A study of water binding, mobility and dehydration in contact lens hydrogels using NMR

Hydrogel polymers are used for the manufacture of soft (or disposable) contact lenses worldwide today, but have a tendency to dehydrate on the eye. In vitro methods that can probe the potential for a given hydrogel polymer to dehydrate in vivo are much sought after. Nuclear magnetic resonance (NMR) has been shown to be effective in characterising water mobility and binding in similar systems (Barbieri, Quaglia et al., 1998, Larsen, Huff et al., 1990, Peschier, Bouwstra et al., 1993), predominantly through measurement of the spin-lattice relaxation time (T1), the spinspin relaxation time (T2) and the water diffusion coefficient (D). The aim of this work was to use NMR to quantify the molecular behaviour of water in a series of commercially available contact lens hydrogels, and relate these measurements to the binding and mobility of the water, and ultimately the potential for the hydrogel to dehydrate. As a preliminary study, in vitro evaporation rates were measured for a set of commercial contact lens hydrogels. Following this, comprehensive measurement of the temperature and water content dependencies of T1, T2 and D was performed for a series of commercial hydrogels that spanned the spectrum of equilibrium water content (EWC) and common compositions of contact lenses that are manufactured today. To quantify material differences, the data were then modelled based on theory that had been used for similar systems in the literature (Walker, Balmer et al., 1989, Hills, Takacs et al., 1989). The differences were related to differences in water binding and mobility. The evaporative results suggested that the EWC of the material was important in determining a material's potential to dehydrate in this way. Similarly, the NMR water self-diffusion coefficient was also found to be largely (if not wholly) determined by the WC. A specific binding model confirmed that the we was the dominant factor in determining the diffusive behaviour, but also suggested that subtle differences existed between the materials used, based on their equilibrium we (EWC). However, an alternative modified free volume model suggested that only the current water content of the material was important in determining the diffusive behaviour, and not the equilibrium water content. It was shown that T2 relaxation was dominated by chemical exchange between water and exchangeable polymer protons for materials that contained exchangeable polymer protons. The data was analysed using a proton exchange model, and the results were again reasonably correlated with EWC. Specifically, it was found that the average water mobility increased with increasing EWe approaching that of free water. The T1 relaxation was also shown to be reasonably well described by the same model. The main conclusion that can be drawn from this work is that the hydrogel EWe is an important parameter, which largely determines the behaviour of water in the gel. Higher EWe results in a hydrogel with water that behaves more like bulk water on average, or is less strongly 'bound' on average, compared with a lower EWe material. Based on the set of materials used, significant differences due to composition (for materials of the same or similar water content) could not be found. Similar studies could be used in the future to highlight hydrogels that deviate significantly from this 'average' behaviour, and may therefore have the least/greatest potential to dehydrate on the eye.

Comparing charge transport predictions for a ternary electrolyte using the Maxwell–Stefan and Nernst–Planck equations

In this work, we investigate and compare the Maxwell–Stefan and Nernst–Planck equations for modeling multicomponent charge transport in liquid electrolytes. Specifically, we consider charge transport in the Li+/I−/I3−/ACN ternary electrolyte originally found in dye-sensitized solar cells. We employ molecular dynamics simulations to obtain the Maxwell–Stefan diffusivities for this electrolyte. These simulated diffusion coefficients are used in a multicomponent charge transport model based on the Maxwell– Stefan equations, and this is compared to a Nernst–Planck based model which employs binary diffusion coefficients sourced from the literature. We show that significant differences between the electrolyte concentrations at electrode interfaces, as predicted by the Maxwell–Stefan and Nernst–Planck models, can occur. We find that these differences are driven by a pressure term that appears in the Maxwell–Stefan equations. We also investigate what effects the Maxwell–Stefan diffusivities have on the simulated charge transport. By incorporating binary diffusivities found in the literature into the Maxwell–Stefan framework, we show that the simulated transient concentration profiles depend on the diffusivities; however, the simulated equilibrium profiles remain unaffected.

Visual field size criteria for mobility rehabilitation referral

Purpose. To investigate evidence-based visual field size criteria for referral of low-vision (LV) patients for mobility rehabilitation. Methods. One hundred and nine participants with LV and 41 age-matched participants with normal sight (NS) were recruited. The LV group was heterogeneous with diverse causes of visual impairment. We measured binocular kinetic visual fields with the Humphrey Field Analyzer and mobility performance on an obstacle-rich, indoor course. Mobility was assessed as percent preferred walking speed (PPWS) and number of obstacle-contact errors. The weighted kappa coefficient of association (κr) was used to discriminate LV participants with both unsafe and inefficient mobility from those with adequate mobility on the basis of their visual field size for the full sample and for subgroups according to type of visual field loss and whether or not the participants had previously received orientation and mobility training. Results. LV participants with both PPWS <38% and errors >6 on our course were classified as having inadequate (inefficient and unsafe) mobility compared with NS participants. Mobility appeared to be first compromised when the visual field was less than about 1.2 steradians (sr; solid angle of a circular visual field of about 70° diameter). Visual fields <0.23 and 0.63 sr (31 to 52° diameter) discriminated patients with at-risk mobility for the full sample and across the two subgroups. A visual field of 0.05 sr (15° diameter) discriminated those with critical mobility. Conclusions. Our study suggests that: practitioners should be alert to potential mobility difficulties when the visual field is less than about 1.2 sr (70° diameter); assessment for mobility rehabilitation may be warranted when the visual field is constricted to about 0.23 to 0.63 sr (31 to 52° diameter) depending on the nature of their visual field loss and previous history (at risk); and mobility rehabilitation should be conducted before the visual field is constricted to 0.05 sr (15° diameter; critical).

Wireless mobility usage: a preliminary study for management in two Australian university settings

Wireless Mobility Usage: A Preliminary Qualitative Study for Management in Two Australian University Settings, Neville Meyers, Heather Gray, Greg Hearn, Louis Sanzogni, and Sandra Lawrence.

Occupational mobility in Queensland’s aged care, automotive and civil construction sectors

Current trends in workforce development indicate the movement of workers within and across occupations to be the norm. In 2009, only one in three vocational education and training (VET) graduates in Australia ended up working in an occupation for which they were trained. This implies that VET enhances the employability of its graduates by equipping them with the knowledge and competencies to work in different occupations and sectors. This paper presents findings from a Government-funded study that examined the occupational mobility of selected associate professional and trades occupations within the Aged Care, Automotive and Civil Construction sectors in Queensland. The study surveyed enrolled nurses and related workers, motor mechanics and civil construction workers to analyse their patterns of occupational mobility, future work intentions, reasons for taking and leaving work, and the factors influencing them to leave or remain in their occupations. This paper also discusses the implications of findings for the training of workers in these sectors and more generally.

Computed success rates of various carrier phase integer estimation solutions and their comparison with statistical success rates

The success rate of carrier phase ambiguity resolution (AR) is the probability that the ambiguities are successfully fixed to their correct integer values. In existing works, an exact success rate formula for integer bootstrapping estimator has been used as a sharp lower bound for the integer least squares (ILS) success rate. Rigorous computation of success rate for the more general ILS solutions has been considered difficult, because of complexity of the ILS ambiguity pull-in region and computational load of the integration of the multivariate probability density function. Contributions of this work are twofold. First, the pull-in region mathematically expressed as the vertices of a polyhedron is represented by a multi-dimensional grid, at which the cumulative probability can be integrated with the multivariate normal cumulative density function (mvncdf) available in Matlab. The bivariate case is studied where the pull-region is usually defined as a hexagon and the probability is easily obtained using mvncdf at all the grid points within the convex polygon. Second, the paper compares the computed integer rounding and integer bootstrapping success rates, lower and upper bounds of the ILS success rates to the actual ILS AR success rates obtained from a 24 h GPS data set for a 21 km baseline. The results demonstrate that the upper bound probability of the ILS AR probability given in the existing literatures agrees with the actual ILS success rate well, although the success rate computed with integer bootstrapping method is a quite sharp approximation to the actual ILS success rate. The results also show that variations or uncertainty of the unit–weight variance estimates from epoch to epoch will affect the computed success rates from different methods significantly, thus deserving more attentions in order to obtain useful success probability predictions.

Effects of magnesium stearate on the efficient dispersion of salbutamol sulphate from carrier-based dry powder inhaler formulations

Dry powder inhaler (DPI) formulations is one of the most useful aerosol preparations in which drugs may be formulated as carrier-based interactive mixtures with micronised drug particles (<5 μm) adhered onto the surface of large inert carriers (lactose powders). The addition of magnesium stearate (MgSt) (1-3), was found to increase dispersion of various drugs from DPI formulations. Recently, some active compounds coated with 5% (wt/wt) MgSt using the mechanofusion method showed significant improvements in aerosolization behavior due to the reduction in intrinsic cohesion force (4). Application of MgSt in powder formulations is not new; however, no studies demonstrated the minimum threshold level for this excipient in efficient aerosolization of drug powders from the interactive mixtures. Therefore, this study investigated the role of MgSt concentration on the efficient dispersion of salbutamol sulphate (SS) from DPI formulations.

Fast hole surface conduction observed for indoline sensitizer dyes immobilized at fluorine-doped tin oxide - TiO2 surfaces

The indoline dyes D102, D131, D149, and D205 have been characterized when adsorved on fluorine-doped tin oxide (FTO) and TiO2 electrode surfaces. Adsorption from 50:50 acetonitrile - tert-butanol onto flourine-doped tin oxide (FTO) allows approximate Langmuirian binding constants of 6.5 x 10(4), 2.01 x 10(3), 2.0 x 10(4), and 1.5 x 10(4) mol-1 dm3, respectively, to be determined. Voltammetric data obtained in acetonitrile/0.1 M NBu4PF6 indicate reversible on-electron oxidation at Emid = 0.94, 0.91, 0.88, and 0.88 V vs Ag/AgCI(3 M KCI), respectively, with dye aggregation (at high coverage) causing additional peak features at more positive potentials. Slow chemical degradation processes and electron transfer catalysis for iodine oxidation were observed for all four oxidezed indolinium cations. When adsorbed onto TiO2 nanoparticle films (ca. 9nm particle diameter and ca.3/um thickness of FTO0, reversible voltammetric responses with Emid = 1.08, 1.156, 0.92 and 0.95 V vs Ag/AgCI(3 M KCI), respectively, suggest exceptionally fast hole hopping diffusion (with Dapp > 5 x 10(-9) m2 s-1) for adsorbed layers of four indoline dyes, presumably due to pie-pie stacking in surface aggregates. Slow dye degradation is shown to affect charge transport via electron hopping. Spectrelectrochemical data for the adsorbed indoline dyes on FTO-TiO2 revealed a red-shift of absorption peaks after oxidation and the presence of a strong charge transfer band in the near-IR region. The implications of the indoline dye reactivity and fast hole mobility for solar cell devices are discussed.

A sense of control : virtual communities for people with mobility impairments

The purpose of this book is to show why we should be concerned about virtual communities for people with physical, or more particularly mobility, impairments. The well-being model through a virtual community introduced here goes towards advancing the work begun by others, by adding for example a socio-political component. The model presented here provides practical insights into how strategic community investment can support people with disabilities and their families. Virtual communities are about engagement, quality of life and support, not just about information. The role of information technology in building and raising community capacity and social capital in socially and economically disadvantaged communities is also examined. Practical insights are offered into community support for people with chronic illness.

Natural balancing of flying capacitor voltages in multicell inverter under PD carrier-based PWM

The flying capacitor multicell inverter (FCMI) possesses natural balancing property. With the phase-shifted (PS) carrier-based scheme, natural balancing can be achieved in a straightforward manner. However, to achieve natural balancing with the harmonically optimal phase-disposition (PD) carrierbased scheme, the conventional approaches require (n-1) x (n-1) trapezoidal carrier signals for an n-level inverter, which is (n-1) x (n-2) times more than that in the standard PD scheme. This paper proposes two improved natural balancing strategies for FMI under PD scheme, which use the same (n-1) carrier signals as used in the standard PD scheme. In the first scheme, on-line detection is performed of the band in which the modulation signal is located, corresponding period number of the carrier, and rising or falling half cycle of the carrier waveform to generate the switching signals based on certain rules. In the second strategy, the output voltage level selection is first processed and the switching signals are then generated according to a rule based on preferential cell selection algorithm. These methods are easy to use and can be simply implemented as compared to the other available methods. Simulation and experimental results are presented for a five-level inverter to verify these proposed schemes.

Mobility, accessibility and activity participation : a comparative assessment of methods to identify rural transport disadvantage

Traditionally, transport disadvantage has been identified using accessibility analysis although the effectiveness of the accessibility planning approach to improving access to goods and services is not known. This paper undertakes a comparative assessment of measures of mobility, accessibility, and participation used to identify transport disadvantage using the concept of activity spaces. A 7 day activity-travel diary data for 89 individuals was collected from two case study areas located in rural Northern Ireland. A spatial analysis was conducted to select the case study areas using criteria derived from the literature. The criteria are related to the levels of area accessibility and area mobility which are known to influence the nature of transport disadvantage. Using the activity-travel diary data individuals weekly as well as day to day variations in activity-travel patterns were visualised. A model was developed using the ArcGIS ModelBuilder tool and was run to derive scores related to individual levels of mobility, accessibility, and participation in activities from the geovisualisation. Using these scores a multiple regression analysis was conducted to identify patterns of transport disadvantage. This study found a positive association between mobility and accessibility, between mobility and participation, and between accessibility and participation in activities. However, area accessibility and area mobility were found to have little impact on individual mobility, accessibility, and participation in activities. Income vis-àvis ´ car-ownership was found to have a significant impact on individual levels of mobility, and accessibility; whereas participation in activities were found to be a function of individual levels of income and their occupational status.

Removing barriers to protection at the exported border : visas, carrier sanctions, and international obligation

Asylum is being gradually denuded of the national institutional mechanisms (judicial, legislative and administrative) that provide the framework for a fair and effective asylum hearing. In this sense, there is an ongoing ‘denationalization’ or ‘deformalization’ of the asylum process. This chapter critically examines one of the linchpins of this trend: the erection of pre-entry measures at ports of embarkation in order to prevent asylum seekers from physically accessing the territory of the state. Pre-entry measures comprise the core requirement that foreigners possess an entry visa granting permission to enter the state of destination. Visa requirements are increasingly implemented by immigration officials posted abroad or by officials of transit countries pursuant to bilateral agreements (so-called ‘juxtaposed’ immigration controls). Private carriers, which are subject to sanctions if they bring persons to a country who do not have permission to enter, also engage in a form of de facto immigration control on behalf of states. These measures constitute a type of ‘externalized’ or ‘exported’ border that pushes the immigration boundaries of the state as far from its physical boundaries as possible. Pre-entry measures have a crippling impact on the ability of asylum seekers to access the territory of states to claim asylum. In effect, states have ‘externalized’ asylum by replacing the legal obligation on states to protect refugees arriving at ports of entry with what are perceived to be no more than moral obligations towards asylum seekers arriving at the external border of the state.