Comparative stability studies of poly(2-methyl-2-oxazoline) and poly(ethylene glycol) brush coatings

Non-fouling surfaces that resist non-specific adsorption of proteins, bacteria, and higher organisms are of particular interest in diverse applications ranging from marine coatings to diagnostic devices and biomedical implants. Poly(ethylene glycol) (PEG) is the most frequently used polymer to impart surfaces with such non-fouling properties. Nevertheless, limitations in PEG stability have stimulated research on alternative polymers that are potentially more stable than PEG. Among them, we previously investigated poly(2-methyl-2-oxazoline) (PMOXA), a peptidomimetic polymer, and found that PMOXA shows excellent anti-fouling properties. Here, we compare the stability of films self-assembled from graft copolymers exposing a dense brush layer of PEG and PMOXA side chains, respectively, in physiological and oxidative media. Before media exposure both film types prevented the adsorption of full serum proteins to below the detection limit of optical waveguide in situ measurements. Before and after media exposure for up to 2 weeks, the total film thickness, chemical composition, and total adsorbed mass of the films were quantified using variable angle spectroscopic ellipsometry (VASE), X-ray photoelectron spectroscopy (XPS), and optical waveguide lightmode spectroscopy (OWLS), respectively. We found (i) that PMOXA graft copolymer films were significantly more stable than PEG graft copolymer films and kept their protein-repellent properties under all investigated conditions and (ii) that film degradation was due to side chain degradation rather than due to copolymer desorption.

Whole body postmortem angiography with a high viscosity contrast agent solution using poly ethylene glycol as contrast agent dissolver

Postmortem minimal invasive angiography has already been implemented to support virtual autopsy examinations. An experimental approach in a porcine model to overcome an initially described artificial tissue edema artifact by using a poly ethylene glycol (PEG) containing contrast agent solution showed promising results. The present publication describes the first application of PEG in a whole corpse angiographic CT examination. A minimal invasive postmortem CT angiography was performed in a human corpse utilizing the high viscosity contrast agent solution containing 65% of PEG. Injection was carried out via the femoral artery into the aortic root in simulated cardiac output conditions. Subsequent CT scanning delivered the 3D volume data of the whole corpse. Visualization of the human arterial anatomy was excellent and the contrast agent distribution was generally limited to the arterial system as intended. As exceptions an enhancement of the brain, the left ventricular myocardium and the renal cortex became obvious. This most likely represented the stage of centralization of the blood circulation at the time of death with dilatation of the precapillary arterioles within these tissues. Especially for the brain this resulted in a distinctively improved visualization of the intracerebral structures by CT. However, the general tissue edema artifact of postmortem minimal invasive angiography examinations could be distinctively reduced.

Bovine primary chondrocyte culture in synthetic matrix metalloproteinase-sensitive poly(ethylene glycol)-based hydrogels as a scaffold for cartilage repair

A poly(ethylene glycol) (PEG)-based hydrogel was used as a scaffold for chondrocyte culture. Branched PEG-vinylsulfone macromers were end-linked with thiol-bearing matrix metalloproteinase (MMP)-sensitive peptides (GCRDGPQGIWGQDRCG) to form a three-dimensional network in situ under physiologic conditions. Both four- and eight-armed PEG macromer building blocks were examined. Increasing the number of PEG arms increased the elastic modulus of the hydrogels from 4.5 to 13.5 kPa. PEG-dithiol was used to prepare hydrogels that were not sensitive to degradation by cell-derived MMPs. Primary bovine calf chondrocytes were cultured in both MMP-sensitive and MMP-insensitive hydrogels, formed from either four- or eight-armed PEG. Most (>90%) of the cells inside the gels were viable after 1 month of culture and formed cell clusters. Gel matrices with lower elastic modulus and sensitivity to MMP-based matrix remodeling demonstrated larger clusters and more diffuse, less cell surface-constrained cell-derived matrix in the chondron, as determined by light and electron microscopy. Gene expression experiments by real-time RT-PCR showed that the expression of type II collagen and aggrecan was increased in the MMP-sensitive hydrogels, whereas the expression level of MMP-13 was increased in the MMP-insensitive hydrogels. These results indicate that cellular activity can be modulated by the composition of the hydrogel. This study represents one of the first examples of chondrocyte culture in a bioactive synthetic material that can be remodeled by cellular protease activity.

Confined crystallization of nanolayered poly(ethylene terephthalate) using X-ray diffraction methods

The development of crystalline lamellae in ultra-thin layers of poly(ethylene terephthalate) PET confined between polycarbonate (PC) layers in an alternating assembly is investigated as a function of layer thickness by means of X-ray diffraction methods. Isothermal crystallization from the glassy state is in-situ followed by means of small-angle X-ray diffraction. It is found that the reduced size of the PET layers influences the lamellar nanostructure and induces a preferential lamellar orientation. Two lamellar populations, flat-on and edge-on, are found to coexist in a wide range of crystallization temperatures (Tc = 117–150 °C) and within layer thicknesses down to 35 nm. Flat-on lamellae appear at a reduced crystallization rate with respect to bulk PET giving rise to crystals of similar dimensions separated by larger amorphous regions. In addition, a narrower distribution of lamellar orientations develops when the layer thickness is reduced or the crystallization temperature is raised. In case of edge-on lamellae, crystallization conditions also influence the development of lamellar orientation; however, the latter is little affected by the reduced size of the layers. Results suggest that flat-on lamellae arise as a consequence of spatial confinement and edge-on lamellae could be generated due to the interactions with the PC interface. En este trabajo se investiga mediante difracción de rayos X a ángulos bajos (SAXS) y a ángulos altos (WAXS), la cristalización de láminas delgadas de Polietilén tereftalato (PET) confinadas entre láminas de Policarbonato (PC), tomando como referencia PET sin confinar. El espesor de las capas de PET varía entre 35nm y 115 nm. Se realizaron medidas de difracción a tres temperaturas de cristalización (117ºC, 132ºC y 150ºC) encontrándose que el reducido espesor de las capas de PET influye en la estructura lamelar que se desarrolla, induciendo una orientación preferente de las láminas. Se integró la intensidad difractada alrededor del máximo en SAXS para obtener una representación de la intensidad en función del ángulo acimutal. Mediante análisis de mínimos cuadrados se separó la curva experimental obtenida en tres contribuciones diferentes: una función Gausiana que describe la distribución de las orientaciones de las lamelas, una función lorenziana asociada a los máximos meridionales (asociados a las interfases PET-PC) y un background constante. Por otra parte la cantidad de material cristalizado se estimó asumiendo que la intensidad del background en el barrido acimutal, una vez restado el background del primer difractograma (sin máximos en SAXS) se asocia con la contribución del material isotrópico que resta en la muestra cristalizada. Se observa la coexistencia de dos poblaciones de lamelas: flat-on y edge-on. A medida que el espesor de las láminas de PET disminuye la población de las lamelas flat-on experimenta los siguientes cambios: 1) la distribución de orientación se estrecha, 2) la fracción de material cristalizado orientado aumenta, 3) la cinética de cristalización se ralentiza y 4) el largo espaciado aumenta es decir las regiones amorfas entre lamelas aumentan su tamaño. Parece demostrarse que es en las primeras etapas del crecimiento lamelar cuando la restricción espacial fuerza a las lamelas a esta orientación tipo flat-on frente a la orientación edge-on.

Measurements of attractive forces between proteins and end-grafted poly(ethylene glycol) chains

The surface force apparatus was used to measure directly the molecular forces between streptavidin and lipid bilayers displaying grafted Mr 2,000 poly(ethylene glycol) (PEG). These measurements provide direct evidence for the formation of relatively strong attractive forces between PEG and protein. At low compressive loads, the forces were repulsive, but they became attractive when the proteins were pressed into the polymer layer at higher loads. The adhesion was sufficiently robust that separation of the streptavidin and PEG uprooted anchored polymer from the supporting membrane. These interactions altered the properties of the grafted chains. After the onset of the attraction, the polymer continued to bind protein for several hours. The changes were not due to protein denaturation. These data demonstrate directly that the biological activity of PEG is not due solely to properties of simple polymers such as the excluded volume. It is also coupled to the competitive interactions between solvent and other materials such as proteins for the chain segments and to the ability of this material to adopt higher order intrachain structures.

Special occupational hazard review with control recommendations for the use of ethylene oxide as a sterilant in medical facilities /

Mode of access: Internet.

References to the use of ethylene oxide for pest control,

Mode of access: Internet.

The thermal decomposition of ethylene oxide. Submitted as a report on the Navy Contract N6onr-241, Task order I [Project NRo56-051] to the University of Rochester.

Bibliography: leaves 86-88.

Analysis of the phase behavior of the aqueous poly(ethylene glycol)-Ficoll system

The PEG-Ficoll polymer phase system is one that has been overlooked in the past for biotechnology applications because of the stability of its emulsions. However, new applications, such as emulsion coating of cells, are appearing that rely on this very property. Ficoll is highly polydisperse and multimodal with three distinct Ficoll peaks in gel permeation chromatography. As a result, the transition between one-phase and two-phase systems is blurred and the binodials obtained through turbidometric titration and tie-line analysis differ significantly. Moreover, since the three Ficoll peaks partition differently, tie-line analysis cannot be described by a simple model of the aqueous two-phase system. A simple modification to the model allowed for excellent fit, and this modification may prove well-suited for the many practical cases where aqueous two-phase systems fail to display parallel tie-lines as implicitly assumed in the simpler model.

Long-term in vivo biostability of poly(dimethylsiloxane) / poly(hexamethylene oxide) mixed macrodiol-based polyurethane elastomers

The long-term biostability of a novel thermoplastic polyurethane elastomer (Elast-Eon(TM) 2 80A) synthesized using poly(hexamethylene oxide) (PHMO) and poly(dimethylsiloxane) (PDMS) macrodiols has been studied using an in vivo ovine model. The material's biostability was compared with that of three commercially available control materials, Pellethane(R) 2363-80A, Pellethane(R) 2363-55D and Bionate(R) 55D, after subcutaneous implantation of strained compression moulded flat sheet dumbbells in sheep for periods ranging from 3 to 24 months. Scanning electron microscopy, attenuated total reflectance-Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy were used to assess changes in the surface chemical structure and morphology of the materials. Gel permeation chromatography, differential scanning calorimetry and tensile testing were used to examine changes in bulk characteristics of the materials. The results showed that the biostability of the soft flexible PDMS-based test polyurethane was significantly better than the control material of similar softness, Pellethane(R) 80A, and as good as or better than both of the harder commercially available negative control polyurethanes. Pellethane(R) 55D and Bionate(R) 55D. Changes observed in the surface of the Pellethane(R) materials were consistent with oxidation of the aliphatic polyether soft segment and hydrolysis of the urethane bonds joining hard to soft segment with degradation in Pellethane(R) 80A significantly more severe than that observed in Pellethane(R) 55D. Very minor changes were seen on the surfaces of the Elast-Eon(TM) 2 80A and Bionate(R) 55D materials. There was a general trend of molecular weight decreasing with time across all polymers and the molecular weights of all materials decreased at a similar relative rate. The polydispersity ratio, M-w/M-n, increased with time for all materials. Tensile tests indicated that UTS increased in Elast-Eon(TM) 2 80A and Bionate(R) 55D following implantation under strained conditions. However, ultimate strain decreased and elastic modulus increased in the explanted specimens of all three materials when compared with their unimplanted unstrained counterparts. The results indicate that a soft, flexible PDMS-based polyurethane synthesized using 20% PHMO and 80% PDMS macrodiols has excellent long-term biostability compared with commercially available polyurethanes. (C) 2004 Elsevier Ltd. All rights reserved.

Determination of domain sizes in blends of poly(ethylene) and poly(styrene) formed in the presence of supercritical carbon dioxide

Well-mixed blends of poly(ethylene) and poly(styrene) have been synthesized using supercritical carbon dioxide as a solvent. The morphology of the blends has been conclusively characterized using differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), Raman microprobe microscopy, and C-13 solid-state cross-polarization magic angle spinning NMR (C-13 CPMAS NMR). DSC measurements demonstrate that poly(styrene) in the blends resides solely in the amorphous regions of the poly(ethylene) matrix; however, corroborative evidence from the SAXS experiments shows that poly(styrene) resides within the interlamellar spaces. The existence of nanometer-sized domains of poly(styrene) was shown within a blend of poly(styrene) and poly(ethylene) when formed in supercritical carbon dioxide using Raman microprobe microscopy and C-13 CPMAS NMR spectroscopy coupled with a spin diffusion model. This contrasts with blends formed at ambient pressure in the absence of solvent, in which domains of poly(styrene) in the micrometer size range are formed. This apparent improved miscibility of the two components was attributed to better penetration of the monomer prior to polymerization and increased swelling of the polymer substrate by the supercritical carbon dioxide solvent.

Thermosetting Blends of Polybenzoxazine and Poly(ε-caprolactone): Phase Behavior and Intermolecular Specific Interactions

Polybenzoxazine (PBA-a)/poly(epsilon-caprolactone) (PCL) blends were prepared by an in situ curing reaction of benzoxazine (BA-a) in the presence of PCL. Before curing, the benzoxazine (BA-a)/PCL blends are miscible, which was evidenced by the behaviors of single and composition-dependant glass transition temperature and equilibrium melting point depression. However, the phase separation induced by polymerization was observed after curing at elevated temperature. It was expected that after curing, the PBA-a/PCL blends would be miscible since the phenolic hydroxyls in the PBA-a molecular backbone have the potential to form inter- molecular hydrogen-bonding interactions with the carbonyls of PCL and thus would fulfil the miscibility of the blends. The resulting morphology of the blends prompted an investigation of the status of association between PBA-a and PCL under the curing conditions. Although Fourier-transform infrared spectroscopy (FT-IR) showed that there were intermolecular hydrogen-bonding interactions between PBA-a and PCL at room temperature, especially for the PCL-rich blends, the results of variable temperature FT-IR spectroscopy by the model compound indicate that the phenolic hydroxyl groups could not form efficient intermolecular hydrogen-bonding interactions at elevated temperatures, i.e., the phenolic hydroxyl groups existed mainly in the non-associated form in the system during curing. The results are valuable to understand the effect of curing temperature on the resulting morphology of the thermosetting blends. SEM micrograph of the dichloromethane-etched fracture surface of a 90:10 PBA-a PCL blend showing a heterogeneous morphology.