Determination of the Composition of Bio-Oils from the Pyrolysis of Orange Waste and Orange Pruning and Use of Biochars for the Removal of Sulphur from Waste Cooking Oils

Waste generated in the agri-food sector is a potential source of biomass and other products of high added value. In this work, the pyrolysis of orange waste and orange pruning was carried out to produce adsorbent biochars and characterise the bio-oils aiming for high-added-value compounds. Pyrolysis was carried out in a vertical tubular furnace on the laboratory scale modifying the temperature (400–600 °C), the heating ramp (5–20 °C·min−1) to reach the previous temperature and the inert gas flow rate (30–300 mL Ar·min−1) throughout the furnace. The most suitable conditions for obtaining biochar were found to be 400 °C, 5 °C·min−1, and 150 mL Ar·min−1 for orange waste, and 400 °C, 10 °C·min−1, and 150 mL Ar·min−1 for orange pruning. Thermogravimetric analysis showed higher thermal stability for orange pruning due to its higher lignin content (20% vs. 5% wt. on a wet basis). The bio-oil composition was determined by GC-MS. Toluene and 5-hydroxymethylfurfural were the main compounds found in orange waste bio-oils, while orange pruning bio-oils were composed mainly of 4-hydroxy-4-methyl-2-pentanone. Finally, the removal of the sulphur content from waste cooking oil was assayed with the biochars from both orange waste and orange pruning, whose BET surface areas were previously determined. Despite their low specific surface areas (≤1 m2·g−1 for orange waste biochars and up to 24.3 m2·g−1 for orange pruning biochars), these biochars achieved a reduction of the initial sulphur content of the waste cooking oil between 66.4% and 78.8%.European Union under the LIFE 13 BIOSEVILLE Programme ENV/ES/1113 (analysis, materials and salaries)European Regional Development Fund (ERDF) through the CARBOENERGY project (materials and salaries) granted by the FEDER INNTERCONECT

Production of Bio-Oils and Biochars from Olive Stones: Application of Biochars to the Esterification of Oleic Acid

Olive stones are a by-product of the olive oil industry. In this work, the valorisation of olive stones through pyrolysis was attempted. Before pyrolysis, half of the samples were impregnated with sulphuric acid. Pyrolysis was carried out in a vertical tubular furnace with a ceramic support. The pyrolysis conditions assayed were: temperature between 400 and 600 °C, heating ramp between 5 and 20 °C∙min−1, and inert gas flow rate between 50 and 300 mL Ar∙min−1. Among them, temperature was the only parameter that influenced the pyrolysis product distribution. The most suitable temperature for obtaining biochar was 400 °C for both non-treated and pre-treated raw material, while for obtaining bio-oil, it was 600 °C for impregnated olive stones and 400 °C for the raw material. The impregnated olives stones led to bio-oils with much higher amounts of high-added-value products such as levoglucosenone and catechol. Finally, the biochars were impregnated with sulphuric acid and assayed as biocatalysts for the esterification of oleic acid with methanol in a stirred tank batch reactor at 60 °C for 30 min. Biochars from non-treated olive stones, which had lower specific surfaces, led to higher esterification yields (up to 96.2%).European Union under grant LIFE 13-Bioseville ENV/1113FEDER funds through the CARBOENERGY project FEDER INNTERCONECTA 2018 cal

Energetic Valorisation of Olive Biomass: Olive-Tree Pruning, Olive Stones and Pomaces

Olive oil industry is one of the most important industries in the world. Currently, the land devoted to olive-tree cultivation around the world is ca. 11 106 ha, which produces more than 20 106 t olives per year. Most of these olives are destined to the production of olive oils. The main by-products of the olive oil industry are olive-pruning debris, olive stones and di erent pomaces. In cultures with traditional and intensive typologies, one single ha of olive grove annually generates more than 5 t of these by-products. The disposal of these by-products in the field can led to environmental problems. Notwithstanding, these by-products (biomasses) have a huge potential as source of energy. The objective of this paper is to comprehensively review the latest advances focused on energy production from olive-pruning debris, olive stones and pomaces, including processes such as combustion, gasification and pyrolysis, and the production of biofuels such as bioethanol and biodiesel. Future research e orts required for biofuel production are also discussed. The future of the olive oil industry must move towards a greater interrelation between olive oil production, conservation of the environment and energy generation

Signaling through the leukocyte integrin LFA-1 in T cells induces a transient activation of Rac-1 that is regulated by Vav and PI3K/Akt-1

12 p.-8 fig.Integrin LFA-1 is a receptor that is able to transmit multiple intracellular signals in leukocytes. Herein we show that LFA-1 induces a potent and transient increase in the activity of the small GTPase Rac-1 in T cells. Maximal Rac-1 activity peaked 10-15 min after LFA-1 stimulation and rapidly declined to basal levels at longer times. We have identified Vav, a guanine nucleotide exchange factor for Rac-1, and PI3K/Akt, as regulators of the activation and inactivation phases of the activity of Rac-1, respectively, in the context of LFA-1 signaling based on the following experimental evidence: (i) LFA-1 induced activation of Vav and PI3K/Akt with kinetics consistent with a regulatory role for these molecules on Rac-1, (ii) overexpression of a constitutively active Vav mutant induces activation of Rac independently of LFA-1 stimulation whereas overexpression of a dominant-negative Vav mutant blocks LFA-1-mediated Rac activation, (iii) pharmacological inhibition of PI3K/Akt prevented the fall in the activity of Rac-1 after its initial activation but had no effect on Vav activity, and (iv) overexpression of a dominant-negative or a constitutively active Akt-1 induced or inhibited, respectively, Rac-1 activity. Finally, we show that T cells with a sustained Rac activity have impaired capacity to elongate onto ICAM-1. These results demonstrate that down-regulation of the activity of this GTPase is a requirement for the regulation of T cell morphology and motility and highlight the importance of temporal regulation of the signaling triggered from this integrin.This work was supported in part by Grants CICYT SAF 2001–2807 from Ministerio de Ciencia y Tecnología and FIS-01/1367 from Ministerio de Sanidad y Consumo (to C. C.), a fellowship from Comunidad de Madrid (to L. S.-M.), a Formación de Profesorado Universitario predoctoral fellowship from Ministerio de Educación, Cultura y Deporte (to N. S.-S.), and a postdoctoral fellowship from Ministerio de Educación, Cultura y Deporte (to M. D. G.-L.).Peer reviewe

Identification of an acetyl esterase in the supernatant of the environmental strain Bacillus sp. HR21-6

Bacillus sp. HR21-6 is capable of the chemo- and regioselective synthesis of lipophilic partially acetylated phenolic compounds derived from olive polyphenols, which are powerful antioxidants important in the formulation of functional foods. In this work, an acetyl esterase was identified in the secretome of this strain by non-targeted proteomics, and classified in the GDSL family (superfamily SGNH). The recombinant protein was expressed and purified from Escherichia coli in the soluble form, and biochemically characterized. Site-directed mutagenesis was performed to understand the role of different amino acids that are conserved among GDSL superfamily of esterases. Mutation of Ser-10, Gly-45 or His-185 abolished the enzyme activity, while mutation of Asn-77 or Thr-184 altered the substrate specificity of the enzyme. This new enzyme is able to perform chemoselective conversions of olive phenolic compounds with great interest in the food industry, such as hydroxytyrosol, 3,4-dihydroxyphenylglycol, and oleuropein.Junta de Andalucía P11-CVI-7427 M

Divulgación en tiempos de pandemia: el poder de las webs

Trabajo presentado en el simposio Micromundo Aprendizaje-Servicio para el descubrimiento de antibiótico

Valorización de un aceite residual de alta acidez generado en las industrias de reciclaje de aceites de desecho de cocinas

A sludge fraction is obtained from the industries which recycle cooking oil and this sludge con-tains a large amount of oil with an extremely high acidity (> 60%). In this work, we propose a scheme for methyl ester production from this residual oil consisting of the esterification of the free fatty acids followed by the trans-esterification of the remaining triglycerides. Esterifications were carried out with different methanol:oil molar ratios, and various catalysts in different weight ratios. The results revealed that homogeneous catalysts produced higher yields than heterogeneous ones in the esterification reaction. With the aim of improving the process, a previous triglyceride hydrolysis was assayed using lipases from Candida rugosa. Finally, the 3-stage process was performed under the most favorable conditions for each stage obtaining 84% wt. fatty acid methyl esters, which shows the potential of this residual oil as a source of biodiesel.En las industrias de recogida y reciclado de aceites de fritura usados se obtiene una fracción de lodos que contiene un gran porcentaje de aceite con un extremadamente alto índice de acidez (> 60%). En este trabajo proponemos un esquema de producción de ésteres metílicos basado en la esterificación de los ácidos grasos libres seguida de la transesterificación de los triglicéridos remanentes. Las esterificaciones se llevaron a cabo usando diferentes relaciones molares metanol: aceite y diversos catalizadores en diferentes concentraciones en peso. Los resultados ilustraron que los catalizadores homogéneos alcanzaron mayores rendimientos en la esterificación que los catalizadores heterogéneos. Para mejorar el proceso, se probó una hidrólisis previa con lipasas de Candida rugosa. Finalmente, se llevó a cabo el proceso con las 3 etapas, en las condiciones más favorables de cada una de ellas, obteniendo un 84% en peso de ésteres metílicos, lo que muestra el potencial de este aceite residual como fuente de biodiésel.European Union Funds grant LIFE 13-Bioseville ENV/111

Estrogen Receptor-Alpha (ESR1) Governs the Lower Female Reproductive Tract Vulnerability to Candida albicans

Estradiol-based therapies predispose women to vaginal infections. Moreover, it has long been known that neutrophils are absent from the vaginal lumen during the ovulatory phase (high estradiol). However, the mechanisms that regulate neutrophil influx to the vagina remain unknown. We investigated the neutrophil transepithelial migration (TEM) into the vaginal lumen. We revealed that estradiol reduces the CD44 and CD47 epithelial expression in the vaginal ectocervix and fornix, which retain neutrophils at the apical epithelium through the estradiol receptor-alpha. In contrast, luteal progesterone increases epithelial expression of CD44 and CD47 to promote neutrophil migration into the vaginal lumen and Candida albicans destruction. Distinctive to vaginal mucosa, neutrophil infiltration is contingent to sex hormones to prevent sperm from neutrophil attack; although it may compromise immunity during ovulation. Thus, sex hormones orchestrate tolerance and immunity in the vaginal lumen by regulating neutrophil TEM.The authors thank the units of flow cytometry, cell culture and statistical analysis. We are grateful to J. Villarejo, M. Fernandez-Garcia, and F. Sanchez-Cobos, for expert help and support. This work was partially supported by Fundacion Mutua Madrilena and the Ministry of Economy and Competitiveness ISCIII-FIS grants PI13/00269, PI16/00050, and PI17/01324, co-financed by ERDF (FEDER) Funds from the European Commission, ``A way of making Europe.´´ MR holds a Miguel Servet II contract (CPII14/00009). LS-M holds a IiSGM intramural contract.S