The potential of electron beam irradiation for simultaneous surface modification and bioresorption control of PLLA for medical device applications

Bioresorbable polymers have been widely investigated as materials exhibiting significant potential for successful application in the medical fields of bone fixation devices 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), L-lactide/ DL-lactide co-polymer (PLDL) and poly(lactic-co-glycolic acid) (PLGA). This work investigates the further potential of e-beam technology to impart added biofunctionality through the manipulation of polymer (PLLA) surface properties. A Dynamatron Continuous DC e-beam unit (Synergy Health, UK), with beam energies of 0.5, 0.75, and 1.5 MeV, was used for the irradiation of PLLA samples with delivered surface doses of 150 or 500 kGy at each energy level. The chosen conditions reflect the need to achieve a specific surface modification for the control of surface degradation as demonstrated in previous work. 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. E-beam irradiation did not seem to affect the surface roughness of PLLA as a direct consequence of the treatment. In conclusion electron beam surface modification has been found to modify both the surface-to-bulk bioresorption profile and the surface hydrophilicity. Both could provide benefits in relation to the performance of implantable medical devices.

Surface modification of LiV3O8 nanosheets via layer-by-layer self-assembly for high-performance rechargeable lithium batteries

In this work, an economical route based on hydrothermal and layer-by-layer (LBL) self-assembly processes has been developed to synthesize unique Al ₂O₃-modified LiV₃O₈ nanosheets, comprising a core of LiV₃O₈ nanosheets and a thin Al ₂O₃ nanolayer. The thickness of the Al₂O ₃ nanolayer can be tuned by altering the LBL cycles. When evaluated for their lithium-storage properties, the 1 LBL Al₂O ₃-modified LiV₃O₈ nanosheets exhibit a high discharge capacity of 191 mA h g^-1 at 300 mA g^-1 (1C) over 200 cycles and excellent rate capability, demonstrating that enhanced physical and/or chemical properties can be achieved through proper surface modification. © 2014 Elsevier B.V. All rights reserved.

Hydrogen-permeation characteristics of a SrCeO3-based ceramic separation membrane:Thermal, ageing and surface-modification effects

Dense ceramics with mixed protonic-electronic conductivity are of considerable interest for the separation and purification of hydrogen and as electrochemical reactors. In this work, the hydrogen permeability of a Sr_0.97Ce_0.9Yb_0.1O_{3 - δ} (SCYb) membrane with a porous Pt catalytic layer on the hydrogen feed-exposed side has been studied over the temperature range 500-804 °C employing Ar as the permeate sweep gas. A SiO₂-B₂O₃-BaO-MgO-ZnO-based glass-ceramic sealant was successfully employed to seal the membrane to the dual-chamber reactor. After 14 h of exposure to 10% H₂:90% N₂ at 804 °C, the H₂ flux reached a maximum of 33 nmol cm^{- 2} s^{- 1}, over an order of magnitude higher than that obtained on membranes of similar thickness without surface modification. The permeation rate then decreased slowly and moderately on annealing at 804 °C over a further 130 h. Thereafter, the flux was both reproducible and stable on thermal cycling in the range 600-804 °C. The results indicate an important role of superficial activation processes in the flux rate and suggest that hydrogen fluxes can be further optimised in cerate-based perovskites. © 2009 Elsevier B.V. All rights reserved.

Wireless electrochemical modification of catalytic activity on a mixed protonic-electronic conductor

A novel approach to electrochemical modification of catalytic activity using a wireless configuration has been undertaken. This paper presents preliminary results on the modification of a platinum catalyst film supported on a pellet of Sr_0.97Ce_0.9Yb_0.1O_3-δ (SCYb), considered to be a mixed protonic-electronic conductor under reducing conditions. The wireless configuration utilises the mixed ionic and electronic conductivity of the supporting membrane to supply an ionic promoting species to the catalyst surface. Control of the flux of this species is achieved by adjusting the effective hydrogen chemical potential difference across the membrane in a dual-chamber reactor with one chamber acting as the "reaction side" and the other as the "sweep side". The reaction rate can be promoted by up to a factor of 1.6, for temperatures around 500 °C and low reactant concentrations, when hydrogen is introduced on the sweep side of the membrane reactor. The use of helium, moist helium and oxygen in helium as sweep gases did not modify the reaction rate. © 2007 Elsevier B.V. All rights reserved.

In situ modification of a Pt catalyst supported on a mixed ionic-electronic conducting membrane

The electrochemical promotion of a platinum catalyst for ethylene oxidation on a dual chamber membrane reactor was studied. The catalyst was supported on a La_0.6Sr_0.4Co_0.2Fe_0.803 membrane. Due the supporting membrane's electronic conductivity it is possible to promote the reaction by controlling the oxygen chemical potential difference across the membrane. Upon establishment of an oxygen potential difference across the membrane, oxygen species can migrate and spillover onto the catalyst surface, modifying the catalytic activity. Initial experiments showed an overall promotion of approximately one order of magnitude of the reaction rate of ethylene, under an oxygen atmosphere on the sweep side of the membrane reactor, as compared with the rate under an inert sweep gas. The reaction rate can keep its promoted state even after the flow of oxygen on the sweep side was interrupted. This behavior caused further promotion with every experiment cycle. The causes of permanent promotion and on demonstrating controllable promotion of the catalytic activity are presented. This is an abstract of a paper presented at the AIChE Annual Meeting (San Francisco, CA 11/12-17/2006).

Building sandstone surface modification by biofilm and iron precipitation: emerging block-scale heterogeneity and system response

Stone surfaces are sensitive to their environment. This means that they will often respond to exposure conditions by manifesting a change in surface characteristics. Such changes can be more than simply aesthetic, creating surface/subsurface heterogeneity in stone at the block scale, promoting stress gradients to be set up as surface response to, for example, temperature fluctuations, can diverge from subsurface response. This paper reports preliminary experiments investigating the potential of biofilms and iron precipitation as surface-modifiers on stone, exploring the idea of block-scale surface-to-depth heterogeneity, and investigating how physical alteration in the surface and near-surface zone can have implications for subsurface response and potentially for long-term decay patterns. Salt weathering simulations on fresh and surface-modified stone suggest that even subtle surface modification can have significant implications for moisture uptake and retention, salt concentration and distribution from surface to depth, over the period of the experimental run. The accumulation of salt may increase the retention of moisture, by modifying vapour pressure differentials and the rate of evaporation.
Temperature fluctuation experiments suggest that the presence of a biofilm can have an impact on energy transfer processes that occur at the stone surface (for example, buffering against temperature fluctuation), affecting surface-to-depth stress gradients. Ultimately, fresh and surface-modified blocks mask different kinds of system, which respond to inputs differently because of different storage mechanisms, encouraging divergent behaviour between fresh and surface modified stone over time.

Comparison of granulometric methods and sampling strategies used in marine habitat classification and Ecological Status assessment

Sediment particle size analysis (PSA) is routinely used to support benthic macrofaunal community distribution data in habitat mapping and Ecological Status (ES) assessment. No optimal PSA Method to explain variability in multivariate macrofaunal distribution has been identified nor have the effects of changing sampling strategy been examined. Here, we use benthic macrofaunal and PSA grabs from two embayments in the south of Ireland. Four frequently used PSA Methods and two common sampling strategies are applied. A combination of laser particle sizing and wet/dry sieving without peroxide pre-treatment to remove organics was identified as the optimal Method for explaining macrofaunal distributions. ES classifications and EUNIS sediment classification were robust to changes in PSA Method. Fauna and PSA samples returned from the same grab sample significantly decreased macrofaunal variance explained by PSA and caused ES to be classified as lower. Employing the optimal PSA Method and sampling strategy will improve benthic monitoring. © 2012 Elsevier Ltd.

Autonomic modification of intestinal smooth muscle contractility

Intestinal smooth muscle contracts rhythmically in the absence of nerve and hormonal stimulation because of the activity of pacemaker cells between and within the muscle layers. This means that the autonomic nervous system modifies rather than initiates intestinal contractions. The practical described here gives students an opportunity to observe this spontaneous activity and its modification by agents associated with parasympathetic and sympathetic nerve activity. A section of the rabbit small intestine is suspended in an organ bath, and the use of a pressure transducer and data-acquisition software allows the measurement of tension generated by the smooth muscle of intestinal walls. The application of the parasympathetic neurotransmitter ACh at varying concentrations allows students to observe an increase in intestinal smooth muscle tone with increasing concentrations of this muscarinic receptor agonist. Construction of a concentration-effect curve allows students to calculate an EC50 value for ACh and consider some basic concepts surrounding receptor occupancy and activation. Application of the hormone epinephrine to the precontracted intestine allows students to observe the inhibitory effects associated with sympathetic nerve activation. Introduction of the drug atropine to the preparation before a maximal concentration of ACh is applied allows students to observe the inhibitory effect of a competitive antagonist on the physiological response to a receptor agonist. The final experiment involves the observation of the depolarizing effect of K+ on smooth muscle. Students are also invited to consider why the drugs atropine, codeine, loperamide, and botulinum toxin have medicinal uses in the management of gastrointestinal problems.

Behaviour-time budget and functional habitat use of a free-ranging European badger (Meles meles)

Background: The European badger (Melesmeles) is involved in the maintenance of bovine tuberculosis infection and onward spread to cattle. However, little is known about how transmission occurs. One possible route could be through direct contact between infected badgers and cattle. It is also possible that indirect contact between cattle and infected badger excretory products such as faeces or urine may occur either on pasture or within and around farm buildings. A better understanding of behaviour patterns in wild badgers may help to develop biosecurity measures to minimise direct and indirect contact between badgers and cattle. However, monitoring the behaviour of free-ranging badgers can be logistically challenging and labour intensive due to their nocturnal and semi-fossorial nature.We trialled a GPS and tri-axial accelerometer-equipped collar on a free-ranging badger to assess its potential value to elucidate behaviour-time budgets and functional habitat use. Results: During the recording period between 16:00 and 08:00 on a single night, resting was the most commonly identified behaviour (67.4%) followed by walking (20.9%), snuffling (9.5%) and trotting (2.3%).When examining accelerometer data associated with each GPS fix and habitat type (occurring 2 min 30 s before and after), walking was themost common behaviour in woodland (40.3%) and arable habitats (53.8%), while snuffling was themost common behaviour in pasture (61.9%). Several nocturnal resting periods were also observed. The total distance travelled was 2.28 km. Conclusions: In the present report, we demonstrate proof of principle in the application of a combined GPS and accelerometer device to collect detailed quantitative data on wild badger behaviour. Behaviour-time budgets allow us to investigate how badgers allocate energy to different activities and how thismight change with disease status. Such information could be useful in the development of measures to reduce opportunities for onward transmission of bovine tuberculosis from badgers to cattle.

Lipopolysaccharide modification in Gram-negative bacteria during chronic infection

The Gram-negative bacterial lipopolysaccharide (LPS) is a major component of the outer membrane that plays a key role in host-pathogen interactions with the innate immune system. During infection, bacteria are exposed to a host environment that is typically dominated by inflammatory cells and soluble factors, including antibiotics, which provide cues about regulation of gene expression. Bacterial adaptive changes including modulation of LPS synthesis and structure are a conserved theme in infections, irrespective of the type or bacteria or the site of infection. In general, these changes result in immune system evasion, persisting inflammation, and increased antimicrobial resistance. Here, we review the modifications of LPS structure and biosynthetic pathways that occur upon adaptation of model opportunistic pathogens (Pseudomonas aeruginosa, Burkholderia cepacia complex bacteria, Helicobacter pylori and Salmonella enterica) to chronic infection in respiratory and gastrointestinal sites. We also discuss the molecular mechanisms of these variations and their role in the host-pathogen interaction.