Hyphenation of aqueous liquid chromatography to pyrolysis-gas chromatography and mass spectrometry for the comprehensive characterization of water-soluble polymers

A recently developed hyphenated system for "organic" size-exclusion chromatography-pyrolysis-gas chromatography-mass spectrometry (SEC-Py-GC-MS) is adapted to allow the use of aqueous LC eluents as applied in the characterization of water-soluble polymers. The system uses syringe-based transfer of multiple LC-fractions to the GC instrument with solvent elimination and subsequent pyrolysis in a programmed temperature vaporization injector. The problems of the large-volume injections of aqueous, salt containing eluents into the Py-GC-MS are solved by using a 'sintered-bed liner' for elimination of the water at a high temperature, a volatile salt and the installation of a back-flush option. After optimization, the system was applied for the determination of the combined molecular weight-chemical composition of a polyethylene glycol-polypropylene glycol block copolymer. This analysis was done with the system in the aqueous SEC-Py-GC-MS mode. Also demonstrated is the automated at-line characterization of a random polystyrene-polymethylmethacrylate copolymer, now with the system in the gradient reversed-phase LC-Py-GC-MS mode. The methods proposed in the present work are very useful for the detailed characterization of water-soluble copolymers.     

Neutron scattering study of the excitation spectrum of solid helium at ultra-low temperatures

There has been a resurgence of interest in the properties of solid helium due to the recent discovery of non-classical rotational inertia (NCRI) in solid ⁴He by Chan and coworkers below 200 mK which they have interpreted as a transition to a ‘supersolid’ phase. We have carried out a series of elastic and inelastic neutron scattering measurements on single crystals of hcp ⁴He at temperatures down to 60 mK. While we have found no direct evidence of any change in the excitation spectrum at low temperatures, we have found that the excitation spectrum of solid ⁴He shows several interesting features, including extra branches in addition to the phonon branches. We interpret these extra branches as single particle excitations due to propagating vacancy waves, which map on to the famous ‘roton minimum’ long known in the excitation spectrum of superfluid liquid ⁴He. The results show that in fact solid ⁴He shares several features in common with the superfluid.      

Microtubule dynamics depart from the wormlike chain model

Thermal shape fluctuations of grafted microtubules were studied using high resolution particle tracking of attached fluorescent beads. First mode relaxation times were extracted from the mean square displacement in the transverse coordinate. For microtubules shorter than approximately 10 microm, the relaxation times were found to follow an L2 dependence instead of L4 as expected from the standard wormlike chain model. This length dependence is shown to result from a complex length dependence of the bending stiffness which can be understood as a result of the molecular architecture of microtubules. For microtubules shorter than approximately 5 microm, high drag coefficients indicate contributions from internal friction to the fluctuation dynamics.     

Weighted Distances in Scale-Free Configuration Models

Journal of Statistical Physics - In this paper we study first-passage percolation in the configuration model with empirical degree distribution that follows a power-law with exponent $$\tau \in...     

How to find all roots of complex polynomials by Newton’s method

We investigate Newton’s method to find roots of polynomials of fixed degree d, appropriately normalized: we construct a finite set of points such that, for every root of every such polynomial, at least one of these points will converge to this root under Newton’s map. The cardinality of such a set can be as small as 1.11 d log² d; if all the roots of the polynomial are real, it can be 1.30 d. Oblatum 24-II-2000 & 14-II-2001?Published online: 20 July 2001     

Cyclic martensitic phase transformation of monocrystals at finite strains

Based on Bain's principle, a C¹-continuous thermo-mechanical micro-macro constitutive model for martensitic phase transformation (PT) of monocrystals at finite strains and hyperelastic free energy function is used. It is represented by a unified non-convex Lagrangian variational functional. The convexification problem is solved here by generalizing the explicit form of the lower Reuss bound for small strains given in [1] to finite strains. Abaqus is used for implementation of 3D finite elements in space, via UMAT-interface which requires Jaumann rate of Kirchhoff stress tensor. Deterministic validation of the model is presented by comparing verified numerical results with experimental data for Cu₈₂Al₁₄Ni₄ [6] for quasiplastic PT. (© 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

UVA and UVB Radiation Differentially Regulate Vascular Endothelial Growth Factor Expression in Keratinocyte-derived Cell Lines and in Human Keratinocytes

Vascular endothelial growth factor (VEGF) is a central regulator of neoangiogenesis in inflammatory and neoplastic conditions. Ultraviolet irradiation is one of the mainstays of dermatological therapy for various inflammatory skin diseases. In the present study we have compared the effects of UV irradiation on the production of VEGF by keratinocytes (KC) and by the KC-derived cell lines A431 and HaCaT. Irradiation of A431 and HaCaT cells with both UVA (10 J/cm2 and 20 J/cm2) and UVB (8 mJ/cm2 and 16 mJ/cm2) led to strong upregulation of VEGF mRNA and protein. Induction of VEGF by UVA and UVB in these cells was mediated by different pathways, i.e. the generation of free radicals and the secretion of (a) soluble factor(s), respectively. Unlike KC-derived cell lines, no increase in VEGF production was observed in KC in primary culture after irradiation with the same UV doses. Increasing the irradiation dose in these cells of UVA to 40 J/cm2 led to a marked decrease in soluble VEGF, whereas doses as high as 32 mJ/cm2 UVB only minimally affected VEGF levels. Reduction of VEGF production by KC might contribute to the effect of UVA irradiation in inflammatory skin diseases. The differential response of primary KC and autonomously growing KC-derived cell lines to the induction of VEGF by UV light could favor neoangiogenesis in the vicinity of epidermal tumor cells in vivo, thereby endowing them with a growth advantage over normal cells.     

Recurrence and Transience of Random Walks¶in Random Environments on a Strip

We explain the necessary and sufficient conditions for recurrent and transient behavior of a random walk in a stationary ergodic random environment on a strip in terms of properties of a top Lyapunov exponent. This Lyapunov exponent is defined for a product of a stationary sequence of positive matrices. In the one-dimensional case this approach allows us to treat wider classes of random walks than before. Received: 15 March 2000 / Accepted: 14 April 2000     

Common Frontiers of the Exact Sciences and the Humanities

The physicist Franz Serafin Exner (1849-1926) was a prominent Austrian spokesman for the new developments that were coupled with turn-of-the-century experiments and theories related to entropy thermodynamics, the internally structured atom, quantum theory, and relativity. The Exner circle found its inspiration in the intellectual world of Ludwig Boltzmann and his teachers, colleagues, and students. Cross-discipline discussions on common and divergent frontiers of the exact sciences and the humanities meaningfully converged on the significance, comparison, and transfer of concepts such as the laws of nature, causality, probability, and chance. Oswald Spengler's Decline of the West, with its pessimistic, subjectivistic, and negative science-directed messages provided Exner with the opportunity to sharpen his support for the new scientific trends in physics - thus to champion the search for objective truth.