The potential of electron beam radiation for simultaneous surface modification and bioresorption control of PLLA

Bioresorbable polymers have been widely investigated as materials exhibiting significant potential for successful application in the fields of tissue engineering and drug delivery. Further to the ability to control degradation, surface engineering of polymers has been highlighted as a key method central to their development. Previous work has demonstrated the ability of electron beam (e-beam) technology to control the degradation profiles and bioresorption of a number of commercially relevant bioresorbable polymers (poly-l-lactic acid (PLLA), Llactide/DL-lactide co-polymer (PLDL) and poly(lactic-co-glycolic acid (PLGA)). This work investigates the further potential of ebeam technology to impart added biofunctionality through the manipulation of polymer (PLLA) surface properties. PLLA samples were subjected to e-beam treatments in air, with varying beam energies and doses. Surface characterization was then performed using contact angle analysis, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and atomic force microscopy. Results demonstrated a significant increase in surface wettability post e-beam treatment. In correlation with this, XPS data showed the introduction of oxygen-containing functional groups to the surface of PLLA. Raman spectroscopy indicated chain scission in the near surface region of PLLA (as predicted). However, e-beam effects on surface properties were not shown to be dependent on beam energy or dose. E-beam irradiation did not seem to affect the surface roughness of PLLA as a direct consequence of the treatment.

An Experimental Assessment of the Effects of Stator Vane Tip Clearance and Back Swept Blading on an Automotive Variable Geometry Turbocharger

Off-design performance is of key importance now in the design of automotive turbocharger turbines. Due to automotive drive cycles, a turbine that can extract more energy at high pressure ratios and lower rotational speeds is desirable. Typically a radial turbine provides peak efficiency at U/C values of 0.7, but at high pressure ratios and low rotational speeds, the U/C value will be low and the rotor will experience high values of positive incidence at the inlet. The positive incidence causes high blade loading resulting in additional tip leakage flow in the rotor as well as flow separation on the suction surface of the blade. An experimental assessment has been performed on a scaled automotive VGS (variable geometry system). Three different stator vane positions have been analyzed: minimum, 25%, and maximum flow position. The first tests were to establish whether positioning the endwall clearance on the hub or shroud side of the stator vanes produced a different impact on turbine efficiency. Following this, a back swept rotor was tested to establish the potential gains to be achieved during off-design operation. A single passage CFD model of the test rig was developed and used to provide information on the flow features affecting performance in both the stator vanes and turbine. It was seen that off-design performance was improved by implementing clearance on the hub side of the stator vanes rather than on the shroud side. Through CFD analysis and tests, it was seen that two leakage vortices form, one at the leading edge and one after the spindle of the stator vane. The vortices affect the flow angle at the inlet to the rotor, in the hub region. The flow angle is shifted to more negative values of incidence, which is beneficial at the off-design conditions but detrimental at the design point. The back swept rotor was tested with the hub side stator vane clearance configuration. The efficiency and MFR were increased at the minimum and 25% stator vane position. At the design point, the efficiency and MFR were decreased. The CFD investigation showed that the incidence angle was improved at the off-design conditions for the back swept rotor. This reduction in the positive incidence angle, along with the improvement caused by the stator vane tip leakage flow, reduced flow separation on the suction surface of the rotor. At the design point, both the tip leakage flow of the stator vanes and the back swept blade angle caused flow separation on the pressure surface of the rotor. This resulted in additional blockage at the throat of the rotor reducing MFR and efficiency.

A field study assessing the impact of on-site wastewater treatment systems on surface water quality in a Co. Monaghan catchment

Poorly functioning on-site wastewater treatment systems (OSWTS) can be among the many sources of pollution to groundwater and surface water, which are of critical concern owing to potential human and ecological health risks. An investigation into the effects of on-site wastewater treatment systems (OSWTS) on surface water quality has been undertaken at several sites within a catchment in Co. Monaghan. The study sites were located in areas of 'low’ permeability, suggesting that run-off usually dominates over infiltration. Poor treatment performance of OSWTS within the catchment were found to be the result of several factors, including location in areas with unsuitable soil and site characteristics, incorrect installation, poor maintenance and inappropriate operation by the home owner.

Experimental studies of near-surface temperature cycling and surface wetting of stone and its implications for salt weathering

It has long been accepted that thermal and moisture regimes within stonework exert a major influence upon patterns of salt movement and, subsequently, the type and severity of salt-induced decay. For example, it is suggested that slow drying is more likely to bring dissolved salts to the surface, whereas rapid drying could result in the retention of some salt at or near the frequent wetting depth. In reality however, patterns of heating, cooling and surface wetting regimes that drive them – are complex and inconsistent responses to a wide range of environmental controls. As a first step to understanding the complexity of these relationships, this paper reports a series of experiments within a climatic cabinet designed to replicate the effects of short-term temperature fluctuations on the surface and sub-surface temperature regimes of a porous Jurassic limestone, and how they are influenced by surface wetting, ambient temperature and surface airflow. Preliminary results confirm the significance of very steep temperature/stress gradients within the outer centimetre or less of exposed stone under short-duration cycles of heating and cooling. This is important because this is the zone in which many stone decay processes, particularly salt weathering, operate, these processes invariably respond to temperature and moisture fluctuations, and short-term interruptions to insolation could, for example,
trigger these fluctuations on numerous occasions over a day. The data also indicate that there are complex patterns of temperature reversal with depth that are influenced in their intensity and location by surface wetting and moisture penetration, airflow across the surface and ambient air temperature. The presence of multiple temperature reversals and their variation over the course of heating and cooling phases belies previous assumtions of smooth, exponential increases and decreases in subsurface temperatures in response, for example to diurnal patterns of heating and cooling

Identification of the F1-ATPase at the cell surface of colonic epithelial cells:role in mediating cell proliferation

F1F0-ATPase was initially believed to be strictly expressed in the mitochondrial membrane. Interestingly, recent reports have shown that the F1 complex can serve as a cell surface receptor for apparently unrelated ligands. Here, we show for the first time the presence of the F1-ATPase at the cell surface of normal or cancerous colonic epithelial cells. Using Surface Plasmon Resonance technology and mass spectrometry, we identified a peptide hormone product of the gastrin gene (glycine-extended gastrin, G-gly), as a new ligand for the F1-ATPase. By molecular modeling, we identified the motif in the peptide sequence (EE/DxY), which directly interacts with the F1-ATPase and the amino-acids in the F1-ATPase which bind this motif. Replacement of the E9 residue by an alanine in the EE/DxY motif resulted in a strong decrease of G-gly binding to the F1-ATPase and the loss of its biological activity. In addition we demonstrated that F1-ATPase mediates the growth effects of the peptide. Indeed, blocking ATPase activity decreases G-gly-induced cell growth. The mechanism likely involves ADP production by the membrane F1-ATPase which is induced by G-gly. These results suggest an important contribution of cell surface ATPase in the pro-proliferative action of this gastrointestinal peptide.

Direct evidence showing the effect of root surface iron plaque on arsenite and arsenate uptake into rice (Oryza sativa) roots

The present study aimed to investigate the effects of root surface iron plaque on the uptake kinetics of arsenite and arsenate by excised roots of rice (Oryza sativa) seedlings. The results demonstrated that the presence of iron plaque enhanced arsenite and decreased arsenate uptake. Arsenite and arsenate uptake kinetics were adequately fitted by the Michaelis-Menten function in the absence of plaque, but produced poor fits to this function in the presence of plaque. Phosphate in the uptake solution did not have a significant effect on arsenite uptake irrespective of the presence of iron plaque; however phosphate had a significant effect on arsenate uptake. Without iron plaque, phosphate inhibited arsenate uptake. The presence of iron plaque diminished the effect of phosphate on arsenate uptake, possibly through a combined effect of arsenate desorption from iron plaque.

Surface energy and surface proton order of the ice Ih basal and prism surfaces

Density-functional theory (DFT) is used to examine the basal and prism surfaces of ice Ih. Similar surface energies are obtained for the two surfaces; however, in each case a strong dependence of the surface energy on surface proton order is identified. This dependence, which can be as much as 50% of the absolute surface energy, is significantly larger than the bulk dependence (< 1%) on proton order, suggesting that the thermodynamic ground state of the ice surface will remain proton ordered well above the bulk order-disorder temperature of about 72 K. On the basal surface this suggestion is supported by Monte Carlo simulations with an empirical potential and solution of a 2D Ising model with nearest neighbor interactions taken from DFT. Order parameters that define the surface energy of each surface in terms of nearest neighbor interactions between dangling OH bonds (those which point out of the surface into vacuum) have been identified and are discussed. Overall, these results suggest that proton order-disorder effects have a profound impact on the stability of ice surfaces and will most likely have an effect on ice surface reactivity as well as ice crystal growth and morphology. S Supplementary data are available from stacks.iop.org/JPhysCM/22/074209/mmedia

An in vitro study of the radiobiological effects of flattening filter free radiotherapy treatments

Flattening filter free (FFF) linear accelerators allow for an increase in instantaneous dose-rate of the x-ray pulses by a factor of 2-6 over the conventional flattened output. As a result, radiobiological investigations are being carried out to determine the effect of these higher dose-rates on cell response. The studies reported thus far have presented conflicting results, highlighting the need for further investigation. To determine the radiobiological impact of the increased dose-rates from FFF exposures a Varian Truebeam medical linear accelerator was used to irradiate two human cancer cell lines in vitro, DU-145 prostate and H460 non-small cell lung, with both flattened and FFF 6 MV beams. The fluence profile of the FFF beam was modified using a custom-designed Nylon compensator to produce a similar dose profile to the flattened beam (6X) at the cell surface but at a higher instantaneous dose-rate. For both cell lines there appeared to be no significant change in cell survival. Curve fitting coefficients for DU145 cells irradiated with constant average dose-rates were 6X: alpha = 0.09 +/- 0.03, beta = 0.03 +/- 0.01 and 6FFF: alpha = 0.14 +/- 0.13, beta = 0.03 +/- 0.02 with a significance of p = 0.75. For H460 cells irradiated with the same instantaneous dose-rate but different average dose-rate the fit coefficients were 6FFF (low dose-rate): alpha = 0.21 +/- 0.11, 0.07 +/- 0.02 and 6FFF (high dose-rate): alpha = 0.21 +/- 0.16, 0.07 +/- 0.03, with p = 0.79. The results indicate that collective damage behaviour does not occur at the instantaneous dose-rates investigated here and that the use of either modality should result in the same clinical outcome, however this will require further validation in vivo.

Effects of sintering temperature on morphology and mechanical characteristics of 3D printed porous titanium used as dental implant

Porous titanium samples were manufactured using the 3D printing and sintering method in order to determine the effects of final sintering temperature on morphology and mechanical properties. Cylindrical samples were printed and split into groups according to a final sintering temperature (FST). Irregular geometry samples were also printed and split into groups according to their FST. The cylindrical samples were used to determine part shrinkage, in compressive tests to provide stress-strain data, in microCT scans to provide internal morphology data and for optical microscopy to determine surface morphology. All of the samples were used in microhardness testing to establish the hardness. Below 1100 C FST, shrinkage was in the region of 20% but increased to approximately 30% by a FST of 1300 C. Porosity varied from a maximum of approximately 65% at the surface to the region of 30% internally. Between 97 and 99% of the internal porosity is interconnected. Average pore size varied between 24 µm at the surface and 19 µm internally. Sample hardness increased to in excess of 300 HV0.05 with increasing FST while samples with an FST of below 1250 C produced an elastic-brittle stress/strain curve and samples above this displayed elastic-plastic behaviour. Yield strength increased significantly through the range of sintering temperatures while the Young's modulus remained fairly consistent. © 2013 Elsevier B.V.

Effects of oscillatory flow on fertilization in the green sea urchin Strongylocentrotus droebachiensis

Broadcast spawning invertebrates that live in shallow, high-energy coastal habitats are subjected to oscillatory water motion that creates unsteady flow fields above the surface of animals. The frequency of the oscillatory fluctuations is driven by the wave period, which will influence the stability of local flow structures and may affect fertilization processes. Using an oscillatory water tunnel, we quantified the percentage of eggs fertilized on or near spawning green sea urchins, Strongylocentrotus droebachiensis. Eggs were sampled in the water column, wake eddy, substratum and aboral surface under a range of different periods (T = 4.5 – 12.7 s) and velocities of oscillatory flow. The root-mean-square wave velocity (rms(uw)) was a good predictor of fertilization in oscillatory flow, although the root-mean-square of total velocity (rms(u)), which incorporates all the components of flow (current, wave and turbulence), also provided significant predictions. The percentage of eggs fertilized varied between 50 – 85% at low flows (rms(uw) < 0.02 m s-1), depending on the location sampled, but declined to below 10% for most locations at higher rms(uw). The water column was an important location for fertilization with a relative contribution greater than that of the aboral surface, especially at medium and high rms(uw) categories. We conclude that gametes can be successfully fertilized on or near the parent under a range of oscillatory flow conditions.

Toward Quantitative Electrochemical Measurements on the Nanoscale by Scanning Probe Microscopy: Environmental and Current Spreading Effects

The application of electric bias across tip–surface junctions in scanning probe microscopy can readily induce surface and bulk electrochemical processes that can be further detected though changes in surface topography, Faradaic or conductive currents, or electromechanical strain responses. However, the basic factors controlling tip-induced electrochemical processes, including the relationship between applied tip bias and the thermodynamics of local processes, remains largely unexplored. Using the model Li-ion reduction reaction on the surface in Li-ion conducting glass ceramic, we explore the factors controlling Li-metal formation and find surprisingly strong effects of atmosphere and back electrode composition on the process. We find that reaction processes are highly dependent on the nature of the counter electrode and environmental conditions. Using a nondepleting Li counter electrode, Li particles could grow significantly larger and faster than a depleting counter electrode. Significant Li ion depletion leads to the inability for further Li reduction. Time studies suggest that Li diffusion replenishes the vacant sites after 12 h. These studies suggest the feasibility of SPM-based quantitative electrochemical studies under proper environmental controls, extending the concepts of ultramicroelectrodes to the single-digit nanometer scale.

Relative Effects of Gamete Compatibility and Hydrodynamics on Fertilization in the Green Sea Urchin Strongylocentrotus droebachiensis

Intraspecific variation in gamete compatibility among male/female pairs causes variation in the concentration of sperm required to achieve equivalent fertilization levels. Gamete compatibility is therefore potentially an important factor controlling mating success. Many broadcast-spawning marine invertebrates, however, also live in a dynamic environment where hydrodynamic conditions can affect the concentration of sperm reaching eggs during spawning. Thus flow conditions may moderate the effects of gamete compatibility on fertilization. Using the green sea urchin Strongylocentrotus droebachiensis as a model system, we assessed the relative effects of gamete compatibility (the concentration of sperm required to fertilize 50% of the eggs in specific male/female pairs; F50) and the root-mean-square of total velocity (urms; 0.01-0.11 m s(-1)) on fertilization in four locations near a spawning female (water column, wake eddy, substratum, and aboral surface) in both unidirectional and oscillatory flows. Percent fertilization decreased significantly with increasing urms at all locations and both flow regimes. However, although gamete compatibility varied by almost 1.5 orders of magnitude, it was not a significant predictor of fertilization for most combinations of position and flow. The notable exception was a significant effect of gamete compatibility on fertilization on the aboral surface under unidirectional flow. Our results suggest that selection on variation in gamete compatibility may be strongest in eggs fertilized on the aboral surface of sea urchins and that hydrodynamic conditions may add environmental noise to selection outcomes.

The effects of global climate change on the cycling and processes of persistent organic pollutants (POPs) in the North Sea

The fate and cycling of two selected legacy persistent organic pollutants (POPs), PCB 153 and gamma-HCH, in the North Sea in the 21st century have been modelled with combined hydrodynamic and fate and transport ocean models
(HAMSOM and FANTOM, respectively). To investigate the impact of climate variability on POPs in the North Sea in the 21st century, future scenario model runs for three 10-year periods to the year 2100 using plausible levels of both in
situ concentrations and atmospheric, river and open boundary inputs are performed. This slice mode under a moderate scenario (A1B) is sufficient to provide a basis for further analysis. For the HAMSOM and atmospheric forcing, results of the IPCC A1B (SRES) 21st century scenario are utilized, where surface forcing is provided by the REMO downscaling of the ECHAM5 global atmospheric model, and open boundary conditions are provided by the MPIOM global ocean model.
Dry gas deposition and volatilization of gamma-HCH increase in the future relative to the present by up to 20% (in the spring and summer months for deposition and in summer for volatilization). In the water column, total mass of
gamma-HCH and PCB 153 remain fairly steady in all three runs. In sediment,
gamma-HCH increases in the future runs, relative to the present, while PCB 153 in sediment decreases exponentially in all three runs, but even faster in the future, due to the increased number of storms, increased duration of gale wind conditions and increased water and air temperatures, all of which are the result of climate change. Annual net sinks exceed sources at the ends of all periods.
Overall, the model results indicate that the climate change scenarios considered here generally have a negligible influence on the simulated fate and transport of the two POPs in the North Sea, although the increased number and magnitude of storms in the 21st century will result in POP resuspension and ensuing revolatilization events. Trends in emissions from primary and secondary sources will remain the key driver of levels of these contaminants over time.

Seasonal differences in the effects of oscillatory and uni-directional flow on the growth and nitrate-uptake rates of juvenile Laminaria digitata (Phaeophyceae)

The influence of oscillatory versus unidirectional flow on the growth and nitrate-uptake rates of juvenile kelp, Laminaria digitata, was determined seasonally in experimental treatments that simulated as closely as possible natural environmental conditions. In winter, regardless of flow condition (oscillatory and unidirectional) or water velocity, no influence of water motion was observed on the growth rate of L. digitata. In summer, when ambient nitrate concentrations were low, increased water motion enhanced macroalgal growth, which is assumed to be related to an increase in the rate of supply of nutrients to the blade surface. Nitrate-uptake rates were significantly influenced by water motion and season. Lowest nitrate-uptake rates were observed for velocities <5 cm · s−1 and nitrate-uptake rates increased by 20%–50% under oscillatory motion compared to unidirectional flow at the same average speed. These data further suggested that the diffusion boundary layer played a significant role in influencing nitrate-uptake rates. However, while increased nitrate-uptake in oscillatory flow was clear, this was not reflected in growth rates and further work is required to understand the disconnection of nitrate-uptake and growth by L. digitata in oscillatory flow. The data obtained support those from related field-based studies, which suggest that in summer, when insufficient nitrogen is available in the water to saturate metabolic demand, the growth rate of kelps will be influenced by water motion restricting mass transfer of nitrogen.

The effects of stepped sites and ruthenium adatom decoration on methanol dehydrogenation over platinum-based catalyst surfaces

A density functional theory study of methanol dehydrogenation over stepped Pt(2 1 1) surfaces without and with Ru modification was carried out to understand fuel catalytic reactions on Pt-based catalysts. Two main pathways of the CH3OH dehydrogenation were examined: the O–H pathway which was initiated by O–H bond scission to form the methoxy (CH3O) intermediate followed by sequential cleavage of C–H bonds to CO, and the C–H pathway which was initiated by C–H bond scission to form the hydroxymethyl (CH2OH) followed by two C–H bond cleavages to COH and then CO. Possible crossover reactions between the O–H and C–H pathways were also computed. Compared to flat Pt(1 1 1), stepped Pt(2 1 1) increases the adsorption energies of intermediates, making no significant contribution to decreasing the reaction barriers of most elementary steps involved, except in the first hydrogen scission. However, on the Ru-modified surface, a significant reduction was found in reaction barriers for the first step of the C–H bond scission and a number of further dehydrogenation steps crossing over to the O–H pathway, with the most facile paths identified. Our data reveals the complexity of methanol catalytic reaction processes at the atomic level and contributes to a fundamental understanding of fuel reactions on Pt-based catalysts.