Self-bonding in an amorphous polymer below the glass transition: A T-peel test investigation

Films of amorphous polystyrene (PS) with a weight-average molecular weight (M_w) of 225 × 10³ g/mol were bonded in a T-peel test geometry, and the fracture energy (G) of a PS/PS interface was measured at the ambient temperature as a function of the healing time (t_h) and healing temperature (T_h). G was found to develop with (t_h)^1/2 at T_h = T_g-bulk − 33 °C (where T_g-bulk is the glass-transition temperature of the bulk sample), and log G was found to develop with 1/T_h at T_g-bulk − 43 °C ≤ T_h ≤ T_g-bulk − 23 °C. The smallest measured value of G = 1.4 J/m² was at least one order of magnitude larger than the work of adhesion required to reversibly separate the PS surfaces. These three observations indicated that the development of G at the PS/PS interface in the temperature range investigated (<T_g-bulk) was controlled by the diffusion of chain segments feasible above the glass-transition temperature of the interfacial layer, in agreement with our previous findings for fracture stress development at several polymer/polymer interfaces well below T_g-bulk. Close values of G = 8–9 J/m² were measured for the symmetric interfaces of polydisperse PS [M_w = 225 × 10³, weight-average molecular weight/number-average molecular weight (M_w/M_n) = 3] and monodisperse PS (M_w = 200 × 10³, M_w/M_n = 1.04) after healing at T_h = T_g-bulk − 33 °C for 24 h. This implies that the self-bonding of high-molecular-weight PS at such relatively low temperatures is not governed by polydispersity. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1861–1867, 2004     

Extending the possibility of an N-Troc-protected sialic acid donor toward variant sialo-glycoside synthesis

The potential of an N-Troc-protected sialic acid donor, equipped with phenylsulfenyl functionality as a leaving group, has been explored. As a result, the entitled donor was proven to be highly reactive and to have broad applicability toward the synthesis of variant sialo-glycans, which have N-glycolyl, de-N-acetyl, 1,5-lactam and 8-O-sulfo sialic acid analogs.     

Assignment of conformation-sensitive near-infrared bands in high-spin ferrous haemoproteins. Low-temperature magnetic circular dichroism data

An assignment of the near-infrared bands in the 600–800 nm spectral region observed in magnetic circular dichroism (MCD) spectra of high-spin ferrous haemoproteins is presented. The assignment is based on a relative energy level scheme for iron d-electrons, a comparison of predicted and measured temperature dependences of MCD intensity, a sign of MCD bands and a group theoretical analysis of allowed transitions. The proposed assignment is consistent with the ∼15-nm red shift of the ∼760 nm band on breakage of the Fe-His bond in deoxy-myoglobin at low pH, with low-temperature photolysis experiments available for CO complexes of several haemoproteins. In accordance with the observations, the intensity of the MCD bands for proteins with a sulphur anion of cysteine as proximal haemligand (cytochrome P450 and chloroperoxidase) is predicted to be diminished by at least one order of magnitude compared to that for proteins with an imidazole of a histidine as a protein-derived haemligand (i.e. myoglobin, haemoglobin and horseradish peroxidase). Received: 4 February 1997 / Accepted: 1 May 1997     

Spatial Vector Solitons in Nonlinear Photonic Crystal Fibers

We study spatial vector solitons in a photonic crystal fiber (PCF) made of a material with the focusing Kerr nonlinearity. We show that such two-component localized nonlinear waves consist of two mutually trapped components confined by the PCF linear and the self-induced nonlinear refractive indices, and they bifurcate from the corresponding scalar solitons. We demonstrate that, in a sharp contrast with an entirely homogeneous nonlinear Kerr medium where both scalar and vector spatial solitons are unstable and may collapse, the periodic structure of PCF can stabilize the otherwise unstable two-dimensional spatial optical solitons. We apply the matrix criterion for stability of these two-parameter solitons, and verify it by direct numerical simulations.     

Optical properties of polarization-dependent geometric phase elements with partially polarized light

The behavior of geometric phase elements illuminated with partially polarized monochromatic beams is investigated both theoretically and experimentally. The element discussed in this paper is composed of wave plates with π-retardation and a space-variant orientation angle. We found that a beam emerging from such an element comprises two polarization orders; right-and left-handed circularly polarized states with conjugate geometric phase modification. This phase equals twice the orientation angle of the space-variant wave plate comprising the element. Apart from the two polarization orders, the emerging beam coherence polarization matrix includes a “vectorial interference matrix” which contains information concerning the correlation between the two orthogonal, circularly polarized portions of the incident beam. In this paper we measure this correlation by a simple interference experiment. In addition, we found that the equivalent mutual intensity of the emerging beam is modulated according to the geometric phase induced by the element. Other interesting phenomena concerning propagation will be discussed theoretically and demonstrated experimentally. The experiment made use of a spherical geometric phase element that was realized by use of a space-variant subwavelength grating illuminated with CO₂ laser radiation of 10.6 μm wavelength.     

Loss in a rectangular optical waveguide induced by the crossover of a second waveguide

We calculate the loss induced in a single-mode rectangular optical waveguide by the presence of a second waveguide, perpendicular to the first, which crosses over the first waveguide at a variable distance d. Our calculation is applied to the analysis of several doped silica waveguides of practical importance for optical circuit design.     

Symmetries of flat rank two distributions and sub-Riemannian structures

Flat sub-Riemannian structures are local approximations -- nilpotentizations -- of sub-Riemannian structures at regular points. Lie algebras of symmetries of flat maximal growth distributions and sub-Riemannian structures of rank two are computed in dimensions 3, 4, and 5.

     

Quantum Stabilization and Decay of Correlations in Anharmonic Crystals

Letters in Mathematical Physics -