Influence network linkages across implementation strategy conditions in a randomized controlled trial of two strategies for scaling up evidence-based practices in public youth-serving systems.

BackgroundGiven the importance of influence networks in the implementation of evidence-based practices and interventions, it is unclear whether such networks continue to operate as sources of information and advice when they are segmented and disrupted by randomization to different implementation strategy conditions. The present study examines the linkages across implementation strategy conditions of social influence networks of leaders of youth-serving systems in 12 California counties participating in a randomized controlled trial of community development teams (CDTs) to scale up use of an evidence-based practice.MethodsSemi-structured interviews were conducted with 38 directors, assistant directors, and program managers of county probation, mental health, and child welfare departments. A web-based survey collected additional quantitative data on information and advice networks of study participants. A mixed-methods approach to data analysis was used to create a sociometric data set (n = 176) to examine linkages between treatment and standard conditions.ResultsOf those network members who were affiliated with a county (n = 137), only 6 (4.4%) were directly connected to a member of the opposite implementation strategy condition; 19 (13.9%) were connected by two steps or fewer to a member of the opposite implementation strategy condition; 64 (46.7%) were connected by three or fewer steps to a member of the opposite implementation strategy condition. Most of the indirect steps between individuals who were in different implementation strategy conditions were connections involving a third non-county organizational entity that had an important role in the trial in keeping the implementation strategy conditions separate. When these entities were excluded, the CDT network exhibited fewer components and significantly higher betweenness centralization than did the standard condition network.ConclusionAlthough the integrity of the RCT in this instance was not compromised by study participant influence networks, RCT designs should consider how influence networks may extend beyond boundaries established by the randomization process in implementation studies.Trial registrationNCT00880126

A new pathway for heterogenization of molecular catalysts by non-covalent interactions with carbon nanoreactors

A novel approach to heterogenisation of catalytic molecules is demonstrated using the nanoscale graphitic step-edges inside hollow graphitised carbon nanofibres (GNFs). The presence of the fullerene C60 moiety within a fullerene-salen CuII complex is essential for anchoring the catalyst within the GNF nanoreactor as demonstrated by comparison with the analogous catalyst complex without the fullerene group. The presence of the catalyst at the step-edges of the GNFs is confirmed by high resolution transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX) with UV/Vis spectroscopy demonstrating only negligible (c.a. 3 %) desorption of the fullerene-salen CuII complex from the GNFs into solution under typical reaction conditions. The catalyst immobilised in GNFs shows good catalytic activity and selectivity towards styrene epoxidation, comparable to the analogous catalyst in solution. Moreover, the fullerene-salen CuII complex in GNFs demonstrates excellent stability and recyclability as it can be readily separated from the reaction mixture and employed in multiple reaction cycles with minimal loss of activity, which is highly advantageous compared to catalysts not stabilised by the graphitic step-edges that desorb rapidly from GNFs

Tuning the interactions between electron spins in fullerene-based triad systems

A series of six fullerene-linker-fullerene triads have been prepared by the stepwise addition of the fullerene cages to bridging moieties thus allowing the systematic variation of fullerene cage (C60 or C70) and linker (oxalate or terephthalate) and enabling precise control over the inter-fullerene separation. The fullerene triads exhibit good solubility in common organic solvents, have linear geometries and are diastereomerically pure. Cyclic voltammetric measurements demonstrate the excellent electron accepting capacity of all triads, with up to 6 electrons taken up per molecule in the potential range between -2.3 and 0.2 V (vs. Fc+/Fc). No significant electronic interactions between fullerene cages are observed in the ground state indicating that the individual properties of each C60 or C70 cage are retained within the triads. The electron-electron interactions in the electrochemically generated dianions of these triads, with one electron per fullerene cage were studied by EPR spectroscopy. The nature of electron-electron coupling observed at 77 K can be described as an equilibrium between a doublet and triplet state biradical which depends on the interfullerene spacing. The shorter oxalate-bridged triads exhibit stronger spin-spin coupling with triplet character, while in the longer terephthalate-bridged triads the intramolecular spin-spin coupling is significantly reduced

A hydrothermally stable Ytterbium metal-organic framework as a bifunctional solid-acid catalyst for glucose conversion

Yb6(BDC)7(OH)4(H2O)4 contains both bridging hydroxyls and metal-coordinated waters, possessing Brønsted and Lewis acid sites. The material crystallises from water at 200C. Using the solid as a heterogenous catalyst, glucose is converted into 5-hydroxymethylfurfural, via fructose, with a total selectivity of ~70 % after 24 hours at 140 C in water alone: the material is recyclable with no loss of crystallinity

Chemical reactions at the graphitic step-edge: changes in product distribution of catalytic reactions as a tool to explore the environment within carbon nanoreactors

A series of explorative cross-coupling reactions have been developed to investigate the local nanoscale environment around catalytically active Pd(II)complexes encapsulated within hollow graphitised nanofiber (GNF). Two new fullerene-containing and fullerene-free Pd(II)Salen catalysts have been synthesised, and their activity and selectivity towards different substrates has been explored in nanoreactors. The catalysts not only show a significant increase in activity and stability upon heterogenisation at the graphitic step-edges inside the GNF channel, but also exhibit a change in selectivity affected by the confinement which alters the distribution of isomeric products of the reaction. Furthermore, the observed selectivity changes reveal unprecedented details regarding the location and orientation of the catalyst molecules inside the GNF nanoreactor, inaccessible by any spectroscopic or microscopic techniques, thus shedding light on the precise reaction environment inside the molecular catalyst-GNF nanoreactor. Keywords: nanoreactor, catalysis, fullerene, salen, cross-couplin

All-fullerene-based cells for nonaqueous redox flow batteries

Redox flow batteries have the potential to revolutionize our use of intermittent sustainable energy sources such as solar and wind power by storing the energy in liquid electrolytes. Our concept study utilizes a novel electrolyte system, exploiting derivatized fullerenes as both anolyte and catholyte species in a series of battery cells, including a symmetric, single species system which alleviates the common problem of membrane crossover. The prototype multielectron system, utilizing molecular based charge carriers, made from inexpensive, abundant, and sustainable materials, principally, C and Fe, demonstrates remarkable current and energy densities and promising long-term cycling stability

Near-Infrared Mapping and Physical Properties of the Dwarf-Planet Ceres

We study the physical characteristics (shape, dimensions, spin axis direction, albedo maps, mineralogy) of the dwarf-planet Ceres based on high-angular resolution near-infrared observations. We analyze adaptive optics J/H/K imaging observations of Ceres performed at Keck II Observatory in September 2002 with an equivalent spatial resolution of ~50 km. The spectral behavior of the main geological features present on Ceres is compared with laboratory samples. Ceres' shape can be described by an oblate spheroid (a = b = 479.7 +/- 2.3 km, c = 444.4 +/- 2.1 km) with EQJ2000.0 spin vector coordinates RA = 288 +/- 5 deg. and DEC = +66 +/- 5 deg. Ceres sidereal period is measured to be 9.0741 +/- 0.0001 h. We image surface features with diameters in the 50-180 km range and an albedo contrast of ~6% with respect to the average Ceres albedo. The spectral behavior of the brightest regions on Ceres is consistent with phyllosilicates and carbonate compounds. Darker isolated regions could be related to the presence of frost.Comment: 11 pages, 8 Postscript figures, Accepted for publication in A&

Nonredox CO2 fixation in solvent-free conditions using a Lewis acid metal–organic framework constructed from a sustainably sourced ligand

CO2 epoxidation to cyclic carbonates under mild, solvent-free conditions is a promising pathway toward sustainable CO2 utilization. Metal–organic frameworks (MOFs) explored for such applications so far are commonly composed of nonrenewable ligands such as benzene dicarboxylate (BDC) or synthetically complex linkers and therefore are not suitable for commercial utilization. Here, we report new yttrium 2,5-furandicarboxylate (FDC)-based MOFs: “UOW-1” and “UOW-2” synthesized via solvothermal assembly, with the former having a unique structural topology. The FDC linker can be derived from biomass and is a green and sustainable alternative to conventionally used BDC ligands, which are sourced exclusively from fossil fuels. UOW-1, owing to unique coordination unsaturation and a high density of Lewis active sites, promotes a high catalytic activity (∼100% conversion; ∼99% selectivity), a high turnover frequency (70 h–1), and favorable first-order kinetics for CO2 epoxidation reactions using an epichlorohydrin model substrate under solvent-free conditions within 6 h and a minimal cocatalyst amount. A systematic catalytic study was carried out by broadening the epoxide substrate scope to determine the influence of electronic and steric factors on CO2 epoxidation. Accordingly, higher conversion efficiencies were observed for substrates with high electrophilicity on the carbon center and minimal steric bulk. The work presents the first demonstration of sustainable FDC-based MOFs used for efficient CO2 utilization

Engineering molecular chains in carbon nanotubes

A range of mono- and bis-functionalised fullerenes have been synthesised and inserted into single-walled carbon nanotubes. The effect of the size and shape of the functional groups of the fullerenes on the resultant 1D arrays formed within the nanotubes was investigated by high resolution transmission electron microscopy and X-ray diffraction. The addition of non-planar, sterically bulky chains to the fullerene cage results in highly ordered 1D structures in which the fullerenes are evenly spaced along the internal nanotube cavity. Theoretical calculations reveal that the functional groups interact with neighbouring fullerene cages to space the fullerenes evenly within the confines of the nanotube. The addition of two functional groups to opposite sides of the fullerene cages results in a further increase in the separation of the fullerene cages within the nanotubes at the cost of lower nanotube filling rates.This work was financially supported by FWF project I83-N20 (ESF IMPrESS), the Royal Society, the European Research Council (ERC), "Fundacao para a Ciencia ea Tecnologia" through the program Ciencia 2008, the project SeARCH (Services and Advanced Research Computing with HTC/HPC clusters) and Nottingham Nanoscience and Nanotechnology Centre (NNNC)