Well-defined amphiphilic poly(ε-caprolactone)-b-poly(N-vinylpyrrolidone) (PCL-b-PNVP) block copolymers were successfully prepared via the combination of ring-opening polymerization (ROP) and xanthate-mediated reversible additionÀfragmentation chain transfer (RAFT) polymerization. Well-defined poly(ε-caprolactone) (PCLÀOH) was synthesized by ROP in bulk at 110 °C using benzyl alcohol as initiator and stannous octate [Sn(Oct) 2 ] as catalyst . The ÀOH end group was then converted into its corresponding xanthate (PCLÀX) via the conversion to its corresponding bromide (PCLÀBr). These are verified by 1 H NMR spectroscopy. PCL-b-PNVP block copolymers were synthesized via RAFT polymerization in tetrahydrofuran (THF) at 80 °C using PCLÀX as macro-chain transfer agent and characterized by 1 H NMR spectroscopy and gel permeation chromatography (GPC). The amphiphilic diblock copolymer PCL 63 -b-PNVP 90 forms spherical micelles of ∼34 nm diameter in water as shown by transmission electron microscopy (TEM), supported by 1 H NMR spectroscopy, and light scattering. The critical micellar concentrations were determined by fluorescence spectroscopy using pyrene as probe. The critical micelle concentration (cmc) value of the block copolymers increases with the increase in the chain length of PNVP block. The overall hydrodynamic radius (R h ) of the micelles remains almost constant over the concentration range above the cmc value and over the angles of scattering measurement.

Atomic force microscopy (AFM) has proven to be a valuable instrument to characterize quantitatively the mechanical and morphological properties of soft materials. For medium and hard samples (E41 MPa), the nanomechanical accuracy of AFM is well established and ascertained. However, for soft samples, the experimental setup and data analysis for AFM are not yet firmly established. A calibration obtained for homogeneous samples with a Young's modulus ranging from 100 Pa to a few kPa will prove its usefulness for nanomechanical AFM investigations of soft biological specimens, such as living cells and extracellular matrices. For this purpose, poly(N-isopropylacrylamide) (PNIPAM) hydrogels were synthesized in different methanol − water mixtures to produce a series of homogeneous samples with finely tunable mechanical properties. These samples allowed the comparison and validation of AFM force spectroscopy results using macroscopic and rheological techniques. In AFM measurements, the geometry of the indenter is fundamental to the model used for data interpretation; therefore, experiments were carried out using spherical micrometric and standard pyramidal sharp probes. Moreover, a PNIPAM gel embedded with hard microspheres was analyzed, which showed the capability of AFM for measuring the local mechanical properties of heterogeneous samples.

For the preparation of thermoresponsive copolymers, for e.g., tissue engineering scaffolds or drug carriers, a precise control of the synthesis parameters to set the lower critical solution temperature (LCST) is required. However, the correlations between molecular parameters and LCST are partially unknown and, furthermore, LCST is defined as an exact temperature, which oversimplifies the real situation. Here, random N-isopropylacrylamide (NIPAM)/dopamine methacrylamide (DMA) copolymers were prepared under a systematical variation of molecular weight and comonomer amount and their LCST in water studied by calorimetry, turbidimetry, and rheology. Structural information was deduced from observed transitions clarifying the contributions of molecular weight, comonomer content, end-group effect or polymerization degree on LCST, which were then statistically modeled. This proved that the LCST can be predicted through molecular structure and conditions of the solutions. While the hydrophobic DMA lowers the LCST especially the onset, polymerization degree has an important but smaller influence over all the whole LCST range.

Macroporous poly(N-isopropylacrylamide) (PNIPAM) hydrogels have been prepared in methanol-water (1:1, v/v) mixture in the presence of 0, 0.05, 0.1, 0.15, and 0.2 M Y(OTf)(3) Lewis acid concentrations. Synthesis of the corresponding linear PNIPAM homopolymers in the absence of a cross-linker keeping all other conditions the same shows that the isotacticity (meso dyad, %) and the cloud point temperature of the resulted in polymers increases and decreases, respectively, with the increase in the concentration of the Lewis acid. SEM micrographs reveal that the resulted hydrogels are highly porous. Swelling ratios of all the hydrogels in water decrease with the increase in the temperature. Moreover, swelling ratios of all the hydrogels in different methanol-water mixtures pass through a minimum in the co-nonsolvency zone, and the co-nonsolvency zone shifts toward the lower methanol-content solvent mixture with gradual increase in the Lewis acid concentration. Deswelling rate of the hydrogel prepared in methanol-water (1:1, v/v) mixture is much faster than that of the conventional hydrogel prepared in water. Moreover, the deswelling rate slightly increases with the hydrogels prepared with the increasing concentrations of Lewis acid. But, the reswelling rate of the hydrogels follows almost the reverse order. All these results have been explained on the basis of the formation of highly porous hydrogels with higher isotactic PNIPAM chain segment owing to the faster polymerization rate in the methanol-water mixture in the presence of Lewis acid and the co-nonsolvency behavior of the methanol-water (1:1, v/v) mixture toward PNIPAM chain segment in the PNIPAM hydrogel.

Poly(N‐isopropylacrylamide) (PNIPAM) hydrogels were simply prepared by free radical polymerization in different methanol–water mixture. A scanning electron microscopy study revealed that the freeze‐dried hydrogels were macroporous. The swelling ratios in water at 20°C of the resulting hydrogels followed the order: X0.43>X0.21>X0.76 ≈ X0.57>X0.31>X0.13>X0.06>X0, where Xm denotes a gel prepared in a methanol–water mixture with m mole fraction of methanol (xm). Below the lower critical solution temperature, the swelling ratio values of all of the hydrogels gradually decreased with the increase in the temperature. The complete collapse of the PNIPAM chain of all the gels occurred at about 38°C, whereas the same was observed at about 35°C for the conventional gel prepared in water. The swelling ratio values of all the PNIPAM gels in the methanol–water mixtures with different xm values at 20°C passed through a minimum in the cononsolvency zone. The deswelling rates of the hydrogels decreased in the following order: X0.43> X0.31> X0.21> X0.57> X0.76 ≈ X0.13> X0.06> X0. The reswelling rates of these hydrogels decreased in the following order: X0> X0.31> X0.06 ≈ X0.13 > X0.76> X0.57> X0.21> X0.43. The release rates of the Tramadol Hydrochloride drug at 37°C from the drug‐loaded hydrogels were almost same for all of the hydrogels. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012