F. McBride

Spherical momentum distribution of the protons in hexagonal ice from modeling of inelastic neutron scattering data

The spherical momentum distribution of the protons in ice is extracted from a high resolution deep inelastic neutron scattering experiment. Following a recent path integral Car-Parrinello molecular dynamics study, data were successfully interpreted in terms of an anisotropic Gaussian model, with a statistical accuracy comparable to that of the model independent scheme used previously, but providing more detailed information on the three dimensional potential energy surface experienced by the proton. A recently proposed theoretical concept is also employed to directly calculate the mean force from the experimental neutron Compton profile, and to evaluate the accuracy required to unambiguously resolve and extract the effective proton potential from the experimental data.

Microencapsulated Phase Change Materials in Solar-Thermal Conversion Systems: Understanding Geometry-Dependent Heating Efficiency and System Reliability

The performance of solar-thermal conversion systems can be improved by incorporation of nanocarbon-stabilized microencapsulated phase change materials (MPCMs). The geometry of MPCMs in the microcapsules plays an important role for improving their heating efficiency and reliability. Yet few efforts have been made to critically examine the formation mechanism of different geometries and their effect on MPCMs-shell interaction. Herein, through changing the cooling rate of original emulsions, we acquire MPCMs within the nanocarbon microcapsules with a hollow structure of MPCMs (h-MPCMs) or solid PCM core particles (s-MPCMs). X-ray photoelectron spectroscopy and atomic force microscopy reveals that the capsule shell of the h-MPCMs is enriched with nanocarbons and has a greater MPCMs-shell interaction compared to s-MPCMs. This results in the h-MPCMs being more stable and having greater heat diffusivity within and above the phase transition range than the s-MPCMs do. The geometry-dependent heating efficiency and system stability may have important and general implications for the fundamental understanding of microencapsulation and wider breadth of heating generating systems.

Bacterial viability on chemically modified silicon nanowire arrays

The global threat of antimicrobial resistance is driving an urgent need for novel antimicrobial strategies. Functional surfaces are essential to prevent spreading of infection and reduce surface contamination. In this study we have fabricated and characterized multiscale-functional nanotopographies with three levels of functionalization: (1) nanostructure topography in the form of silicon nanowires, (2) covalent chemical modification with (3-aminopropyl)triethoxysilane, and (3) incorporation of chlorhexidine digluconate. Cell viability assays were carried out on two model microorganisms E. coli and S. aureus over these nanotopographic surfaces. Using SEM we have identified two growth modes producing distinctive multicellular structures, i.e. in plane growth for E. coli and out of plane growth for S. aureus. We have also shown that these chemically modified SiNWs arrays are effective in reducing the number of planktonic and surface-attached microorganisms.

Strain relief and disorder in commensurate water layers formed on Pd(111)

Water adsorbs and desorbs intact on Pd(111), forming a hydrogen-bonded wetting layer whose structure we examine by low energy electron diffraction (LEED) and He atom scattering (HAS). LEED shows that water forms commensurate (√3 × √3)R30° clusters that aggregate into a partially ordered, approximately (7 × 7) superstructure as the layer completes. HAS indicates that the water layer remains disordered on a local (approximately 10 Å) scale. Based on workfunction measurements and density functional theory simulations we propose that water forms small, flat domains of a commensurate (√3 × √3)R30° water network, separated by disordered domain boundaries containing largely H-down water. This arrangement allows the water layer to adapt its density and relieve the lateral strain associated with adsorbing water in the optimum flat atop adsorption site. We discuss different possibilities for the structure of these domain walls and compare this strain relief mechanism to the highly ordered, large unit cell structures formed on surfaces such as Pt(111).

Nitric Oxide Releasing Polymeric Coatings for the Prevention of Biofilm Formation

The ability of nitric oxide (NO)-releasing polymer coatings to prevent biofilm formation is described. NO-releasing coatings on (poly(ethylene terephthalate) (PET) and silicone elastomer (SE)) were fabricated using aminosilane precursors. Pristine PET and SE were oxygen plasma treated, followed by immobilisation of two aminosilane molecules: N-(3-(trimethoxysilyl)propyl)diethylenetriamine (DET3) and N-(3-trimethoxysilyl)propyl)aniline (PTMSPA). N-diazeniumdiolate nitric oxide donors were formed at the secondary amine sites on the aminosilane molecules producing NO-releasing polymeric coatings. The NO payload and release were controlled by the aminosilane precursor, as DET3 has two secondary amine sites and PTMSPA only one. The antibacterial efficacy of these coatings was tested using a clinical isolate of Pseudomonas aeruginosa (PA14). All NO-releasing coatings in this study were shown to significantly reduce P. aeruginosa adhesion over 24 h with the efficacy being a function of the aminosilane modification and the underlying substrate. These NO-releasing polymers demonstrate the potential and utility of this facile coating technique for preventing biofilms for indwelling medical devices.

Water and its partially dissociated fragments at metal surfaces

Abstract Water and its fragments are present on metal surfaces under all but the most extreme conditions, acting both as a reactive species and as a ligand in ways that have yet to be fully explored. This review focuses on experimental studies of the chemical species and hydrogen bonding structures that form in the first layer adsorbed on a metal surface. The development of non-invasive probes that avoid dissociating water, or disrupting fragile bonding structures, now allows experiments to distinguish between different structural models for water and its fragments at the surface, allowing us to test the accuracy of modern structural calculations and provide a better picture of how the metal surface influences the structures and chemical species present. We start by describing the behaviour of Pt(1 1 1), whose redox chemistry is important in electrochemical fuel cells and has been studied in detail, providing a good reference system against which to discuss the effect changing the surface symmetry and metal reactivity has on the interface structure. Evidence for the presence and the role of hydroxyl and hydrated ‘hydronium’ species is described and we discuss the outlook for future experiments and identify some questions that remain to be resolved.

Linker-free covalent immobilization of nisin using atmospheric pressure plasma induced grafting

The linker-free covalent immobilization of polymers on surfaces has the potential to impart new properties and functions to surfaces for a wide range of applications. However, most current methods for the production of these surfaces involve multiple chemical steps and do not have a high degree of control over the chemical functionalities at the surface. A comprehensive study detailing the facile two-step covalent grafting of the antimicrobial peptide nisin onto polystyrene surfaces is reported. Functionalization is achieved using an atmospheric pressure plasma jet, and the reaction is monitored and compared with a standard wet chemical functionalization approach using a variety of analytical techniques. The reactive species produced by the atmospheric pressure plasma jet were analyzed by mass spectrometry and optical emission spectroscopy. The surface chemistry and topography of the functionalized surfaces were determined using contact angle measurements, Fourier infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy and atomic force microscopy respectively. Following surface analysis, the antimicrobial efficacy of the covalently grafted nisin against two major food borne pathogens (Staphylococcus aureus and Listeria monocytogenes) was assessed at two different pHs. The results demonstrated that a post-plasma treatment step after nisin deposition is required to covalently graft the peptide onto the surface. The covalent immobilization of nisin resulted in a significant reduction in bacterial counts within a short 30 minutes contact time. These surfaces were also significantly more antimicrobial compared to those prepared via a more traditional wet chemical approach indicating that the reported method could be a less expensive and less time consuming alternative.