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.

Development and evaluation of hydrocarbon sorbent materials with the aid of chemometrics

Hydrocarbon spills on roads are a major safety concern for the driving public and can have severe cost impacts both on pavement maintenance and to the economy through disruption to services. The time taken to clean-up spills and re-open roads in a safe driving condition is an issue of increasing concern given traffic levels on major urban arterials. Thus, the primary aim of the research was to develop a sorbent material that facilitates rapid clean-up of road spills. The methodology involved extensive research into a range of materials (organic, inorganic and synthetic sorbents), comprehensive testing in the laboratory, scale-up and field, and product design (i.e. concept to prototype). The study also applied chemometrics to provide consistent, comparative methods of sorbent evaluation and performance. In addition, sorbent materials at every stage were compared against a commercial benchmark. For the first time, the impact of diesel on asphalt pavement has been quantified and assessed in a systematic way. Contrary to conventional thinking and anecdotal observations, the study determined that the action of diesel on asphalt was quite rapid (i.e. hours rather than weeks or months). This significant finding demonstrates the need to minimise the impact of hydrocarbon spills and the potential application of the sorbent option. To better understand the adsorption phenomenon, surface characterisation techniques were applied to selected sorbent materials (i.e. sand, organo-clay and cotton fibre). Brunauer Emmett Teller (BET) and thermal analysis indicated that the main adsorption mechanism for the sorbents occurred on the external surface of the material in the diffusion region (sand and organo-clay) and/or capillaries (cotton fibre). Using environmental scanning electron microscopy (ESEM), it was observed that adsorption by the interfibre capillaries contributed to the high uptake of hydrocarbons by the cotton fibre. Understanding the adsorption mechanism for these sorbents provided some guidance and scientific basis for the selection of materials. The study determined that non-woven cotton mats were ideal sorbent materials for clean-up of hydrocarbon spills. The prototype sorbent was found to perform significantly better than the commercial benchmark, displaying the following key properties: • superior hydrocarbon pick-up from the road pavement; • high hydrocarbon retention capacity under an applied load; • adequate field skid resistance post treatment; • functional and easy to use in the field (e.g. routine handling, transportation, application and recovery); • relatively inexpensive to produce due to the use of raw cotton fibre and simple production process; • environmentally friendly (e.g. renewable materials, non-toxic to environment and operators, and biodegradable); and • rapid response time (e.g. two minutes total clean-up time compared with thirty minutes for reference sorbents). The major outcomes of the research project include: a) development of a specifically designed sorbent material suitable for cleaning up hydrocarbon spills on roads; b) submission of patent application (serial number AU2005905850) for the prototype product; and c) preparation of Commercialisation Strategy to advance the sorbent product to the next phase (i.e. R&D to product commercialisation).

International rigid contact lens prescribing

Rigid lenses have been fitted less since the introduction of soft lenses nearly 40 years ago. Data that we have gathered from annual contact lens fitting surveys conducted in Australia, Canada, Japan, the Netherlands, Norway, the UK and the USA between 2000 and 2008 facilitate an accurate characterization of the pattern of the decline of rigid lens fitting during the first decade of this century. There is a trend for rigid lenses to be utilized primarily for refitting those patients who are already successful rigid lens wearers—most typically older females being refit with higher Dk materials. Rigid lenses are generally fitted on a full-time basis (four or more days of wear per week) without a planned replacement schedule. Orthokeratology is especially popular in the Netherlands, but is seldom prescribed in the other countries surveyed.

Trends in Australian contact lens prescribing during the first decade of the 21st Century (2000–2009)

Purpose: The aim was to document contact lens prescribing trends in Australia between 2000 and 2009. ---------- Methods: A survey of contact lens prescribing trends was conducted each year between 2000 and 2009. Australian optometrists were asked to provide information relating to 10 consecutive contact lens fittings between January and March each year. ---------- Results: Over the 10-year survey period, 1,462 practitioners returned survey forms representing a total of 13,721 contact lens fittings. The mean age (± SD) of lens wearers was 33.2 ± 13.6 years and 65 per cent were female. Between 2006 and 2009, rigid lens new fittings decreased from 18 to one per cent. Low water content lenses reduced from 11.5 to 3.2 per cent of soft lens fittings between 2000 and 2008. Between 2005 and 2009, toric lenses and multifocal lenses represented 26 and eight per cent, respectively, of all soft lenses fitted. Daily disposable, one- to two-week replacement and monthly replacement lenses accounted for 11.6, 30.0 and 46.5 per cent of all soft lens fittings over the survey period, respectively. The proportion of new soft fittings and refittings prescribed as extended wear has generally declined throughout the past decade. Multi-purpose lens care solutions dominate the market. Rigid lenses and monthly replacement soft lenses are predominantly worn on a full-time basis, whereas daily disposable soft lenses are mainly worn part-time.---------- Conclusions: This survey indicates that technological advances, such as the development of new lens materials, manufacturing methods and lens designs, and the availability of various lens replacement options, have had a significant impact on the contact lens market during the first decade of the 21st Century.

Global trends in prescribing contact lenses for extended wear

Extended wear has long been the ‘holy grail’ of contact lenses by virtue of the increased convenience and freedom of lifestyle which they accord; however, this modality enjoyed only limited market success during the last quarter of the 20th century. The introduction of silicone hydrogel materials into the market at the beginning of this century heralded the promise of successful extended wear due to the superior oxygen performance of this lens type. To assess patterns of contact lens fitting, including extended wear, over the past decade, up to 1000 survey forms were sent to contact lens fitters in Australia, Canada, Japan, the Netherlands, Norway, the UK and the USA each year between 2000 and 2009. Practitioners were asked to record data relating to the first 10 contact lens fits or refits performed after receiving the survey form. Analysis of returned forms revealed that, averaged over this period, 9% of all soft lenses prescribed were for extended wear, with national figures ranging from 2% in Japan to 17% in Norway. The trend over the past decade has been for an increase from about 5% of all soft lens fits in 2000 to a peak of between 9 and 12% between 2002 and 2007, followed by a decline to around 7% in 2009. A person receiving extended wear lenses is likely to be an older female who is being refitted with silicone hydrogel lenses for full-time wear. Although extended wear has yet again failed to fulfil the promise of being the dominant contact lens wearing modality, it is still a viable option for many people.