Absorption of hydrophobic compounds into the poly(dimethylsiloxane) coating of solid-phase microextraction fibers: high partition coefficients and fluorescence microscopy images

The use of solid-phase microextraction with poly(dimethylsiloxane) (PDMS)-coated glass fibers for the extraction and analysis of hydrophobic organic analytes is increasing. The literature on this topic is characterized by large discrepancies in partition coefficients and an uncertainty of whether highly hydrophobic analytes are retained by absorption into the fiber coating or by adsorption to the fiber surface. We applied a new method, which minimizes the impact of experimental artifacts, to determine PDMS water partition coefficients of 17 hydrophobic analytes including chlorinated benzenes, PCBs, PAHs, and p,p'-DDE. These partition coefficients are several orders of magnitude higher than some reported values. Two observations strongly suggest that the retention of hydrophobic organic substances is governed by partitioning into the PDMS coating. (1) The partition coefficients are proportional with octanol/water partition coefficients. (2) The fluorescence of fluoranthene was observed to be homogeneously distributed within the polymer coating when studied by means of fluorescence microscopy. Implications of these findings for the application of solid-phase microextraction with respect to potential detection limits, with respect to biomimetic extraction, and with respect to measurements in multicompartment systems are discussed.     

Achieving One‐Step Surface Coating of Highly Hydrophilic Poly(Carboxybetaine Methacrylate) Polymers on Hydrophobic and Hydrophilic Surfaces

It is highly desirable to develop a universal nonfouling coating via a simple one‐step dip‐coating method. Developing such a universal coating method for a hydrophilic polymer onto a variety of surfaces with hydrophobic and hydrophilic properties is very challenging. This work demonstrates a versatile and simple method to attach zwitterionic poly(carboxybetaine methacrylate) (PCB), one of the most hydrophilic polymers, onto both hydrophobic and hydrophilic surfaces to render them nonfouling. This is achieved by the coating of a catechol chain end carboxybetaine methacrylate polymer (DOPA‐PCB) assisted by dopamine. The coating process was carried out in water. Water miscible solvents such as methanol and tetrahydrofuran (THF) are added to the coatings if surface wettability is an issue, as for certain hydrophobic surfaces. This versatile coating method was applied to several types of surfaces such as polypropylene (PP), polydimethyl siloxane (PDMS), Teflon, polystyrene (PS), polymethylmethacrylate (PMMA), polyvinyl chloride (PVC) and also on metal oxides such as silicon dioxide.     

Transformation of poly(dimethylsiloxane) into thin surface films of SiO x by UV/ozone treatment. Part II: segregation and modification of doped polymer blends

UV/ozone treatment of organic polymers having silicone additives to produce oxidized layers was achieved by doping a host polymer or prepolymer with a silicone additive, poly(dimethylsiloxane) (PDMS). The concentration of PDMS in the host polymer was low, typically in the range of 0.1–2.0% by weight. Host polymers were polyethylene, polyimide, and polyurethane. After film formation, the presence of PDMS was detected on the surface using X-ray photoelectron spectroscopy (XPS), consistent with wetting angle measurements that revealed a hydrophobic surface. The doped blend was then subjected to exposure in a UV/ozone environment such that a thin, stable barrier of SiO _x was formed at the surface of the film. Rate of film modification was monitored by XPS and measurement of advancing contact angle using deionized water. XPS measurements also showed some evidence of modified fragments of the host polymer near the surface. Significant segregation of PDMS and subsequent transformation to silicon oxides has been demonstrated to occur in these doped systems. The stability of the modified glassy surface formed by UV/ozone treatment of a commercially available epoxy formulation containing a silicone additive was shown to be superior to that obtained by other treatment techniques, e.g., oxygen plasma modification.     

Synthesis and characterization of biodegradable poly (ethylene glycol) and poly (caprolactone diol) end capped poly (propylene fumarate) cross linked amphiphilic hydrogel as tissue engineering scaffold material

Biodegradable poly (caprolactone diol-co-propylene fumarate-co-ethylene glycol) amphiphilic polymer with poly (ethylene glycol) and poly (caprolactone diol) chain ends (PCL-PPF-PEG) was prepared. PCL-PPF-PEG undergoes fast setting with acrylamide (aqueous solution) by free radical polymerization and produces a crosslinked hydrogel. The cross linked and freeze-dried amphiphilic material has porous and interconnected network. It undergoes higher degree of swelling and water absorption to form hydrogel with hydrophilic and hydrophobic domains at the surface and appreciable tensile strength. The present hydrogel is compatible with L929 fibroblast cells. PCL-PPF-PEG/acrylamide hydrogel is a candidate scaffold material for tissue engineering applications.     

Synthesis and characterization of biodegradable poly (ethylene glycol) and poly (caprolactone diol) end capped poly (propylene fumarate) cross linked amphiphilic hydrogel as tissue engineering scaffold material

Biodegradable poly (caprolactone diol-co-propylene fumarate-co-ethylene glycol) amphiphilic polymer with poly (ethylene glycol) and poly (caprolactone diol) chain ends (PCL–PPF–PEG) was prepared. PCL–PPF–PEG undergoes fast setting with acrylamide (aqueous solution) by free radical polymerization and produces a crosslinked hydrogel. The cross linked and freeze-dried amphiphilic material has porous and interconnected network. It undergoes higher degree of swelling and water absorption to form hydrogel with hydrophilic and hydrophobic domains at the surface and appreciable tensile strength. The present hydrogel is compatible with L929 fibroblast cells. PCL–PPF–PEG/acrylamide hydrogel is a candidate scaffold material for tissue engineering applications.     

An oxygen plasma treated poly(dimethylsiloxane) bioscaffold coated with polydopamine for stem cell therapy

In this study, 3D macroporous bioscaffolds were developed from poly(dimethylsiloxane) (PDMS) which is inert, biocompatible, non-biodegradable, retrievable and easily manufactured at low cost. PDMS bioscaffolds were synthesized using a solvent casting and particulate leaching (SCPL) technique and exhibited a macroporous interconnected architecture with 86?±?3% porosity and 300?±?100?µm pore size. As PDMS intrinsically has a hydrophobic surface, mainly due to the existence of methyl groups, its surface was modified by oxygen plasma treatment which, in turn, enabled us to apply a novel polydopamine coating onto the surface of the bioscaffold. The addition of a polydopamine coating to bioscaffolds was confirmed using composition analysis. Characterization of oxygen plasma treated-PDMS bioscaffolds coated with polydopamine (polydopamine coated-PDMS bioscaffolds) showed the presence of hydroxyl and secondary amines on their surface which resulted in a significant decrease in water contact angle when compared to uncoated-PDMS bioscaffolds (35?±?3%, P?<?0.05). Seeding adipose tissue-derived mesenchymal stem cells (AD-MSCs) into polydopamine coated-PDMS bioscaffolds resulted in cells demonstrating a 70?±?6% increase in viability and 40?±?5% increase in proliferation when compared to AD-MSCs seeded into uncoated-PDMS bioscaffolds (P?<?0.05). In summary, this two-step method of oxygen plasma treatment followed by polydopamine coating improves the biocompatibility of PDMS bioscaffolds and only requires the use of simple reagents and mild reaction conditions. Hence, our novel polydopamine coated-PDMS bioscaffolds can represent an efficient and low-cost bioscaffold platform to support MSC therapies.     

Resistance to nonspecific protein adsorption by poly(vinyl alcohol) thin films adsorbed to a poly(styrene) support matrix studied using surface plasmon resonance.

Thin films of poly(vinyl alcohol) (PVA) polymer were prepared on a flat, nonporous, poly(styrene) support matrix by adsorption from aqueous solution and were characterized in order to investigate the nonspecific adsorption of proteins to a chromatographically relevant surface. The integrity and surface coverage of the PVA thin films were established by surface analysis and atomic force microscopy imaging. The adsorption of the PVA polymers to the poly(styrene) substrate and the nonspecific adsorption of proteins to the PVA-coated surface were monitored using surface plasmon resonance. PVA was strongly bound to the poly(styrene) surface, but the surface density of the adsorbed PVA polymers was affected substantially by the concentration, molecular weight, and degree of hydrolysis of PVA polymers used. There was evidence of increasing degrees of unfolding of the PVA polymer onto the poly(styrene) surface as the concentration of the the PVA coating solution increased. Complete PVA coverage of the poly(styrene) surface was observed at PVA concentrations of 0.1 mg/mL or greater but with significant influence of both molecular weight and degree of hydrolysis of the PVA polymers. Resistance of the PVA-coated poly(styrene) surface to the nonspecific adsorption of human serum albumin (HSA) correlated with the degree of surface coverage of the PVA. The use of anti-HSA as a probe for adsorbed HSA suggested that HSA was displacing PVA from the poly(styrene) surface at the lower PVA surface coverage. A complete barrier to nonspecific protein adsorption was observed with a PVA coating solution concentration of greater than 0.1 mg/ mL with a degree of hydrolysis of <88%.     

Iron-included carbon nanocapsules coated with biocompatible poly(ethylene glycol) shells

Nanoparticles of iron carbides wrapped in multilayered graphitic sheets (carbon nanocapsules) were synthesized by electric plasma discharge in an ultrasonic cavitation field in liquid ethanol and purified by selective oxidation and magnetic separation. The particles had 100–200 nm in diameter after centrifuging for 10 min at 4000 rpm. Carbon nanocapsules were covered by wispy poly(ethylene glycol) PEG coating about 7–10 nm in thickness. The number of PEG chains coated on carbon nanocapsules could be estimated as 9.15%. The values of saturation magnetization Ms and coercivity Hc of purified carbon nanocapsules without PEG coating were 112 emu g⁻¹ and 75 Oe respectively. Magnetically soft carbon nanocapsules with a poly(ethylene glycol) coating on the surface may possibly be used as biocompatible magnetic nanoparticles in medical applications.     

Optimized inductively coupled plasma etching for poly(methyl-methacrylate-glycidly-methacrylate) optical waveguide

Optical loss is a crucial quality for the application of polymer waveguide devices. The optimized oxygen inductively coupled plasma etching conditions, including antenna power, bias power, chamber pressure, O₂ flow rate and etching time for the fabrication of smooth vertical poly(methyl-methacrylate-glycidly-methacrylate) channel waveguide were systematically investigated. Atomic force microscopy and scanning electron microscopy were used to characterize the etch rate, surface roughness and vertical profiles. The increment of etch rate with the antenna power, bias power and O₂ flow rate was observed. Bias power and chamber pressure were found to be the main factor affecting the interface roughness. The vertical profiles were proved to be closely related to antenna power, bias power and O₂ flow rate. Surface roughness increment was observed when the etching time increased.     

Modifications of rigid rod poly(1,4-phenylene-cis-benzobisoxazole) fibers by gas plasma treatments

The surface modifications of poly(1,4-phenylene-cis-benzobisoxazole) fibers by gas plasma treatments have been investigated in this paper. Oxygen, nitrogen, argon, and ammonia were regarded as inlet gas, respectively. After the plasma treatments, the effects on the morphology of the fiber surface, the tensile strength, the surface free energy, and the polymer crystallization behavior in the interface were carefully studied. The results showed that the total surface free energy of the fiber was increased by 35.3%, from 47.6 to 64.4 mJ/m², after the oxygen plasma treatment for 15 min. The increase has been 32.4% for N₂ plasma, 28.8% for argon plasma, and 28.6% for NH₃ plasma. The interfacial crystallization behavior of thermoplastic polyether ether ketone was also presented.