ALBERT

Notes: Thin films of poly(p-phenylene biphenyltetracarboximide) (BPDA-PDA), prepared by thermal imidization of the precursor poly(amic acid) on substrates, have been investigated by optical waveguide, ultraviolet-visible (UV-VIS), infrared (IR), and dielectric spectroscopies. The polyimide films exhibit an extraordinarily large anisotropy in the refractive indices with the in-plane index n∥ = 1.806 and the out-of-plane index n⊥ = 1.589 at 1064 nm wavelength. No discernible effect of the film thickness on this optical anisotropy is found between films of ca. 2.1 and ca. 7.8 μm thickness. This large birefringence is attributed to the preferential orientation of the biphenyltetracarboximide moieties with their planes parallel to the film surface, coupled with the strong preference of BPDA-PDA chains to align along the film plane. The frequency dispersion of the in-plane refractive index n∥ is consistent with the results calculated by the Lorentz-Lorenz equation from the UV-visible spectrum exhibiting several absorption bands in the 170-500 nm region. The contribution from the IR absorption in the range 7000-400 cm,-1 computed by the Spitzer-Kleinmann dispersion relations from the measured spectra, adds ca. 0.046 to the in-plane refractive index n∥. Tilt-angle-dependent polarized IR results indicate nearly the same increase for the out-of-plane index n⊥. Application of the Maxwell relation then leads to the out-of-plane dielectric constant ε⊥ ≃ 2.7 at 1.2 × 1013 Hz, as compared with the measured value of ca. 3.0 at 106 Hz. Assuming this small difference to remain the same for the in-plane dielectric constants ε∥, we obtain a very large anisotropy in the dielectric properties of these polyimide films with the estimated in-plane dielectric constant ε∥ ≃ 3.4 at 1.2 × 1013 Hz, and ε∥ ≃ 3.7 at 106 Hz. © 1992 John Wiley & Sons, Inc.

Notes: We have studied the surface chemistry of two lots of Biomer™ (BSP067 and BSUAOOl), and widely used commercial poly(ether urethane) (PEU). Although transmission infrared adsorption studies revealed no differences in the bulk chemistry of the two lots, the surface chemistry, as seen by x-ray photoelectron spectroscopy (XPS) and static secondary ion mass spectrometry (SIMS), was different. Lot BSP067 showed softsegment enrichment at the surface, which is typical of PEU. Lot BSUAOOl showed no evidence of either hard- or soft-segment PEU components at the surface. The surface of this lot was completely covered with a nonextractable additive identified as poly(diisopropy1 amino ethyl methacrylate). Small amounts of a low-molecular-weight antioxidant were observed at the surface of both samples. Because the biological response to polymers is dependent on surface structure, these results are of considerable importance to biomaterials research.

Notes: Films of amorphous NbSi prepared by magnetron sputtering were found to have a higher concentration of silicon at the surface than in the bulk material. In this paper we report on measurements of both ultraviolet photoemission spectroscopy and Auger electron spectroscopy carried out on samples prepared in situ at the UK Synchrotron Radiation Source, Daresbury. Spectr taken immediately after sputter deposition show that the surface is rich in silicon, while following argon ion bombardment the bulk composition is slowly revealed with a much greater concentration of niobium. This is observed by a comparison of the relative heights of peaks in the Auger spectra and by resonance effects and the sharpening of the Fermi edge in the UP spectra. Of particular interest are changes around the metal-insulator transition that occur at approximately 11 at.% niobium.

Notes: HNBR rubbers, which are made by selective hydrogenation of the olefinic bonds of NBR rubbers, have been developed, because they show improved resistance towards heat and chemicals. In this study, two other properties are discussed that arise from the fact that HNBR rubbers are fairly alternating copolymers of unpolar butylene and polar acrylonitrile units: At intermediate compostions, HNBR rubbers form homogeneous blends with PVC, and near the symmetric composition they exhibit strain-induced crystallisation. The thermal transitions of the HNBR rubbers and their miscibility with PVC were analyzed, as well as the crystallisation and the stress-strain behaviour of a HNBR of symmetric composition.

Notes: Microwave radiation has been clearly shown to result in enhancement of the rate of reaction for an imidization reaction. Analysis of the kinetic parameters showed that the apparent activation energy for the reaction was reduced from 105 to 55 kJ/mol, under the conditions of this experiment. The mechanism which has been proposed to explain this enhancement is based on the concept of a nonuniform temperature on a molecular scale, rather than a true reduction in the activation energy. © 1992 John Wiley & Sons, Inc.

Notes: Selected grades of low density polyethylene (LDPE) and linear low density polyethylene (LLDPE) were melt-mixed and the physical, mechanical and rheological properties evaluated. The blends were found to combine the good mechanical properties of LLDPE and processing properties of LDPE. The effect of crosslinking the blends with dicumyl peroxide (1 phrParts per hundred rubber) was also investigated. The level of crosslinking increased with increase in LLDPE content. While the mechanical properties of the crosslinked blends were more uniform, the physical properties controlled by the crystallinity of the polymer, such as density, hardness and volume loss on abrasion, decreased on crosslinking.

Notes: The crystal structure of a synthetic analogue of valinomycin, cyclo [-(D-Val-L-Hyi-L-Val-D-Hyi)2-] (octa-meso-valinomycin) (I) (C40H68N4O12 · 1.5 · C4H8O2, Mr = 937.01 + 88.10), has been determined. Crystals grown from dioxane are monoclinic, space group P21/a, with cell parameters a = 21.487(8), b = 16.836(5), c = 16.089(4) Å, β = 111.70(4), and Z = 4. The atomic coordinates for nonhydrogen atoms were refined in the anisotropic thermal motion approximation. H atom positions were included in the structure factor calculations at their geometrically expected positions. Values of the standard and weighted R factors after refinement are 0.11 and 0.13, respectively. The conformation of the depsipeptide crystallized from dioxane is different from that crystallized from chloroform (II). The molecule adopts a rectangular shape with two type IV β-turns containing a hydrogen bond and possesses pseudorotational symmetry. The side chains are located on the molecular periphery. The orientation of the carbonyl groups of the molecule is not conducive for efficient metal-ion coordination and in the observed conformation cannot behave as an ionophore.In the crystal the molecules form infinite chains parallel to the c axis, and are stabilized by two intermolecular hydrogen bonds that are shorter and have better geometry than the intramolecular hydrogen bonds.A φ/Ψ plot for dodecadepsipeptides with a (DLLD)3 sequence has well-defined areas for Val and Hyi residues only in cases when the crystals have been grown from nonpolar or medium-polar solvents. The Φ/Ψ plot for octadepsipeptides crystallized from chloroform (II) shows this behavior also. There also is a correlation between the polarity of the solvent from which crystals of octa-meso-valinomycin or valinomycin analogues with a (DLLD) sequence of configuration have been grown and the number of the intramolecular hydrogen bonds that are formed. The more polar the solvent the fewer the number of intramolecular hydrogen bonds.Empirical energy calculations on octa-meso-valinomycin indicate that for isolated molecules, the energy of the bracelet form (II) is 4.7 kcal/mole lower than that of the rectangular form (I).

Notes: We suggest, using dynamical simulations of a simple heteropolymer modelling the α-carbon sequence in a protein, that genetically the folded states of globular proteins correspond to statistically well-defined metastable states. This hypothesis, called the metastability hypothesis, states that there are several free energy minima separated by barriers of various heights such that the folded conformations of a polypeptide chain in each of the minima have similar structural characteristics but have different energies from one another. The calculated structural characteristics, such as bond angle and dihedral angle distribution functions, are assumed to arise from only those configurations belonging to a given minimum. The validity of this hypothesis is illustrated by simulations of a continuum model of a heteropolymer whose low temperature state is a well-defined β-barrel structure. The simulations were done using a molecular dynamics algorithm (referred to as the “noisy” molecular dynamics method) containing both friction and noise terms. It is shown that for this model there are several distinct metastable minima in which the structural features are similar.Several new methods of analyzing fluctuations in structures belonging to two distinct minima are introduced. The most notable one is a dynamic measure of compactness that can in principle provide the time required for maximal compactness to be achieved. The analysis shows that for a given metastable state in which the protein has a well-defined folded structure the transition to a state of higher compactness occurs very slowly, lending credence to the notion that the system encounters a late barrier in the process of folding to the most compact structure. The examination of the fluctuations in the structures near the unfolding → folding transition temperature indicates that the transition state for the unfolding to folding process occurs closer to the folded state.

Notes: The effect of side-chain cyclization on accessible backbone conformations of tripeptides, X-Ala-Y (X and/or Y = Cys, Hey (Hcy: homocysteine), cis 4-mercaptoproline (MPc), and trans 4-mercaptoproline (MPt)), was elucidated using two variants of systematic conformational search. In addition to cyclization through a disulfide bond, the thioether (-S-CH2-) and amide (-CO-NH-) side-chain analogues of Cys-Ala-Cys and Hcy-Ala-Hcy were evaluated. The number of valid backbone conformations and the allowed φ Ψ;space were evaluated for each compound, and the ability of the cyclic tripeptides to accommodate β-turn conformations was examined in order to assess the value of cyclization in limiting conformational freedom. Based on the number of conformations, cyclization was highly effective in reducing the backbone degree of freedom: in order of decreasing number of conformations, Ala-Ala-Ala 1 ≫ Hcy-Ala-Hcy 2 ≫ Cys-Ala-Hcy 3≅ Hcy-Ala-Cys 4 ≫ MPc-Ala-Hcy 5, 7 〉 Cys-Ala-Cys 6 〉 MPc-Ala-Cys 8 〉 Hcy-Ala-MI't 9 〉 Cys-Ala-MPt 10 ≅ MPc-Ala-MPt 11. Although Hcy-Ala-Hcy 2 had the greatest number of conformations of the cyclic peptides studied, it was still greatly constrained relative to its linear analogue 1. The bicyclic ring system introduced by MP was even more effective in constraining the cycle, having greater impact at position 3 than at position 1. Under the conditions of the study, cyclization of MP-containing analogues could be effected only with the cis isomer (MPc) at position 1 and/or the trans isomer (MPt) at position3. Sterically allowed conformations of Ala2 for the cyclic tripeptides 2-4 were generally similar to those of the linear tripeptide 1, while those of Cys-Ala-Cys 6 and MPc-Ala-Hey 7 were restricted to a smaller region of φ2, Ψ2 space: the right- and left-handed α-helical conformation and the β-conformation. This trend was even more pronounced for Hcy-Ala-MPt 9, Cys-Ala-MPt 10, and MPc-Ala-MPt 11, in which Ala2 was severely restricted to a very small region of φ, Ψ space: the left-handed α-helical conformation for 9-11, plus the β-conformation for 9. This suggests that MP at the 3-position is incompatible with a right-handed α-helical conformation at position 2. A similar analysis of the thioether-bridged analogs of 2 and 6 revealed their number of conformers and accessible φ, Ψ regions to be slightly smaller than those of the parent disulfide-bridged compounds. By the same measures, amide-bridged derivatives based on 2 and 6 were even more restricted. N-membered cyclic peptides having an amide (CH2-CO-NH-CH2) bridge yielded results similar to that of the corresponding (n - 1)-membered cyclic peptide having a disulfide bridge.N-acetyl-cyclotripeptides and cyclotripeptide-N-methylamides were used as a model of the four consecutive residues of β-turns to determine if β-turns. could be accommodated. Positions i + 1 and i + 2 of β-turns were aligned with residues 1 and 2 of the N-acetyl-cyclotripeptides (form A), and with residues 2 and 3 of the cyclotripeptide-N-methylamides (form B). Cyclic tripeptides having MP at residue 3 could not accommodate any type of β-turn, while MP at residue 1 ruled out a form B III' β-turn. Peptides not containing MP could accommodate a form A III' β-turn as well as form B I and III β-turns. The thioether-and amide-bridged peptides yielded results similar to the disulfide-bridged peptides on which they were based, although the amide analogue of Cys-Ala-Cys 16 was consistent with only form A β III' and form B βIII turns. None of the cyclic tripeptides examined could accommodate a form A βI turn. Cyclizations were effective in increasing the probability of inducing the backbone of these peptides to adopt β-turns.These results were used, as an example, in the analysis of structure-activity data of cyclically constrained analogues of angiotensin II. A receptor-bound conformation in which Tyr4 assumes the backbone conformation associated with a left-handed a-helix is consistent with the data in the literature. © 1992 John Wiley & Sons, Inc.

Notes: Folded chain single crystals 35 Å thick have been grown from the liquid crystal state of an aromatic-aliphatic azomethine ether polymer (AZMEP-n) having a 10-carbon flexible segment (n = 10). Electron diffraction has permitted refinement of the triclinic unit cell. The molecular axes lie at an ca. 65° angle to the lamella normal and fold every third chemical repeat distance. For AZMEP-1 and -8 extended chain lamellae are formed; for AZMEP-7 both folded and extended chain lamellae are found. The observations of folded chain lamallae are in agreement with prior suggestions from our laboratory of chain folding in the liquid crystalline state in thin films. © 1992 John Wiley & Sons, Inc.