Hollow ruthenium nanoparticles with small dimensions derived from Ni@Ru core@shell structure: synthesis and enhanced catalytic dehydrogenation of ammonia borane

Hollow Ru nanoparticles with ~14 nm diameter and ~2 nm shell thickness are reported for the first time, by removal of Ni from the delicately designed Ni@Ru core@shell NPs. Such hollow Ru NPs exhibit enhanced catalytic activity in the dehydrogenation of ammonia borane with respect to solid ones.     

Synthesis of Ni–Ru Alloy Nanoparticles and Their High Catalytic Activity in Dehydrogenation of Ammonia Borane

We report the synthesis and characterization of new Ni_xRu_1?x (x=0.56–0.74) alloy nanoparticles (NPs) and their catalytic activity for hydrogen release in the ammonia borane hydrolysis process. The alloy NPs were obtained by wet‐chemistry method using a rapid lithium triethylborohydride reduction of Ni²⁺ and Ru³⁺ precursors in oleylamine. The nature of each alloy sample was fully characterized by TEM, XRD, energy dispersive X‐ray spectroscopy (EDX), and X‐ray photoelectron spectroscopy (XPS). We found that the as‐prepared Ni–Ru alloy NPs exhibited exceptional catalytic activity for the ammonia borane hydrolysis reaction for hydrogen release. All Ni–Ru alloy NPs, and in particular the Ni_0.74Ru_0.26 sample, outperform the activity of similar size monometallic Ni and Ru NPs, and even of Ni@Ru core‐shell NPs. The hydrolysis activation energy for the Ni_0.74Ru_0.26 alloy catalyst was measured to be approximately 37 kJ mol^?1. This value is considerably lower than the values measured for monometallic Ni (≈70 kJ mol^?1) and Ru NPs (≈49 kJ mol^?1), and for Ni@Ru (≈44 kJ mol^?1), and is also lower than the values of most noble‐metal‐containing bimetallic NPs reported in the literature. Thus, a remarkable improvement of catalytic activity of Ru in the dehydrogenation of ammonia borane was obtained by alloying Ru with a Ni, which is a relatively cheap metal.     

Assessment of heavy metal background values in the soils of inland coastal areas of Venice,Italy

The main aim of this project was to assess background levels of heavy metals in soil in the inland coastal area of Venice, Italy. The pilot study area is located near the industrial area of Porto Marghera, considered of national interest in terms of contaminated soil remediation (Environmental Ministerial Decree n. 471/1999). The Decree under consideration emphasises the importance of the assessment of background values in soil remediation. Results will show cases (As and Sn) in which background values are greater than concentration limit standards given by legislation.     

Self-assembled monolayers and electrostatically self-assembled multilayers of polyalkylviologens on sulfonate-modified gold and indium–tin–oxide electrodes

Self-assembly (SA) of polyviologens with linear alkyl spacers PVn (n = 3–10) on sulfonate-primed gold and ITO electrode surfaces has been investigated by CV, QCM, XPS and AFM. The polymers form stable and relatively dense monolayers even from 10⁻⁴ M PVn concentration. The viologen surface density is decreased as n is increased but for n = 10 and on alkylsulfonate-primed surfaces a strong adsorption takes place, with decreased redox potential and very narrow cyclic voltammogram of the absorbed layer due to organized structures on the surface.Stable and regular electrostatically self-assembled (ESA) multilayers are built on sulfonate-primed surfaces with PV3 and polysulfonates. From XPS analysis, the composition of the PVn/polysulfonate multilayers corresponds to a 1:1 ratio of polyanion and polycation charges, i.e., no extra non-polymeric ion is present, independently from the alkane chain length. The rate of electron transfer within the multilayers (diffusion coefficient = ca. 10⁻⁹ cm² s⁻¹) is higher than for analogous bulk materials.     

Synthetic Applications of Stereodefined 2-Substituted 1-Silyl-1-stannylethenes: A New Synthesis of 5-Ethenyl-5′-(1-propynyl)-2,2′-bithiophene,a Naturally-Occurring Phototoxin)

(E)-2-(5-Trimenthylstannyl-2-thienyl)ethenyldimethylphenylsilane. (E)-8, which can be stereospecifically prepared from (Z)-1-dimethylphenylsilyl-2-(2-thienyl)-1-trimethylstannyl-ethene, (Z)-6, or from (E)-2-(2-thienyl)ethenyldimethylphenylsilane, (E)-9, serves as an equivalent to the 2-ethenylthiophene d ¹', d ⁵-synthon, 20, in an efficient two-step synthesis of 5-ethenyl-5′-(1-propynyl)-2,2′-bithiophene, 10, a naturally-occurring phototoxin. In the first step of this synthesis compound (E)-8 undergoes a palladium-catalyzed cross-coupling reaction with 2-iodo-5-(1-propynyl)thiophene, 16, and in th second step the so obtained cross-coupling product, (E)-17, undergoes a protodesilylation reaction.     

Wall crossings for double Hurwitz numbers

Double Hurwitz numbers count covers of P¹ by genus g curves with assigned ramification profiles over 0 and ∞, and simple ramification over a fixed branch divisor. Goulden, Jackson and Vakil have shown double Hurwitz numbers are piecewise polynomial in the orders of ramification (Goulden et al., 2005) [10], and Shadrin, Shapiro and Vainshtein have determined the chamber structure and wall crossing formulas for g=0 (Shadrin et al., 2008) [15]. This paper gives a unified approach to these results and strengthens them in several ways — the most important being the extension of the results of Shadrin et al. (2008) [15] to arbitrary genus.The main tool is the authors? previous work (Cavalieri et al., 2010) [6] expressing double Hurwitz number as a sum over certain labeled graphs. We identify the labels of the graphs with lattice points in the chambers of certain hyperplane arrangements, which give rise to piecewise polynomial functions. Our understanding of the wall crossing for these functions builds on the work of Varchenko (1987) [17], and could have broader applications.     

One-pot preparation of piperazines by regioselective ring-opening of non-activated arylaziridines

Herein we report a new straightforward synthesis of cis and trans 2,5-disubstituted N,N-dialkylpiperazines, even in enantioenriched form, by reacting non-activated N-alkyl arylaziridines in the presence of a catalytic amount of a Lewis acid. A stereochemical and NMR investigation revealed useful mechanistic insights for this process.     

Supercritically-Dried Alginate Aerogels Retain the Fibrillar Structure of the Hydrogels

Summary: SAXS patterns of a Ca-alginate hydrogel and of the derived alcogel and aerogel have been recorded. All patterns correspond to disordered arrays of rod-like fibrils. The calculated size of the fibrils of the aerogel, 8 nm, is in good agreement with the results of scanning electron microscopy and N₂ adsorption. The results suggest that ethanol exchange and CO₂ supercritical drying do not affect the spatial organisation of the secondary structures of the gel and that characterisations of the aerogel can provide information on the organisation of the parent hydrogel.