Tools for fluorescent molecularly imprinted polymers

A linear co-polymer of hexyl acrylate and quinine acrylate was prepared anchored to cellulose filtration membranes. These were used to probe quenching of the tethered fluorophore by test compounds in solution for the validation of imprinted polymer fluorescence studies. The results are compared with simple solution phase quenching studies and also for two membrane-bound imprinted polymers containing the same fluorophore. © 2004 Elsevier B.V. All rights reserved.

Bragg Gratings, Photosensitivity and Poling in Glass Waveguides (BGPP

Polymer optical fibre Bragg gratings are useful for strain sensor applications for large dynamic range. We report recent progress in developing polymer optical fibres with higher photosensitivity and fabricating POF gratings at alternative wavelength.

In vitro characterization of a collagen scaffold enzymatically cross-linked with a tailored elastin-like polymer

Collagen, the main structural component of the extracellular matrix (ECM), provides tensile stiffness to different structures and organs against rupture. However, collagen tissue-engineered implants are hereto still lacking in mechanical strength. Attempts to create stiffer scaffolds have resulted in increased brittleness of the material, reducing the versatility of the original component. The hypothesis behind this research is that the introduction of an elastic element in the scaffold will enhance the mechanical properties of the collagen-based scaffolds, as elastin does in the ECM to prevent irreversible deformation. In this study, an elastin-like polymer (ELP) designed and synthesized using recombinant DNA methodology is used with the view to providing increased proteolytic resistance and increased functionality to the scaffolds by carrying specific sequences for microbial transglutaminase cross-linking, endothelial cell adhesion, and drug delivery. Evaluation of the effects that cross-linking ELP-collagen has on the physicochemical properties of the scaffold such as porosity, presence of cross-linking, thermal behavior, and mechanical strength demonstrated that the introduction of enzymatically resistant covalent bonds between collagen and ELP increases the mechanical strength of the scaffolds in a dose-dependent manner without significantly affecting the porosity or thermal properties of the original scaffold. Importantly, the scaffolds also showed selective behavior, in a dose (ELP)-dependent manner toward human umbilical vein endothelial cells and smooth muscle cells when compared to fibroblasts.

Dipole moments and Kerr effect of poly(n-vinylcarbazole) and its complexes with trinitrofluorenone

N-vinylcarbazole was polymerised using the free radical catalyst (azo-bisisobutyronitrile) and cationic catalysts (boron-trifluoride etherate and aluminium chloride). The polymers produced were characterised by molecular weight measurements and powder x-ray diffraction. The tacticity of the polymer samples was determined using proton and carbon-13 nuclear magnetic resonance spectroscopy. Measurements of their static dielectric permittivity and electro-optical birefringence (Kerr effect) in solution in 1,4-dioxane were carried out over a range of temperatures. The magnitudes of the dipole moments and Kerr constants were found to vary with changes in the tacticity of poly(N-vinylcarbazole). The results of these measurements support the view that the stereostructure of poly(N-vinylcarbazole) is sensitive to the mechanism of polymerisation. These results, together with proton and carbon-13 N.M.R. data, are discussed in terms of the possible conformations of the polymer chains and the relative orientation of the bulky carbazole side groups. The dielectric and molecular Kerr effect studies have also been carried out on complexes formed between 2,4,7-trinitro-9-fluorenone (TNF) and different stereoregular forms of poly(N-vinylcarbazole) in solution in 1,4-dioxane. The differences in the molar Kerr constants between pure (uncomplexed) and complexed poly(N-vinylcarbazole) samples were attributed to changes in optical anisotropy and dipole moments. A molecular modelling computer program Desktop Molecular Modeller was used to examine the 3/1 helical isotactic and 2/1 helical syndiotactic forms of poly(N-vinylcarbazole). These models were used to calculate the pitch distances of helices and the results were interpreted in terms of van der Waal's radii on TNF. This study indicated that the pitch distance in 3/1 isotactic helices was large enough to accommodate the bulky TNF molecules to form sandwich type charge transfer complexes whereas the pitch distance in syndiotactic poly(N-vinylcarbazole) was smaller and would not allow a similar type of complex formation.

Surface coating deterioration studies

This project is concerned with the deterioration of surface coatings as a result of weathering and exposure to a pollutant gas (in this case nitric oxide). Poly(vinyl chloride) (PVC) plastisol surface coatings have been exposed to natural and artificial weathering and a comparison of the effects of these two types of weathering has been made by use of various analytical techniques. These techniques have each been assessed as to their value in providing information regarding changes taking place in the coatings during ageing, and include, goniophotometry, micro-penetrometry, surface energy measurements, weight loss measurements, thermal analysis and scanning electron microscopy. The results of each of these studies have then been combined to show the changes undergone by PVC plastisol surface coatings during ageing and to show the effects which additives to the coatings have on their behaviour and in particular the effects of plasticiser, pigment and uv and thermal stabilisers. Finally a preliminary study of the interaction between five commercial polymers and nitric oxide has been carried out, the polymers being polypropylene, cellulose acetate butyrate, polystyrene, polyethylene terephthalate and polycarbonate. Each of the samples was examined using infra-red spectroscopy in the transmission mode.

Steric stabilization and dissolution characteristics of aqueous suspensions of pharmaceutical interest

The adsorption of two qroups of nonionic surface active agents and a series of hiqh molecular weiqht hydrophilic polymer fractions onto a polystyrene latex and a drug substance diloxanide furoate B.P. has been investigated. The presence of pores within the drug surface has been demonstrated and this is shown to increase the adsorption of low molecular weight polymer species. Differences in the maximum amount of polymer adsorbed at both solid-solution interfaces have been ascribed to the different hydrophobicities of the surface as determined by contact angle measurements. Adsorbed layer thicknesses of polymer on polystyrene latex have been determined by three techniques: microelectrophoresis, intensity fluctuation spectroscopy and by viscometric means. These results, in combination with adsorption data, were used to interpret the configuration of the adsorbed polymer molecules at the interface. The type of druq suspension produced on adsorbing the different polymers in the absence of electrostatic stabilization was correlated with theoretical prediuctions of suspension characteristics deduced from potential energy diagrams, The agreement was good for the adsorption of short chain length surfactants, but for the polyvinylalcohols, discrepancies were found between experiment and theory. This was attributed to the inappropriate use of a mean segment density approximation within the adsorbed layer to calculate attractive potentials between particles. A maximum in the redispersibility values for suspensions coated with adsorbed nonylphenylethoxylates was attributed to "partial static stabilization" of the particles in conjunction with the attractive forces operating in the sediment between bare surface patches on neighbouring particles. No significant change in the dissolution of the drug was observed when nonylphenylethoxylates were adsorbed due to desorption upon contact with the dissolution medium. Pluronic F68 and all the polyvinylalcohol fractions caused a reduction in the dissolution rate which is explained by the decreased diffusion of drug' through the adsorbed polymer layer.

Interactions between organic polymers and cement hydration products

Organic substances, particularly polymers, are finding increasing use in modifying the properties of cements and concrete. Although a significant amount of research has been conducted into the modification of the mechanical properties of cements by polymers, little is known about the nature of the interface and interactions taking place between the two phases. This thesis addresses the problem of elucidating such interactions. Relevant literature is reviewed, covering the general use of polymers with cements, the chemistry of cements and polymers, adhesion and known interactions between polymers and both cements and related minerals. Although several polymer systems were studied, two in particular were selected, as being well characterized. These were: - 1) polymethyl methacrylate (PMMA), the polymer derived from methyl methacrylate (MMA), and 2) an amine-cured epoxy resin system. By this approach, a methodology was developed for the examination of other polymer/cement interactions. Experiments were conducted in five main areas:- 1) polymer-cement adhesion and the feasibility of revealing interfacial regions mechanically, 2) chemical reactions between polymers and cements, 3) characterization of cement adhesion surfaces, 4) interactions affecting overall polymerisation rates, and 5) studies of polymer impregnated cements. The following conclusions were reached:- 1) The PMMA/cement interface contains calcium methacrylate as an interfacial reaction product, water being a reactant. Calcium methacrylate is detrimental to the properties of PMMA/cement composites, being highly water-soluble. 2) The pore surface of cement accelerates the polymerisation of MMA, leading to an increased molecular weight compared to polymerisation of pure MMA, minerals in hydrated cement powders having the opposite effect. 3) The investigation of reaction products presents a number of experimental problems, selection of appropriate techniques depending upon the system studied. For the two systems examined in detail, ion chromatography proved particularly useful; DTA, IRS and XPS indicated reactions, though the data was hard to interpret; XRD proving inconclusive. 4) It is impractical to reveal interfacial regions mechanically, but may be accomplished by chemical means.

Polymeric films for buccal drug delivery

The aim of this research project is to evaluate whether or not pullulan films are suitable to buccal drug delivery of a phosphodiesterase5 (PDE5) inhibitor yonkenafil, which was discovered in our research group and currently is under phase II clinical trial for treatment of erectile dysfunction. Variable formulations of pullulan films were designed and the films were prepared. Mechanical properties of the films, in vitro drug release and polymer dissolution, in vitro drug penetration through porcine esophageal mucosa were investigated. The plasticization effects of solvents, polyols and acids to the films were studied by tensile test, and differential scanning calorimetry, thermogravimetric analysis, fourier transform-infrared, scanning electron microscopy, optical microscopy was applied to analyse the structure and chemical-bonding between pullulan and the additives within the films. Release mathematics models were used in the study of the mechanism of drug releases and polymer dissolutions. Ethanol, menthol, fatty acids, and sodium dodecyl sulphate were employed as penetration enhancers to pretreat the tissue. Various plasticizers and acids were applied into the films and the result showed polyethylene glycol 400 and 600 had the excellent plasticization effect on the drug-free pullulan films, while lactic acid was the best plasticizer for the drug-loaded films. Both PEG400 and lactic acid had a great effect on the drug release from the films in vitro, and all the results indicated that the hydroxyl and carboxyl groups of pullulan and the additives influenced the mechanical properties of the films significantly, and also altered drug release mechanisms. Ethanol shows the greatest enhancing ability on the drug permeation through the porcine esophageal mucosa. A possible mechanism for this is that ethanol interferes with the structure of the lipids in the mucosa, resulting in increased partitioning of the drug into the membrane.

Pulse oximetry as a screening test for congenital heart defects in newborn infants: a test accuracy study with evaluation of acceptability and cost-effectiveness

Background: Screening for congenital heart defects (CHDs) relies on antenatal ultrasound and postnatal clinical examination; however, life-threatening defects often go undetected. Objective: To determine the accuracy, acceptability and cost-effectiveness of pulse oximetry as a screening test for CHDs in newborn infants. Design: A test accuracy study determined the accuracy of pulse oximetry. Acceptability of testing to parents was evaluated through a questionnaire, and to staff through focus groups. A decision-analytic model was constructed to assess cost-effectiveness. Setting: Six UK maternity units. Participants: These were 20,055 asymptomatic newborns at = 35 weeks’ gestation, their mothers and health-care staff. Interventions: Pulse oximetry was performed prior to discharge from hospital and the results of this index test were compared with a composite reference standard (echocardiography, clinical follow-up and follow-up through interrogation of clinical databases). Main outcome measures: Detection of major CHDs – defined as causing death or requiring invasive intervention up to 12 months of age (subdivided into critical CHDs causing death or intervention before 28 days, and serious CHDs causing death or intervention between 1 and 12 months of age); acceptability of testing to parents and staff; and the cost-effectiveness in terms of cost per timely diagnosis. Results: Fifty-three of the 20,055 babies screened had a major CHD (24 critical and 29 serious), a prevalence of 2.6 per 1000 live births. Pulse oximetry had a sensitivity of 75.0% [95% confidence interval (CI) 53.3% to 90.2%] for critical cases and 49.1% (95% CI 35.1% to 63.2%) for all major CHDs. When 23 cases were excluded, in which a CHD was already suspected following antenatal ultrasound, pulse oximetry had a sensitivity of 58.3% (95% CI 27.7% to 84.8%) for critical cases (12 babies) and 28.6% (95% CI 14.6% to 46.3%) for all major CHDs (35 babies). False-positive (FP) results occurred in 1 in 119 babies (0.84%) without major CHDs (specificity 99.2%, 95% CI 99.0% to 99.3%). However, of the 169 FPs, there were six cases of significant but not major CHDs and 40 cases of respiratory or infective illness requiring medical intervention. The prevalence of major CHDs in babies with normal pulse oximetry was 1.4 (95% CI 0.9 to 2.0) per 1000 live births, as 27 babies with major CHDs (6 critical and 21 serious) were missed. Parent and staff participants were predominantly satisfied with screening, perceiving it as an important test to detect ill babies. There was no evidence that mothers given FP results were more anxious after participating than those given true-negative results, although they were less satisfied with the test. White British/Irish mothers were more likely to participate in the study, and were less anxious and more satisfied than those of other ethnicities. The incremental cost-effectiveness ratio of pulse oximetry plus clinical examination compared with examination alone is approximately £24,900 per timely diagnosis in a population in which antenatal screening for CHDs already exists. Conclusions: Pulse oximetry is a simple, safe, feasible test that is acceptable to parents and staff and adds value to existing screening. It is likely to identify cases of critical CHDs that would otherwise go undetected. It is also likely to be cost-effective given current acceptable thresholds. The detection of other pathologies, such as significant CHDs and respiratory and infective illnesses, is an additional advantage. Other pulse oximetry techniques, such as perfusion index, may enhance detection of aortic obstructive lesions.

Bragg Gratings, Photosensitivity and Poling in Glass Waveguides (BGPP

Polymer optical fibre Bragg gratings are useful for strain sensor applications for large dynamic range. We report recent progress in developing polymer optical fibres with higher photosensitivity and fabricating POF gratings at alternative wavelength.

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.

Investigation into the performance and emissions of a stationary diesel engine fuelled by sewage sludge intermediate pyrolysis oil and biodiesel blends

This paper studies the characteristics of blends of biodiesel and a new type of SSPO (sewage sludge derived intermediate pyrolysis oil) in various ratios, and evaluates the application of such blends in an unmodified Lister diesel engine. The engine performance and exhaust emissions were investigated and compared to those of diesel and biodiesel. The engine injectors were inspected and tested after the experiment. The SSPO-biodiesel blends were found to have comparable heating values to biodiesel, but relatively high acidity and carbon residue. The diesel engine has operated with a 30/70 SSPO-biodiesel blend and a 50/50 blend for up to 10h and there was no apparent deterioration in operation observed. It is concluded that with 30% SSPO, the engine gives better overall performance and fuel consumption than with 50% SSPO. The exhaust temperatures of 30% SSPO and 50% SSPO are similar, but 30% SSPO gives relatively lower NO emission than 50% SSPO. The CO and smoke emissions are lower with 50% SSPO than with 30% SSPO. The injectors of the engine operated with SSPO blends were found to have heavy carbon deposition and noticeably reduced opening pressure, which may lead to deteriorated engine performance and exhaust emissions in extended operation. © 2013 Elsevier Ltd.

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.

Anomalies in stiffness and damping of a 2D discrete viscoelastic system due to negative stiffness components

The recent development of using negative stiffness inclusions to achieve extreme overall stiffness and mechanical damping of composite materials reveals a new avenue for constructing high performance materials. One of the negative stiffness sources can be obtained from phase transforming materials in the vicinity of their phase transition, as suggested by the Landau theory. To understand the underlying mechanism from a microscopic viewpoint, we theoretically analyze a 2D, nested triangular lattice cell with pre-chosen elements containing negative stiffness to demonstrate anomalies in overall stiffness and damping. Combining with current knowledge from continuum models, based on the composite theory, such as the Voigt, Reuss, and Hashin-Shtrikman model, we further explore the stability of the system with Lyapunov's indirect stability theorem. The evolution of the microstructure in terms of the discrete system is discussed. A potential application of the results presented here is to develop special thin films with unusual in-plane mechanical properties. © 2006 Elsevier B.V. All rights reserved.

Investigations on birefringence effects in polymer optical fiber Bragg gratings

Step-index polymer optical fiber Bragg gratings (POFBGs) and microstructured polymer optical fiber Bragg gratings (mPOFBGs) present several attractive features, especially for sensing purposes. In comparison to FBGs written in silica fibers, they are more sensitive to temperature and pressure because of the larger thermo-optic coefficient and smaller Young's modulus of polymer materials. (M)POFBGs are most often photowritten in poly(methylmethacrylate) (PMMA) materials using a continuous-wave 325 nm HeCd laser. For the first time to the best of our knowledge, we study photoinduced birefringence effects in (m)POFBGs. To achieve this, highly reflective gratings were inscribed with the phase mask technique. They were then monitored in transmission with polarized light. For this, (m)POF sections a few cm in length containing the gratings were glued to angled silica fibers. Polarization dependent loss (PDL) and differential group delay (DGD) were computed from the Jones matrix eigenanalysis using an optical vector analyser. Maximum values exceeding several dB and a few picoseconds were obtained for the PDL and DGD, respectively. The response to lateral force was finally investigated. As it induces birefringence in addition to the photo-induced one, an increase of the PDL and DGD values were noticed. © 2014 Copyright SPIE.