Annealing-Induced Changes in Double-Brush Langmuir-Blodgett Films of α-Helical Diblock Copolypeptides

The effect of annealing on the structure and the helix orientation in Langmuir-Blodgett (LB) monolayers of diblock copolymers (PLGA-b-PMLGSLGs) of poly(α-L-glutamic acid) (PLGA) and poly(γ-methyl-L-glutamate-ran-γ-stearyl-L-glutamate) with 30 mol % of stearyl substituents (PMLGSLG) with unidirectional helix orientation deposited on hydrophilic silicon substrates was characterized by means of small-angle X-ray reflectivity, transmission Fourier transform infrared spectroscopy, and atomic force microscopy. Upon annealing at 100 °C for 24 h, the α-helices became less tilted toward the substrate surface normal. Surface area shrinkage accompanied the change in tilt, indicated by an increase in both film thickness and electron density, resulting in more compact and uniform films. The enhancement of the helix orientation by thermal annealing was greater for the PMLGSLG block and for the diblock copolymers with the shorter block lengths. For these diblock copolymers, annealing resulted in postorientation of the PMLGSLG block helices almost perpendicular to the substrate surface. This effect originates from a considerable increase in intermolecular packing of the PLGA block caused by hydrogen bonds between the carboxylic groups upon annealing, as well as the high mobility of the PMLGSLG block helices for rearrangement favored by the melted side chain mantle at elevated temperatures.

New insight into the formation of structural defects in poly(vinyl chloride)

The monomer conversion dependence of the formation of the various types of defect structures in radical suspension polymerization of vinyl chloride was examined via both H-1 and C-13 NMR spectrometry. The rate coefficients for model propagation and intra- and intermolecular hydrogen abstraction reactions were obtained via high-level ab initio molecular orbital calculations. An enormous increase in the formation of both branched and internal unsaturated structures was observed at conversions above 85%, and this is mirrored by a sudden decrease in stability of the resulting PVC polymer. Above this threshold-conversion, the monomer is depleted from the polymer-rich phase, and the propagation rate is thus substantially reduced, thereby allowing the chain-transfer processes to compete more effectively. In contrast to the other defects, the chloroallylic end groups were found to decrease at high conversions. On the basis of the theoretical and experimental data obtained in this study, this decrease was attributed to copolymerization and abstraction reactions that are expected to be favored at high monomer conversions. Finally, a surprising increase in the concentration of the methyl branches was reported. Although a definitive explanation for this behavior is yet to be obtained, the involvement of transfer reactions of an intra- or intermolecular nature seems likely, and (in the latter case) these could lead to the presence of tertiary chlorine in these defects

Impurity effects in superconducting UPt3

Superconducting UPt3 is characterized by a novel and complex magnetic field‐temperature phase diagram, with two superconducting transitions at Tc1 and Tc2 in zero field. We have studied the effects of Pd and Y impurities on the zero field superconducting properties of UPt3. Resistance measurements show that both dopants increase the residual resistivity and decrease the spin fluctuation temperature in the normal state. Tc1 is depressed by both dopants, but more effectively by Pd. ‖Tc1 − Tc2‖ is essentially unaffected by Y doping, but increases dramatically with Pd doping.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/70706/2/JAPIAU-69-8-5487-1.pd

Identifying the pairing symmetry in the Sr2RuO4 superconductor

We have analyzed heat capacity and thermal conductivity measurements of Sr2RuO4 in the normal and superconducting state and come to the conclusion that an order parameter with nodal lines on the Fermi surface is required to account for the observed low-temperature behavior. A gapped order parameter is inconsistent with the reported thermodynamic and transport data. Guided by a strongly peaked dynamical susceptibility along the diagonals of the Brillouin zone in neutron scattering data, we suggest a spin-fluctuation mechanism that would favor the pairing state with the gap maxima along the zone diagonals (such as for a d_{xy} gap). The most plausible candidates are an odd parity, spin-triplet, f-wave pairing state, or an even parity, spin-singlet, d-wave state. Based on our analysis of possible pairing functions we propose measurements of the ultrasound attenuation and thermal conductivity in the magnetic field to further constrain the list of possible pairing states.Comment: 7 pages, 5 figures; updated list of references and extended introduction; to appear in Phys. Rev. B (Oct. 2000

Superconductivity in heavy-fermion U(Pt,Pd)3 and its interplay with magnetism

The effect of Pd doping on the superconducting phase diagram of the unconventional superconductor UPt3 has been measured by (magneto)resistance, specific heat, thermal expansion and magnetostriction. Experiments on single- and polycrystalline U(Pt1-xPdx)3 for x<= 0.006 show that the superconducting transition temperatures of the A phase, Tc+, and of the B phase, Tc-, both decrease, while the splitting DTc increases at a rate of 0.30(2)K/at.%Pd. We find that DTc(x) correlates with an increase of the weak magnetic moment m(x) upon Pd doping. This provides further evidence for Ginzburg-Landau scenarios with magnetism as the symmetry breaking field, i.e. the 2D E representation and the 1D odd parity model. Only for small splittings DTc is proportional to m^2(Tc+) (DTc<= 0.05 K) as predicted. The results at larger splittings call for Ginzburg-Landau expansions beyond 4th order. The tetracritical point in the B-T plane persists till at least x= 0.002 for B perpendicular to c, while it is rapidly suppressed for B||c. Upon alloying the A and B phases gain stability at the expense of the C phase.Comment: 25 pages text (PS), 8 pages with 14 figures (PS), submitted to Phys.Rev.

Stacking faults in UPt3

Atomic resolution transmission electron microscopy and X-ray diffraction measurements have been combined to investigate the microstructure of superconducting UPt3. Regions of a second double hexagonal phase with a typical dimension of 25-30 A are found to occupy approximately 3% of the total sample volume.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/30799/1/0000453.pd

Suppression of Superconductivity in Single Crystals of UPt_3 by Pd Substitution

The suppression of superconductivity by substitution effects has been measured in high quality single crystals of U(Pt_{1-x} Pd_x)_3 with 0 <= x <= 0.002. While the superconducting transition temperature T_c varies linearly with residual resistivity r_0, consistent with pair-breaking by impurity potential scattering, the rate of suppression of T_c with r_0 is much larger for Pd substitution than for other impurity substitutions or by increased defect density. This effect is correlated with an increase in the inelastic scattering coefficient, and may be related to Pd-induced changes in the magnetic fluctuation spectrum.Comment: 12 page in manuscript, plus 4 figure