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.

Synthesis and evaluation of novel polymer modifiers for biodegradable polymers

The effects of ester plasticizers and copolymers on the mechanical properties of the natural biodegradable polymers, poly(3-hydroxybutyrate) [PHB] and poly(lactic acid) [PLA] have been studied after subjecting to melt processing conditions. Ester plasticizers were synthesized from citric, tartaric and maleic acids using various alcohols. A variety of PLA copolymers have also been prepared from poly(ethylene glycol) derivatives using stannous octanoate catalysed ring opening polymerisations of DL-lactide. A novel PLA star copolymer was also prepared from an ethoxylated pentaerythritol. The structures of these copolymers were determined by NMR spectroscopy. The plasticizing effect of the synthesised additives at various concentrations was determined. While certain additives were capable of improving the mechanical properties of PLA, none were effective in PHB. Moreover, it was found that certain combinations of additives exhibited synergistic effects. Possible mechanisms are discussed. Biotic and abiotic degradation studies showed that the plasticizers (esters and copolymers) did not inhibit the biodegradability of PHB or PLA in compost at 60°C. Simple toxicity tests carried out on compost extract and its ability to support the growth of cress seeds was established. PLA was found to be susceptible to limited thermal degradation under melt processing conditions. Conventional phenolic antioxidants showed no significant effect on this process, suggesting that degradation was not predominantly a free radical process. PLA also underwent photo-oxidative degradation with UV light and the process could be accelerated in the presence of a photoactivator such as iron (III) diisononyl dithiocarbamate. The mechanisms for the above processes are discussed. Finally, selected compounds were prepared on a pilot plant scale. Extruded and blown films were prepared containing these additives with conventional polymer processing equipment. The mechanical properties were similar to those obtained with laboratory produced compression moulded films.

Oxidation studies of a novel barrier polymer system

The thermal oxidation of two model compounds representing the aromatic polyamide, MXD6 (poly m-xylylene adipamide) have been investigated. The model compounds (having different chemical structures, viz, one corresponding to the aromatic part of the chain and the other to the aliphatic part), based on the structure of MXD6 were prepared and reactions with different concentrations of cobalt ions examined with the aim of identifying the role of the different structural components of MXD6 on the mechanism of oxidation. The study showed that cobalt, in the presence of sodium phosphite (which acts as an antioxidant for MXD6 and the model compounds), increases the oxidation of the model compounds. It is believed that the cobalt acts predominantly as a catalyst for the decomposition of hydroperoxides, formed during oxidation of the models in the melt phase, to free radical products and to a lesser extent as a catalyst for the initiation of the oxidation reaction by complex formation with the amide, which is more likely to take place in the solid phase. An oxidation cycle has been proposed consisting of two parts both of which will occur, to some extent under all conditions of oxidation (in the melt and in the solid phase), but their individual predominance must be determined by the prevailing oxygen pressure at the reaction site. The different aspects of this proposed mechanism were examined from extensive model compound studies, and the evidence based on the nature of product formation and the kinetics of these reactions. Main techniques used to compare the rates of oxidation and the study of kinetics included, oxygen absorption, FT-IR, UV and TGA. HPLC was used for product separation and identification.

Polymer modified cement: hydration microstructure and diffusion properties

Investigations concentrated on the styrene butadiene rubber (SBR) latex and formulations included standard carboxylated and special carboxylated latexes. The aqueous component, containing the stabilisers and antifoaming agent but not the polymer solids, was also used. For comparison, limited investigations were carried out using other polymer types e.g. acrylic, ethylene-vinyl acetate (EVA), and redispersible powders rather than emulsions. The major findings were: 1) All latex systems investigated acted as retarders for cement hydration. The extent of retardation depends on the type of polymer. The mechanism for cement hydration may be changed, and excessive retardation influences properties. 2) Polymer modified cements exhibited either similar or coarser pore structures compared with unmodified cements. Results suggest that polymer mainly exists in a mixture of cement hydrates and polymer phase. Very little evidence was found for the formation of a distinct polymer film phase. 3) During the first few days of curing the polymer solids are removed from the pore solution and concentrations of OH-, Na+ and K+ are reduced. These observations are probably a result of polymer-cement surface interactions since there was no evidence of any chemical reactions or degradation of the polymer. 4) Improved diffusional resistance of modified cements depends on the ability to achieve adequate workability at low w/c ratio, rather than modification of matrix structure.

In situ imaging and height reconstruction of phase separation processes in polymer blends during spin coating

Spin coating polymer blend thin films provides a method to produce multiphase functional layers of high uniformity covering large surface areas. Applications for such layers include photovoltaics and light-emitting diodes where performance relies upon the nanoscale phase separation morphology of the spun film. Furthermore, at micrometer scales, phase separation provides a route to produce self-organized structures for templating applications. Understanding the factors that determine the final phase-separated morphology in these systems is consequently an important goal. However, it has to date proved problematic to fully test theoretical models for phase separation during spin coating, due to the high spin speeds, which has limited the spatial resolution of experimental data obtained during the coating process. Without this fundamental understanding, production of optimized micro- and nanoscale structures is hampered. Here, we have employed synchronized stroboscopic illumination together with the high light gathering sensitivity of an electron-multiplying charge-coupled device camera to optically observe structure evolution in such blends during spin coating. Furthermore the use of monochromatic illumination has allowed interference reconstruction of three-dimensional topographies of the spin-coated film as it dries and phase separates with nanometer precision. We have used this new method to directly observe the phase separation process during spinning for a polymer blend (PS-PI) for the first time, providing new insights into the spin-coating process and opening up a route to understand and control phase separation structures. © 2011 American Chemical Society.

Polymer-peptide conjugate hydrogels:towards controlled drug delivery

Peptide-based materials exhibit remarkable supramolecular self-assembling behavior, owing to their overwhelming propensity to from hierarchical structures from a-helices and ß-sheets. Coupling a peptide sequence to a synthetic polymer chain allows greater control over the final physical properties of the supermolecular material. So-called ‘polymer-peptide conjugates’ can be used to create biocompatible hydrogels which are held together by reversible physical interactions. Potentially, the hydrogels can be loaded with aqueous-based drug molecules, which can be injected into targeted sites in the body if they can exhibit a gel-sol-gel transition under application and removal of a shear force. In this review, we introduce this topic to readers new to the field of polymer-peptide conjugates, discussing common synthetic strategies and their self-assembling behavior. The lack of examples of actual drug delivery applications from polymer-peptide conjugates is highlighted in an attempt to incite progress in this area.

Investigating the molecular structures of solid dispersions by the simulated annealing method

Knowledge of the molecular structures of solid dispersions is vital, yet, despite thousands of reports in this area, it remains unclear. The aim of this research is to investigate the molecular structure of solid dispersions with hot melt preparation method by the simulated annealing method. Simulation results showed linear polymer chains form the random coils under heat and the drug molecules stick on the surface of polymer coils, while drug molecules are dispersed molecularly but irregularly within the amorphous low molecular weight carriers. This research presents more reasonable molecular images of solid dispersions than the existed theory.

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.

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.

Synthesis and evaluation of nanoparticle-polymer composites

This thesis describes the synthesis of functionalised polymeric material by variety of free-radical mediated polymerisation techniques including dispersion emulsion, seeded emulsion, suspension and bulk polymerisation reactions. Organic fluorophores and nanoparticles such as quantum dots were incorporated within polymeric materials, in particular, thiol-functionalised polymer microspheres, which were fluorescently labelled either during synthesis or by covalent attachment post synthesis. The resultant fluorescent polymeric conjugates were then assessed for their utility in biological systems as an analytical tool for cells or biological structures. Quantum dot labelled, thiol-functionalised microspheres were assessed for their utility in the visualisation and tracking of red blood cells. Determination of the possible internalisation of fluorescent microspheres into red blood cells was required before successful tracking of red blood cells could take place. Initial work appeared to indicate the presence of fluorescent microspheres inside red blood cells by the process of beadfection. A range of parameters were also investigated in order to optimise beadfection. Thiol-functionalised microspheres labelled successfully with organic fluorophores were used to image the tear film of the eye. A description of problems encountered with the covalent attachment of hydrophilic, thiol-reactive fluorescent dyes to a variety of modified polymer microspheres is also included in this section. Results indicated large microspheres were particularly useful when tracking the movement of fluid along the tear meniscus. Functional bulk polymers were synthesised for assessment of their interaction with titanium dioxide nanoparticles. Thiol-functionalised polymethyl methacrylate and spincoated thiouronium-functionalised polystyrene appeared to facilitate the attachment of titanium dioxide nanoparticles. Interaction assays included the use of XPS analysis and processes such as centrifugation. Attempts to synthesise 4-vinyl catechol, a compound containing hydroxyl moieties with potential for coordination with titanium dioxide nanoparticles, were also carried out using 3,4-dihydroxybenzaldehyde as the starting material.

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.

Monitoring of deployment process of shape memory polymers for morphing structures with embedded fibre Bragg grating sensors

This article demonstrates the use of embedded fibre Bragg gratings as vector bending sensor to monitor two-dimensional shape deformation of a shape memory polymer plate. The shape memory polymer plate was made by using thermal-responsive epoxy-based shape memory polymer materials, and the two fibre Bragg grating sensors were orthogonally embedded, one on the top and the other on the bottom layer of the plate, in order to measure the strain distribution in both longitudinal and transverse directions separately and also with temperature reference. When the shape memory polymer plate was bent at different angles, the Bragg wavelengths of the embedded fibre Bragg gratings showed a red-shift of 50 pm/°caused by the bent-induced tensile strain on the plate surface. The finite element method was used to analyse the stress distribution for the whole shape recovery process. The strain transfer rate between the shape memory polymer and optical fibre was also calculated from the finite element method and determined by experimental results, which was around 0.25. During the experiment, the embedded fibre Bragg gratings showed very high temperature sensitivity due to the high thermal expansion coefficient of the shape memory polymer, which was around 108.24 pm/°C below the glass transition temperature (Tg) and 47.29 pm/°C above Tg. Therefore, the orthogonal arrangement of the two fibre Bragg grating sensors could provide a temperature compensation function, as one of the fibre Bragg gratings only measures the temperature while the other is subjected to the directional deformation. © The Author(s) 2013.

Polymer-lipid interactions:biomimetic self-assembly behaviour and surface properties of poly(styrene-alt-maleic acid) with diacylphosphatidylcholines

Abstract Various lubricating body fluids at tissue interfaces are composed mainly of combinations of phospholipids and amphipathic apoproteins. The challenge in producing synthetic replacements for them is not replacing the phospholipid, which is readily available in synthetic form, but replacing the apoprotein component, more specifically, its unique biophysical properties rather than its chemistry. The potential of amphiphilic reactive hypercoiling behaviour of poly(styrene-alt-maleic acid) (PSMA) was studied in combination with two diacylphosphatidylcholines (PC) of different chain lengths in aqueous solution. The surface properties of the mixtures were characterized by conventional Langmuir-Wilhelmy balance (surface pressure under compression) and the du Noüy tensiometer (surface tension of the non-compressed mixtures). Surface tension values and 31P NMR demonstrated that self-assembly of polymer-phospholipid mixtures were pH and concentration-dependent. Finally, the particle size and zeta potential measurements of this self-assembly showed that it can form negatively charged nanosized structures that might find use as drug or lipids release systems on interfaces such as the tear film or lung interfacial layers. The structural reorganization was sensitive to the alkyl chain length of the PC.

Fabry-Perot micro-structured polymer optical fibre sensors for opto-acoustic endoscopy

Opto-Acoustic Endoscopy (OAE) requires sensors with a high sensitivity and small physical dimensions in order to facilitate integration into an endoscope of less than 1mm in diameter. We present fibre Bragg grating (FBG) and Fabry- Perot intrinsic fibre sensors for ultrasound detection. We present a structure profile characterisation setup to analyse tune the fibre sensors in preparation for ultrasonic detection. We evaluate the suitability of the different structures and grating parameters for ultrasonic sensing. By analysing the prepared gratings, we enable the optimisation of the profile and a simplification of the detection regime for an optimal interferometric OAE configuration.