Macromolecular prodrugs. V. Simultaneous determination of high-molecular-weight dextran metronidazole monosuccinate ester prodrugs and the hydrolysis products metronidazole and the corresponding monosuccinate ester on nucleosil diol

A high-performance size-exclusion chromatography procedure using Nucleosil Diol has been developed which provides the simultaneous determination of macromolecular dextran metronidazole monosuccinate ester prodrugs and the hydrolysis products metronidazole and metronidazole monosuccinate. Various factors influencing the chromatographic behaviour of the compounds are discussed. Baseline separation of the three substances was achieved within 8 min by using a 0.05 M phosphate buffer pH 7.5 eluent at a flow-rate of 2 ml min-1. The detection limit at 320 nm for a conjugate with a degree of substitution of 4.61 was found to be 3.5 micrograms ml-1.     

The structure of self-assembled multilayers with polyoxometalate nanoclusters

Using electrostatic layer-by-layer self-assembly (ELSA), the formation of multilayers with polyelectrolytes and nanoscopic polyoxometalate (POM) clusters of different sizes and charges is investigated. The multilayers are characterized by UV-vis absorption spectroscopy, optical ellipsometry, cyclic voltammetry, and atomic force microscopy. In all cases, it is possible to find experimental conditions to achieve irreversible adsorption and regular multilayer deposition. Most importantly, the surface coverage is directly related to the total charge of the POM anion and can be controlled from submonolayer to multilayer coverage by adjusting the ionic strength of the dipping solutions. Imaging the interfaces after POM deposition by atomic force microscopy reveals a granular surface texture with nanometer-sized features. The average interfacial roughness amounts to approximately 1 nm. Cyclic voltammetry indicates that the electrochemical properties of the POM clusters are fully maintained in the polyelectrolyte matrix, which opens a route toward practical applications such as sensors or heterogeneous catalysts. Moreover, the permeability toward electrochemically active probe molecules can be tailored through the multilayer architecture and deposition conditions. Finally, we note that despite the low total charge and comparably small size of the discrete POM anions, the multilayers are remarkably stable. This work provides basic guidelines for the assembly of POM-containing ELSA multilayers and provides detailed insight into characteristic surface coverage, permeability, and electrochemical properties.     

On the theory of the weighing method for automatic crystal shape control in czochralski growth

We derive the exact analytical expression for the meniscus volume in terms of the crystal radius R, the melt contact angle θ_L, and the meniscus height h for the axisymmetric planar growth interface Czochralski configuration. This relation is applied together with motion and mass balance considerations to find the general rate of change in the force experience by the weighing cell in a standard diameter control arrangement. In contrast to the classical work of Bardsley et al. (1977), which is limited to the close viscinity of stationary right cylinder growth, our results are valid for growth developing any crystal profile. In addition, they also account for the fall of melt level due to finite crucible size. The magnitudes of the capillary contributions to the force, and their implications for diameter servo control, are discussed over a wide range of profile parameters using the Tsivinskii formula for h = h (R, θ_L).     

Corrective measures in turbulent pipe flows and extended self-similarity

Significant statistical bias in LDA measurements and how to adequately deal with it is a subtle problem when dealing with turbulent flows. In order to attempt a clarification we have performed measurements on a non-standard “grid experiment” where a clear bias effect is found. We have investigated the effect of several corrective measures and find that best results, in the sense of having the first moment converge to zero, are obtained when using the time between events as statistical weights. The corrected time series have been used to check for extended self-similarity (ESS). Even though no scaling regime is seen for the third moment and the flow certainly is neither isotropic nor homogeneous, perfect ESS scaling based on the absolute third moment is observed up to the twelfth moment, extending into a time domain regime where the Taylor hypothesis of frozen turbulence is obviously violated. Reversing the argument this indicates that the correction scheme needed can be experimentally decided on using the criterion stated above and especially so if ESS is to be expected. Finally we have used the corrected data to quantify the deviations from Gaussian behavior of the velocity difference probability density function for a weakly turbulent flow. Through comparison with results on the Gaussian-Lorentzian distribution we find that the even part of the experimental distribution can be reproduced quite well by a single-parameter family of distributions with second moment equal unity. Received 5 August 1998 and Received in final form 21 December 1998     

Invariant manifolds, global attractors, almost automorphic and almost periodic solutions of non-autonomous differential equations

The paper is devoted to the study of non-autonomous evolution equations: invariant manifolds, compact global attractors, almost periodic and almost automorphic solutions. We study this problem in the framework of general non-autonomous (cocycle) dynamical systems. First, we prove that under some conditions such systems admit an invariant continuous section (an invariant manifold). Then, we obtain the conditions for the existence of a compact global attractor and characterize its structure. Third, we derive a criterion for the existence of almost periodic and almost automorphic solutions of different classes of non-autonomous differential equations (both ODEs (in finite and infinite spaces) and PDEs).     

Model cellulose films exposed to H. insolens glucoside hydrolase family 45 endo-cellulase--the effect of the carbohydrate-binding module

The effects of enzyme structure and activity on the degradation of model cellulose substrates were investigated by ellipsometry for the cellulase Humicola insolens GH45. The inactive variant D10N was found to adsorb at the cellulose surface but also to be incorporated into the cellulose films to an extent that depended on pH. For the native protein, the initial adsorption monitored for the inactive variant D10N was followed by enzyme-mediated degradation of the cellulose films. Again, a dependence on pH was found, such that higher pH resulted in slower enzymatic degradation. Removing the carbohydrate-binding module eliminated this pH dependence but also resulted in a decreased adsorption to the cellulose surface, and in a decreased net catalytic effect.     

Characterization of monofluorinated polycyclic aromatic compounds by 1H, 13C and 19F NMR spectroscopy

Monofluorinated polycyclic aromatic hydrocarbons (F-PAHs) have attracted much attention in analytical, environmental, toxicological and mechanistic studies because of their physico-chemical properties, which are closely similar to those of the parent PAHs. Because of this, full NMR characterization has become of interest. Complete 1H, 13C and 19F NMR chemical shifts, and also 1J(H,C), (n)J(C,F), (n)J(H,F) and (n)J(H,H) coupling constants, have been assigned for the F-PAHs 1-fluoronaphthalene, 2-fluorofluorene, 5-fluoroacenaphthylene, 2-fluorophenanthrene, 3-fluorophenanthrene, 3-fluorofluoranthene, 1-fluoropyrene, 1-fluorochrysene, 2-fluorochrysene, 3-fluorochrysene and 9-fluorobenzo[k]fluoranthene. To allow comparison with the corresponding parent PAHs, the 1H and 13C chemical shifts of acenaphthylene, phenanthrene, fluoranthene, pyrene and benzo[k]fluoranthene were determined. Chemical shift increments and the effects on the coupling constants from the fluorine substitution are discussed.     

Four-Component Gas/Oil Displacements in One Dimension: Part I: Global Triangular Structure

This paper presents an analysis of the mathematical structure of three-component and four-component gas displacements. The structure of one-dimensional flows in which components partition between two phases is governed by the geometry of a set of equilibrium tie lines. We demonstrate that for systems of four components, the governing mass conservation laws for the displacement can be represented by an eigenvalue system whose coefficient matrix has a global triangular structure, which is defined in the paper, for only specific types of phase behavior. We show that four-component systems exhibit global triangular structure if and only if (1) tie lines meet at one edge of the quaternary phase diagram or (2) if tie lines lie in planes. For such systems, shock and rarefaction surfaces coincide and are planes. We prove that systems are of category (2) if equilibrium ratios (K-values) are independent of mixture composition. In particular, for such systems shock and rarefaction curves will coincide. We also show that for systems with variable K-values, the rarefaction surfaces are almost planar in a precise sense, which is described in the paper. Therefore, systems with variable K-values may be well approximated by assuming shock and rarefaction surfaces do coincide. For these special systems the construction of solutions for one-dimensional, two-phase flow with phase behavior simplifies considerably. In Part II, we describe an application of these ideas to systems in which K-values are constant.     

A simple algorithm for building the 3-D convex hull

A new algorithm is given for finding the convex hull of a finite set of distinct points in three-dimensional space. The algorithm finds the faces of the hull one by one, thus gradually building the polyhedron that constitutes the hull. The algorithm is described as developed through stepwise refinement.     

Valence photoelectron spectrum of CoO. Ab initio calculations of energies and relative intensities within a limited CI framework

The valence spectrum of CoO has been calculated using the CoO₆^10? cluster, stabilized by an electrostatic field, as a model of bulk CoO. The wave functions were generated using basis sets of better than double-zeta quality. SCF wave functions were obtained for the ground state and for the first ionized state of the cluster. Limited CI calculations were performed using these orbital sets. The lowest states of the ion correspond to the main lines in the spectrum, while higher states can give rise to high-energy satellites to the main lines. The relative intensities of these satellites were estimated in the case of high-energy incident photons.