerio de Economía y Competitividad de España for Grant Juan de la Cierva, FJCI-2015-25741.

Ionic liquids (diimidazol-1-ium esters) prepared from wastes, crude glycerol and carboxylic acids are investigated as potential phase change materials (PCM). The ionic liquids (IL) with best thermophysical properties were those with also better production yield (higher than 75%). The chemical composition of those IL was with R1 being (CH3)3CCO, CH3(CH2)14CO or C2H3CO; R2 being BIM+; R3 being BIM+; and X- being 2 Cl‾. Phase change of state (solid-liquid) of this IL was 85 ºC, 264 ºC and 128 ºC, which means potential application in different fields such as domestic hot water, solar cooling and industry, respectively. The measured melting enthalpy 328 kJ/kg, 408 kJ/kg, and 660 kJ/kg is much higher in all cases than the usual found in commercial PCM (100 kJ/kg), therefore, these ILs synthetized in this study are proper candidates to be used as PCM because of the huge amounts of energy that they are able to store and their low cost. Moreover, biobPCM are sustainable materials since its obtaining process is based on oil. ; The work is partially funded by the Spanish government (ENE2015-64117-C5-1-R (MINECO/FEDER) and CTQ2015-70982-C3-1-R (MINECO/FEDER)). The authors would like to thank the Catalan Government for the quality accreditation given to the research groups GREA (2014 SGR 123), Agricultural Biotechnology (2014 SGR 1296) and DIOPMA (2014 SGR 1543). Dr. Camila Barreneche would like to thank Ministerio de Economia y Competitividad de España for Grant Juan de la Cierva, FJCI-2014-22886.The research leading to these results has received funding from the European Union's Seventh Framework Program (FP7/2007–2013) under grant agreement n° PIRSES-GA-2013-610692 (INNOSTORAGE) and from the European Union's Horizon 2020 research and innovation program under grant agreement No 657466 (INPATH-TES).