Adsorption and surface dynamics of short DNA and LNA oligonucleotides on single-crystal Au(1 1 1) electrode surfaces

We have studied the surface dynamics of a double-strand decanucleotide (HS-10AT^L) with 10 adenine-thymine base pairs linked to a Au(1 1 1)-electrode surface via a hexamethylene thiol linker. The study is based on a combination of voltammetry, interfacial capacitance data, electrochemical in situ scanning tunnelling microscopy, and X-ray photoelectron spectroscopy. The thymine bases of the oligonucleotide are connected to furanoses locked in a C3′-endo configuration called LNA (locked nucleic acid). Hybridization in solution is effected prior to linking to the Au(1 1 1)-surface. The melting point of the linker-free locked decanucleotide, 10AT^L is >63 °C. However, voltammetric reductive desorption of the adsorbed thiol-modified double-strand decanucleotide, HS-10AT^L, gives almost the same charge as single-strand HS-10A, 29 ± 3 and 27 ± 5 μC cm⁻², respectively. In situ STM after HS-10AT^L-immobilization also gives images showing highly ordered domains, virtually indistinguishable from those of immobilized HS-10A. X-ray photoelectron spectroscopy gives an N/P ration of 5.0 for HS-10AT^L in line with the expected value for single-strand HS-10A (5.0).All three sets of data suggest that HS-10AT^L hybridized in solution is significantly dissociated on binding to the Au(1 1 1)-electrode surface. This points to an adsorption mechanism in which a stable high density of Au-S bonds is achieved but at the expense of significant unzipping of the more voluminous duplex form.     

Deformation in lamellar and crystalline structures: in situ simultaneous small‐angle X‐ray scattering and wide‐angle X‐ray diffraction measurements on polyethylene terephthalate fibers

Changes in the lamellar and crystalline structures were followed as a function of applied stress to understand the influence of the interactions between the crystalline and amorphous domains on the fiber properties. We observed a reversible transformation from a structure giving a four‐point small‐angle pattern to a structure giving a two‐point pattern; these structures corresponded to the lamellae with oblique and normal lamellar surfaces, respectively. The characteristics of these two structures such as the stack diameter, stack height, and tilt angle were different and were determined by the processing conditions and did not change when the fiber was elastically deformed. The structure giving a two‐point pattern was probably the load‐carrying lamellar entity in these fibers. The diameter of the lamellar stacks, tilt angle of the lamellae, and the strain in the lamellar spacing appeared to have the most influence on properties such as tenacity and dimensional stability. The long‐spacing strain, which is about the same as the fiber strain, determined the modulus at low elongation as well as ultimate elongation. These indicate that the lamellar stacks have at least as much influence as the interfibrillar chains on fiber properties. Structural features that determine the performance in semicrystalline polymers were investigated by analyzing four generations of polyethylene terephthalate fibers. Some of the fiber properties correlate with changes in the crystalline domains such as the crystalline orientation, size, and unit cell dimensions. Fibers in which the crystalline strain was large because of their strong linkages to the amorphous chains, and better load transfer, had the highest modulus and lowest ultimate elongation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1538–1553, 2003     

Lamellar morphology of polyethylene: Electron microscopy of a melt-crystallized sharp fraction

The morphology of linear polyethylene of M_w/M_n 1.19 crystallized isothermally from the melt has been investigated. Electron microscopy (EM) of stained thin sections gave exceptionally well-defined images. There were no qualitative differences between Regime I and Regime II crystallization, but the lamellae grown at lower supercooling were thicker, larger, and had fewer spiral growths per unit area of fold surface. Small-angle x-ray scattering indicated a much sharper distribution of lamellar thicknesses than EM and Raman LAM did. This is evidence of the complementary nature of the techniques and not a contradiction. EM also revealed nonrepresentative features in detail. There were extremely thin lamellae formed on cooling, indicating molecular weight segregation even in this fractionated material, and there were extremely thick lamellae, attributed to isothermal thickening. As the representative lamellae are also supposed to have thickened isothermally, this raises the issue of when and how the lamellae which are the primary products of crystallization can be identified.     

Weakly parametric pseudodifferential operators and Atiyah-Patodi-Singer boundary problems

Oblatum 9-IX-1993 & 20-II-1995     

Effects of Additives on the Laser-Initiated Polymerization of 1,6-Hexanediol Diacrylate

Polymerization exotherms of 1,6-hexanediol diacrylate (HDDA) were generated by a pulsed laser source and recorded on a modified differential scanning calorimeter. Several aromatic carbonyl-based photoinitiators were compared with respect to maximum rate and extent of polymerization in the absence and presence of oxygen. α-Cleavage photoinitiators were more efficient than the hydrogen-abstracting benzophenone. The addition of an amine to a photocleavable initiator improved the polymerization of HDDA under an inert atmosphere, whereas triarylphosphines under similar conditions were effective in reducing the air inhibition. This synergistic effect depends on the type and structure of the additive and the photoinitiator.

The use of benzophenone in combination with an α-cleavage photoinitiator showed no significant effect upon polymerization, while extra thermal energy imposed upon the system slightly improved the polymerization.     

Reduction of the basic initial-boundary value problems for the Navier-Stokes equations to initial-boundary value problems for nonlinear parabolic systems of pseudodifferential equations

We consider initial-boundary value problems for systems of Navier-Stokes equations, prescribing on the boundary the velocities, the stresses or the normal component of the velocity and the tangential stresses. We show that they can be reduced to initial-boundary value problems for systems of the form v_t + Av + Kv=f, where A is a linear elliptic operator, containing a nonlocal term, while K is a nonlinear operator. For these problems we prove a local solvability theorem in the Sobolev-Slobodetskii spaces W ₂ ^{, /2} .Translated from Zapiski Nauchnykh Seminarov Leningradskogo Otdeleniya Matematicheskogo Instituta im. V. A. Steklova AN SSSR, Vol. 171, pp. 36–52, 1989.     

M ‐functions for closed extensions of adjoint pairs of operators with applications to elliptic boundary problems

In this paper, we combine results on extensions of operators with recent results on the relation between the M ‐function and the spectrum, to examine the spectral behaviour of boundary value problems. M ‐functions are defined for general closed extensions, and associated with realisations of elliptic operators. In particular, we consider both ODE and PDE examples where it is possible for the operator to possess spectral points that cannot be detected by the M ‐function (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)