Photochemical studies of cis-[Ru(bpy)2(4-bzpy)(CO)](PF6)2 and cis-[Ru(bpy)2(4-bzpy)(Cl)](PF6): Blue light-induced nucleobase binding.

The ruthenium(II) compounds cis-[Ru(bpy)2(4-bzpy)(CO)](PF6)2 (I) and cis-[Ru(bpy)2(4-bzpy)(Cl)](PF6) (II) (4-bzpy=4-benzoylpyridine, bpy=2,2'-bipyridine) were synthesized and characterized by spectroscopic and electrochemical techniques. The crystal structure of II was determined by X-ray diffraction. The photochemical behavior of I in aqueous solution shows that irradiation with ultraviolet light (365nm) releases both CO and 4-bzpy leading to the formation of the cis-[Ru(bpy)2(H2O)2]2+ ion as identified by NMR and electronic spectroscopy. Carbon monoxide release was confirmed with the myoglobin method and by gas chromatographic analysis of the headspace. CO release was not observed when aqueous I was irradiated with blue light (453nm). Changes in the electronic and 1H NMR spectra indicate that I undergoes photoaquation of 4-bzpy to form cis-[Ru(bpy)2(CO)(H2O)]2+. Blue light irradiation of aqueous II released the coordinated 4-bzpy to give the cis-[Ru(bpy)2(H2O)(Cl)]2+ ion. When the latter reaction was carried out in the presence of the nucleobase guanine, Ru-guanine adducts were formed, indicating that the metal containing photoproduct may also participate in biologically relevant reactions. The photochemical behavior of I indicates that it can release either CO or 4-bzpy depending on the wavelength chosen, a feature that may have therapeutic application

Determination of the elastic properties of graphene by indentation and the validity of classical models of indentation

Ab initio and empirical force field methods are used to simulate the loading of a large graphene membrane under an indenter analogous to an atomic force microscope tip. From these calculations we attempt to resolve ambiguities around determination of the elastic constants of graphene from such indentation experiments. We investigate the effect of the formation of wrinkles and more importantly the applicability of modelling the membrane as a continuous elastic sheet. By comparing empirical potential and large scale density functional theory calculations we have also assessed the performance of classical potentials in describing bending in this system. We find that the in-plane Young's modulus deduced from the indentation simulations using the classical expression for a clamped elastic membrane under a central point load is not consistent with that calculated directly from the in-plane stress-strain curve. © 2014 IOP Publishing Ltd

Hydrogen adsorption capacity of adatoms on double carbon vacancies of graphene: A trend study from first principles

Structural stability and hydrogen adsorption capacity are two key quantities in evaluating the potential of metal-adatom decorated graphene for hydrogen storage and related devices. We have carried out extensive density functional theory calculations for the adsorption of hydrogen molecules on 12 different adatom (Ag, Au, Ca, Li, Mg, Pd, Pt, Sc, Sr, Ti, Y, and Zr) decorated graphene surfaces where the adatoms are found to be stabilized on double carbon vacancies, thus overcoming the "clustering problem" that occurs for adatoms on pristine graphene. Ca and Sr are predicted to bind the greatest number, namely six, of H2 molecules. We find an interesting correlation between the hydrogen capacity and the change of charge distribution with increasing H2 adsorption, where Ca, Li, Mg, Sc, Ti, Y, Sr, and Zr adatoms are partial electron donors and Ag, Au, Pd, and Pt are partial electron acceptors. The "18-electron rule" for predicting maximum hydrogen capacity is found not to be a reliable indicator for these systems. © 2013 American Physical Society

Site-specific associations of muscle thickness with bone mineral density in middle-aged and older men and women

It is unknown whether age-related site-specific muscle loss is associated with areal bone mineral density (aBMD) in older adults. To examine the relationships between aBMD and whole-body muscle thickness distribution, 97 healthy adults (46 women and 51 men) aged 50–78 years volunteered. Total and appendicular lean soft tissue mass, aBMD of the lumbar spine (LS-aBMD) and femoral neck (FN-aBMD) were determined using dual-energy X-ray absorptiometry. Muscle thickness (MT) was measured by ultrasound at nine sites of the body (forearm, upper arm, trunk, upper leg, and lower leg). Relationships of each co-variate with aBMD were tested partialling out the effect of age. aBMD was not correlated with either MT of the trunk or anterior lower leg in either sex. In men, significant and relatively strong correlations were observed between anterior and posterior upper arms, posterior lower leg, and anterior upper leg MT and LS-aBMD or FN-aBMD. In women, significant correlations were observed between anterior and posterior upper legs, posterior lower leg, and anterior upper arm MT and FN-aBMD. LS-aBMD was only correlated with forearm and posterior upper leg MT in women. In conclusion, the site-specific association of MT and aBMD differs between sexes and may be associated with the participants’ daily physical activity profile

Fructosamine; is the current interest in alternative glycaemic markers justified?

This is an accepted manuscript of an article published by Wiley in Diabetic Medicine on 27/03/2015, available online: https://doi.org/10.1111/dme.12767 The accepted version of the publication may differ from the final published version.Published versio

Older adults experiences of rehabilitation in acute health care

Rehabilitation is a key component of nursing and allied healthcare professionals’ roles in most health and social care settings. This paper reports on stage 2 of an action research project to ascertain older adult's experience of rehabilitation. Twenty postdischarge interviews were conducted and the interview transcripts were analysed using thematic content analysis. All older adults discharged from an acute older acute rehabilitation ward to their own homes in the community were eligible to participate. The only exclusion criterion was older adults who were thought to be unable to give consent to participate by the nurse in charge and the researcher. Whilst 92 older adults were eligible to participate in this research study, only 20 were interviewed. The findings from this study suggest that older adults valued communication with health professionals but were aware of their time constraints that hindered communication. This study suggests that both nurses and allied health professionals are not actively providing rehabilitative services to promote health and well-being, which contradicts the focus of active ageing. Furthermore, there was evidence of unmet needs on discharge, and older adults unable to recall the professions that were involved in their interventions and the rationale for therapy input. It is suggested that further research is needed to explore the effectiveness of allied health rehabilitation in the acute setting. This study highlights the need for further research into older adults’ perceptions of the rehabilitation process in the acute setting