Preparation of controlled porosity carbon-aerogels for energy storage in rechargeable lithium oxygen batteries

Porous carbon aerogels are prepared by polycondensation of resorcinol and formaldehyde catalyzed by sodium carbonate followed by carbonization of the resultant aerogels in an inert atmosphere. Pore structure of carbon aerogels is adjusted by changing the molar ratio of resorcinol to catalyst during gel preparation and also pyrolysis under Ar and activation under CO2 atmosphere at different temperatures. The prepared carbons are used as active materials in fabrication of composite carbon electrodes. The electrochemical performance of the electrodes has been tested in a Li/O2 cell. Through the galvanostatic charge/discharge measurements, it is found that the cell performance (i.e. discharge capacity and discharge voltage) depends on the morphology of carbon and a combined effect of pore volume, pore size and surface area of carbon affects the storage capacity. A Li/O2 cell using the carbon with the largest pore volume (2.195cm3/g) and a wide pore size (14.23 nm) showed a specific capacity of 1290mAh g-1.

The effects of a volunteer mentoring programme on reading outcomes among eight- to nine-year-old children: A follow up randomized controlled trial

This article presents the findings of a randomized controlled trial evaluation of the effects of a revised version of the volunteer mentoring programme, Time to Read. Participating children received two 30-minute mentoring sessions per week from volunteer mentors who carried out paired reading activities with the children. The current trial involved 512 children aged eight to nine years from 50 primary schools. The programme was found to be effective in improving decoding skills (d=+.15), reading rate (d=+.22) and reading fluency (d=+.14) and there was some evidence of a positive effect in relation to the children’s aspirations for the future (d=+.11). However, no evidence was found of the programme having an effect on reading comprehension or reading confidence and enjoyment of reading. The article concludes by suggesting that mentoring programmes using non-specialist volunteers can be effective in improving foundational reading skills but would appear to be less effective in terms of improving higher-order skills such as comprehension. The article also suggests that such programmes are likely to be most effective if concentrating on core reading activities rather than attempting to address reading outcomes indirectly through improving children’s confidence or wider enjoyment of reading.

Physicochemical and drug diffusion analysis of rifampicin containing polyethylene glycol-poly(epsilon-caprolactone) networks designed for medical device applications

This study reports the physicochemical and drug diffusion properties of rifampicin containing poly(epsilon-caprolactone) (PCL)/polyethylene glycol (PEG) networks, designed as bioactive biomaterials. Uniquely, the effects of the states of both rifampicin and PEG and the interplay between these components on these properties are described. PCL matrices containing rifampicin (1-5%, w/w) and PEG 200 (0-15%, w/w) were prepared by casting from an organic solvent (dichloromethane). The films were subsequently characterized in terms of their thermal/thermorheological, surface and tensile properties, biodegradation and drug diffusion/release properties. Incorporation of PEG and/or rifampicin significantly affected the tensile and surface properties of PCL, lowering the ultimate tensile strength, % elongation at break, Young modulus and storage and loss moduli. Both in the absence and presence of PEG, solubilisation of rifampicin within the crystalline domains of PCL was observed. PEG was present as a dispersed liquid phase. The release of rifampicin (3% loading) was unaffected by the presence of PEG. Similarly the release of rifampicin (5%) was unaffected by low concentrations of PEG (5-10%) however, at higher loadings, the release rate of rifampicin was enhanced by the presence of PEG. Rifampicin release (10% loading) was enhanced by the presence of PEG in a concentration dependent fashion. These observations were accredited to enhanced porosity of the matrix. In all cases, diffusion-controlled release of rifampicin occurred which was unaffected by polymer degradation. This study has uniquely illustrated the effect of hydrophilic pore formers on the physicochemical properties of PCL. Interestingly, enhanced diffusion controlled release was only observed from biomaterials containing high loadings of PEG and rifampicin (5, 10%), concentrations that were shown to affect the mechanical properties of the biomaterials. Care should therefore be shown when adopting this strategy to enhance release of bioactive agents from biomaterials. (C) 2011 Elsevier B.V. All rights reserved.

Mucoadhesive, syringeable drug delivery systems for controlled application of metronidazole to the periodontal pocket: In vitro release kinetics, syringeability, mechanical and mucoadhesive properties

Novel mucoadhesive formulations containing hydroxyethylcellulose (HEC; 3 and 5%, w/w) or Carbopol (3 and 5%, w/w), polycarbophil (PC; 1 and 3%, w/w) and metronidazole (5%, w/w) at pH 6.8 were designed for the treatment of periodontal diseases. Each formulation was characterised in terms of hardness, compressibility, adhesiveness and cohesiveness (using Texture Profile Analysis), drug release, adhesion to a mucin disc (measured as a detachment force using the texture analyser in tensile mode) and, finally, syringeability (using the texture analyser in compression mode). Drug release from all formulations was non-diffusion controlled. Drug release was significantly decreased as the concentration of each polymeric component was increased, due to both the concomitant increased viscosity of the formulations and, additionally, the swelling kinetics of PC following contact with dissolution fluid. Increasing the concentrations of each polymeric component significantly increased formulation hardness, compressibility, adhesiveness, mucoadhesion and syringeability, yet decreased cohesiveness. Increased product hardness, compressibility and syringeability were due to polymeric effects on formulation viscosity. The effects on cohesiveness may be explained both by increased viscosity and also by the increasing semi-solid nature of products containing 5% HEC or Carbopol and PC (1 or 3%). The observations concerning formulation adhesiveness/mucoadhesion illustrate the adhesive nature of each polymeric component. Greatest adhesion was noted in formulations where neutralisation of PC was maximally suppressed. For the most part, increased time of contact between formulation and mucin significantly increased the required force of detachment, due to the greater extent of mucin polymer hydration and interpenetration with the formulations. Significant statistical interactions were observed between the effects of each polymer on drug release and mechanical/mucoadhesive properties. These interactions may be explained by formulatory effects on the extent of swelling of PC. In conclusion, the formulations described offered a wide range of mechanical and drug release characteristics. Formulations containing HEC exhibited superior physical characteristics for improved drug delivery to the periodontal pocket and are now the subject of long-term clinical investigations. (C) 1997 Elsevier Science B.V.

Oblique propagation of arbitrary amplitude electron acoustic solitary waves in magnetized kappa-distributed plasmas

The linear and nonlinear properties of large-amplitude electron-acoustic waves are investigated in a magnetized plasma comprising two distinct electron populations (hot and cold) and immobile ions. The hot electrons are assumed to be in a non-Maxwellian state, characterized by an excess of superthermal particles, here modeled by a kappa-type long-tailed distribution function. Waves are assumed to propagate obliquely to the ambient magnetic field. Two types of electrostatic modes are shown to exist in the linear regime, and their properties are briefly analyzed. A nonlinear pseudopotential-type analysis reveals the existence of large-amplitude electrostatic solitary waves and allows for an investigation of their propagation characteristics and existence domain, in terms of the soliton speed (Mach number). The effects of the key plasma configuration parameters, namely the superthermality index and the cold electron density, on the soliton characteristics and existence domain, are studied. The role of obliqueness and magnetic field is discussed.

Infection-Responsive Drug Delivery from Urinary Biomaterials Controlled by a Novel Kinetic and Thermodynamic Approach

Purpose. The pH-dependent physicochemical properties of the antimicrobial quinolone, nalidixic acid, were exploited to achieve ‘intelligent’ drug release from a potential urinary catheter coating, poly(2-hydroxyethylmethacrylate) (p(HEMA)), in direct response to the elevated pH which occurs at the onset of catheter infection.
Methods. p(HEMA) hydrogels, and reduced-hydrophilicity copolymers incorporating methyl methacrylate, were loaded with nalidixic acid by a novel, surface particulate localization method, and characterized in terms of pH-dependent drug release and microbiological activity against the common urease-producing urinary pathogen Proteus mirabilis.
Results. The pH-dependent release kinetics of surface-localized nalidixic acid were 50- and 10-fold faster at pH 9, representing the alkaline conditions induced by urease-producing urinary pathogens, compared to release at pH 5 and pH 7 respectively. Furthermore, microbiological activity against P. mirabilis was significantly enhanced after loading surface particulate nalidixic acid in comparison to p(HEMA) hydrogels conventionally loaded with dispersed drug. The more hydrophobic methyl methacrylate-containing copolymers also demonstrated this pH responsive behavior, but additionally exhibited a sustained period of zero-order release.
Conclusions. The paradigm presented here provides a system with latent, immediate infection-responsive drug release followed by prolonged zero-order antimicrobial delivery, and represents an ‘intelligent’, infection-responsive, self-sterilizing biomaterial.

Systematic Engineering of Uniform, Highly Efficient, Targeted and Shielded Viral-Mimetic Nanoparticles

In the past decades, numerous types of nanomedicines have been developed for the efficient and safe delivery of nucleic acid-based drugs for cancer therapy. Given that the destination sites for nucleic acid-based drugs are inside cancer cells, delivery systems need to be both targeted and shielded in order to overcome the extracellular and intracellular barriers. One of the major obstacles that has hindered the translation of nanotechnology-based gene-delivery systems into the clinic has been the complexity of the design and assembly processes, resulting in non-uniform nanocarriers with unpredictable surface properties and efficiencies. Consequently, no product has reached the clinic yet. In order to address this shortcoming, a multifunctional targeted biopolymer is genetically engineered in one step, eliminating the need for multiple chemical conjugations. Then, by systematic modulation of the ratios of the targeted recombinant vector to PEGylated peptides of different sizes, a library of targeted-shielded viral-mimetic nanoparticles (VMNs) with diverse surface properties are assembled. Through the use of physicochemical and biological assays, targeted-shielded VMNs with remarkably high transfection efficiencies (>95%) are screened. In addition, the batch-to-batch variability of the assembled targeted-shielded VMNs in terms of uniformity and efficiency is examined and, in both cases, the coefficient of variation is calculated to be below 20%, indicating a highly reproducible and uniform system. These results provide design parameters for engineering uniform, targeted-shielded VMNs with very high cell transfection rates that exhibit the important characteristics for in vivo translation. These design parameters and principles could be used to tailor-make and assemble targeted-shielded VMNs that could deliver any nucleic acid payload to any mammalian cell type.

Dynamical characteristics of solitary waves, shocks and envelope modes in kappa-distributed non-thermal plasmas: an overview

Space plasmas provide abundant evidence of highly energetic particle population, resulting in a long-tailed non-Maxwellian distribution. Furthermore, the first stages in the evolution of plasmas produced during laser-matter interaction are dominated by nonthermal electrons, as confirmed by experimental observation and computer simulations. This phenomenon is efficiently modelled via a kappa-type distribution. We present an overview, from first principles, of the effect of superthermality on the characteristics of electrostatic plasma waves. We rely on a fluid model for ion-acoustic excitations, employing a kappa distribution function to model excess superthermality of the electron distribution. Focusing on nonlinear excitations (solitons), in the form of solitary waves (pulses), shocks and envelope solitons, and employing standard methodological tools of nonlinear plasmadynamical analysis, we discuss the role of excess superthermality in their propagation dynamics (existence laws, stability profile), geometric characteristics and stability. Numerical simulations are employed to confirm theoretical predictions, namely in terms of the stability of electrostatic pulses, as well as the modulational stability profile of bright- and dark-type envelope solitons.

The use and meanings of 'time of wetness' in understanding stone decay

Moisture is a well documented, and crucial, control on the nature of stone decay. The term time of wetness has frequently been adopted to describe how long a stone block is wet, with a view to understanding the impact of this on decay processes. Although this term has proved conceptually useful, it has been used in different ways, by different groups to mean mean quite different things. For example, the time of wetness for a stone block surface (the traditional understanding) may be quite different from that of a block interior, controlled by the different dynamics of wetting and drying in those zones. Thus, surface wetting will occur regularly (sometimes swiftly followed by drying, depending on the time of year), with block interior wetting requiring the accumulation of surface moisture to penetrate to depth (more likely in autumn and winter months), and drying out much more slowly. This relatively new but important perspective, framed in the context of climate change, is crucial to understanding the length of time stone may remain damp at depth following a period of prolonged precipitation. The nature and speed of drying is also relevant in quantifying time of wetness of both surfaces and the interior of building stones.
These ideas related to time of wetness have implications for decay processes, specifically how a prolonged time of deep wetness may re-focus the emphasis of salt weathering in natural building stones toward chemical action. Literature on chemical change is discussed, suggesting that chemical change occurring during periods of prolonged wetness is likely to be significant in itself, with implications for weakening the stone (in terms of, for example, cement dissolution or grain boundary weakening) and exacerbating physical damage from salt crystallisation when blocks finally dry out.

Ethylene oxidation over platinum: In situ electrochemically controlled promotion using Na-beta'' alumina and studies with a Pt(111)/Na model catalyst

Electrochemically modified ethylene oxidation over a PI film supported on the Na+ ion conductor beta '' alumina has been studied over a range of conditions encompassing both promotion and poisoning, The system exhibits reversible behavior, and the data are interpreted in terms of (i) Na-enhanced oxygen chemisorption and (ii) poisoning of the surface by accumulation of Na compounds. At low Na coverages the first effect results in increased competitive adsorption of oxygen at the expense of ethylene, resulting in an increased rate, At very negative catalyst potentials (high Na coverage) both effects operate to poison the system: the increased strength of the Pt-O bond and coverage of the catalytic surface by compounds of Na strongly suppress the rate, Kinetic and spectroscopic results for ethylene oxidation over a Pt(111)-Na model catalyst shed light on important aspects of the electrochemically controlled system, Low levels of Na promote the reaction and high levels poison it, mirroring the behavior observed under electrochemical control and strongly suggesting that sodium pumped from the solid electrolyte is the key species, XP and Auger spectra show that under reaction conditions, the sodium exists as a surface carbonate. Post-reaction TPD spectra and the use of (CO)-C-13 demonstrate that CO is formed as a stable reaction intermediate, The observed activation energy (56 +/- 3 kJ/mol) is similar to that measured for CO oxidation under comparable conditions, suggesting that the rate limiting step is CO oxidation. (C) 1996 Academic Press, Inc.

Fatigue behavior of laser-welded NiTi wires in small-strain cyclic bending

NiTi wires and their weldments are commonly used in micro-electro-mechanical systems (MEMS), and in such applications, cyclic loading are commonly encountered. In this paper, the bending-rotation fatigue (BRF) test was used to study the bending fatigue behavior of NiTi wire laser weldment in the small-strain regime. The fracture mechanism, which includes crack initiation, crack growth and propagation of the weldment in the BRF test, was investigated with the aid of SEM fractography and discussed in terms of the microstructure. It was found that crack initiation was primarily surface-condition dependent. The cracks were found to initiate at the surface defects at the weld zone (WZ) surface, and the crack propagation was assisted by the gas inclusions in the WZ. The weldment was finally fractured in a ductile manner. The fatigue life was found to decrease with increasing surface strain and also with increasing bending frequency (controlled by the rotational speed in the BRF test). In comparison, the fatigue life of the unwelded NiTi wires was higher than their welded counterparts at all strain levels and bending frequencies. The decrease in fatigue resistance of the weldment could be attributed to the surface and microstructural defects introduced during laser welding.

Solvent induced phase inversion-based in situ forming controlled release drug delivery implants

In situ forming (ISF) drug delivery implants have gained tremendous levels of interest over the last few decades. This is due to their wide range of biomedical applications such as in tissue engineering, cell encapsulation, microfluidics, bioengineering and drug delivery. Drug delivery implants forming upon injection has shown a range of advantages which include localized drug delivery, easy and less invasive application, sustained drug action, ability to tailor drug delivery, reduction in side effects associated with systemic delivery and also improved patient compliance and comfort. Different factors such as temperature, pH, ions, and exchange of solvents are involved in in situ implant formation. This review especially focuses on ISF implants that are formed through solvent induced phase inversion (SPI) technique. The article critically reviews and compares a wide range of polymers, solvents, and co-solvents that have been used in SPI implant preparation for control release of a range of drug molecules. Major drawback of SPI systems has been their high burst release. In this regard, the article exhaustively discusses factors that affect the burst release and different modification strategies that has been utilised to reduce the burst effect from these implants. Performance and controversial issues associated with the use of different biocompatible solvents in SPI systems is also discussed. Biodegradation, formulation stability, methods of characterisation and sterilisation techniques of SPI systems is comprehensively reviewed. Furthermore, the review also examines current SPI-based marketed products, their therapeutic application and associated clinical data. It also exemplifies the interest of multi-billion dollar pharma companies worldwide for further developments of SPI systems to a range of therapeutic applications. The authors believe that this will be the first review article that extensively investigate and discusses studies done to date on SPI systems. In so doing, this article will undoubtedly serve as an enlightening tool for the scientists working in the concerned area.

Twinning anisotropy of tantalum during nanoindentation

Unlike other BCC metals, the plastic deformation of nanocrystalline Tantalum during compression is regulated by deformation twinning. Whether or not this twinning exhibits anisotropy was investigated through simulation of displacement-controlled nanoindentation test using molecular dynamics simulation. MD data was found to correlate well with the experimental data in terms of surface topography and hardness measurements. The mechanism of the transport of material was identified due to the formation and motion of prismatic dislocations loops (edge dislocations) belonging to the 1/2<111> type and <100> type Burgers vector family. Further analysis of crystal defects using a fully automated dislocation extraction algorithm (DXA) illuminated formation and migration of twin boundaries on the (110) and (111) orientation but not on the (010) orientation and most importantly after retraction all the dislocations disappeared on the (110) orientation suggesting twinning to dominate dislocation nucleation in driving plasticity in tantalum. A significant finding was that the maximum shear stress (critical Tresca stress) in the deformation zone exceeded the theoretical shear strength of tantalum (Shear modulus/ 2π~10.03 GPa) on the (010) orientation but was lower than it on the (110) and the (111) orientations. In light to this, the conventional lore of assuming the maximum shear stress being 0.465 times the mean contact pressure was found to break down at atomic scale.

Different frequencies of acupuncture for treatment for chronic low back pain: an-assessor blinded pilot randomised controlled trial.

OBJECTIVES:
To examine the feasibility of a main RCT to compare the effectiveness of two frequencies (2 versus 5 times/week) of acupuncture treatment for chronic low back pain (LBP).
METHODS:
Participants (n=30) with chronic LBP were randomised into two groups to receive 10 acupuncture treatments: Low Frequency Group, 2 times/week for five weeks (n=15); High Frequency Group, 5 times/week for two weeks (n=15). The following outcomes were measured blindly at baseline, 2 weeks, 5 weeks, 3 months and 1 year: pain on a VAS, functional disability using the RMDQ, quality of life using the Measure Yourself Medical Outcome Profile (MYMOP-2), psychological impact with the Coping Strategies Questionnaire (CSQ) and Pain Locus of Control (PLC) questionnaire. Two objective outcomes, the Shuttle Walk Test (SWT) and Lateral Trunk Flexibility (LTF), were also measured.
RESULTS:
The compliance rate was 100% for each group. Some of the measurements were shown to be sensitive (VAS, RMDQ, MYMOP-2 Wellbeing). 66-330 participants would be required for a fully powered non-inferiority trial. The groups were balanced at baseline for LBP and demographic characteristics. There were no significant differences between the groups in terms of any of the outcomes, at each follow-up time point. It was notable however that the clinically important improvement in terms of pain, functional disability, quality of life, and SWT in both groups was achieved within the first two weeks, which was maintained at one year follow-up.
CONCLUSIONS:
It is feasible to conduct a main RCT, to compare different frequencies of acupuncture for LBP, using sensitive measurements. Also the trend for early clinically important improvement within a minimum of four measurements is worthy of further study.