Comparison of hydrophilic and hydrophobic active molecules release from polymer-phospholipid complexes

Hypercoiling polymers can be suited for application to living systems because they are similar in structure to the protein-based lipid assemblies found at fluid interfaces within the body. This leads to a range of exciting possibilities, not only in membrane transport applications but also in biosensors, drug delivery and mechanistic studies of biological membrane function. This study is focused in the study of the stability and suitability of nanostructures made of a hypercoiling polymer for drug delivery applications. The polymer poly (styrene-maleic acid) (PSMA) was combined with the phospholipid dimyristoylphosphatidylcholine (DMPC) to form amphiphilic nanostructures. The stability and suitability of these polymer-phospholipid nanocarriers for hydrophobic and hydrophilic molecules load and release was analyzed by several techniques. It was found that several of the studied molecules had a substantial effect on the surface charge and stability of the nanocarrier. It was also demonstrated that two types of nanocarriers, chemically modified and unmodified, were able to control the release of the molecules, especially in the case of hydrophobic compounds. In addition, as the hydrophobicity increased the release slowed down. These clear nanocarriers have the potential to behave very favorably at interfaces such as the tear lipid film were transparency is a requirement, giving a new way of controlled drug release in the eye.

Identification of optically clear regions of ternary polymer blends using a novel rapid screening method

The application of a rapid screening method for the construction of ternary phase diagrams is described for the first time, providing detailed visualization of phase boundaries in solvent-mediated blends. Our new approach rapidly identifies ternary blend compositions that afford optically clear materials, useful for applications where transparent films are necessary. The use of 96-well plates and a scanning plate reader has enabled rapid optical characterization to be carried out by transmission spectrophotometry (450 nm), whilst the nature and extent of crystallinity was examined subsequently by wide angle X-ray scattering (WAXS). The moderating effect of cellulose acetate butyrate can be visualized as driving the position of the phase boundaries in poly(l-lactic acid)/polycaprolactone (PLLA/PCL) blends. More surprisingly, the boundaries are critically dependent on the molecular weight of the crystallizable PLLA and PCL, with higher molecular weight polymers leading to blends with reduced phase separation. On the other hand, the propensity to crystallize was more evident in shorter chains. WAXS provides a convenient way of characterizing the contribution of the individual blend components to the crystalline regions across the range of blend compositions. © 2013 Society of Chemical Industry.

Investigating polymer-peptide conjugates and electrospinning for the production of advanced materials

This thesis describes the production of advanced materials comprising a wide array of polymer-based building blocks. These materials include bio-hybrid polymer-peptide conjugates, based on phenylalanine and poly(ethylene oxide), and polymers with intrinsic microporosity (PIMs). Polymer-peptides conjugates were previously synthesised using click chemistry. Due to the inherent disadvantages of the reported synthesis, a new, simpler, inexpensive protocol was sought. Three synthetic methods based on amidation chemistry were investigated for both oligopeptide and polymerpeptide coupling. The resulting conjugates produced were then assessed by various analytical techniques, and the new synthesis was compared with the established protocol. An investigation was also carried out focussing on polymer-peptide coupling via ester chemistry, involving deprotection of the carboxyl terminus of the peptide. Polymer-peptide conjugates were also assessed for their propensity to self-assemble into thixotropic gels in an array of solvent mixtures. Determination of the rules governing this particular self-assembly (gelation) was required. Initial work suggested that at least four phenylalanine peptide units were necessary for self-assembly, due to favourable hydrogen bond interactions. Quantitative analysis was carried out using three analytical techniques (namely rheology, FTIR, and confocal microscopy) to probe the microstructure of the material and provided further information on the conditions for self-assembly. Several polymers were electrospun in order to produce nanofibres. These included novel materials such as PIMs and the aforementioned bio-hybrid conjugates. An investigation of the parameters governing successful fibre production was carried out for PIMs, polymer-peptide conjugates, and for nanoparticle cages coupled to a polymer scaffold. SEM analysis was carried out on all material produced during these electrospinning experiments.

Influence of mounting on the hysteresis of polymer fiber Bragg grating strain sensors

Fiber Bragg grating sensors recorded in poly(methyl methacrylate) fiber often exhibit hysteresis in the response of Bragg wavelength to strain, particularly when exposed to high levels of strain. We show that, when such a fiber grating sensor is bonded directly to a substrate, the hysteresis is reduced by more than 12 times, compared to the case where the sensor is suspended freely between two supports. © 2013 Optical Society of America.

Acousto-optic effect in microstructured polymer fiber bragg gratings : simulation and experimental overview

A fine control of the microstructured polymer fiber Bragg grating spectrum properties, such as maximum reflected power and 3-dB bandwidth, through acousto-optic modulation is presented. For simulation purposes, the device is modelled as a single structure, comprising a silica horn and a fiber Bragg grating. For similar sized structures a good correlation between the numerical results and the experimental data is obtained, allowing the strain field to be completely characterized along the whole structure. It is also shown that the microstructured polymer fiber Bragg grating requires less effort from the piezoelectric actuator to produce modification in the grating spectrum when compared with a silica fiber Bragg grating. This technique has potential to be applied on tunable optical filters and tunable cavities for photonic applications.

Enhancing the humidity response time of polymer optical fiber Bragg grating by using laser micromachining

The humidity sensors constructed from polymer optical fiber Bragg gratings (POFBG) respond to the water content change in the fiber induced by varying environmental condition. The water content change is a diffusion process. Therefore the response time of the POFBG sensor strongly depends on the geometry and size of the fiber. In this work we investigate the use of laser micromachining of D-shaped and slotted structures to improve the response time of polymer fiber grating based humidity sensors. A significant improvement in the response time has been achieved in laser micromachined D-shaped POFBG humidity sensors. The slotted geometry allows water rapid access to the core region but this does not of itself improve response time due to the slow expansion of the bulk of the cladding. We show that by straining the slotted sensor, the expansion component can be removed resulting in the response time being determined only by the more rapid, water induced change in core refractive index. In this way the response time is reduced by a factor of 2.5.

Humidity insensitive TOPAS polymer fiber Bragg grating sensor

We report the first experimental demonstration of a humidity insensitive polymer optical fiber Bragg grating (FBG), as well as the first FBG recorded in a TOPAS polymer optical fiber in the important low loss 850nm spectral region. For the demonstration we have fabricated FBGs with resonance wavelength around 850 nm and 1550 nm in single-mode microstructured polymer optical fibers made of TOPAS and the conventional poly (methyl methacrylate) (PMMA). Characterization of the FBGs shows that the TOPAS FBG is more than 50 times less sensitive to humidity than the conventional PMMA FBG in both wavelength regimes. This makes the TOPAS FBG very appealing for sensing applications as it appears to solve the humidity sensitivity problem suffered by the PMMA FBG. © 2011 Optical Society of America.

Optical bend sensor for vector curvature measurement based on Bragg grating in eccentric core polymer optical fibre

We present an optical bend sensor based on a Bragg grating written in an eccentric core polymer optical fibre. The grating wavelength shifts are studied as a function of bend curvature and fibre orientation and the device exhibits strong fibre orientation dependence, wide bend curvature range of ± 22.7 m-1 and high bend sensitivity of 63 pm/m-1, which is 80 times higher than the reported sensor based on an offset-FBG in standard single mode silica fibre.

Polymer photonic sensing skin

A highly flexible sensing skin with embedded polymer optical fibre Bragg gratings is characterised The response to pressure and strain compare favourably to a similar skin instrumented with silica fibre Bragg grating sensors.

Narrow bandwidth Bragg gratings imprinted in polymer optical fibers for different spectral windows

The production and characterization of narrow bandwidth fiber Bragg gratings (FBGs) in different spectral regions using polymer optical fibers (POFs) is reported. Narrow bandwidth FBGs are increasingly important for POF transmission systems, WDM technology and sensing applications. Long FBGs with resonance wavelength around 600-nm, 850-nm and 1550-nm in several types of polymer optical fibers were inscribed using a scanning technique with a short optical path. The technique allowed the inscription in relative short periods of time. The obtained 3-dB bandwidth varies from 0.22 down to 0.045 nm considering a Bragg grating length between 10 and 25-mm, respectively.

Grating based devices in polymer optical fibre

We describe recent research into devices based on fibre Bragg gratings in polymer optical fibre. Firstly, we report on the inscription of gratings in a variety of microstructured polymer optical fibre: single mode, few moded and multimoded, as well as fibre doped with trans-4-stilbenmethanol. Secondly, we describe research into an electrically tuneable filter using a metallic coating on a polymer fibre Bragg grating. Finally we present initial results from attempts to produce more complex grating structures in polymer fibre: a Fabry-Perot cavity and a phase-shifted grating.

Transition metal ion co-ordination in hydrophilic polymer membrane

This thesis is concerned with the investigation of transition metal (TM) ion complexation with hydrophilic membranes composed of copolymers of 4-vinyl pyridine & 4-methyl-4'vinyl- 2,2'-bipyridine with 2-hydroxyethyl methacrylate. The Cu(II), CoCII) & Fe(II) complexes with these coordinating membranes were characterised by a variety of techniques, in order to assess the effect of the polymer on the properties of the complex, and vice versa. A detailed programme of work was instigated into the kinetics of formation for the polymer-bound tris(bipyridyl) iron(II) complex; the rate and extent of complex formation was found to be anion-dependent. This is explained in terms of the influence of the anion on the transport properties and water content of the membrane, the controlling factor in the development of the tris-complex being the equilibrium concentration of Fe(II) in the gel matrix. A series of transport studies were performed with a view to the potential application of complexing hydrogel membranes for aqueous TM ion separations. A number of salts were studied individually and shown to possess a range of permeabilities; the degree of interaction between particular metal-ion:ligand combinations is given by the lag-time observed before steady-state permeation is achieved. However, when two TM salts that individually display different transport properties were studied in combination, they showed similar lag-times & permeabilities, characteristic of the more strongly coordinating metal ion. This 'anti-selective' nature thus renders the membrane systems unsuitable for TM ion separations. Finally, attempts were made to synthesise and immobilise a series of N ,0-donor macrocyclic ligands into hydrogel membranes. Although the functionalisation reactions failed, limited transport data was obtained from membranes in which the ligands were physically entrapped within the polymer matrix.

Concentration effects in polymer-bound antioxidants

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