Base-Free Catalytic Hydrogen Production from Formic Acid Mediated by a Cubane-Type Mo3S4 Cluster Hydride

Formic acid (FA) dehydrogenation is an attractive process in the implementation of a hydrogen economy. To make this process greener and less costly, the interest nowadays is moving toward non-noble metal catalysts and additive-free protocols. Efficient protocols using earth abundant first row transition metals, mostly iron, have been developed, but other metals, such as molybdenum, remain practically unexplored. Herein, we present the transformation of FA to form H2 and CO2 through a cluster catalysis mechanism mediated by a cuboidal [Mo3S4H3(dmpe)3]+ hydride cluster in the absence of base or any other additive. Our catalyst has proved to be more active and selective than the other molybdenum compounds reported to date for this purpose. Kinetic studies, reaction monitoring, and isolation of the [Mo3S4(OCHO)3(dmpe)3]+ formate reaction intermediate, in combination with DFT calculations, have allowed us to formulate an unambiguous mechanism of FA dehydrogenation. Kinetic studies indicate that the reaction at temperatures up to 60 °C ends at the triformate complex and occurs in a single kinetic step, which can be interpreted in terms of statistical kinetics at the three metal centers. The process starts with the formation of a dihydrogen-bonded species with Mo–H···HOOCH bonds, detected by NMR techniques, followed by hydrogen release and formate coordination. Whereas this process is favored at temperatures up to 60 °C, the subsequent β-hydride elimination that allows for the CO2 release and closes the catalytic cycle is only completed at higher temperatures. The cycle also operates starting from the [Mo3S4(OCHO)3(dmpe)3]+ formate intermediate, again with preservation of the cluster integrity, which adds our proposal to the list of the infrequent cluster catalysis reaction mechanisms.Funding for open access charge: CRUE-Universitat Jaume

Efficient (Z)-selective semihydrogenation of alkynes catalyzed by air-stable imidazolyl amino molybdenum cluster sulfides

Imidazolyl amino cuboidal Mo3(μ3-S)(μ-S)3 clusters have been investigated as catalysts for the semihydrogenation of alkynes. For that purpose, three new air-stable cluster salts [Mo3S4Cl3(ImNH2)3]BF4 ([1]BF4), [Mo3S4Cl3(ImNH(CH3))3]BF4 ([2]BF4) and [Mo3S4Cl3(ImN(CH3)2)3]BF4 ([3]BF4) have been isolated in moderate to high yields and fully characterized. Crystal structures of complexes [1]PF6 and [2]Cl confirm the formation of a single isomer in which the nitrogen atoms of the three imidazolyl groups of the ligands are located trans to the capping sulfur atom which leaves the three bridging sulfur centers on one side of the trimetallic plane while the amino groups lie on the opposite side. Kinetic studies show that the cluster bridging sulfurs react with diphenylacetylene (dpa) in a reversible equilibrium to form the corresponding dithiolene adduct. Formation of this adduct is postulated as the first step in the catalytic semihydrogenation of alkynes mediated by molybdenum sulfides. These complexes catalyze the (Z)-selective semihydrogenation of diphenylacetylene (dpa) under hydrogen in the absence of any additives. The catalytic activity lowers sequentially upon replacement of the hydrogen atoms of the N–H2 moiety in 1+ without reaching inhibition. Mechanistic experiments support a sulfur centered mechanism without participation of the amino groups. Different diphenylacetylene derivatives are selectively hydrogenated using complex 1+ to their corresponding Z-alkenes in excellent yields. Extension of this protocol to 3,7,11,15-tetramethylhexadec-1-yn-3-ol, an essential intermediate for the production of vitamin E, affords the semihydrogenation product in very good yield

Cycloaddition of alkynes to diimino Mo3S4 cubane-type clusters: a combined experimental and theoretical approach

A heterocyclic ligand 4,40-di-tert-butyl-2,20-bipyridine (dbbpy) has been coordinated to the Mo3S4 cluster unit affording the complex [Mo3S4Cl3(dbbpy)3]+ ([1]+) in a one-step ligand-exchange protocol from [Mo3S4(tu)8(H2O)]Cl4 4H2O (tu = thiourea). The new cluster was isolated as [1]PF6 and [1]Cl salts in high yields and the crystal structure of the latter determined by X-ray analysis. The synthetic procedure was extended to tungsten to afford [W3S4Cl3(dbbpy)3]+ ([2]+). Kinetic and NMR studies show that [1]+ reacts with several alkynes to form dithiolene species via concerted [3+2] cycloaddition reactions whereas [2]+ remains inert under similar conditions. The different rates for the reactions of [1]+ are rationalised by computational (DFT) calculations, which show that the more electron-withdrawing the substituents of the alkyne the faster the reaction. The inertness of [2]+ is due to the endergonicity of its reactions, which feature DGr values systematically 5–7 kcal mol 1 more positive than for those of [1]+

Study of the effect of instant controlled pressure drop (DIC) treatment on IgE-reactive legume-protein patterns by electrophoresis and immunoblot

Détente Instantanée Contrôlée (DIC) technology was used to reduce immunoglobulin E (IgE) reactivity of legume proteins. Soybean, roasted peanut, chickpea and lentil seeds were treated at three or six bars for 60 or 180s. The effect of this treatment on the IgE-binding pattern of the legume proteins - separated by sodium-dodecyl-sulphate polyacrylamide gel electrophoresis - was monitored by five individual paediatric legume allergic and - two individual negative control human sera. A highly cross-reactive legume positive serum was selected for the two-dimensional electrophoreses immunoblots to compare the IgE reactive protein patterns, before and after the DIC treatment. The number of the identified IgE reactive spots was highly reduced for soybean (0/7) and chickpea (2/7), and moderately reduced for lentil (4/7) when the seeds were treated at a higher pressure (6 bar) and for a longer time (180 s), but this treatment was not effective for roasted peanut (6/8) where the intensity of the IgE reactive resistant spots were even stronger. © 2013 Taylor & Francis

Kinetics Aspects of the Reversible Assembly of Copper in Heterometallic Mo3CuS4 Clusters with 4,4′-Di-tert-butyl-2,2′- bipyridine

Treatment of the triangular [Mo3S4Cl3(dbbpy)3]Cl cluster ([1]Cl) with CuCl produces a novel tetrametallic cuboidal cluster [Mo3(CuCl)S4Cl3(dbbpy)3][CuCl2] ([2][CuCl2]), whose crystal structure was determined by X-ray diffraction (dbbpy = 4,4′-di-tert-butyl-2,2′-bipyridine). This species, which contains two distinct types of Cu(I), is the first example of a diimine-functionalized heterometallic M3M′S4 cluster. Kinetics studies on both the formation of the cubane from the parent trinuclear cluster and its dissociation after treatment with halides, supported by NMR, electrospray ionization mass spectrometry, cyclic voltammetry, and density functional theory calculations, are provided. On the one hand, the results indicate that addition of Cu(I) to [1]+ is so fast that its kinetics can be monitored only by cryo-stopped flow at −85 °C. On the other hand, the release of the CuCl unit in [2]+ is also a fast process, which is unexpectedly assisted by the CuCl2 − counteranion in a process triggered by halide (X−) anions. The whole set of results provide a detailed picture of the assembly−disassembly processes in this kind of cluster. Interconversion between trinuclear M3S4 clusters and their heterometallic M3M′S4 derivatives can be a fast process occurring readily under the conditions employed during reactivity and catalytic studies, so their occurrence is a possibility that must be taken into account in future studies

Effect of fermented soy beverage in aged female mice model

11 Pág.Soy beverage is a rich source of phytoestrogens isoflavones, with potential benefits on health. The effect of those compounds depends greatly on their bacterial metabolization into their aglycone forms. This study evaluated the health effects of two soy beverages, non-fermented (SB) and fermented with Bifidobacterium pseudocatenulatum INIA P815 (FSB), in acyclic and cyclic C57BL/6J aged female mice as a model of menopause and premenopause, respectively. SB and FSB treatments were administrated for 36 days and, subsequently, body weight, lipid and inflammatory profile and fertility were analyzed and compared. In addition, hepatic gene expression and faecal microbiota composition were also assessed. After fermentation, FSB presented a high content in the aglycones daidzein and genistein and a higher antioxidant activity. FSB treated cyclic mice showed a significant increase in the number of retrieved oocytes and zigotes. Differences in serum lipids were observed in triglycerides, which were lower in FSB than in SB groups. None of the treatments influenced the inflammatory profile or caused a dramatic change in the intestinal microbiota profile or hepatic gene expression in any of the groups. Our data showed that FSB provided greater health benefits than SB in lipid profile and fertility in cyclic mice. These beneficial effects could be attributed to the fermentation process, which produces more bioavailable and bioactive compounds, achieving a greater impact on health.This work was supported by projects RTA2017-00002-00-00, PID2020-11960RB-I00, and RTI2018-093548-B-I00 from the Spanish Ministry of Science and Innovation. We appreciate the help of Doctors Javier Ortego and Eva Calvo from CISA-CSIC in the analysis of inflammatory profile. We are grateful to the ICTAN (Institute of Food Science, Technology and Nutrition, Madrid, Spain) Analysis Services Unit for providing chromatography and mass spectrometry facilities.Peer reviewe

Structural characterization of water-soluble polysaccharides from the fruiting bodies of Lentinus edodes mushrooms

Water-soluble polysaccharides have been extracted from the fruiting bodies of Lentinus edodes mushrooms. Three carbohydrate fractions (cold water, hot water and hot aqueous NaOH) from the mushrooms were separated by ethanol precipitation. Size exclusion chromatography revealed the presence of a unique polysaccharide in each fraction. Cold water fraction polysaccharide (PLeC) was composed of glucose and galactose bound by (1→3) and (1→4) linkages with a high degree of branching at O-3 and O-4 of galactose residues. Hot water fraction polysaccharide (PLeH) showed (1→4),(1→6)-linked glucopyranosyl residues with branches at O-4 and O-6. Differently, hot aqueous NaOH fraction (PLeB) consisted of a (1→3),(1→6)-linked glucan branched at O-3 and O-6. NMR studies revealed that the polysaccharides PLeC and PLeH displayed both α and β configurations whereas PLeB presented β anomeric configuration. The analysis of molecular arrangement by complexation with Congo red showed that the three polysaccharides (PLeC, PLeH and PLeB) displayed a triple helix conformation

Identification and quantification of ergosterol and phenolic compounds occurring in Tuber spp. truffles

A study was conducted to quantify the mycochemical composition of the truffles Tuber melanosporum, Tuber aestivum and Tuber indicum in terms of ergosterol and phenolic contents. The ergosterol concentration ranged from 1.28 to 1.80. mg/g of dried matter. An ergosteryl ester was found in all truffles, and the concentration was considerably higher in T. aestivum (0.36. mg of ergosterol equivalents/g of dried matter) in comparison to T. melanosporum (0.10. mg/g) and T. indicum (0.09. mg/g). The total phenolic content was determined by the Folin-Ciocalteu assay, and the truffles contained between 1 and 2. mg of phenolics per g of dried matter. The individual phenolic compounds were separated and identified by high performance liquid chromatography. Diverse phenolic acids, namely gallic, homogentisic, protocatechuic, p-hydroxybenzoic, o- and p-coumaric acids and other phenolic derivatives, such as 3,4-dihydroxybenzaldehyde, were found. The profile and content depended on the truffle species; thus, the hydroxycinnamic acid derivatives, o- and p-coumaric acids, were only detected in T. aestivum. All the truffles showed inhibition of lipid oxidation, being T. aestivum the most effective (24% inhibition) followed by T. indicum (23% inhibition) whereas T. melanosporum was the truffle with the lowest antioxidant activity (18% inhibition)

Novel isolation of water-soluble polysaccharides from the fruiting bodies of Pleurotus ostreatus mushrooms

Novel water-soluble polysaccharides have been isolated from the fruiting bodies of the edible mushroom Pleurotus ostreatus. Three polysaccharide fractions were obtained by ethanol precipitation from cold water, hot water and hot aqueous NaOH extracts. The fractions were purified by size exclusion chromatography showing a unique carbohydrate occurring in each fraction PC from the cold fraction, PH from the hot fraction and PB from the hot aqueous NaOH fraction. The analysis of the methylated alditol acetates and the NMR studies revealed that all the polysaccharides displayed a linear backbone. PC was formed by α-(1→3),(1→6)-linked galactopyranosyl residues whereas PH and PB consisted of glucose-linked units. PH was exclusively composed of glucopyranosyl units bound by α-(1→4) linkages whereas PB was a β-linked glucan showing (1→3) and (1→6) glycosidic bonds. The analysis of molecular arrangement by complexation with Congo red showed that only the β-linked polysaccharide (PB) displayed a triple helix conformation

Cooking and sensorial quality, nutritional composition and functional properties of cold-extruded rice/white bean gluten-free fettuccine fortified with whole carob fruit flour

A different rice/white bean-based gluten-free fettuccine (rice 0-100%, bean 0-100%) fortified with 10% carob fruit has been developed. The proximate composition, total and resistant starch, and total, soluble and insoluble dietary fibre content as well as the cooking and sensorial quality of uncooked and cooked pasta were determined. All the novel gluten-free fettuccine forms showed good cooking quality (cooking loss < 10%) highlighting that those containing the carob fruit had better nutritional and healthy profiles than the commercial gluten-free rice pasta; they were low in fat (10-fold) and high in protein (on average 3.6-fold) with resistant starch (16%) and dietary fibres (2.4-fold). The cooking process increased (p < 0.05) the protein and total dietary fibre content but reduced the total and resistant starch. The addition of carob fruit increased the total dietary fibre content, thus improving the functional value of fettuccine. Considering the sensorial analysis, fettuccine produced with 40% bean and 10% carob could be well accepted by consumers and can be advised as a functional food.The Spanish Ministry of Economy and Competitiveness (Project RTA2012-00042-C02) and the Spanish Ministry of Science, Innovation and Universities (Project RTA2015-00003-C02-01) financed this work. C. Arribas was supported by INIA, the European Regional Development Fund (ERDF) and the European Social Fund (ESF) through a PhD contract (CPR2014-0068).Peer reviewe