The thermoresponsive surfaces of brush structure (linear polymer chains tethered on the surface) based on poly(2-isopropyl-2-oxazoline)s and copolymers of 2-ethyl-2-oxazoline and 2-nonyl-2-oxazoline were obtained using the grafting-to method. The living oxazoline (co)polymers have been synthesized by cationic ring-opening polymerization and subsequently terminated by the reactive amine groups present on the surface. The changes in the surface morphology, philicity and thickness occurring during surface modification were monitored via atomic force microscopy, contact angle and ellipsometry. The thickness of the (co)poly(2-substituted-2-oxazoline) layers ranged from 4 to 11 nm depending on the molar mass of immobilized polymer and reversibly varied with the temperature changes. This confirmed thermoresponsive properties of obtained surfaces. The obtained polymer surfaces were used as a support for dermal fibroblast culture and detachment. The fibroblasts' adhesion and proliferation on the polymer surfaces were observed when the culture temperature was above the cloud point temperature of the immobilized polymer. Lowering the temperature resulted in the detachment of the dermal fibroblast sheets from the polymer layers, which makes these surfaces suitable for the treatment of wounds and in skin tissue engineering.

The crystallization of polymers from organic solvents is a common phenomenon. Poly(2-isopropyl-2-oxazoline) (PIPOx) is known to crystallize in aqueous or aqueous/organic solvent solutions. This process is associated with the dehydration of polymer chains above the polymer’s lower critical solution temperature (LCST). In this work, the ability of PIPOx to crystallize in nonaqueous media is presented. The annealing of a solution of PIPOx in organic solvents, such as acetonitrile, dimethyl sulfoxide, or propylene carbonate, leads to the precipitation of insoluble material. DSC and WAXS studies confirm the formation of a crystalline phase in the solution, with the degree of crystallinity dependent on the solvent and the polymer concentration. SEM analysis reveals micron-sized fibril structures of the PIPOx crystalline fraction. The glass transition temperature (T g) and the melting temperature (T m) of PIPOx crystallized in organic solutions are equal to those of the polymer crystallized in bulk. The enthalpy of melting (ΔH) of the PIPOx crystalline fraction versus its degree of crystallinity (χc) is shown. The value of the enthalpy of melting for hypothetical, fully crystalline PIPOx (ΔH 100%) is determined.

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The synthesis and aggregation behavior of well‐defined thermosensitive (co)polymers of oligo(ethylene glycol) methacrylates (POEGMA) in aqueous solutions were investigated. The cloud points of the POEGMAs solutions were determined by turbidimetry and dynamic light scattering. For POEGMA (co)polymers the cloud point temperature (TCP) increased linearly with increasing content of more hydrophilic comonomer. The mesoglobules formed by POEGMAs in dilute aqueous solutions above TCP were studied by light scattering. The size of mesoglobules depended on the concentration and the heating procedures. The aggregates became smaller with decreasing initial concentration of polymer and increasing rates of temperature change. By selecting the proper heating and dilution procedures, the influence of the (co)polymer structure on the size of the mesoglobules could be determined. The size of the mesoglobules decreased with the length of the OEG side chains and increased with increasing content of more hydrophilic comonomer. The light scattering parameters of the mesoglobules—A2 values and shape factors ${R_{\rm g}\over R_{\rm h}}$—suggested that the hydrophilic OEG side chains placed at the periphery of the mesoglobules in direct contact with the surrounding water controlled the size of mesoglobules and their stability. Shape factors for all POEGMA mesoglobules indicated that the mesoglobules remained highly hydrated after formation. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

Well-defined thermosensitive poly[tri(ethylene glycol) monoethyl ether methacrylate] (P(TEGMA-EE)) brushes were synthesized on a solid substrate by the surface-initiated atom transfer radical polymerization of TEGMA-EE. The polymerization reaction was initiated by 2-bromo-2-methylpropionate groups immobilized on the surface of the wafers. The changes in the surface composition, morphology, philicity, and thickness that occurred at each step of wafer functionalization confirmed that all surface modification procedures were successful. Both the successful modification of the surface and bonding of the P(TEGMA-EE) layer were confirmed by X-ray photoelectron spectroscopy (XPS) measurements. The thickness of the obtained P(TEGMA-EE) layers increased with increasing polymerization time. The increase of environmental temperature above the cloud point temperature of P(TEGMA-EE) caused the changes of surface philicity. A simultaneous decrease in the polymer layer thickness confirmed the thermosensitive properties of these P(TEGMA-EE) layers. The thermosensitive polymer surfaces obtained were evaluated for the growth and harvesting of human fibroblasts (basic skin cells). At 37 °C, seeded cells adhered to and spread well onto the P(TEGMA-EE)-coated surfaces. A confluent cell sheet was formed within 24 h of cell culture. Lowering the temperature to an optimal value of 17.5 °C (below the cloud point temperature of the polymer, TCP, in cell culture medium) led to the separation of the fibroblast sheet from the polymer layer. These promising results indicate that the surfaces produced may successfully be used as substrate for engineering of skin tissue, especially for delivering cell sheets in the treatment of burns and slow-healing wounds.

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Semicrystalline, thermoresponsive poly(2-isopropyl-2-oxazoline) (PIPOx) layers covalently bonded to glass or silica wafers were obtained via the surface-termination of the living polymer chains. Polymer solutions in acetonitrile were exposed to 50 °C for various time periods and were poured onto the functionalized solid wafers. Fibrillar crystallites formed in polymerization solutions settled down onto the wafers next to the amorphous polymer. The amount of crystallites adsorbed on thermoresponsive polymer layers depended on the annealing time of the PIPOx solution. The wettability of PIPOx layers decreased with the increasing amount of crystallites. The higher content of crystallites weakened the temperature response of the layer, as evidenced by the philicity and thickness measurements. Semicrystalline thermoresponsive PIPOx layers were used as biomaterials for human dermal fibroblasts (HDFs) culture and detachment. The presence of crystallites on the PIPOx layers promoted the proliferation of HDFs. Changes in the physicochemical properties of the layer, caused by the temperature response of the polymer, led to the change in the cells shape from a spindle-like to an ellipsoidal shape, which resulted in their detachment. A supporting membrane was used to assist the detachment of the cells from PIPOx biosurfaces and to prevent the rolling of the sheet.

The review gathers together data concerning the influence of poly(2-substituted-2-oxazoline)s structure on their thermal and crystalline properties, and how this relationship can be adjusted in controlled manner.