ABA triblock copolymers: from controlled synthesis to controlled function

The ABA amphiphilic block copolymers, poly(hydroxyethyl methacrylate-hlock-methylphenylsilane-block-hydroxyethyl methacrylate) (PHEMA-PMPS-PHEMA) and poly[oligo(ethylene glycol) methyl ether methacrylate-block-methylphenylsilane-block-oligo(ethylene glycol). methyl ether methacrylate] (POEGMA-PMPS-POEGMA) were successfully synthesised via atom transfer radical polymerisation (ATRP). Macroinitiators suitable for the ATRP of oligo(ethylene glycol) methyl ether methacrylate and 2-hydroxyethyl methacrylate were synthesised from the condensation reaction of alpha,omega-dihalopolymethylphenylsilane and 2'-hydroxyethyl 2-bromo-2-methylpropanoate. The copolymers were characterised using H-1 NMR and C-13 NMR spectroscopy and molecular weight characteristics were determined using size exclusion chromatography and H-1 NMR. The aggregation behaviour of some of the copolymers in water was studied using transmission and scanning electron microscopy and dynamic light scattering. These revealed the prevalent aggregate species to be micelles. Larger aggregates of 300-1000 nm diameter were also observed. The UV induced degradation of the aggregates was studied by UV-Vis spectroscopy. The thermal behaviour of selected copolymers was studied by differential scanning calorimetry and microphase separation of the two components was demonstrated

Addressing the challenges of modeling the scattering from bottlebrush polymers in solution

Small‐angle scattering measurements of complex macromolecules in solution are used to establish relationships between chemical structure and conformational properties. Interpretation of the scattering data requires an inverse approach where a model is chosen and the simulated scattering intensity from that model is iterated to match the experimental scattering intensity. This raises challenges in the case where the model is an imperfect approximation of the underlying structure, or where there are significant correlations between model parameters. We examine three bottlebrush polymers (consisting of polynorbornene backbone and polystyrene side chains) in a good solvent using a model commonly applied to this class of polymers: the flexible cylinder model. Applying a series of constrained Monte‐Carlo Markov Chain analyses demonstrates the severity of the correlations between key parameters and the presence of multiple close minima in the goodness of fit space. We demonstrate that a shape‐agnostic model can fit the scattering with significantly reduced parameter correlations and less potential for complex, multimodal parameter spaces. We provide recommendations to improve the analysis of complex macromolecules in solution, highlighting the value of Bayesian methods. This approach provides richer information for understanding parameter sensitivity compared to methods which produce a single, best fit

Hybrid Nanocomposites with Tunable Alignment of the Magnetic Nanorod Filler

For many important applications, the performance of polymer-anisotropic particle nanocomposite materials strongly depends on the orientation of the nanoparticles. Using the very peculiar magnetic properties of goethite ({\alpha}-FeOOH) nanorods, we produced goethite-poly(hydroxyethyl methacrylate) nanocomposites in which the alignment direction and the level of orientation of the nanorods could easily be tuned by simply adjusting the intensity of a magnetic field applied during polymerization. Because the particle volume fraction was kept low (1-5.5 vol \%), we used the orientational order induced by the field in the isotropic phase rather than the spontaneous orientational order of the nematic phase. At the strongest field values (up to 1.5 T), the particles exhibit almost perfect antinematic alignment, as measured by optical birefringence and small-angle X-ray scattering. The results of these two techniques are in remarkably good agreement, validating the use of birefringence measurements for quantifying the degree of orientational order. We also demonstrate that the ordering induced by the field in the isotropic suspension is preserved in the final material after field removal. This work illustrates the interest, for such problems, of considering the field-induced alignment of anisotropic nanoparticles in the isotropic phase, an approach that is effective at low filler content, that avoids the need of controlling the nematic texture, and that allows tuning of the orientation level of the particles at will simply by adjusting the field intensity

Synthesis, thermal behavior, and aggregation in aqueous solution of poly(methyl methacrylate)-b-poly(2-hydroxyethyl methacrylate)

Indexación: ScieloABSTRACT Amphiphilic block copolymers of poly(methyl methacrylate) PMMA and poly(2-hidroxyethyl methacrylate) PHEMA were synthesized by a two-step atom transfer radical polymerization (ATRP). Copolymers with various degrees of polymerization and different relative block sizes were obtained. The structure of the resulting polymers have been characterized and verified by FT-IR and 1H-NMR, molecular weight were determined by size exclusion chromatography analyses. The thermal properties of these polymers were investigated by differential scanning calorimetry DSC and thermogravimetric analysis TGA. The glass transition temperature of mono halogenated PMMA increases from 116 °C to 123 °C with increasing molecular weight, whereas the glass transition temperature of block copolymers depends slightly on polymer structure. The derivatives of TGA curves indicate that thermal degradation occurs in one stage. The self-assembly of PMMA-b-PHEMA in aqueous solution have been investigated by fluorescence probing methods. The critical micelle concentrations are in the range 10-6 - 10-7 M. The micropolarity sensed by pyrene is higher than in aggregates formed by block copolymers based on polystyrene. Keywords: Block copolymers, glass transition temperature, thermogravimetric analysis, critical micelle concentration, fluorescence probing methods

An all-glass microfluidic network with integrated amorphous silicon photosensors for on-chip monitoring of enzymatic biochemical assay

A lab-on-chip system, integrating an all-glass microfluidics and on-chip optical detection, was developed and tested. The microfluidic network is etched in a glass substrate, which is then sealed with a glass cover by direct bonding. Thin film amorphous silicon photosensors have been fabricated on the sealed microfluidic substrate preventing the contamination of the micro-channels. The microfluidic network is then made accessible by opening inlets and outlets just prior to the use, ensuring the sterility of the device. The entire fabrication process relies on conventional photolithographic microfabrication techniques and is suitable for low-cost mass production of the device. The lab-on-chip system has been tested by implementing a chemiluminescent biochemical reaction. The inner channel walls of the microfluidic network are chemically functionalized with a layer of polymer brushes and horseradish peroxidase is immobilized into the coated channel. The results demonstrate the successful on-chip detection of hydrogen peroxide down to 18 mu M by using luminol and 4-iodophenol as enhancer agent

Bacterial Growth Kinetics under a Novel Flexible Methacrylate Dressing Serving as a Drug Delivery Vehicle for Antiseptics

A flexible methacrylate powder dressing (Altrazeal®) transforms into a wound contour conforming matrix once in contact with wound exudate. We hypothesised that it may also serve as a drug delivery vehicle for antiseptics. The antimicrobial efficacy and influence on bacterial growth kinetics in combination with three antiseptics was investigated in an in vitro porcine wound model. Standardized in vitro wounds were contaminated with Staphylococcus aureus (MRSA; ATCC 33591) and divided into six groups: no dressing (negative control), methacrylate dressing alone, and combinations with application of 0.02% Polyhexamethylene Biguanide (PHMB), 0.4% PHMB, 0.1% PHMB + 0.1% betaine, 7.7 mg/mL Povidone-iodine (PVP-iodine), and 0.1% Octenidine-dihydrochloride (OCT) + 2% phenoxyethanol. Bacterial load per gram tissue was measured over five days. The highest reduction was observed with PVP-iodine at 24 h to log10 1.43 cfu/g, followed by OCT at 48 h to log10 2.41 cfu/g. Whilst 0.02% PHMB resulted in a stable bacterial load over 120 h to log10 4.00 cfu/g over 120 h, 0.1% PHMB + 0.1% betaine inhibited growth during the first 48 h, with slightly increasing bacterial numbers up to log10 5.38 cfu/g at 120 h. These results indicate that this flexible methacrylate dressing can be loaded with various antiseptics serving as drug delivery system. Depending on the selected combination, an individually shaped and controlled antibacterial effect may be achieved using the same type of wound dressing

Hydroxyapatite promotes superior adhesion and proliferation of telomerase transformed keratocytes in comparison with inert plastic skirt materials used in leading contemporary keratoprostheses

Aim: Published clinical series suggest the osteoodontokeratoprosthesis (OOKP) may have a lower extrusion rate than current synthetic keratoprostheses. The OOKP is anchored in the eye wall by autologous tooth. The authors’ aim was to compare adhesion, proliferation, and morphology for telomerase transformed keratocytes seeded on calcium hydroxyapatite (the principal mineral constituent of tooth) and materials used in the anchoring elements of commercially available synthetic keratoprostheses. Methods: Test materials were hydroxyapatite, polytetrafluoroethylene (PTFE), polyhydroxyethyl methacrylate (HEMA), and glass (control). Cell adhesion and viability were quantified at 4 hours, 24 hours, and 1 week using a calcein-AM/EthD-1 viability/cytotoxicity assay. Focal contact expression and cytoskeletal organisation were studied at 24 hours by confocal microscopy with immunoflourescent labelling. Further studies of cell morphology were performed using light and scanning electron microscopy. Results: Live cell counts were significantly greater on hydroxyapatite surfaces at each time point (p<0.04). Dead cell counts were significantly higher for PTFE at 7 days (p<0.002). Β1 integrin expression was highest on hydroxyapatite. Adhesion structures were well expressed in flat, spread out keratocytes on both HA and glass. Keratocytes tended to be thinner and spindle shaped on PTFE. The relatively few keratocytes visible on HEMA test surfaces were rounded and poorly adherent. Conclusions: Keratocyte adhesion, spreading, and viability on hydroxyapatite test surfaces is superior to that seen on PTFE and HEMA. Improving the initial cell adhesion environment in the skirt element of keratoprostheses may enhance tissue integration and reduce device failure rates

Surface induced selective delamination of amphiphilic ABA block copolymer thin films

This is the result of an ongoing collaboration with Dr. N. Sommerdijk’s Biomaterials group at the University of Eindhoven (the Netherlands) and illustrates the close collaboration that exists in pursuing the design and application of novel polymeric materials between the two groups. This details work on a physical phenomenon (selective delamination) and key materials (amphiphilic block copolymers) that have subsequently been applied in the design of novel biomaterials. These results have appeared in a larger body of work including Advanced Materials, Angewandtie Chemie International Edition and the Journal of Materials Chemistry

Preparation and characterization of methacrylate hydrogels for zeta potential control

A technique based on the measurement of streaming potentials has been developed to evaluate the effects of hydrophilic coatings on electroosmotic flow. The apparatus and procedure are described as well as some results concerning the electrokinetic potential of glass capillaries as a function of ionic strength, pH, and temperature. The effect that turbulence and entrance flow conditions have on accurate streaming potential measurements is discussed. Various silane adhesion promoters exhibited only a slight decrease in streaming potential. A coating utilizing a glycidoxy silane base upon which methylcellulose is applied affords a six-fold decrease over uncoated tubes. Hydrophilic methacrylate gels show similar streaming potential behavior, independent of the water content of the gel. By introduction of positive or negative groups into the hydrophilic methacrylate gels, a range of streaming potential values are obtained having absolute positive or negative signs

Adhesion of coagulase-negative staphylococci to methacrylate polymers and copolymers

Adhesion of coagulasef-negative staphylococci (CNS) was studied onto a homologous series of methacrylate polymers and copolymers. The materials varied in wettability (contact angles) and were either positively or negatively charged (zetapotential). Bacterial adhesion experiments performed in a parallel-plate perfusion system showed that positively charged TMAEMA-Cl copolymers significantly promoted the adhesion of CNS as compared with all other methacrylate (co)polymers tested. The bacterial adhesion rates onto the positively charged surfaces are diffusion-controlled, whereas those onto the surfaces with a negative zeta-potential are more surface-reaction-controlled due to the presence of a potential energy barrier. The bacterial adhesion rates onto various poly (alkyl methacrylates) were similar. The number of adhering bacteria onto the negatively charged MMA/MAA copolymer did not differ from that onto pMMA, indicating that sufficient sites on the copolymer surface with the same potential energy barrier as that on pMMA, were available for adhesion. Decreasing rates of adhesion of CNS were observed onto MMA/HEMA copolymers with increasing HEMA content coinciding with increasing hydrophilicity. Low plateau values for the bacterial adhesion were observed on 50MMA/50HEMA, pHEMA, and 85HEMA/15MAA, indicating that the adhesion onto these materials was reversible. Four CNS strains with different surface characteristics all showed higher numbers of adhering bacteria onto 85MMA/15TMAEMA-Cl than onto 85MMA/15MAA and pMMA