Studies of Black Diamond as an antibacterial surface for Gram Negative bacteria: the interplay between chemical and mechanical bactericidal activity.

'Black silicon' (bSi) samples with surfaces covered in nanoneedles of length ~5 µm were fabricated using a plasma etching process and then coated with a conformal uniform layer of diamond using hot filament chemical vapour deposition to produce 'black diamond' (bD) nanostructures. The diamond needles were then chemically terminated with H, O, NH2 or F using plasma treatment, and the hydrophilicity of the resulting surfaces were assessed using water droplet contact-angle measurements, and scaled in the order O > H ≈NH2 >F, with the F-terminated surface being superhydrophobic. The effectiveness of these differently terminated bD needles in killing the Gram-negative bacterium E. coli was semi-quantified by Live/Dead staining and fluorescence microscopy, and visualised by environmental scanning electron microscopy. The total number of adhered bacteria was consistent for all the nanostructured bD surfaces at around 50% of the value for the flat diamond control. This, combined with a chemical bactericidal effect of 20-30%, shows that the nanostructured bD surfaces supported significantly fewer viable E. coli than flat surfaces. Moreover, the bD surfaces were particularly effective at preventing the establishment of bacterial aggregates - a precursor to biofilm formation. The percentage of dead bacteria also decreased as a function of hydrophilicity. These results are consistent with a predominantly mechanical mechanism for bacteria death based on the stretching and disruption of the cell membrane, combined with an additional effect from the chemical nature of the surface.

Studies of black silicon and black diamond as materials for antibacterial surfaces.

'Black silicon' (bSi) samples with surfaces covered in nanoneedles of varying length, areal density and sharpness, have been fabricated using a plasma etching process. These nanostructures were then coated with a conformal uniform layer of diamond using hot filament chemical vapour deposition to produce 'black diamond' (bD) surfaces. The effectiveness of these bSi and bD surfaces in killing Gram-negative (E. coli) and Gram-positive (S. gordonii) bacteria was investigated by culturing the bacteria on the surfaces for a set time and then measuring the live-to-dead ratio. All the nanostructured surfaces killed E. coli at a significantly higher rate than the respective flat Si or diamond control samples. The length of the needles was found to be less important than their separation, i.e. areal density. This is consistent with a model for mechanical bacteria death based on the stretching and disruption of the cell membrane, enhanced by the cells motility on the surfaces. In contrast, S. gordonii were unaffected by the nanostructured surfaces, possibly due to their smaller size, thicker cell membrane and/or their lack of motility.

Diamond thin films: giving biomedical applications a new shine.

Progress made in the last two decades in chemical vapour deposition technology has enabled the production of inexpensive, high-quality coatings made from diamond to become a scientific and commercial reality. Two properties of diamond make it a highly desirable candidate material for biomedical applications: first, it is bioinert, meaning that there is minimal immune response when diamond is implanted into the body, and second, its electrical conductivity can be altered in a controlled manner, from insulating to near-metallic. In vitro, diamond can be used as a substrate upon which a range of biological cells can be cultured. In vivo, diamond thin films have been proposed as coatings for implants and prostheses. Here, we review a large body of data regarding the use of diamond substrates for in vitro cell culture. We also detail more recent work exploring diamond-coated implants with the main targets being bone and neural tissue. We conclude that diamond emerges as one of the major new biomaterials of the twenty-first century that could shape the way medical treatment will be performed, especially when invasive procedures are required.

Photochemically modified diamond-like carbon surfaces for neural interfaces.

Diamond-like carbon (DLC) was modified using a UV functionalization method to introduce surface-bound amine and aldehyde groups. The functionalization process rendered the DLC more hydrophilic and significantly increased the viability of neurons seeded to the surface. The amine functionalized DLC promoted adhesion of neurons and fostered neurite outgrowth to a degree indistinguishable from positive control substrates (glass coated with poly-L-lysine). The aldehyde-functionalized surfaces performed comparably to the amine functionalized surfaces and both additionally supported the adhesion and growth of primary rat Schwann cells. DLC has many properties that are desirable in biomaterials. With the UV functionalization method demonstrated here it may be possible to harness these properties for the development of implantable devices to interface with the nervous system.

Diamond-coated 'black silicon' as a promising material for high-surface-area electrochemical electrodes and antibacterial surfaces.

This report describes a method to fabricate high-surface-area boron-doped diamond (BDD) electrodes using so-called 'black silicon' (bSi) as a substrate. This is a synthetic nanostructured material that contains high-aspect-ratio nano-protrusions, such as spikes or needles, on the Si surface produced via plasma etching. We now show that coating a bSi surface composed of 15 µm-high needles conformably with BDD produces a robust electrochemical electrode with high sensitivity and high electroactive area. A clinically relevant demonstration of the efficacy of these electrodes is shown by measuring their sensitivity for detection of dopamine (DA) in the presence of an excess of uric acid (UA). Finally, the nanostructured surface of bSi has recently been found to generate a mechanical bactericidal effect, killing both Gram-negative and Gram-positive bacteria at high rates. We will show that BDD-coated bSi also acts as an effective antibacterial surface, with the added advantage that being diamond-coated it is far more robust and less likely to become damaged than Si.

Three-dimensional kinetic Monte Carlo simulations of diamond chemical vapor deposition.

A three-dimensional kinetic Monte Carlo model has been developed to simulate the chemical vapor deposition of a diamond (100) surface under conditions used to grow single-crystal diamond (SCD), microcrystalline diamond (MCD), nanocrystalline diamond (NCD), and ultrananocrystalline diamond (UNCD) films. The model includes adsorption of CHx (x = 0, 3) species, insertion of CHy (y = 0-2) into surface dimer bonds, etching/desorption of both transient adsorbed species and lattice sidewalls, lattice incorporation, and surface migration but not defect formation or renucleation processes. A value of ∼200 kJ mol(-1) for the activation Gibbs energy, ΔG(‡) etch, for etching an adsorbed CHx species reproduces the experimental growth rate accurately. SCD and MCD growths are dominated by migration and step-edge growth, whereas in NCD and UNCD growths, migration is less and species nucleate where they land. Etching of species from the lattice sidewalls has been modelled as a function of geometry and the number of bonded neighbors of each species. Choice of appropriate parameters for the relative decrease in etch rate as a function of number of neighbors allows flat-bottomed etch pits and/or sharp-pointed etch pits to be simulated, which resemble those seen when etching diamond in H2 or O2 atmospheres. Simulation of surface defects using unetchable, immobile species reproduces other observed growth phenomena, such as needles and hillocks. The critical nucleus for new layer growth is 2 adjacent surface carbons, irrespective of the growth regime. We conclude that twinning and formation of multiple grains rather than pristine single-crystals may be a result of misoriented growth islands merging, with each island forming a grain, rather than renucleation caused by an adsorbing defect species.

Assisted deposition of nano-hydroxyapatite onto exfoliated carbon nanotube oxide scaffolds.

Electrodeposited nano-hydroxyapatite (nHAp) is more similar to biological apatite in terms of microstructure and dimension than apatites prepared by other processes. Reinforcement with carbon nanotubes (CNTs) enhances its mechanical properties and increases adhesion of osteoblasts. Here, we carefully studied nHAp deposited onto vertically aligned multi-walled CNT (VAMWCNT) scaffolds by electrodeposition and soaking in a simulated body fluid (SBF). VAMWCNTs are porous biocompatible scaffolds with nanometric porosity and exceptional mechanical and chemical properties. The VAMWCNT films were prepared on a Ti substrate by a microwave plasma chemical vapour deposition method, and then oxidized and exfoliated by oxygen plasma etching (OPE) to produce graphene oxide (GO) at the VAMWCNT tips. The attachment of oxygen functional groups was found to be crucial for nHAp nucleation during electrodeposition. A thin layer of plate-like and needle-like nHAp with high crystallinity was formed without any need for thermal treatment. This composite (henceforth referred to as nHAp-VAMWCNT-GO) served as the scaffold for in vitro biomineralization when soaked in the SBF, resulting in the formation of both carbonate-rich and carbonate-poor globular-like nHAp. Different steps in the deposition of biological apatite onto VAMWCNT-GO and during the short-term biomineralization process were analysed. Due to their unique structure and properties, such nano-bio-composites may become useful in accelerating in vivo bone regeneration processes.

Amine functionalized nanodiamond promotes cellular adhesion, proliferation and neurite outgrowth.

In this study, we report the production of amine functionalized nanodiamond. The amine functionalized nanodiamond forms a conformal monolayer on a negatively charged surface produced via plasma polymerization of acrylic acid. Nanodiamond terminated surfaces were studied as substrates for neuronal cell culture. NG108-15 neuroblastoma-glioma hybrid cells were successfully cultured upon amine functionalized nanodiamond coated surfaces for between 1 and 7 d. Additionally, primary dorsal root ganglion (DRG) neurons and Schwann cells isolated from Wistar rats were also successfully cultured over a period of 21 d illustrating the potential of the coating for applications in the treatment of peripheral nerve injury.

Nanofocusing optics for synchrotron radiation made from polycrystalline diamond.

Diamond possesses many extreme properties that make it an ideal material for fabricating nanofocusing x-ray optics. Refractive lenses made from diamond are able to focus x-ray radiation with high efficiency but without compromising the brilliance of the beam. Electron-beam lithography and deep reactive-ion etching of silicon substrates have been used in a transfer-molding technique to fabricate diamond optics with vertical and smooth sidewalls. Latest generation compound refractive lenses have seen an improvement in the quality and uniformity of the optical structures, resulting in an increase in their focusing ability. Synchrotron beamline tests of two recent lens arrays, corresponding to two different diamond morphologies, are described. Focal line-widths down to 210 nm, using a nanocrystalline diamond lens array and a beam energy of E = 11 keV, and 230 nm, using a microcrystalline diamond lens at E = 15 keV, have been measured using the Diamond Light Source Ltd. B16 beamline. This focusing prowess is combined with relatively high transmission through the lenses compared with silicon refractive designs and other diffractive optics.

Porous boron-doped diamond/carbon nanotube electrodes.

Nanostructuring boron-doped diamond (BDD) films increases their sensitivity and performance when used as electrodes in electrochemical environments. We have developed a method to produce such nanostructured, porous electrodes by depositing BDD thin film onto a densely packed "forest" of vertically aligned multiwalled carbon nanotubes (CNTs). The CNTs had previously been exposed to a suspension of nanodiamond in methanol causing them to clump together into "teepee" or "honeycomb" structures. These nanostructured CNT/BDD composite electrodes have been extensively characterized by scanning electron microscopy, Raman spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. Not only do these electrodes possess the excellent, well-known characteristics associated with BDD (large potential window, chemical inertness, low background levels), but also they have electroactive areas and double-layer capacitance values ∼450 times greater than those for the equivalent flat BDD electrodes.

Field emission from hybrid diamond-like carbon and carbon nanotube composite structures.

A thin diamond-like carbon (DLC) film was deposited onto a densely packed "forest" of vertically aligned multiwalled carbon nanotubes (VACNT). DLC deposition caused the tips of the CNTs to clump together to form a microstructured surface. Field-emission tests of this new composite material show the typical low threshold voltages for carbon nanotube structures (2 V µm(-1)) but with greatly increased emission current, better stability, and longer lifetime.

Prevalence of urinary incontinence and associated risk factors in nursing home residents: a systematic review.

AIMS: To determine not only prevalence rates of urinary incontinence (UI) in nursing home residents but also factors influencing these prevalence rates, and to provide an overview of risk factors associated with UI in this group. METHODS: A systematic review was performed using multiple databases including MEDLINE, EMBASE, CINAHL, PsycINFO and the Cochrane Library from January 1997 to April 2008. In addition, the bibliographies of all relevant articles were searched. Two authors independently assessed the eligibility of all studies and extracted data on study design, population characteristics, definition of incontinence, measurement instrument, risk factors and prevalence rates. RESULTS: Twelve articles containing 16 studies met the eligibility criteria. Prevalence rates of UI in nursing home residents ranged from 43% to 77% (median 58%). When comparing studies, the influencing factors on UI prevalence of age and sex were identified. In total 45 risk factors were described. Within individual study populations, sex, age, cognitive function, dementia, bedfast and locomotion were associated with UI. CONCLUSIONS: UI prevalence rates in nursing homes are high and the influencing factors poorly understood. Although important risk factors similar to those in the general population have been identified, risk factors related to the care process should be further investigated.

Phosphorus carbides: theory and experiment.

The recent finding that radio frequency plasma activation of CH(4)/PH(3) gas mixtures can yield films with P : C ratios < or = 3 has served to trigger further research into new 'phosphorus carbide' materials. Theoretical and experimental results relating to periodic and amorphous materials, respectively, are presented here: (i) The electronic structure and stability of different crystalline phosphorus carbide P(x)C(y) phases have been studied using first-principles density-functional theory. Calculations have been carried out for P(4)C(3+8 n) (n= 0-4), PC, and PC(3) and the most likely periodic structures examined in detail. Particular attention is paid to the composition PC(3), for which there are several possibilities of similar energy. (ii) Recent experimental efforts have involved use of pulsed laser ablation methods to produce hydrogen-free phosphorus carbide thin films. Mechanically hard, electrically conducting diamond like carbon films containing 0- approximately 26 at.% P have been deposited on both Si and quartz substrates by 193 nm PLA of graphite/phosphorus targets (containing varying percentages of phosphorus), at a range of substrate temperatures (T(sub)= 298-700 K), in vacuum, and analysed via laser Raman and X-ray photoelectron spectroscopy.