Towards Multipotent Coatings: Chemical Vapor Deposition and Biofunctionalization of Carbonyl‐Substituted Copolymers

Future advances in designing bioactive materials, such as antithrombotic coatings for cardiovascular stents, will require widely applicable and robust methods of surface modification. In this paper, we report on the development of multifunctional polymer coatings made by chemical vapor deposition (CVD) copolymerization. Polymer coatings of various [2.2]paracyclophane derivatives were co‐deposited in controlled ratios and their chemical composition verified by FT‐IR and X‐ray photoelectron spectroscopy. Furthermore, preliminary biocompatibility of these coatings was assessed using human umbilical vein endothelial cells and 3T3 murine fibroblasts. The parallel immobilization of two different antithrombotic biomolecules onto a CVD‐based copolymer is also demonstrated by orthogonal immobilization strategies.

     

Optical biochemical sensor for determining hydroperoxides in nonpolar organic liquids as archetype for sensors consisting of amphiphilic conetworks as immobilisation matrices

This paper reports the successful design of a prototype of an optical biochemical sensor for the determination of hydroperoxides in nonpolar organic liquids. The sensor consists of a matrix of an amphiphilic polymer conetwork (APCN), a novel class of very promising polymeric materials for easy preparation of biochemical sensor matrices. APCNs are characterised by nanoscopic phase separation between the hydrophilic and the hydrophobic phases. For medium ratios of conetwork composition, the domains of both phases are interconnected both on the surface of the conetworks and throughout the bulk. The APCNs have peculiar swelling properties—the hydrophilic phase swells in hydrophilic media and the hydrophobic phase swells in hydrophobic media. In both types of media dissolved reagents can diffuse from the solution into the swollen phase of the polymeric conetwork. This enables loading of the hydrophilic phase of the APCNs with enzymes and indicator reagents by simple impregnation. Hydrophobic analytes can diffuse into the polymeric conetwork via its hydrophobic phase and react with indicator reagents immobilised in the hydrophilic phase at the huge internal interface between the two opposite phases. To prepare the described hydroperoxide-sensitive biosensors, we used APCN films consisting of 58% (w/w) poly(2-hydroxyethyl acrylate) (PHEA) as hydrophilic chains and 42% (w/w) polydimethylsiloxane (PDMS) as hydrophobic linkers. Horseradish peroxidase (HRP) and diammonium 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS) as indicator reagent were co-immobilised in this optically clear and transparent matrix. In this feasibility study the conditions investigated were principally those relevant to characterisation of the innovative matrix material and the disposable biosensor produced from it; the biosensor was not optimised. Sensitivity toward tert-butylhydroperoxide (tBuOOH) dissolved in n-heptane was acceptable, between approximately 1 and at least 50 mmol L⁻¹, even in the dry state. The response time was 1.7 to 5.0 min. No leaching of immobilised reagents was observed during a period of at least one hour. Pre-swelling the sensors with water increased the reaction rate and the total turnover number of the enzyme. In a dry atmosphere at 4 °C the sensors were found to be stable for at least two weeks.     

Thermal and environmental stability of poly(4-ethynyl-p-xylylene-co-p-xylylene) thin films

The aim of this paper was to test the thermal and environmental stability of poly(4-ethynyl-p-xylyleneco-p-xylylene) thin films prepared by chemical vapor deposition(CVD) and to optimize the reaction conditions of the polymer.Fourier transformed infrared spectroscopy(FTIR),thermogravimetric analysis(TGA) and fluorescence microscopy were employed to investigate the stability of the reactive polymer coatings in various environmental conditions.Chemical reactivity of the thin films were then tested by Huisgen 1,3-dipolar cycloaddition reaction(‘‘click' reaction).The alkyne functional groups on poly(4-ethynyl-p-xylylene-co-p-xylylene) thin films were found to be stable under ambient storage conditions and thermally stable up to 100 8C when annealed at 0.08 Torr in argon.We also optimized the click reaction conditions of azide-functionalized molecules with poly(4-ethynyl-p-xylylene-co-p-xylylene).The best reaction result was achieved,when copper concentration was 0.5 mmol/L,sodium ascorbate concentration to copper concentration was 5:1.In contrast,the azide concentration and temperature had no obvious effect on the surface reaction.     

Stress‐Induced Melting of Crystals in Natural Rubber: a New Way to Tailor the Transition Temperature of Shape Memory Polymers

Lightly cross‐linked natural rubber (NR, cis‐1,4‐polyisoprene) was found to be an exceptional cold programmable shape memory polymer (SMP) with strain storage of up to 1000%. These networks are stabilized by strain‐induced crystals. Here, we explore the influence of mechanical stress applied perpendicular to the elongation direction of the network on the stability of these crystals. We found that the material recovers its original shape at a critical transverse stress. It could be shown that this is due to a disruption of the strain‐stabilizing crystals, which represents a completely new trigger for SMPs. The variation of transverse stress allows tuning of the trigger temperature T_trig(σ) in a range of 45 to 0 °C, which is the first example of manipulating the transition of a crystal‐stabilized SMP after programming.     

Thermal and acid labile polyurethanes as a new class of responsive materials in polymeric nanoparticles and nanocapsules

A new class of polyurethanes has been designed, containing tertiary carbamate groups in the main chain of the polymer, which enable the resulting polymer to degrade completely under acid and thermal treatment. The decomposition temperatures of the polymers were determined by measuring the evolution of carbon dioxide and other decomposition products using TGA‐MS. Until decomposition of the polymer, no glass transition was found. The polymers exhibit excellent solubility in common organic solvents like chloroform and tetrahydrofuran, making them to suitable materials for film formation. From the obtained polymers, nanoparticles were synthesized by the solvent evaporation method combined with the miniemulsion technique. The resulting nanoparticles can be used as intelligent fillers in films and sensors, since they degrade at temperatures of above 180 °C, which can be detected by a color change reaction with ninhydrin. Polymeric nanocapsules were prepared by an interfacial polyaddition reaction from 2,4‐toluene diisocyanate and tertiary diols performed at the droplet's interface in inverse (water‐in‐oil) miniemulsions. These nanocapsules with an encapsulated photoacid generator can act as a release system, whereby an acidic release through irradiation with ultraviolet light can be triggered. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Mechanisms of reduced human vascular cell migration after photodynamic therapy

Restenosis results from intimal hyperplasia and constrictive remodeling following cardiovascular interventions. Photodynamic therapy (PDT) has been shown to inhibit intimal hyperplasia in vivo by preventing neointimal repopulation of the treated vessel. This study was undertaken in an attempt to further dissect the mechanisms by which PDT acts on secreted and extracellular matrix proteins to inhibit migration of cultured human vascular cells. PDT of three-dimensional collagen gels inhibited invasive human smooth muscle cell (SMC) migration, whereas cell-derived matrix metalloproteinase production remained unaltered. Additionally, PDT generated cross-links in the collagen gels, a result substantiated in an ex vivo model whereby PDT rendered the treated vessels resistant to pepsin digestion and inhibited invasive migration of SMC and fibroblasts. These data support the premise that by inducing matrix protein cross-links, rendering the vessel resistant to degradation, in vivo PDT inhibits repopulation of the vessel and therefore intimal hyperplasia.     

Nanostructured Materials for Skeletal Repair

The treatment of bone and cartilage defects with bioengineered constructs of artificial scaffolds and autogenous cells became the main challenge of contemporary regenerative medicine. Early defect repair may prevent secondary injury. Recent studies could prove that bone and cartilage cells are sensitive to microscale and nanoscale patterns of surface topography and chemical structure. Nanostructured materials provide an environment for tissue regeneration mimicking the physiological range of extracellular matrix. The article reviews several studies substantiating the superiority of nanostructured materials for bone and cartilage repair along with own results on cell attachment.