Selective Benzyl Alcohol Oxidation over Pd Catalysts

In the last decades, the selective liquid phase oxidation of alcohols to the corresponding carbonyl compounds has been a subject of growing interest. Research has focused on green methods that use "clean" oxidants such as O-2 in combination with supported metal nanoparticles as the catalyst. Among the alcohols, benzyl alcohol is one of the most studied substrates. Indeed, benzyl alcohol can be converted to benzaldehyde, largely for use in the pharmaceutical and agricultural industries. This conversion serves as model reaction in testing new potential catalysts, that can then be applied to other systems. Pd based catalysts have been extensively studied as active catalytic metals for alcohol oxidation for their high activity and selectivity to the corresponding aldehyde. Several catalytic materials obtained by careful control of the morphology of Pd nanoparticles, (including bimetallic systems) and by tuning the support properties have been developed. Moreover, reaction conditions, including solvent, temperature, pressure and alcohol concentration have been investigated to tune the selectivity to the desired products. Different reaction mechanisms and microkinetic models have been proposed. The aim of this review is to provide a critical description of the recent advances on Pd catalyzed benzyl alcohol oxidation

Simplified amino acid alphabets based on deviation of conditional probability from random background

The primitive data for deducing the Miyazawa-Jernigan contact energy or BLOSUM score matrix consists of pair frequency counts. Each amino acid corresponds to a conditional probability distribution. Based on the deviation of such conditional probability from random background, a scheme for reduction of amino acid alphabet is proposed. It is observed that evident discrepancy exists between reduced alphabets obtained from raw data of the Miyazawa-Jernigan's and BLOSUM's residue pair counts. Taking homologous sequence database SCOP40 as a test set, we detect homology with the obtained coarse-grained substitution matrices. It is verified that the reduced alphabets obtained well preserve information contained in the original 20-letter alphabet.Comment: 9 pages,3figure

Untangling the role of the capping agent in nanocatalysis : recent advances and perspectives

Capping agents (organic ligands, polymers, surfactants, etc.) are a basic component in the synthesis of metal nanoparticles with controlled size and well-defined shape. However, their influence on the performances of nanoparticle-based catalysts is multifaceted and controversial. Indeed, capping agent can act as a "poison", limiting the accessibility of active sites, as well as a "promoter", producing improved yields and unpredicted selectivity control. These effects can be ascribed to the creation of a metal-ligand interphase, whose unique properties are responsible for the catalytic behavior. Therefore, understanding the structure of this interphase is of prime interest for the optimization of tailored nanocatalyst design. This review provides an overview of the interfacial key features affecting the catalytic performances and details a selection of related literature examples. Furthermore, we highlight critical points necessary for the design of highly selective and active catalysts with surface and interphase control

N-Modified Carbon-Based Materials: Nanoscience for Catalysis

Carbon-based materials constitute a large family of materials characterized by some peculiarities such as resistance to both acidic and basic environments, flexibility of structure, and surface chemical groups. Moreover, they can be deeply modified by simple organic reactions (acid-base or redox) to acquire different properties. In particular, the introduction of N-containing groups, achieved by post-treatments or during preparation of the material, enhances the basic properties. Moreover, it has been revealed that the position and chemical nature of the N-containing groups is important in determining the interaction with metal nanoparticles, and thus, their reactivity. The modified activity was addressed to a different metal dispersion. Moreover, experiments on catalysts, showing the same metal dispersion, demonstrated that the best results were obtained when N was embedded into the carbon structure and not very close to the metal active site

Comparison of K+K^+ and e−e^- Quasielastic Scattering

We formulate $K^+$-nucleus quasielastic scattering in a manner which closely parallels standard treatments of $e^-$-nucleus quasielastic scattering. For $K^+$ scattering, new responses involving scalar contributions appear in addition to the Coulomb (or longitudinal) and transverse $(e,e')$ responses which are of vector character. We compute these responses using both nuclear matter and finite nucleus versions of the Relativistic Hartree Approximation to Quantum Hadrodynamics including RPA correlations. Overall agreement with measured $(e,e')$ responses and new $K^+$ quasielastic scattering data for $^{40}$Ca at |\qs|=500 MeV/c is good. Strong RPA quenching is essential for agreement with the Coulomb response. This quenching is notably less for the $K^+$ cross section even though the new scalar contributions are even more strongly quenched than the vector contributions. We show that this ``differential quenching'' alters sensitive cancellations in the expression for the $K^+$ cross section so that it is reduced much less than the individual responses. We emphasize the role of the purely relativistic distinction between vector and scalar contributions in obtaining an accurate and consistent description of the $(e,e')$ and $K^+$ data within the framework of our nuclear structure model.Comment: 26 pages, 5 uuencoded figures appended to end of this fil

The confinement effect on the activity of Au NPs in polyol oxidation

We demonstrate a confinement effect where gold nanoparticles trapped within N-functionalized carbon nanofibers (N-CNFs) are more active for polyol oxidation and promote selectivity towards di-acid products, whereas AuNPs trapped on the surface produce as a major by-product the one derived from C-C cleavage. The behaviour of NPs confined inside the N-CNF channels can be attributed to a different, possibly multiple, coordination of glycerol on the active site

Global DNA methylation and cognitive and behavioral outcomes at 4 years of age: A cross‐sectional study

Background Accumulating evidence suggests that breastfeeding exclusivity and duration are positively associated with child cognition. This study investigated whether DNA methylation, an epigenetic mechanism modified by nutrient intake, may contribute to the link between breastfeeding and child cognition. The aim was to quantify the relationship between global DNA methylation and cognition and behavior at 4 years of age. Methods Child behavior and cognition were measured at age 4 years using the Wechsler Preschool and Primary Scale of Intelligence, third version (WPPSI‐III), and Child Behavior Checklist (CBC). Global DNA methylation (%5‐methylcytosines (%5mC)) was measured in buccal cells at age 4 years, using an enzyme‐linked immunosorbent assay (ELISA) commercial kit. Linear regression models were used to quantify the statistical relationships. Results Data were collected from 73 children recruited from the Women and Their Children's Health (WATCH) study. No statistically significant associations were found between global DNA methylation levels and child cognition or behavior (p > .05), though the estimates of effect were consistently negative. Global DNA methylation levels in males were significantly higher than in females (median %5mC: 1.82 vs. 1.03, males and females, respectively, (p < .05)). Conclusion No association was found between global DNA methylation and child cognition and behavior; however given the small sample, this study should be pooled with other cohorts in future meta‐analyses

Au-Based Catalysts : Electrochemical Characterization for Structural Insights

Au-based catalysts are widely used in important processes because of their peculiar characteristics. The catalyst performance depends strongly on the nature and structure of the metal nanoparticles, especially in the case of bimetallic catalysts where synergistic effects between the two metals can be occasionally seen. In this paper, it is shown that electrochemical characterisation (cyclovoltammetry CV and electrochemical impedance spectroscopy EIS) of AuPd systems can be used to determine the presence of an electronic interaction between the two metals, thus providing a strong support in the determination of the nature of the synergy between Au and Pd in the liquid phase oxidation of alcohols. However, it seems likely that the strong difference in the catalytic behavior between the single metals and the bimetallic system is connected not only to the redox behaviour, but also to the energetic balance between the different elementary steps of the reaction

Tailored N-containing carbons as catalyst supports in alcohol oxidation

The introduction of N-containing functionalities in carbon-based materials is brought to stable and highly active metal-supported catalysts. However, up to now, the role of the amount and the nature of N-groups have not been completely clear. This study aims to clarify these aspects by preparing tailored N-containing carbons where different N-groups are introduced during the synthesis of the carbon material. These materials were used as the support for Pd nanoparticles. Testing these catalysts in alcohol oxidations and comparing the results with those obtained using Pd nanoparticles supported on different N-containing supports allowed us to obtain insight into the role of the different N-containing groups. In the cinnamyl alcohol oxidation, pyridine-like groups seem to favor both activity and selectivity toward cinnamaldehyde

Relationship of dietary monounsaturated fatty acids to blood pressure: the international study of macro/micronutrients and blood pressure

Objective: In short-term feeding trials, replacement of other macronutrients with monounsaturated fatty acid reduces blood pressure. However, observational studies have not clearly demonstrated a relationship between monounsaturated fatty acid intake and blood pressure. We report associations of monounsaturated fatty acid intake of individuals with blood pressure in a cross-sectional study. Methods: The International Study of Macro/Micronutrients and Blood Pressure is a cross-sectional epidemiologic study of 4,680 men and women ages 40-59 from 17 population samples in China, Japan, United Kingdom, and United States. Nutrient intake data were based on four in-depth multi-pass 24-hour dietary recalls/person and two timed 24-hour urine collections/person. Blood pressure was measured eight times at four visits. Results: Mean monounsaturated fatty acid intake ranged from 8.1 %kcal (China) to 12.2%kcal (United States). With sequential models to control for possible confounders (dietary, other), linear regression analyses showed significant inverse relationship of total monounsaturated fatty acid intake with diastolic blood pressure for all participants; for 2,238 “non-intervened” individuals, the relationship was stronger. Estimated diastolic blood pressure differences with 2-SD higher monounsaturated fatty acids (5.35 %kcal) were -0.82 mm Hg (P<0.05) for all participants and -1.70 mm Hg (P<0.01) for non-intervened individuals. Inverse associations of dietary total oleic acid (main monounsaturated) with blood pressure in non-intervened individuals were not significant, but those of oleic acid from vegetable sources were stronger and significant (P<0.05). Conclusions: Dietary monounsaturated fatty acid intake, especially oleic acid from vegetable sources, may contribute to prevention and control of adverse blood pressure levels in general populations. Condensed Abstract The associations of monounsaturated fatty acid intake of individuals with blood pressure was investigated in a cross-sectional epidemiologic study of 4,680 men and women ages 40-59 from 17 population samples in China, Japan, United Kingdom, and United States. Linear regression analyses showed significant inverse relationship of total monounsaturated fatty acid intake with diastolic blood pressure. Inverse associations of dietary total oleic acid from vegetable sources with blood pressure in non-intervened individuals were stronger and significant. Dietary monounsaturated fatty acid intake, especially oleic acid from vegetable sources, may contribute to prevention and control of adverse blood pressure levels in general populations