Structural, energetic and kinetic database of catalytic reactions: Benzyl alcohol to benzaldehyde oxidation on MnOx clusters

Data here reported are connected with the research article “Benzyl Alcohol to Benzaldehyde Oxidation on MnOx Clusters: Unraveling Atomistic Features” Gueci et al. [1]. This work described and discussed structural and energetic results, calculated by Density Functional Theory (DFT). In order to get kinetic information, DFT results were refined by an original approach, which will be shortly described in the following article. The crossed analysis of experimental and computational energetic and kinetic data allowed to (i) reconstruct the complicated lattice that connects the primary and secondary mechanisms of the reaction and (ii) identify alternative process pathways capable of by-passing parasitic mechanisms, decreasing selectivity. On the other hand, the data here presented show what is the basic information necessary to obtain the modeling of a complex process of heterogeneous catalysis. Moreover, they can be used either to verify the validity of the discussion outlined in the original article Gueci et al. [1] or as a starting point to computationally explore alternative routes and the related kinetics of the same oxidation processes, in the aim to further optimize the corresponding experimental approach

Benzyl alcohol to benzaldehyde oxidation on MnOx clusters: Unraveling atomistic features

The catalytic oxidation of benzyl alcohol with O2 is a promising option for the production of benzaldehyde, from both environmental and economical viewpoints. In particular, highly dispersed MnOx systems feature good activity and selectivity in a wide range of temperatures, although deactivation phenomena by over-oxidation and/or poisoning of active sites are generally recorded. On this account, a density functional theory study was performed on cluster-sized catalyst models, namely Mn4O8 and over-oxygenated Mn4O9 fragments, to predict the reactivity pattern of MnOx catalysts in the selective aerobic oxidation of benzyl alcohol. Several pathways concur to determine the whole reaction process and all of them were compared to unveil the atomistic details of the alcohol oxidation mechanism. Moreover, assuming that the consecutive formation of benzoic acid affects the activity-stability pattern of the MnOx based catalyst, also the benzaldehyde oxidation mechanism was computationally addressed. A systematic comparison of the benzyl alcohol and benzaldehyde oxidation mechanisms on the Mn4O8 and Mn4O9 fragments reveals some experimental strategies to test the reaction mechanisms and design alternative catalytic routes to decrease undesired parasitic reactions leading to catalyst deactivation. The matching structural, energetic and kinetic data are published in the Data in Brief journal [1]

Application of technological protocols on an industrial scale to improve Seville-style table olive production in Italy and Spain

Improving the fermentation performance of starter strains used in the fermentation of table olives is a biotechnological solution of current interest to improve the quality characteristics of the final product. The aim of this study was to evaluate the use of Lactiplantibacillus pentosus OM13 as a starter culture for the fermentation of Seville-type table olives in two different production areas: Italy and Spain. The starter strain L. pentosus OM13 was inoculated into two different table olive varieties: Nocellara del Belice in Italy and Manzanilla in Spain. Lactiplantibacillus plantarum Vege-Start 60 was used as a commercial control, while an additional control pro- duction was carried out by spontaneous fermentation. The industrial productions consisted of three different protocols, differing in the type of nutrient and the presence/absence of acclimatisation of the starter strain. All trials were subjected to microbiological monitoring, evaluation of acidification dynamics and sensory analysis of the final product. After 90 days, the pH reached values below 5 in the different treatments. The LAB reached microbial loads varying between 6.5 and 8.7 log CFU/mL throughout the monitoring period. The microbial populations of spoilage and/or potential pathogenic microorganisms were variable depending on the microbial group monitored. However, after 12 days of fermentation, Enterobacteriaceae showed values below the detection limit. In contrast, a fluctuating trend was observed for yeasts, Pseudomonadaceae and Staphylococcaceae. Sensory analyses showed variable differences depending on the technological protocol used. Table olives ob- tained with L. pentosus OM13 in the presence of nutrient, activator and acclimatisation period achieved higher overall acceptability values compared to the other trials. The use of adjuvants (nutrients and activators) is a strategy used in the production of table olives fermented with L. pentosus OM13 to improve the sensory char- acteristics of table olives

Improving the Aromatic Profiles of Catarratto Wines: Impact of Metschnikowia pulcherrima and Glutathione-Rich Inactivated Yeasts

Catarratto is one of the most widely cultivated grape varieties in Sicily. It is an indigenous non-aromatic white grape variety. Despite its widespread use in winemaking, knowledge of the aroma and chemical and microbiological properties of Catarratto wines is quite limited. The influence of Metschnikowia pulcherrima combined with Saccharomyces cerevisiae on the aromatic expression of Catarratto wines was investigated with and without the addition of glutathione-rich inactivated yeast. The substance is a natural specific inactivated yeast with a guaranteed glutathione level used to limit oxidative processes. The aromatic profiles of the final wines were determined through analysis of the volatile organic compounds using a solid-phase microextraction technique that identified 26 aromatic compounds. The addition of M. pulcherrima in combination with the natural antioxidant undoubtedly increased the aromatic complexity of the wines. Dodecanal was exclusively detected in the wines processed with glutathione-rich inactivated yeasts. Furthermore, the presence of this natural antioxidant increased the concentration of six esters above the perception threshold. Sensory analysis was also performed with a panel of trained judges who confirmed the aromatic differences among the wines. These results suggest the suitability of glutathione-rich inactivated yeasts for determining the oxidative stability of Catarratto wines, thus preserving its aromatic compounds and colour

A novel microbiological approach to impact the aromatic composition of sour loquat beer

The growing interest in novel beer development determined the exploitation of unconventional yeasts isolated from novel ecological niches to generate unexplored sensory profiles. In recent years, there is an increasing interest in generating beers brewed with the addition of fruits. For the first time, Lachancea thermotolerans MNF105 and Saccharomyces cerevisiae MN113 isolated from manna, were tested as starter cultures to process loquat beer to improve the sensory profile. Innovatively, the yeast species L. thermotolerans was investigated for the production of sour fruit beer. Sour fruit beers produced with L. thermotolerans MNF105 were more balanced than the respective control, especially in terms of perceived acidity during sensory analysis. This could be due to the lower lactic acid production (0.49 g/L) compared to the respective control (1.74 g/L). The overall organoleptic investigation showed a preference for S. cerevisiae MN113 (TF1) isolated from manna. Experimental trials conducted with the selected strains demonstrated the absence of off-odour and off-flavour and improved aroma perception. Aldehydes and alcohols were the most abundant compounds emitted from the beers. S. cerevisiae MN113 and L. thermotolerans MNF105, manna related yeasts, showed great technological properties, representing promising starters for the production of fruit beer and sour fruit beer

Impact of two new non-conventional yeasts, Candida oleophila and Starmerella lactis-condensi, isolated from sugar-rich substrates, on Frappato wine aroma

The interest of non-Saccharomyces yeasts in wine fermentation increased constantly in last years. This study reports for the first time the enological potential of two strains Starmerella lactis-condensi MN412 and Candida oleophila YS209. In an innovative way, these strains were used in winemaking to improve floral and fruity aroma of Frappato red wine, which has not been explored. The enological performances of the two non-Saccharomyces strains were compared to a wine strain of Starmerella bacillaris, namely Cz3, previously characterized in winemaking conditions. In these three cases, the non-Saccharomyces strain was sequentially inoculated with S. cerevisiae wine strain NF213, used as control. The St. lactis-condensi MN412 was isolated from Sicilian manna, a sugar-rich matrix, extracted from Fraxinus angustifolia trees (Oleaceae). The strain C. oleophila YS209 was isolated from honey by-products. Microbiological counts showed the ability of MN412 and YS209 to maintain high counts up to 6 days of alcoholic fermentation. Regarding chemical parameters, Cz3 showed the highest glycerol production. Analysis of VOCs revealed that the trials with non-Saccharomyces yeasts were characterized by a higher concentration of esters that contributed positively to the fruity aroma of the wines. The sensory analysis confirmed that the use of MN412 and YS209 impacted positively the final wines in terms of fruity and floral intensity, respectively, while did not generate sensory defects. In conclusion, non-conventional yeasts represent strategy to improve floral-fruity freshness of wine aroma and sugar-rich matrices such as manna ash and honey might represent novel ecological niches as source of potential oenological yeast

Rinistachya hilleri gen. et sp. nov.(Sphenophyllales), from the upper Devonian of South Africa

A rich and diverse plant assemblage has been excavated from latest Devonian (Famennian) black shales of the Witpoort Formation (Witteberg Group) at Waterloo Farm, close to the city of Grahamstown (South Africa). Several specimens of a new sphenopsid have been collected. The description of this as a new taxon, here named Rinistachya hilleri, gen. et sp. nov., provides an important addition to the scarce early record of the group. Rinistachya hilleri presents a novel architecture that include apparently plesiomorphic characters, reminiscent of the organisation of the Iridopteridales (including the production of two types of laterals at one node, the location of fertile parts in loose whorls on lateral branches and an organisation of the fertile parts in which they branch several times before bearing distally elongate sporangia). Other characters unambiguously nest Rinistachya within the Sphenopsida (including presence of planate and slightly webbed ultimate appendages and lateral strobili made of successive whorls of fertile leaves with fertile parts located at their axil). This provides strong support for a close relationship between Sphenopsida and Iridopteridales. Rinistachya furthermore represents the first record of a Devonian sphenopsid from Gondwana and extends the known distribution of the Sphenopsida from the tropics to very high palaeolatitudes. It is a new sphenopsid with a peculiar organisation. The new taxon allows better characterization of the initial evolutionary radiation at the base of the group

H2 transformations on graphene supported palladium cluster: Dft-md simulations and neb calculations

Molecular dynamics simulations based on density functional theory were employed to investigate the fate of a hydrogen molecule shot with different kinetic energy toward a hydrogenated palladium cluster anchored on the vacant site of a defective graphene sheet. Hits resulting in H2 adsorption occur until the cluster is fully saturated. The influence of H content over Pd with respect to atomic hydrogen spillover onto graphene was investigated. Calculated energy barriers of ca. 1.6 eV for H-spillover suggest that the investigated Pd/graphene system is a good candidate for hydrogen storage