Microphase separation in copolymers of hydrophilic PEG blocks and hydrophobic tyrosine-derived segments using simultaneous SAXS/WAXS/DSC

Abstract

Hydration-and temperature-induced microphase separations were investigated by simultaneous small-and wide-angle X-ray scattering (SAXS and WAXS) and differential scanning calorimetry (DSC) in a family of copolymers in which hydrophilic poly(ethylene glycol) (PEG) blocks are inserted randomly into a hydrophobic polymer made of either desaminotyrosyl-tyrosine ethyl ester (DTE) or iodinated I 2 DTE segments. Iodination of the tyrosine rings in I 2 DTE increased the X-ray contrast between the hydrophobic and hydrophilic segments in addition to facilitating the study of the effect of iodination on microphase separation. The formation of phase-separated, hydrated PEG domains is of considerable significance as it profoundly affects the polymer properties. The copolymers of DTE (or I 2 DTE) and PEG are a useful model system and the findings presented here may be applicable to other PEG-containing random copolymers as well. In copolymers of PEG and DTE and I 2 DTE, the presence of PEG depressed the glass transition temperature (T g ) of the copolymer relative to the homopolymer, poly(DTE carbonate), and the DTE/ I 2 DTE segments hindered the crystallization of the PEG segments. In the dry state, at large PEG fractions (> 70 vol %), the PEG domains self-assembled into an ordered structure with 14-18 nm distance between the domains. These domains gave rise to a SAXS peak at all temperatures in the iodinated polymers, but only above the T g in non-iodinated polymers, due to the unexpected contrast-match between the crystalline PEG domains and the glassy DTE segments. Irrespective of whether PEG was crystalline or not, immersion of these copolymers in water resulted in the formation of hydrated PEG domains that were 10-20 nm apart. Since both water and the polymer chains must be mobile for the phase separation to occur, the PEG domains disappeared when the water froze, and reappeared as the ice began to melt. This transformation was reversible, and showed hysteresis as did the melting of ice and freezing of the water incorporated into the polymer. PEG-water complexes and PEG-water eutectics were observed in WAXS and DSC scans, respectively.

Study of nanoscale structures in hydrated biomaterials using small-angle neutron scattering

“…Despite this contrast, no interference peak was observed in dry samples. Thus, consistent with the conclusion based on SAXS data [28], there is no phase separation in the dry samples. The absence of any scattering in the wet sample could be because at ~ 0.9 D 2 O molecules per EG monomer hydrated PEG will match DTE in scattering contrast.…”

Biodegradable PEG-Based Amphiphilic Block Copolymers for Tissue Engineering Applications

“…One hypothesis explaining this phenomena is that hydration-induced phase segregation in the amphiphilic network results in a change in load transfer within the polymer. 70,72 Another competing hypothesis is that the swelling of the hydrophilic (PEG) domains stiffens the polymer. 71 For tissue engineering applications, hydration-induced stiffening may be exploited to engineer amphiphilic scaffolds with self-fixation behaviors.…”

Hydrophilic polyurethane matrix promotes chondrogenesis of mesenchymal stem cells

“…WAXD of PEG shows the characteristic diffraction pattern and pure DTH, a viscous liquid, shows a broad peak with moderate intensity at a 2θ value of 20.75°. DTH molecules can self-assemble by H-bonding and π–π interactions leading to small crystallites oriented in all directions which results in a broad peak [21–23]. Both PUs show similar diffraction patterns but with different intensities.…”