Examination of surface properties and in vitro biological performance of amorphous diamond-like carbon-coated polyurethane

Despite the emerging use of diamond-like carbon (DLC) as a coating for medical devices, few studies have examined the resistance of DLC coatings onto medical polymers to both microbial adherence and encrustation. In this study, amorphous DLC of a range of refractive indexes (1.7-1.9) and thicknesses (100-600 nm) was deposited onto polyurethane, a model polymer, and the resistance to microbial adherence (Escherichia coli; clinical isolate) and encrustation examined using in vitro models. In comparison to the native polymer, the advancing and receding contact angles of DLC-coated polyurethane were lower, indicating greater hydrophilic properties. No relationship was observed between refractive index, thickness, and advancing contact angle, as determined using multiple correlation analysis. The resistances of the various DLC-coated polyurethane films to encrustation and microbial adherence were significantly greater than that to polyurethane; however, there were individual differences between the resistances of the various DLC coatings. In general, increasing the refractive index of the coatings (100 nm thickness) decreased the resistance of the films to both hydroxyapatite and struvite encrustation and to microbial adherence. Films of lower thicknesses (100 and 200 nm; of defined refractive index, 1.8), exhibited the greatest resistance to encrustation and to microbial adherence. In conclusion, this study has uniquely illustrated both the microbial antiadherence properties and resistance to urinary encrustation of DLC-coated polyurethane. The resistances to encrustation and microbial adherence were substantial, and in light of this, it is suggested that DLC coatings of low thickness and refractive index show particular promise as coatings of polymeric medical devices. (c) 2006 Wiley Periodicals, Inc.

Relationship between biomedical catheter surface properties and lubricity as determined using textural analysis and multiple regression analysis

In this study, the surface properties of and work required to remove 12 commercially available and developmental catheters from a model biological medium (agar), a measure of catheter lubricity, were characterised and the relationships between these properties were examined using multiple regression and correlation analysis. The work required for removal of catheter sections (7 cm) from a model biological medium (1% w/w agar) were examined using tensile analysis. The water wettability of the catheters were characterised using dynamic contact angle analysis, whereas surface roughness was determined using atomic force microscopy. Significant differences in the ease of removal were observed between the various catheters, with the silicone-based materials generally exhibiting the greatest ease of removal. Similarly, the catheters exhibited a range of advancing and receding contact angles that were dependent on the chemical nature of each catheter. Finally, whilst the microrugosities of the various catheters differed, no specific relationship to the chemical nature of the biomaterial was apparent. Using multiple regression analysis, the relationship between ease of removal, receding contact angle and surface roughness was defined as: Work done (N mm) 17.18 + 0.055 Rugosity (nm)-0.52 Receding contact angle (degrees) (r = 0.49). Interestingly, whilst the relationship between ease of removal and surface roughness was significant (r = 0.48, p = 0.0005), in which catheter lubricity increased as the surface roughness decreased, this was not the case with the relationship between ease of removal and receding contact angle (r = -0.18, p > 0.05). This study has therefore uniquely defined the contributions of each of these surface properties to catheter lubricity. Accordingly, in the design of urethral catheters. it is recommended that due consideration should be directed towards biomaterial surface roughness to ensure maximal ease of catheter removal. Furthermore, using the method described in this study, differences in the lubricity of the various catheters were observed that may be apparent in their clinical use. (C) 2003 Elsevier Ltd. All rights reserved.

SrTiO3(001)(2x1) reconstructions: First-principles calculations of surface energy and atomic structure compared with scanning tunneling microscopy images

(1x1) and (2x1) reconstructions of the (001) SrTiO3 surface were studied using the first-principles full-potential linear muffin-tin orbital method. Surface energies were calculated as a function of TiO2 chemical potential, oxygen partial pressure and temperature. The (1x1) unreconstructed surfaces were found to be energetically stable for many of the conditions considered. Under conditions of very low oxygen partial pressure the (2x1) Ti2O3 reconstruction [Martin R. Castell, Surf. Sci. 505, 1 (2002)] is stable. The question as to why STM images of the (1x1) surfaces have not been obtained was addressed by calculating charge densities for each surface. These suggest that the (2x1) reconstructions would be easier to image than the (1x1) surfaces. The possibility that the presence of oxygen vacancies would destabilise the (1x1) surfaces was also investigated. If the (1x1) surfaces are unstable then there exists the further possibility that the (2x1) DL-TiO2 reconstruction [Natasha Erdman Nature (London) 419, 55 (2002)] is stable in a TiO2-rich environment and for p(O2)>10(-18) atm.

Surface alloying and mixing at the Mn/Fe(001) interface: Real-time photoelectron spectroscopy and modified embedded atom simulations

Structural and magnetic properties of thin Mn films on the Fe(001) surface have been investigated by a combination of photoelectron spectroscopy and computer simulation in the temperature range 300 Kless than or equal toTless than or equal to750 K. Room-temperature as deposited Mn overlayers are found to be ferromagnetic up to 2.5-monolayer (ML) coverage, with a magnetic moment parallel to that of the iron substrate. The Mn atomic moment decreases with increasing coverage, and thicker samples (4-ML and 4.5-ML coverage) are antiferromagnetic. Photoemission measurements performed while the system temperature is rising at constant rate (dT/dtsimilar to0.5 K/s) detect the first signs of Mn-Fe interdiffusion at T=450 K, and reveal a broad temperature range (610 Kless than or equal toTless than or equal to680 K) in which the interface appears to be stable. Interdiffusion resumes at Tgreater than or equal to680 K. Molecular dynamics and Monte Carlo simulations allow us to attribute the stability plateau at 610 Kless than or equal toTless than or equal to680 K to the formation of a single-layer MnFe surface alloy with a 2x2 unit cell and a checkerboard distribution of Mn and Fe atoms. X-ray-absorption spectroscopy and analysis of the dichroic signal show that the alloy has a ferromagnetic spin structure, collinear with that of the substrate. The magnetic moments of Mn and Fe atoms in the alloy are estimated to be 0.8mu(B) and 1.1mu(B), respectively.

Post-depositional modification of atmospheric dust on a granite building in central Rio de Janeiro: implications for surface induration and subsequent stone decay

Extensive contour scaling of a 200 year old granite church is associated with the breaching of an apparently iron-rich crust and the widespread deposition of atmospheric dust within the canyon-like streetscape of Rio de Janeiro. Contemporary dust, accumulated dust from within the a depression on the building surface, the surface crust and the underlying granite are examined by a combination of total element analysis and sequential extraction, X-ray diffraction and energy dispersive X-ray fluorescence. Results indicate an increase in total organic carbon and a marked decrease in pH within the accumulated dust, and a rapid mobilization of anions and cations from the water-soluble and carbonate phases. It is considered that the latter is linked to salt accumulation within and eventual salt weathering of the granite. Post-depositional alteration of the dust is also linked with the de-silicification of clay minerals (Illite to kaolinite) and the loss of silica from the amorphous Fe/Mn phase of the accumulated dust under the initially saline and progressively more acidic conditions experienced at the stone - atmosphere interface. This mobilization of silica is associated with the formation of what is, in effect, a thin silica-rich surface crust or glaze. Within the glaze, assessory amounts of extractable iron are concentrated within the amorphous and crystalline Fe/Mn phases at levels that are significantly elevated with respect to the underlying granite, but much lower than the equivalent phases of the accumulated dust from which it is principally assumed to derive. The protection afforded to the stone work by the crust is not, however, permanent and within the last 15 years it has been possible to observe a rapid increase in the surface delamination of the church close to street level.

Isotopic assessment of sources and processes affecting sulfate and nitrate in surface water and groundwater of Luxembourg

Surface water and deep and shallow groundwater samples were taken from selected parts of the Grand-Duchy of Luxembourg to determine the isotopic composition of nitrate and sulfate, in order to identify sources and/or processes affecting these solutes. Deep groundwater had sulfate concentrations between 20 and 40 mg/L, d34Ssulfate values between -3.0 and -20.0‰, and d18Osulfate values between +1.5 and +5.0‰; nitrate was characterized by concentrations varying between

Estimation of speed of sound of ionic liquids using surface tensions and densities: A volume based approach

The limited availability of experimental data and their quality have been preventing the development of predictive methods and Computer Aided Molecular Design (CAMD) of ionic liquids (ILs). Based on experimental speed of sound data collected from the literature, the inter-relationship of surface tension (s), density (?), and speed of sound (u) has been examined for imidazolium based ILs containing hexafluorophosphate (PF6), tetrafluoroborate (BF4), bis(trifluoromethanesulphonyl) amide (NTf2), methyl sulphate (MeSO4), ethyl sulphate (EtSO4), and trifluoromethanesulphonate (CF3SO3) anions, covering wide ranges of temperature, 278.15–343.15 K and speed of sound, 1129.0–1851.0 m s-1. The speed of sound was correlated with a modified Auerbach's relation, by using surface tension and density data obtained from volume based predictive methods previously proposed by the authors. It is shown that a good agreement with literature data is obtained. For 133 data points of 14 ILs studied a mean percent deviation (MPD) of 1.96% with a maximum deviation inferior to 5% was observed. The correlations developed here can thus be used to evaluate the speeds of sound of new ionic liquids.

A density functional theory study of the surface relaxation and reactivity of Cu2O(100)

Density functional theory has been used to investigate the surface relaxation of Cu2O(100) and the adsorption of NO. The calculations indicate the formation of surface copper dimers on relaxation coupled with a large contraction of the spacing between the first and second layers. Local density of states for atoms in the top three layers shows that the third layer copper atoms have the greatest change in bonding character. Adsorption energies have been calculated for the N-down and O-down adsorption of NO on the Cu2O(100) surface. These indicate that N-down adsorption is favoured and that in this case NO-lattice oxygen interactions dominate the adsorbate structure. (C) 2000 Elsevier Science B.V. All rights reserved.