Rheological studies of the gelation of aqueous solutions of acrylamide-acrylic acid copolymers in the presence of chromium chloride

The gelation kinetics of aqueous solutions of acrylamideacrylic acid copolymers in the presence of chromium ions was studied with different rheometers. The gel time is found to vary with the principle of the apparatus because of a low shear dependence of the elongation of the macromolecules. The variations of the gel time with the experimental conditions of the gel preparation were investigated and we conclude that the gelation is governed by the oligornerization kinetics of the chromium ions which are instantaneously, complexated by the carboxylate groups of the polymer. The variation laws of the gel time and of the elastic modulus with chromium and polymer concentrations, temperature and ionic strength are in qualitative agreement with the structure of the temporary network of the semi-dilute solutions of these copolymers.     

From hetero- to homochiral bis(metallahelicene)s based on a Pt(III)-Pt(III) bonded scaffold: isomerization, structure, and chiroptical properties

Hetero- and homochiral diastereomeric bis(metallahelicene)s have been synthesized. They possess a rare Pt(III)-Pt(III) scaffold bridged by benzoato ligands. It is shown that heterochiral (P,M)-bis(Pt(III)-[6]helicene) can isomerize into the homochiral (P,P)- and (M,M)-bis(Pt(III)-[6]helicene). A theoretical study shows a unique σ-π conjugation between the two π-helices and the σ-Pt(III)-Pt(III) scaffold that impacts the strong chiroptical properties.     

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A matrix problem associated with computing Cohen-Macaulay type

Suppose A∈M_n×m(F), B∈M_n×t(F) for some field F. Define Г(AB) to be the set of n×n diagonal matrices D such that the column space of DA is contained in the column space of B. In this paper we determine dim Г(AB). For matrices AB of the same rank we provide an algorithm for computing dim Г(AB).     

Double-exchange contributions to the first-order interaction energy between closed-shell molecules

Explicit formulas are presented for the double-exchange first-order interaction energy of two closed-shell molecules. Calculations on He₂ show that the double-exchange terms contribute significantly for R < 3.5 au.     

Chlorofluoroiodomethane as a potential candidate for parity violation measurements

CHFClI is among the more favorable molecules for parity violation (PV) measurements in molecules. Despite the fact that calculated PV effects are two orders of magnitude smaller than in some organometallic compounds, CHFClI displays interesting features which could make possible a new experimental PV test on this molecule. Indeed, ultrahigh resolution spectroscopy using an ultrastable CO(2) laser is favored by several intrinsic properties of this molecule. For example, the high vapor pressure of CHFClI allows investigation by supersonic beam spectroscopy. Indeed, the spectroscopic constants have been accurately determined by microwave and millimetre wave spectroscopy. This is important for the subsequent selection of an appropriate absorption band of CHFClI that could be brought to co?ncide with the absorption of CO(2). Partially resolved (+)- and (-)-CHFClI enantiomers with respectively 63.3 and 20.5% ee's have been recently prepared and analyzed by molecular recognition using chiral hosts called cryptophanes. Finally, the S-(+)/R-(-) absolute configuration was ascertained by vibrational circular dichro?sm (VCD) in the gas phase.     

Parameter estimation using balanced synchronization

Synchronization between experimental observations and a dynamical model with undetermined parameters can assist in completing the specification of the model parameters. The quality of the synchronization, a cost function to be minimized, typically depends on the difference between the data time series and the model time series. If the coupling between the data and the model is too strong, this cost function is small for any data and any model, and the variation of the cost function with respect to the parameters of interest is too small to permit selection of a value of the parameters. If the coupling is too small, synchronization is lost. We introduce two methods for balancing the competing desires of a small cost function and the numerical ability to determine parameters accurately. One method of ‘balanced’ synchronization adds a requirement that the conditional Lyapunov exponent of the model system, conditioned on being driven by the data, remain negative but small. The other method allows the coupling to vary in time according to the error in synchronization. This second method succeeds because the data and the model exhibit generalized synchronization in the region where the parameters of the model are well determined.