Direct Biocatalytic Processes for CO2 Capture as a Green Tool to Produce Value-Added Chemicals.

Direct biocatalytic processes for CO2 capture and transformation in value-added chemicals may be considered a useful tool for reducing the concentration of this greenhouse gas in the atmosphere. Among the other enzymes, carbonic anhydrase (CA) and formate dehydrogenase (FDH) are two key biocatalysts suitable for this challenge, facilitating the uptake of carbon dioxide from the atmosphere in complementary ways. Carbonic anhydrases accelerate CO2 uptake by promoting its solubility in water in the form of hydrogen carbonate as the first step in converting the gas into a species widely used in carbon capture storage and its utilization processes (CCSU), particularly in carbonation and mineralization methods. On the other hand, formate dehydrogenases represent the biocatalytic machinery evolved by certain organisms to convert CO2 into enriched, reduced, and easily transportable hydrogen species, such as formic acid, via enzymatic cascade systems that obtain energy from chemical species, electrochemical sources, or light. Formic acid is the basis for fixing C1-carbon species to other, more reduced molecules. In this review, the state-of-the-art of both methods of CO2 uptake is assessed, highlighting the biotechnological approaches that have been developed using both enzymes.

Plasma Exchange: An Effective Rescue Therapy in Critically Ill Patients With Coronavirus Disease 2019 Infection.

OBJECTIVES: Infection by severe acute respiratory syndrome coronavirus-2 can induce uncontrolled systemic inflammation and multiple organ failure. The aim of this study was to evaluate if plasma exchange, through the removal of circulating mediators, can be used as rescue therapy in these patients. DESIGN: Single center case series. SETTING: Local study. SUBJECTS: Four critically ill adults with coronavirus disease 19 pneumonia that failed conventional interventions. INTERVENTIONS: Plasma exchange. Two to six sessions (1.2 plasma volumes). Human albumin (5%) was used as the main replacement fluid. Fresh frozen plasma and immunoglobulins were administered after each session to avoid coagulopathy and hypogammaglobulinemia. MEASUREMENTS AND MAIN RESULTS: Serum markers of inflammation and macrophage activation. All patients showed a dramatic reduction in inflammatory markers, including the main cytokines, and improved severity scores after plasma exchange. All survived to ICU admission. CONCLUSIONS: Plasma exchange mitigates cytokine storm, reverses organ failure, and could improve survival in critically ill patients with coronavirus disease 2019 infection.

Sustainable Setups for the Biocatalytic Production and Scale-Up of Panthenyl Monoacyl Esters under Solvent-Free Conditions.

A sustainable scaling-up process for the biocatalytic production of new bioactive provitamin-B5 monoacyl esters has been demonstrated. A solvent-free reaction protocol, based on the formation of eutectic mixtures between neat substrates, renders highly efficient direct esterification of free fatty acids (i.e., from C6 to C18 alkyl-chain length) with panthenol catalyzed by lipase. The scale-up from 0.5 to 500 g was evaluated by means of using several reaction systems (i.e., ultrasound assistance, orbital shaking, rotary evaporator, and mechanical stirring coupled to vacuum). For all reactor systems, the yield in panthenyl monoacyl esters was improved by increasing the length of the alkyl chain of the fatty acid (i.e., from 63% yield for panthenyl butyrate to 83% yield for panthenyl myristate). The best results (87-95% product yield, for all cases) were obtained upon a scale-up (50-500 g size) and when a vacuum system was coupled to the biocatalytic reaction unit. Under the optimized conditions, a 5-fold reduction of the amount of biocatalysts with respect to reactors without vacuum was achieved. The recovery and reuse of the immobilized enzyme for five operation cycles were also demonstrated. Finally, different metrics have been applied to assess the greenness of the solvent-free biocatalytic synthesis of panthenyl monoesters here reported.

Ultrasound-assisted enzymatic synthesis of xylitol fatty acid esters in solvent-free conditions.

A commercial immobilized lipase was successfully used for the synthesis of five xylityl acyl esters by means of the esterification of free fatty acids (caprylic, capric, lauric and myristic, respectively) with xylitol under solvent-free conditions. Ultrasound-assistance was shown to be a key tool to overcome the handicap imposed by both the mutual immiscibility of fatty acids and xylitol substrates, and the semisolid character of the initial reaction mixtures. In such semisolid systems, ultrasonic irradiation may enable the transport of substrate molecules to the enzyme catalytic-site, leading to the efficient synthesis of xylityl fatty ester (e.g. up to 95% yield after 90 min at 40 °C), with xylityl monoacyl ester and xylitol diacyl ester appearing as the main products (greater than 96%), assessed by HPLC and NMR analyses. The separation of products was carried out by heating and simple centrifugation of the reaction medium, which was possible due to different densities of the resulting fractions.

Active biopolymers in green non-conventional media: a sustainable tool for developing clean chemical processes.

The greenness of chemical processes turns around two main axes: the selectivity of catalytic transformations, and the separation of pure products. The transfer of the exquisite catalytic efficiency shown by enzymes in nature to chemical processes is an important challenge. By using appropriate reaction systems, the combination of biopolymers with supercritical carbon dioxide (scCO2) and ionic liquids (ILs) resulted in synergetic and outstanding platforms for developing (multi)catalytic green chemical processes, even under flow conditions. The stabilization of biocatalysts, together with the design of straightforward approaches for separation of pure products including the full recovery and reuse of enzymes/ILs systems, are essential elements for developing clean chemical processes. By understanding structure-function relationships of biopolymers in ILs, as well as for ILs themselves (e.g. sponge-like ionic liquids, SLILs; supported ionic liquids-like phases, SILLPs, etc.), several integral green chemical processes of (bio)catalytic transformation and pure product separation are pointed out (e.g. the biocatalytic production of biodiesel in SLILs, etc.). Other developments based on DNA/ILs systems, as pathfinder studies for further technological applications in the near future, are also considered.

Effect of supplementation with docosahexaenoic acid ethyl ester and sn-2 docosahexaenyl monoacylglyceride on plasma and erythrocyte fatty acids in rats.

BACKGROUND/AIMS: Docosahexaenoic acid (C22:6, DHA) is an omega-3 fatty acid required for the normal development of the mammalian nervous and visual system. DHA is provided by the mother during pregnancy and lactating period. Mother's DHA supplementation during pregnancy, and even before pregnancy, has been suggested. DHA can be provided by marine oils, egg's yolk phospholipids, single cell algae oils, the pure fatty acid, or by the ethyl ester derivative (DHA-EE). Another way to provide DHA can be by sn-2 docosahexaenyl monoacylglyceride (DHA-MG), obtained by the treatment of fish oil with stereospecific lipases. sn-2 Fatty acid monoacylglycerides can be more easily absorbed at the intestine than other fatty acid derivatives. METHODS: Female rats fed with a synthetic, which provided essentially no DHA, received a 40-day supplementation of either DHA-EE or DHA-MG. Plasma and erythrocyte fatty acid composition were assessed by gas chromatography at day 0 and 40 of supplementation. RESULTS: DHA-EE increased plasma and erythrocyte DHA by 15 and 11.9%, respectively, with no modification of arachidonic acid (AA) content. DHA-MG supplementation increased plasma and erythrocyte DHA by 24 and 23.8%, respectively, but reduced AA by 5.5 and 3%, respectively. CONCLUSIONS: We conclude that in the rat, DHA-MG supplementation allows a higher plasma and erythrocyte DHA content than DHA-EE with minor modification of AA content.

Tissue accretion and milk content of docosahexaenoic acid in female rats after supplementation with different docosahexaenoic acid sources.

BACKGROUND: Docosahexaenoic acid (DHA) is highly concentrated in the mammalian nervous and visual system. The fatty acid, which is required by the fetus and the newborn, is supplied by the mother from their tissue reservoirs. It has been suggested that mother's supplementation with DHA during pregnancy and even before pregnancy. Different sources of DHA are available for supplementation such as: single-cell algae triglycerides (TG), egg's yolk phospholipids (PL), DHA ethyl esther (EE), and sn-2 DHA monoacylglyceride (MG). We evaluated comparatively the effectiveness of these different DHA sources to produce tissue DHA accretion and to increase milk DHA content. METHODS: Female Wistar rats fed a diet which provided no DHA, were daily supplemented by 40 days before mating (BM) and during the pregnancy with either TG, PL, EE, or MG to an amount which provided 8 mg/kg b.w. of DHA. Samples of blood plasma, erythrocytes, hepatic and adipose tissue were obtained from rats at the BM condition and after the delivery (AD), and milk samples were also obtained from the gastric content of the pups nursed by the rats at day 3, 11 and 20 of suckling. Samples were processed to assess DHA and arachidonic acid (AA) content by gas-chromatography. RESULTS: TG, PL, EE, and MG supplementation produced a similar intestinal absorption of DHA as estimated from the plasma DHA at the BM condition. However, PL and MG supplementation produced a higher accretion of DHA into erythrocytes, hepatic, and adipose tissue than TG and EE supplementation at the BM condition. AA content was not modified by the different supplementing oils. A reduction of the DHA content of plasma, erythrocytes, hepatic and adipose tissue at the AD condition was observed, and a reduction of AA for the hepatic and adipose tissues was also observed, suggesting the importance of these tissues as DHA and AA reservoirs. Milk secretion from PL and MG supplemented rats showed a higher DHA content than secretion from TG- and EE-supplemented rats. CONCLUSIONS: We conclude that PL and MG supplementation provides higher tissue DHA accretion and higher milk DHA content than TG and EE supplementation. However, we were not able to visualize the comparative advantages derived from PL vs. MG supplementation.

Cholesterol oxidation: health hazard and the role of antioxidants in prevention.

Cholesterol is a molecule with a double bond in its structure and is therefore susceptible to oxidation leading to the formation of oxysterols. These oxidation products are found in many commonly-consumed foods and are formed during their manufacture and/or processing. Concern about oxysterols consumption arises from the potential cytotoxic, mutagenic, atherogenic, and possibly carcinogenic effects of some oxysterols. Eggs and egg-derived products are the main dietary sources of oxysterols. Thermally-processed milk and milk-derived products are another source of oxysterols in our diet. Foods fried in vegetable/animal oil, such as meats and French-fried potatoes, are major sources of oxysterols in the Western diet. Efforts to prevent or to reduce cholesterol oxidation are directed to the use of antioxidants of either synthetic or natural origin. Antioxidants are not only able to inhibit triglyceride oxidation, some of them can also inhibit cholesterol oxidation. Among synthetic antioxidants 2,6-ditertiarybutyl-4-methylphenol (BHT), and tertiary butylhydroquinone (TBHQ) can efficiently inhibit the thermal-induced oxidation of cholesterol. Some natural antioxidants, such as alpha- and gamma-tocopherol, rosemary oleoresin extract, and the flavonoid quercetin, show strong inhibitory action against cholesterol oxidation.

Effect of the degree of hydrogenation of fish oil on the enzymatic activity and on the fatty acid composition of hepatic microsomes from young and aged rats.

By modifying the degree of hydrogenation of dietary fat, it is possible to modify the fatty acid composition and the biochemical activity of cellular tissues. The age can be another variable influencing these modifications. The effect of isocaloric diets containing oils with different degrees of hydrogenation: fish oil (FO, 0.3% TRANS), partially hydrogenated fish oil (PHFO, 29% TRANS), or highly hydrogenated fish oil (HHFO, 2.3% TRANS), in the fatty acid composition (CIS and TRANS isomers) of hepatic microsomes from young (70-day-old) and aged (18-month-old) rats, in the microsomal cytochrome P-450 (C-450) content, and in the aminopyrine N-demethylase (AND), aniline hydroxylase (AH), NADPH cytochrome P-450 reductase (NCR), UDP-glucuronyl transferase (UGT), and GSH-S transferase (GST) enzymatic activities were studied. Fatty acid composition and n-6/n-3 ratio of microsomal membranes was modified to a higher extent in young rats. C-450 content and AND activity were reduced when the degree of hydrogenation of dietary fat was increased in the young and the aged rats. AH activity was higher after the PHFO diet in the young rats only. NCR activity was reduced in the young animals when the hydrogenation of the fat was increased. However, in aged rats the enzyme exhibited a higher activity after the PHFO and HHFO diet. UGT and GST activities where not affected by the level of hydrogenation of the dietary fat in both the young and the aged rats. However, UGT activity was higher in the young rats, while GST activity was higher in the aged animals. We conclude that hydrogenation of dietary fat can modify the fatty acid composition of hepatic microsomes, young animals being more sensitive to these changes than aged animals. These effects were also reflected in the amount and/or the activity of some molecular components of the hepatic microsomal mixed-function oxidase enzyme system. Microsomal TRANS fatty acid composition is not affecting the activity of the enzymes, the age of the animals being the most important factor.

Inhibitory action of conventional food-grade natural antioxidants and of natural antioxidants of new development on the thermal-induced oxidation of cholesterol.

Cholesterol is a molecule with an unsaturated bond; therefore, like polyunsaturated fatty acids, it is prone to oxidation. Cholesterol oxidation products (COPs) are found in many common foods and have been shown to be atherogenic, cytotoxic, mutagenic and possibly carcinogenic. Therefore, efforts to prevent or to avoid COPs formation during manufacture and/or processing of foods are of high priority. The effect of natural antioxidants on COPs formation has not been extensively studied. We assayed the effect of some widely applied natural antioxidants, such as tocopherol homologs (alpha-T, gamma-T, and delta-T) and rosemary extract, and of some natural products of newly developed as antioxidants, such as the flavonoids quercetin, catechin, morin, and rutin, and also of an alkaloid-derived product, boldine, to inhibit cholesterol oxidation of soybean oil, added of cholesterol, induced in the Rancimat test conditions (150 degrees C and air bubbling). Formation of six different COPs at the induction period and at the 100 microS conductivity value was monitored by gas chromatography. Under the experimental conditions gamma-T, quercetin, and rosemary extract prove effective to inhibit both soybean oil oxidation and COP formation. alpha-T, catechin, and morin are less efficient to prevent COP formation. delta-T, rutin and boldine are devoid of protective action against COP formation. gamma-T, quercetin and rosemary extract may inhibit COP formation from the nucleus and from the lateral chain of the cholesterol molecule.

Supplementation of female rats with alpha-linolenic acid or docosahexaenoic acid leads to the same omega-6/omega-3 LC-PUFA accretion in mother tissues and in fetal and newborn brains.

BACKGROUND: Maternal omega-3 fatty acid supplementation has been suggested to provide docosahexaenoic acid (DHA) for the normal brain development during gestation. DHA can be given as such (preformed) or through the omega-3 precursor alpha-linolenic acid (LNA) which is transformed into DHA by elongation and desaturation reactions. Western diet provides low amounts of LNA and DHA; therefore, supplementation with these omega-3 fatty acids has been suggested for pregnant women. However, the bioequivalence of LNA ingestion to DHA supplementation has not been established. METHODS: Recently weaning female Wistar rats were fed a diet containing a small amount of LNA and no DHA. The animals were daily supplemented 40 days before mating, during pregnancy, and until delivery with 60 mg/kg of LNA or 6 mg/kg of DHA dissolved in coconut oil. Fatty acids were given as ethyl ester derivatives. Controls received coconut oil. The fatty acid composition of blood plasma, erythrocytes, liver, visceral adipose tissue, and brain segments (frontal cortex, hippocampus, and cerebellum) was analyzed. Brain segments obtained from 16- and 19-day-old fetuses and from 2- and 21-day-old rats were also analyzed for fatty acid composition. RESULTS: Supplementation with LNA and DHA induced a similar accretion of DHA in plasma, erythrocytes, liver, and brain segments of the mothers. The adipose tissue showed a higher DHA accretion after DHA-supplementation. The DHA accretion in frontal cortex, hippocampus, and cerebellum obtained from the fetuses and the newborn rats was similar when the mothers were supplemented with LNA and DHA. Our results show that under our experimental conditions a similar accretion of DHA in the different tissues of the mothers and in the brain segments of fetuses and newborn rats is obtained after LNA and DHA supplementation. CONCLUSION: LNA and DHA, at the amounts given in this study, show a similar bioequivalence for DHA accretion in different tissues of the mother and in brain segments of fetuses and newborn rats.

Cholesterol oxidation: health hazard and the role of antioxidants in prevention

Cholesterol is a molecule with a double bond in its structure and is therefore susceptible to oxidation leading to the formation of oxysterols. These oxidation products are found in many commonly-consumed foods and are formed during their manufacture and/or processing. Concern about oxysterols consumption arises from the potential cytotoxic, mutagenic, atherogenic, and possibly carcinogenic effects of some oxysterols. Eggs and egg-derived products are the main dietary sources of oxysterols. Thermally-processed milk and milk-derived products are another source of oxysterols in our diet. Foods fried in vegetable/animal oil, such as meats and French-fried potatoes, are major sources of oxysterols in the Western diet. Efforts to prevent or to reduce cholesterol oxidation are directed to the use of antioxidants of either synthetic or natural origin. Antioxidants are not only able to inhibit triglyceride oxidation, some of them can also inhibit cholesterol oxidation. Among synthetic antioxidants 2,6-ditertiarybutyl-4-methylphenol (BHT), and tertiary butylhydroquinone (TBHQ) can efficiently inhibit the thermal-induced oxidation of cholesterol. Some natural antioxidants, such as alpha- and gamma-tocopherol, rosemary oleoresin extract, and the flavonoid quercetin, show strong inhibitory action against cholesterol oxidation.

Acido docosahexaenoico (dha), desarrollo cerebral, memoria y aprendizaje: la importancia de la suplementación perinatal / Docosahexaenoic acid (dha), brain development, memory and learning: the importance of perinatal supplementation

El ácido docosahexaenoico (DHA) es un ácido graso omega-3 de cadena larga derivado del ácido alfa-linolénico. El DHA, junto con el ácido araquidónico, es el ácido graso poliinsaturado que se encuentran en mayor concentración en el tejido nervioso. Se ha propuesto que el DHA tiene un importante rol en la formación y en la función del sistema nervioso, particularmente en el cerebro. Su mecanismo de acción aún no está totalmente dilucidado pero se propone que actuaría a nivel de las membranas celulares regulando sus funciones metabólicas y también a nivel de la expresión de genes relacionados con la función cerebral. Se ha correlacionado el contenido cerebral de DHA con la capacidad de aprendizaje y con el nivel de inteligencia de los recién nacidos y lactantes. Numerosos ensayos en animales de experimentación y en niños han demostrado la necesidad del ácido graso durante el desarrollo cerebral. El DHA, formado a partir de su precursor, proveniente de la dieta, o desde las reservas tisulares, es aportado por la madre al feto durante el período gestacional y a través de la leche durante la lactancia. Se ha sugerido la necesidad de suplementar a la madre con DHA durante el período gestacional, e incluso antes de este, para asegurar el adecuado aporte del ácido graso para el normal desarrollo del cerebro fetal. La suplementación se puede realizar a través de aceites con alto contenido de DHA, a partir de fosfolípidos, en la forma de etil esteres de DHA, o como monoglicéridos que contienen DHA como único ácido graso. En este trabajo se discute el rol del DHA en el desarrollo del sistema nervioso y en la funcionalidad del cerebro, y las evidencias que lo relacionan con una mayor capacidad de aprendizaje de las crías provenientes de madres previamente suplementadas con DHA. Además, se discute cual podría ser la mejor forma de suplementar con DHA la nutrición de la madre y del recién nacido a partir de los productos disponible para la suplementación.

Acido docosahexaenoic, DHA, en el desarrollo fetal y en la nutrición materno infantil / Docosahexanoic acid, DHA, in fetal development and infant nutrition

Docosahexanoic acid (C22:6, DHA) is a highly unsaturated omega-3 fatty acid that forms part of the central nervous and visual system structures. DHA is synthesized from its precursor, alfa-linolenic acid, that is also a omega-3 fatty acid and can be obtained from vegetable oils. Marine organisms, specially fish, are good nutritional sources of DHA and eicosapentanoic acid (EPA), another omega-3 fatty acid that has a role in vascular homeostasis. DHA increases membrane fluidity, improving neurogenesis, synaptogenesis and the activity of retinal photoreceptors. The fetus, specially during the last trimester of pregnancy, has high DHA requirements. It is provided by the mother, since fetal DHA synthesis is negligible in this stage of development. Breast feeding provides DHA to the child, but most replacement artificial formulas do not provide this fatty acid. At the present moment, many products for infant nutrition contain DHA

Innovación tecnológica aplicable a los aceites marinos ricos en ácidos grasos N-3 para permitir su uso nutricional y farmacológico: un desafío para la presente década / Technological innovation applicable to marine oils rich in N-3 fatty acids to allow its nutritional and pharmacological use: a challenge for the current decade

Las importantes propiedades fisiológicas y nutricionales descritas para los ácidos grasos poliinsaturados n-3 de origen marino han motivado la búsqueda de procedimientos que permitan obternerlos, preservarlos, con la finalidad de poder incorporarlos a productos de uso farmacológico o nutricional. La industria de harina de pescado provee importantes cantidades de aceites de pescado, sin embargo este aceite debe ser sometido a diferentes procedimientos de purificación para ser utilizado con fines alimenticios. Este trabajo describe el estatus actual de la investigación sobre los procedimientos aplicables para incorporar ácidos grasos poliinsaturados n-3 en nuestra alimentación. Se discute la factibilidad de aplicar técnicas de concentración química, procedimientos de transesterificación mediante enzimas estereospecíficas y la estabilización mediante sustancias naturales. Se plantea, además la posibilidad que algunas aves, como el pollo, alimentadas con una dieta rica en ácidos grasos n-3 pueden constituir un buen vehículo para que el hombre pueda adquirir estos ácidos grasos en forma sana, segura y nutricionalmente recomendable