525 resultados para IPN HYDROGELS
Resumo:
The ingress of water into copolymers of 2-hydroxyethyl methacrylate (HEMA) and tetrahydrofurfuryl methacrylate (THFMA) loaded with either one of two model drugs, ie vitamin B-12 or aspirin, was studied at 310 K using three-dimensional nuclear magnetic resonance (3D NMR) imaging. The poly(HEMA) was loaded with 5 wt% of the drugs. From the imaging profiles it was observed that incorporation of vitamin B-12 into the polymers rich in HEMA resulted in crack formation at the interface between the rubbery region and the glassy core on sorption of water, although these cracks were 'healed' behind the diffusion front. However, for the copolymers with low HEMA contents and for those containing aspirin, no evidence for similar crack formation was found. For the copolymers loaded with 5 wt% of aspirin or vitamin B-12 the values of the water diffusion coefficients, determined by curve-fitting the relative water concentration profiles from magnetic resonance imaging (MRI) measurements, were found to be smaller than those obtained from a mass uptake study. (C) 2004 Society of Chemical Industry.
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We present optical, near-IR, and radio follow-up of 16 Swift bursts, including our discovery of nine afterglows and a redshift determination for three. These observations, supplemented by data from the literature, provide an afterglow recovery rate of 52% in the optical/near-IR, much higher than in previous missions (BeppoSAX, HETE-2, INTEGRAL, and IPN). The optical/near-IR afterglows of Swift events are on average 1.8 mag fainter at t = 12 hr than those of previous missions. The X-ray afterglows are similarly fainter than those of pre-Swift bursts. In the radio the limiting factor is the VLA threshold, and the detection rate for Swift bursts is similar to that for past missions. The redshift distribution of pre-Swift bursts peaked at z similar to 1, whereas the six Swift bursts with measured redshifts are distributed evenly between 0.7 and 3.2. From these results we conclude that ( 1) the pre-Swift distributions were biased in favor of bright events and low-redshift events, ( 2) the higher sensitivity and accurate positions of Swift result in a better representation of the true burst redshift and brightness distributions ( which are higher and dimmer, respectively), and (3) similar to 10% of the bursts are optically dark, as a result of a high redshift and/or dust extinction. We remark that the apparent lack of low-redshift, low-luminosity Swift bursts and the lower event rate than prelaunch estimates ( 90 vs. 150 per year) are the result of a threshold that is similar to that of BATSE. In view of these inferences, afterglow observers may find it advisable to make significant changes in follow-up strategies of Swift events. The faintness of the afterglows means that large telescopes should be employed as soon as the burst is localized. Sensitive observations in RIz and near-IR bands will be needed to discriminate between a typical z similar to 2 burst with modest extinction and a high-redshift event. Radio observations will be profitable for a small fraction (similar to 10%) of events. Finally, we suggest that a search for bright host galaxies in untriggered BAT localizations may increase the chance of finding nearby low-luminosity GRBs.
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The diffusion of styrene into linear low density polyethylene in a solution of supercritical CO2 was investigated using NMR microimaging. For both pure styrene and styrene dissolved in supercritical CO2, the diffusion was found to follow Fickian kinetics. Supercritical CO2 was found to enhance the rate and extent of diffusion of styrene into the substrate by up to three times under the conditions of this investigation, compared to pure styrene. NMR imaging was used to measure the concentration profiles of the styrene penetrants in real time, and the results were fitted to a Fickian model for diffusion. At a CO2 pressure of 150 bar and temperature of 40 degrees C, the diffusion coefficient of a 30 wt-% solution of styrene into LLDPE was calculated to be 1 X 10(-11) m(2). s(-1). This is significantly faster than the diffusion coefficient measured for pure styrene diffusion at 40 degrees C (3 x 10(-12) m(2). s(-1)). The diffusion coefficients determined by gravimetric analysis were slightly higher than those determined by the imaging method. This was probably due to residual styrene and/or polystyrene adhering to the surface of the films in the gravimetric technique.
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PFG-NMR was used to study the chemical exchange of linear PHEMA having a range of molecular weights with water in DMSO containing varying quantities of water. The aim was to investigate the use of PFG-NMR to study chemical exchange between a polymer with exchangeable protons and a small fast diffusing molecule to provide insight into the conformation adopted by a polymer in solution. The experimental data were simulated closely for the two-site exchange case using the Bloch equations modified for chemical exchange and diffusion. The exchange rate could be used to detect changes in polymer conformation resulting from changes in the solvent. PHEMA of MW 10 000 showed significant time-dependent changes in exchange rate, resulting from preferential solvation of the OH sites by water, and subsequent conformational changes which altered accessibility of the OH sites to water. This behavior was not observed for larger MW PHEMA, which adopted a stable conformation immediately. Large changes in the exchange rate were not reflected in changes to the hydrodynamic radius, suggesting that a minimal overall change in the chain dimensions occurred. DMSO was found to be a poor solvent for PHEMA, which adopts a compact conformation in DMSO. This work has demonstrated that PFG-NMR is a sensitive method for detecting subtle changes in polymer conformation in polymers with exchangeable protons.
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Esta pesquisa investiga a influência de intervenções lúdicas na diminuição da ansiedade materna com mães de recém-nascidos pré-termo hospitalizados, em um hospital universitário da Grande São Paulo. São estudadas 30 mães que tiveram parto prematuro, com faixa etária entre 16 e 40 anos e escolaridade até 2º grau, por meio de estudo avaliativo-interventivo-evolutivo. Inicia-se por uma entrevista psicológica semidirigida, com o objetivo de traçar o histórico gestacional, seguida de aplicação da Escala de Ansiedade, Depressão e Irritabilidade IDA, visando identificar o nível de ansiedade materna e do Inventário de Percepção Neonatal IPN-I para verificar a expectativa das mães em relação ao comportamento de choro, alimento e vômito de seus bebês pré-termo. A seguir são efetuadas intervenções grupais lúdicas em 16 encontros, um a cada semana, de 60 minutos, segundo modelo piagetiano, que estimula processos afetivosemocionais e cognitivos. Os dados relativos ao histórico gestacional revelam que 75% das mães encontram-se na segunda gestação e já sofreram aborto ou óbito fetal; têm ida de gestacional média de 31 semanas; peso médio do bebê ao nascer de 1.640g. e tempo de internação médio de 39,93 dias. Na análise do IDA em relação à ansiedade, 75% delas apresentam escore de alta intensidade (11,25), também alto quanto à depressão (10); o escore médio (3,73) da irritabilidade exteriorizada acompanha o da irritabilidade interiorizada (3,23). A correlação entre depressão e ansiedade indica que uma reação emocional segue a outra, não havendo diferença significativa importante entre ambas (p=0,306). O IPN-I comprova que as 30 mães têm expectativas em relação ao próprio filho similares aos bebês em geral, mostrando escores médios de 8,63 e 9,20, respectivamente, confirmados pelo escore 10,0 apontado em 75% da amostra, o que configura uma alta expectativa quanto aos aspectos de sono, alimentação e vômito dos bebês. A análise qualitativa revela que a criação de grupos lúdicos mostra-se favorável, com alta adesão e motivação das mães, favorecendo a diminuição da ansiedade, a adaptação à realidade vivida e a interação mãe-bebê de forma saudável durante a internação. O estudo apresenta a trajetória interventiva de três casos emblemáticos de diferentes níveis de ansiedade, ilustrando esta evolução. Estes dados sugerem que esta modalidade de intervenção caracterize-se como uma medida de prevenção, promoção e preservação da saúde física e psíquica da mãe e do recémnascido prematuro, com repercussões na família e na sociedade.(AU)
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Purpose: To determine the critical fitting characteristics of modern soft contact lens fits and from this to devise a simplified recording scheme. Methods: Ten subjects (aged 28.1 ± 7.4 years) wore eight different modern soft contact lenses. Video was captured and analysed of blink (central and up-gaze), excursion lag (up, down, right and left gaze) and push-up movement, centration and coverage. Results: Lens centration was on average close to the corneal centre. Movement on blink was significantly smaller in up-gaze than in primary-gaze (p<0.001). Lag was greatest in down-gaze and least in up-gaze (p<0.001). Push-up test recovery speed was 1.32±0.73mm/s. Overall lens movement was determined best by assessing horizontal lag, movement on blink in up-gaze and push-up recovery speed. Steeper lens base-curves did not have a significant effect on lens fit characteristics. Contact lens material did influence lens fit characteristics, particularly silicone-hydrogels which generally had lower centration and a faster push-up speed of recovery than HEMA lenses (p<0.05). Conclusion: Lag on vertical gaze, and movement on blink in primary gaze generally provide little extra information on overall lens movement compared to horizontal lag, movement on blink in up gaze and push-up recovery speed. They can therefore be excluded from a simplified recording scheme. A simplified and comprehensive soft contact lens fit recording system could consist of a cross-hairs indicating the centre of the cornea; a circle to indicate the lens centration; a mark on the relevant position of the circle to indicate any limbal incursion; a grade (‘B’) below for movement with blink in up-gaze, a grade (‘L’) to the side for horizontal lag and a grade above (‘P’) for the assessed push-up recovery speed.
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Purpose: Meibomian-derived lipid secretions are well characterised but their subsequent fate in the ocular environment is less well understood. Phospholipids are thought to facilitate the interface between aqueous and lipid layers of the tear film and to be involved in ocular lubrication processes. We have extended our previous studies on phospholipid levels in the tear film to encompass the fate of polar and non-polar lipids in progressive accumulation and aging processes on both conventional and silicone-modified hydrogel lenses. This is an important aspect of the developing understanding of the role of lipids in the clinical performance of silicone hydrogels. Method: Several techniques were used to identify lipids in the tear film. Mass-spectrometric methods included Agilent 1100-based liquid chromatography coupled to mass spectrometry (LCMS) and Perkin Elmer gas chromatography mass spectrometry (GCMS). Thin layer chromatography (TLC) was used for separation of lipids on the basis of increasing solvent polarity. Routine assay of lipid extractions from patient-worn lenses was carried out using a Hewlett Packard 1090 liquid chromatograph coupled to both uv and Agilent 1100 fluorescence detection. A range of histological together with optical, and electron microscope techniques was used in deposit analysis. Results: Progressive lipid uptake was assessed in various ways, including: composition changes with wear time, differential lipid penetrate into the lens matrix and, particularly, the extent to which lipids become unextractable as a function of wear time. Solvent-based separation and HPLC gave consistent results indicating that the polarity of lipid classes decreased as follows: phospholipids/fatty acids > triglycerides > cholesterol/cholesteryl esters. Tear lipids were found to show autofluorescence—which underpinned the value of fluorescence microscopy and fluorescence detection coupled with HPLC separation. The most fluorescent lipids were found to be cholesteryl esters; histological techniques coupled with fluorescence microscopy indicated that white spots (’’jelly bumps’’) formed on silicone hydrogel lenses contain a high proportion of cholesteryl esters. Lipid profiles averaged for 30 symptomatic and 30 asymptomatic contact lens wearers were compiled. Peak classes were split into: cholesterol (C), cholesteryl esters (CE), glycerides (G), polar fatty acids/phospholipids (PL). The lipid ratio for ymptomatic/symptomatic was 0.6 ± 0.1 for all classes except one—the cholesterol ratio was 0.2 ± 0.05. Significantly the PL ratio was no different from that of any other class except cholesterol. Chromatography indicated that: lipid polarity decreased with depth of penetration and that lipid extractability decreased with wear time. Conclusions: Meibomian lipid composition differs from that in the tear film and on worn lenses. Although the same broad lipid classes were obtained by extraction from all lenses and all patients studied, quantities vary with wear and material. Lipid extractability diminishes with wear time regardless of the use of cleaning regimes. Dry eye symptoms in contact lens wear are frequently linked to lipid layer behaviour but seem to relate more to total lipid than to specific composition. Understanding the detail of lipid related processes is an important element of improving the clinical performance of materials and care solutions.
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This thesis is concerned with the design and synthesis of a novel, injectable proteoglycan analogue for tissue repair. This is of particular relevance to the restoration of disc height to a degraded nucleus pulposus of the intervertebral disc. The focus is on the use of sulfonate monomers as proteoglycan analogues, in particular sodium 2-acrylamido-2-methylpropane sulfonic acid and the potassium salt of 3-sulfopropyl acrylate. For most biomedical applications, synthetic hydrogels need to show dimensional stability to changes in pH, osmolarity, and temperature. This is readily achieved by neutral structures however ionic sulfonate containing hydrogels are responsive to environmental change which renders them difficult to manage in most tissue replacement applications. In this case osmotic responsiveness rather than stability is desirable. Therefore sulfonate based materials possess advantageous properties. This is a result of the sulfonate becoming an ideal surrogate for the sulfate group present within the structure of natural proteoglycans. This thesis reports polymerisation studies based on the production of a redox initiated copolymer system capable of polymerising in situ within a timescale of circa. 5-7 minutes. The rheological properties, osmotic drive, and residual monomer content of successful compositions is analysed. Properties are adapted to mimic those of the target natural tissue. The adaptation of the material for use as an injectable intra-ocular lens, with hyaluronic acid as an interpenetrate is reported. The synthesis of a radiopaque macromer to allow visibility of the repair system once in situ is investigated and discussed. The results presented in this thesis describe a suitable proteoglycan tissue analogue which is injectable, biomimetic, osmotically responsive and mechanically stable in its desired application.
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The work described in this thesis is concerned with mechanisms of contact lens lubrication. There are three major driving forces in contact lens design and development; cost, convenience, and comfort. Lubrication, as reflected in the coefficient of friction, is becoming recognised as one of the major factors affecting the comfort of the current generation of contact lenses, which have benefited from several decades of design and production improvements. This work started with the study of the in-eye release of soluble macromolecules from a contact lens matrix. The vehicle for the study was the family of CIBA Vision Focus® DAILIES® daily disposable contact lenses which is based on polyvinyl alcohol (PVA). The effective release of linear soluble PVA from DAILIES on the surface of the lens was shown to be beneficial in terms of patient comfort. There was a need to develop a novel characterisation technique in order to study these effects at surfaces; this led to the study of a novel tribological technique, which allowed the friction coefficients of different types of contact lenses to be measured reproducibly at genuinely low values. The tribometer needed the ability to accommodate the following features: (a) an approximation to eye lid load, (b) both new and ex-vivo lenses, (c) variations in substrate, (d) different ocular lubricants (including tears). The tribometer and measuring technique developed in this way was used to examine the surface friction and lubrication mechanisms of two different types of contact lenses: daily disposables and silicone hydrogels. The results from the tribometer in terms of both mean friction coefficient and the friction profiles obtained allowed various mechanisms used for surface enhancement now seen in the daily disposable contact lens sector to be evaluated. The three major methods used are: release of soluble macromolecules (such as PVA) from the lens matrix, irreversible surface binding of a macromolecule (such as polyvinyl pyrrolidone) by charge transfer and the simple polymer adsorption (e.g. Pluoronic) at the lens surface. The tribological technique was also used to examine the trends in the development of silicone hydrogel contact lenses. The focus of the principles in the design of silicone hydrogels has now shifted from oxygen permeability, to the improvement of surface properties. Presently, tribological studies reflect the most effective in vitro method of surface evaluation in relation to the in-eye comfort.
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Purpose: Most published surface wettability data are based on hydrated materials and are dominated by the air-water interface. Water soluble species with hydrophobic domains (such as surfactants) interact directly with the hydrophobic domains in the lens polymer. Characterisation of relative polar and non-polar fractions of the dehydrated material provides an additional approach to surface analysis. Method: Probe liquids (water and diiodomethane) were used to characterise polar and dispersive components of surface energies of dehydrated lenses using the method of Owens and Wendt. A range of conventional and silicone hydrogel soft lenses was studied. The polar fraction (i.e. polar/total) of surface energy was used as a basis for the study of the structural effects that influence surfactant persistence on the lens surface. Results: When plotted against water content of the hydrated lens, polar fraction of surface energy (PFSE) values of the dehydrated lenses fell into two rectilinear bands. One of these bands covered PFSE values ranging from 0.4 to 0.8 and contained only conventional hydrogels, with two notable additions: the plasma coated silicone hydrogels lotrafilcon A and B. The second band covered PFSE values ranging from 0.04 to 0.28 and contained only silicone hydrogels. Significantly, the silicone hydrogel lenses with lowest PFSE values (p<0.15) are found to be prone to lipid deposition duringwear. Additionally, more hydrophobic surfactants were found to be more persistent on lenses with lower PFSE values. Conclusions: Measurement of polar fraction of surface energy provides an importantmechanistic insight into surface interactions of silicone hydrogels.
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The objective of this thesis is to report the behaviour of mammalian cells with biocompatible synthetic polymers with potential for applications to the human body. Composite hydrogel materials were tested as possible keratoprosthetic devices. It was found that surface topography is an important consideration, pores, channels and fibres exposed on the surface of the hydrogels tested can have significant effects on the extent of cell adheson and proliferation. It is recommended that the core component is fabricated out of one of the following to provide a non cell adhesive base; A8, A11, A13, A22, A23. The haptic periphery fabricated out of one of the following would provide a cell adhesive composite; A16, A30, A33, A37, A38, A42, A43, A44. The presence of vitronectin in the ocular tissue appears to lead to higher cell adhesion to the posterior surface of a contact lens when compared to the anterior surface. Group IV contact lenses adhere more cells than Group II contact lenses - this may indicate that more protein (including vitronectin) is able to adhere to the contact lens due to the Group IV contact lenses high water content and ionic hydrogel matrix. Artificial lung surfactant analogues were found to be non cytotoxic but also decreased cell proliferation when tested at higher concentrations. Poly(lysine ethyl ester adipamide) [PLETESA] had the most favourable response on cell proliferation and commercial styrene/maleic anhydride (pMA/STY sp2) the most pronounced inhibitory response. The mode of action that decreases cell proliferation appears to be through membrane destabilization. Tissue culture well plates coated with PLETESA allowed cells to adhere in a concentration dependent manner, multilaminar liposomes possibly of PLETESA were observed in solution in PLETESA coated wells. Polyhydroxybutryate (PHB) and polyhydroxyvalerate (PHV) blends that contained hydroxyapatite were found to be the most cell adhesive material of those materials tested. The blends that were most susceptible to degradation adhered the most cells in initial stages of degradation. The initial slight increase in cell adhesion may be due to the increased rugosity of the material. As the degradation continued the number of cells adhering to the samples decreased, this may indicate that the polarity was inhibitory to cell adhesion during the later stages of degradation.
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A fundamental if poorly understood problem that hydrogels display is the tendency of these contact lens materials to dehydrate, causing certain complications of the corneal epithelium. However, recent studies have indicated that the evaporation rate of water from different hydrogel lenses is the same and the severity of conditions such as corneal staining is controlled by the states of water in the material. A study was therefore undertaken which concluded that increased corneal desiccating staining occurred as the proportion of water existing in the bound state decreased. The possibility of using dehydrated hydrogels as packaging materials with desiccating properties has also been investigated. As hydrogels have a high affinity for water they have adequate ability to function as a moisture scavenger in an enclosed atmosphere. It was concluded that this ability is maximised by a high total water content and an increase in the proportion of this water existing in the bound state for the material when it is fully hydrated. N-vinyl pyrrolidone has a low reactivity in vinyl polymerisation reactions which results in polymers with local domains of the same chemical type which can lead to deposition. As contact lenses comprising of this monomer are susceptible to deposition, a monomer with a higher reactivity in vinyl polymerisations is acryloylmorpholine and its incorporation in favour of NVP is encouraged. Unfortunately a large proportion of high EWC hydrogels are mechanically weak and attempts to increase this property by increasing hydrophobicity or cross-linking results in a decrease in EWC. Monomers with the potential to carry a positive charge were incorporated into a high EWC, AMO-HEMA copolymer and the physical properties were investigated. Although EWC increased, mechanical properties decreased only slightly. Therefore simultaneous incorporation of a positively charged monomer and a negatively charged monomer was investigated. The resulting copolymers showed increased water content and increased initial modulus. A technique for measuring the coefficient of friction of contact lenses during lubrication has been developed.
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Hydrogels, water swollen polymer matrices, have been utilised in many biomedical applications, as there is the potential to manipulate the properties for a given application by changing the chemical structure of the constituent monomers The eye provides an excellent site to examne the interaction between a synthetic material and a complex biological fluid without invasive surgery. There is a need for the development of new synthetic hydrogels for use in the anterior eye, Three applications of hydrogels in the eye were considered in this thesis. For some patients, the only hope of any visual improvement lies in the use of an artificial cornea, or keratoprosthesis, Preliminary investigations of a series of simple homogeneous hydrogel copolymers revealed that the mechanical properties required to withstand surgery and in eye stresses, were not achieved This lead to work on the development of semi-interpenetrating polymer networks based on the aforementioned copolymers, Manufacture of the device and cell response were also studied. Lasers have been employed in ocular surgery to correct refractive defects. If an irregular surface is ablated, an irregular surface is obtained. A hydrogel system was investigated that could be applied to the eye prior to ablation to create a smooth surface. Factors that may influence ablation rate were explored, Soft contact lenses can be used as a probe to study the interaction between synthetic materials and the biological constituents of tears. This has lead to the development of many sensitive analytical techniques for protein and lipid deposition, one of which is fluorescence spectrophotometry. Various commercially available soft contact lenses were worn for different periods of time and then analysed for protein and lipid deposition using fluorescence spectrophotometry, The influence of water content, degree of ionicity and the lens material on the level and type of deposition was investigated.
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Interpenetrating polymer networks (lPN's), have been defined as a combination of two polymers each in network form, at least one of which has been synthesised and / or crosslinked in the presence of the other. A semi-lPN, is formed when only one of the polymers in the system is crosslinked, the other being linear. lPN's have potential advantages over homogeneous materials presently used in biomedical applications, in that their composite nature gives them a useful combination of properties. Such materials have potential uses in the biomedical field, specifically for use in hard tissue replacements, rigid gas permeable contact lenses and dental materials. Work on simply two or three component systems in both low water containing lPN's supplemented by the study of hydrogels (water swollen hydrophilic polymers) can provide information useful in the future development of more complex systems. A range of copolymers have been synthesised using a variety of methacrylates and acrylates. Hydrogels were obtained by the addition of N-vinyl pyrrolidone to these copolymers. A selection of interpenetrants were incorporated into the samples and their effect on the copolymer properties was investigated. By studying glass transition temperatures, mechanical, surface, water binding and oxygen permeability properties samples were assessed for their suitability for use as biomaterials. In addition copolymers containing tris-(trimethylsiloxy)-y-methacryloxypropyl silane, commonly abbreviated to 'TRlS', have been investigated. This material has been shown to enhance oxygen permeability, a desirable property when considering the design of contact lenses. However, 'TRIS' has a low polar component of surface free energy and hence low wettability. Copolymerisation with a range of methacrylates has shown that significant increases in surface wettability can be obtained without a detrimental effect on oxygen permeability. To further enhance to surface wettability 4-methacryloxyethyl trimellitic anhydride was incorporated into a range of promising samples. This study has shown that by careful choice of monomers it is possible to synthesise polymers that possess a range of properties desirable in biomedical applications.
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One of the main problems with the use of synthetic polymers as biomaterials is the invasion of micro-organisms causing infection. A study of the properties of polymeric antibacterial agents, in particular polyhexamethylene biguanide, has revealed that the essential components for the design of a novel polymeric antibacterial are a balance between hydrophilicity and hydrophobicity coupled with sites of cationicity. The effect of cation incorporation on the physical properties of hydrogels has been investigated. Hydrogel systems copolymerised with either N-vinyl imidazole or dimethylaminoethyl methacrylate have been characterised in terms of their water binding, mechanical and surface properties. It has been concluded that the incorporation of these monomers does not adversely affect the properties of such hydrogels and that these materials are potential candidates for further development for use in biomedical applications. It has been reported that hydro gels with ionic character may increase the deposition of biological material onto the hydrogel surface when it is in contact with body fluids. An investigation into the deposition characteristics of hydrogels containing the potentially cationic monomers has been carried out, using specific protein adsorption and in vitro spoilation techniques. The results suggest that at low levels of cationicity, the deposition of positively charged proteins is reduced without adversely affecting the uptake of the other proteins. The gross deposition characteristics were found to be comparable to some commercially available contact lens materials. A preliminary investigation into the development of novel antibacterial polymers has been completed and some novel methods of bacterial inhibition discussed. These methods include development of an hydrogel whose potential application is as a catheter coating.