Role of hydration and water coordination in micellization of Pluronic block copolymers.

Raman, attenuated total reflectance FTIR, near-infrared spectroscopy, and DFT calculations have been used in a study of aqueous solutions of three tri-block copolymers poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) or PEO-PPO-PEO with commercial names Pluronic PE6200, PE6400 and F68. It is shown that the process of micellization as a response to increased temperature is reflected in the hydroxyl stretching region of infrared and Raman spectra, which contains information both about restructuring of water and changes of polymer chains in polymer/water aggregates. Raman spectra exhibit differences between individual Pluronics even at temperatures below the critical micellization temperature (CMT). According to the attenuated total reflection (ATR) FTIR spectra, the same five water coordination types defined by the number of donated/accepted hydrogen bonds are present in interacting water as in bulk water. It indicates that models considering mixed states of water with different hydrogen bonding environments provide appropriate descriptions of bound water both below and above the CMT. Above the CMT, aggregate hydration increases in the order PE6400 < PE6200 < F68, although that does not fully correspond to the EO/PO ratio, and points to the differences in microstructure of aggregates formed by each copolymer. This study relates nanoscale phenomena (hydrophobic and hydrophilic hydration) with the mesoscale phenomenon of micellization.

Structural changes of UHMWPE after e-beam irradiation and thermal treatment.

Ultra-high molecular weight polyethylene (UHMWPE) was irradiated with accelerated electrons (1 MeV in air) using high dose rates (> 25 kGy/min) and thin specimens (thickness 1 mm). Parts of the specimens were remelted (200 degrees C for 10 min; 150 degrees C for 0, 2, 10, 30, 60 min). All specimens were stored in nitrogen in the dark at 5 degrees C. Supermolecular structure, extent of crosslinking, oxidative degradation, and macroradical content were studied by a number of methods (SAXS, WAXS, SEM, DSC, FTIR, ESR, TGA, solubility experiments, image analysis). The results obtained with irradiated samples were compared with those obtained with irradiated and remelted samples. It was confirmed that crosslinking predominates over chain scission at very high dose rates, even if the irradiation is performed in air. Discrepancies concerning supermolecular structure changes in UHMWPE after irradiation and thermal treatment, found in various studies in the literature, are discussed. A simple model, which describes and explains all supermolecular structure changes, is introduced. An effective way of eliminating residual macroradicals in UHMWPE is proposed.

Role of water in structural changes of poly(AVGVP) and poly(GVGVP) Studied by FTIR and Raman spectroscopy and ab initio calculations.

Two elastin-like poly(pentapeptides), poly(AV1GV2P) and poly(G1V1G2V2P), have been studied in water and in solid state by ATR FTIR and Raman spectroscopy in combination with model ab initio calculations. In aqueous solutions below the transition temperature T(t), a part of the amide groups and of the methyl groups of both polypentapeptides interacts with neighboring water molecules, whereas the other part of amide groups mutually interacts forming a beta-sheetlike structure. Below T(t), poly(AV1GV2P) is dissolved more perfectly, and the water shells around the polymer chains are more closely structured. The suspension of poly(AV1GV2P) formed above T(t) is more compact and, on cooling, resists more to the reverse dissolution, whereas the suspension of poly(G1V1G2V2P) contains more water molecules bound to the carbonyl of amide groups and on backward cooling dissolves fairly reversibly. The measured poly(pentapeptides) tend to form beta-turns due to the conformational transition on the residue between P and V1.

Structure and dynamics of two elastin-like polypentapeptides studied by NMR spectroscopy.

The structure and dynamics of two synthetic elastin-like polypentapeptides, poly(G(1)V(1)G(2)V(2)P) and poly(AV(1)GV(2)P), were studied in D(2)O and H(2)O at various temperatures by using (1)H, (2)H,(13)C, and (15)N NMR spectra, relaxations, and PGSE self-diffusivity measurement. Signal assignments were made using COSY, NOESY, HXCORR, HSQC, HMBC, and SSLR INEPT techniques. Temperature-induced conformation changes were studied using (3)J(NHCH) couplings, NOESY connectivity, chemical shifts, and signal intensities. Hydrodynamic radii were derived from self-diffusion coefficients measured by the pulsed-gradient spin-echo (PGSE) method. Selective hydration (hydrophilic or hydrophobic) was explored using NOESY and ROESY spectral methods and longitudinal and transverse (1)H relaxation of HOD and quadrupolar (2)H relaxation of D(2)O. Four different physical states were discerned in different temperature regions for both polymers: state I of a rather extended, statistically shaped and fully hydrated polymer below the critical temperature (approximately 299-300 K); state II, a relatively coiled and globular but disordered preaggregation state, developing in a rather narrow region, 300-303 K, in the case of poly(AV(1)GV(2)P) and in a broader region, overlapping with the next one, in poly(G(1)V(1)G(2)V(2)P); state III, a tightly coiled, more compact state in the region 303-313 K; and, finally, state IV, an aggregated (and eventually flocculating and sedimenting) state beyond 313 K. States II-IV coexist in varying proportions in the whole temperature range above 299 K. A structure characterized by a beta-turn stabilized by H-bonding between the Ala carbonyl and Val(2) NH groups of poly(AV(1)GV(2)P) was detected by NOESY just above the transition temperature. States II and III are progressively more stripped of their hydration sheath but retain some molecules of water confined and relatively immobilized in their coils.