Distinguishing Linear from Star‐Branched Polystyrene Solutions with Fourier‐Transform Rheology

Summary: Fourier‐Transform rheology (FT rheology) was used to study the influence of the degree of branching on the nonlinear relaxation behaviour of polystyrene solutions. The results were compared with those obtained under oscillatory shear and step‐shear conditions. The different topologies could be distinguished using FT rheology where the other rheological measurements failed. Significant differences occurred under large amplitude oscillatory shear (LAOS) conditions as particularly reflected in the phase difference of the third harmonic, Φ₃, which could be related to strain‐softening and strain‐hardening behaviour. Currently, this work is extended towards different topologies in polyolefins (e.g. long chain branched).

Phase difference Φ₃ as a function of the Deborah number De at γ₀ = 2 for the polystyrene solutions measured at temperatures from 295 to 350.5 K.     

Block copolymers with Zwitterionic groups at specific sites: Synthesis and aggregation behavior in dilute solutions

Well‐defined linear diblock and triblock copolymers of styrene and isoprene, nearly symmetric in composition, with one or two sulfobetaine associogenic groups at the ends of the polymer chain or the junction points between blocks, were synthesized by anionic polymerization high‐vacuum techniques. The synthetic strategy used the combined initiation of polymerization with 3‐dimethylaminopropyllithium, living end‐capping with 1‐(4‐dimethylaminophenyl)‐1‐phenylethylene, and postpolymerization reaction with cyclopropanesultone. The association behavior of these macromolecules in dilute solutions in the nonpolar solvent CCl₄, good for both blocks, was studied by a number of methods, including static and dynamic light scattering and viscometry. The number and position of the associogenic groups dramatically influenced the association behavior of these model block copolymers. The end‐functionalized samples formed larger aggregates than the junction‐point‐functionalized ones. The difference was attributed to stronger excluded volume effects when the zwitterion group was located within the chain than when the group was at the chain end(s). © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3791–3801, 2000     

A kinetic study of the formation of polystyrene stars using 1,2-bis(trichlorosilyl)ethane

The kinetics of formation of a chlorosilane-linked polystyrene six-arm star is reported. The precursor arm material (M_n = 88,000) was made using anionic polymerization in benzene. Prior to addition to the 1,2-bis(trichlorosilyl) ethane linking agent, the anions were endcapped with about five units of isoprene. Size exclusion chromatography using multiangle laser light scattering and viscosity detectors was utilized for characterization. This technique has allowed the molecular weights, radii of gyration, and intrinsic viscosities to be measured for star components in aliquots taken from the reactor at various times. It was found that four-arm star is formed within 30 min after the addition of the chlorosilane linking agent. There is a linear relationship between the logarithm of molecular weight of the star samples and logarithm of time of the reaction after the formation of the four-arm star. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 587–594, 1997     

Bergman polynomials on an archipelago: Estimates, zeros and shape reconstruction

Growth estimates of complex orthogonal polynomials with respect to the area measure supported by a disjoint union of planar Jordan domains (called, in short, an archipelago) are obtained by a combination of methods of potential theory and rational approximation theory. The study of the asymptotic behavior of the roots of these polynomials reveals a surprisingly rich geometry, which reflects three characteristics: the relative position of an island in the archipelago, the analytic continuation picture of the Schwarz function of every individual boundary and the singular points of the exterior Green function. By way of explicit example, fine asymptotics are obtained for the lemniscate archipelago |z^m−1|<r^m, 0<r<1, which consists of m islands. The asymptotic analysis of the Christoffel functions associated to the same orthogonal polynomials leads to a very accurate reconstruction algorithm of the shape of the archipelago, knowing only finitely many of its power moments. This work naturally complements a 1969 study by H. Widom of Szegő orthogonal polynomials on an archipelago and the more recent asymptotic analysis of Bergman orthogonal polynomials unveiled by the last two authors and their collaborators.     

A Hardy field extension of Szemerédi's theorem

In 1975 Szemerédi proved that a set of integers of positive upper density contains arbitrarily long arithmetic progressions. Bergelson and Leibman showed in 1996 that the common difference of the arithmetic progression can be a square, a cube, or more generally of the form p(n) where p(n) is any integer polynomial with zero constant term. We produce a variety of new results of this type related to sequences that are not polynomial. We show that the common difference of the progression in Szemerédi's theorem can be of the form [nδ] where δ is any positive real number and [x] denotes the integer part of x. More generally, the common difference can be of the form [a(n)] where a(x) is any function that is a member of a Hardy field and satisfies a(x)/xk→∞ and a(x)/xk+1→0 for some non-negative integer k. The proof combines a new structural result for Hardy sequences, techniques from ergodic theory, and some recent equidistribution results of sequences on nilmanifolds.     

An argument-based approach to reasoning with clinical knowledge

Better use of biomedical knowledge is an increasingly pressing concern for tackling challenging diseases and for generally improving the quality of healthcare. The quantity of biomedical knowledge is enormous and it is rapidly increasing. Furthermore, in many areas it is incomplete and inconsistent. The development of techniques for representing and reasoning with biomedical knowledge is therefore a timely and potentially valuable goal. In this paper, we focus on an important and common type of biomedical knowledge that has been obtained from clinical trials and studies. We aim for (1) a simple language for representing the results of clinical trials and studies; (2) transparent reasoning with that knowledge that is intuitive and understandable to users; and (3) simple computation mechanisms with this knowledge in order to facilitate the development of viable implementations. Our approach is to propose a logical language that is tailored to the needs of representing and reasoning with the results of clinical trials and studies. Using this logical language, we generate arguments and counterarguments for the relative merits of treatments. In this way, the incompleteness and inconsistency in the knowledge is analysed via argumentation. In addition to motivating and formalising the logical and argumentation aspects of the framework, we provide algorithms and computational complexity results.     

The interaction of diphosphonates with calcitic surfaces: understanding the inhibition activity in marble dissolution

The rates of dissolution of calcitic Carrara marble have been reported to be significantly reduced in alkaline pH (pH 8.25) at 25 degrees C in the presence of (1-hydroxyethylidene)-1,1 diphosphonic acid (HEDP). The adsorption takes place at the calcite/water interface at the double layer through the interaction of charged surface species with the charged solution species of the adsorbate. The present work focused on obtaining a better understanding of the interaction of the calcite surface with HEDP. Calculations were performed according to the triple layer model, assuming the formation of surface complexes between the charged surface species of calcite and the species of HEDP dominant at pH 8.25. According to the model, the adsorbed species are located at the inner Helmholtz plane of the electrical double layer. Strong lateral interactions between the adsorbed species were suggested and were corroborated from the calculation of the respective energy, which was equal to 69 kJ mol(-1). The adsorption isotherm was consistent with the proposed model at low surface coverage values, while discrepancies between the values experimentally measured and the predicted were found at higher adsorbate concentrations. The deviations from the predicted values were attributed to the fact that HEDP adsorption on calcite resulted in the formation of multiple layers. The model explained adequately the changes in the zeta-potential values of calcite in the presence of HEDP in the solution which resulted in charge reversal upon adsorption.     

Simultaneous EEG and fMRI in the macaque monkey at 4.7 Tesla

Simultaneous electroencephalography (EEG)/functional magnetic resonance imaging (fMRI) acquisition can identify the brain networks involved in generating specific EEG patterns. Yet, the combination of these methodologies is hampered by strong artifacts that arise due to electromagnetic interference during magnetic resonance (MR) image acquisition. Here, we report corrections of the gradient-induced artifact in phantom measurements and in experiments with an awake behaving macaque monkey during fMRI acquisition at a magnetic field strength of 4.7 T. Ninety-one percent of the amplitude of a 10 microV, 10 Hz phantom signal could successfully be recovered without phase distortions. Using this method, we were able to extract the monkey EEG from scalp recordings obtained during MR image acquisition. Visual evoked potentials could also be reliably identified. In conclusion, simultaneous EEG/fMRI acquisition is feasible in the macaque monkey preparation at 4.7 T and holds promise for investigating the neural processes that give rise to particular EEG patterns.