Self-assembly and characterization of Ca-Al-LDH nanohybrids containing casein proteins as guest anions

Casein, a natural biopolymer contained in milk, has been successfully intercalated into a Ca-Al-LDH host structure. Synthesis was performed by rehydration of tricalcium aluminate in the presence of casein. The resulting nanohybrids were characterized by powder X-ray diffraction (XRD), elemental analysis, infrared spectroscopy (IR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Further experiments revealed that the single protein strains intercalate instead of the entire casein sub micelles, which are present in milk. Additionally, the pure phospho protein fractions α- and β-casein, which make up ∼80 wt% of total casein were isolated and intercalated into the Ca-Al-LDH host structure, yielding a biopolymer-inorganic hybrid material.     

Average crossing number of Gaussian and equilateral chains with and without excluded volume

We study the influence of excluded volume interactions on the behaviour of the mean average crossing number (mACN) for random off-lattice walks. We investigated Gaussian and equilateral off-lattice random walks with and without ellipsoidal excluded volume up to chain lengths of N = 1500 and equilateral random walks on a cubic lattice up to N = 20000. We find that the excluded volume interactions have a strong influence on the behaviour of the local crossing number 〈 a(l₁,l₂) 〉 at very short distances but only a weak one at large distances. This behaviour is the basis of the proof in [ Y. Diao et al., Math. Gen. 36, 11561 (2003); Y. Diao and C. Ernst, Physical and Numerical Models in Knot Theory Including Applications to the Life Sciences] for the dependence of the mean average crossing number on the chain length N. We show that the data is compatible with an Nln(N)-bahaviour for the mACN, even in the case with excluded volume.     

The effect of oxygen exposure on pentacene electronic structure

We use ultraviolet photoelectron spectroscopy to investigate the effect of oxygen and air exposure on the electronic structure of pentacene single crystals and thin films. It is found that O₂ and water do not react noticeably with pentacene, whereas singlet oxygen/ozone readily oxidize the organic compound. Also, we obtain no evidence for considerable p-type doping of pentacene by O₂ at low pressure. However, oxygen exposure lowers the hole injection barrier at the interface between Au and pentacene by 0.25 eV, presumably due to a modification of the Au surface properties.     

Viscoelastic characterization of compacted pharmaceutical excipient materials by analysis of frequency-dependent mechanical relaxation processes

A newly developed method for determining the frequency-dependent complex Young's modulus was employed to analyze the mechanical response of compacted microcrystalline cellulose, sorbitol, ethyl cellulose and starch for frequencies up to 20 kHz. A Debye-like relaxation was observed in all the studied pharmaceutical excipient materials and a comparison with corresponding dielectric spectroscopy data was made. The location in frequency of the relaxation peak was shown to correlate to the measured tensile strength of the tablets, and the relaxation was interpreted as the vibrational response of the interparticle hydrogen and van der Waals bindings in the tablets. Further, the measured relaxation strength, holding information about the energy loss involved in the relaxation processes, showed that the weakest material in terms of tensile strength, starch, is the material among the four tested ones that is able to absorb the most energy within its structure when exposed to external perturbations inducing vibrations in the studied frequency range. The results indicate that mechanical relaxation analysis performed over relatively broad frequency ranges should be useful for predicting material properties of importance for the functionality of a material in applications such as, e.g., drug delivery, drug storage and handling, and also for clarifying the origin of hitherto unexplained molecular processes.     

Resonantly enhanced off-specular X-ray scattering from polymer/polymer interfaces<Superscript>⋆</Superscript>

We have used measurements of the absolute intensity of diffuse X-ray scattering to extract the interfacial tension of a buried polymer/polymer interface. Diffuse scattering was excited by an X-ray standing wave whose phase was adjusted to have a high intensity at the polymer/polymer interface and simultaneously a node at the polymer/air interface. This method permits the capillary-wave-induced roughness of the interface, and hence the interfacial tension, to be measured independently of the polymer/polymer interdiffusion.     

Effects of confinement on static and dynamical properties of water

Molecular-dynamics results on water confined in a silica pore are reviewed and discussed in connection with experiments performed on water in Vycor and with studies of water in contact with proteins. The properties of confined water are studied as a function of both temperature and hydration level. The interaction of water in the film close to the substrate with the silica atoms induces a strong distortion of the hydrogen bond network. At high hydration levels a double dynamical regime is observed. At low hydration an anomalous diffusion is found upon supercooling with a transition from a Brownian to a non-Brownian regime on approaching the substrate in agreement with results found in studies of water in contact with globular proteins.Received: 1 January 2003, Published online: 14 October 2003PACS: 61.20.-p Structure of liquids - 61.20.Ja Computer simulation of liquid structure     

Characteristic variations in the effect of diluents on polymer crystallization and melting observed for a sample of poly(ethylene-co-octene)

Melting points in mixtures of a crystallizable polymer with a low-molar-mass diluent depend on both, the diluent fraction and the crystal thickness. A differentiation of the two factors can be achieved by temperature-dependent SAXS experiments. A corresponding study, complemented by DSC, dilatometry, microscopy and AFM-imaging, was carried out for mixtures of a poly(ethylene-co-octene) with n-C₁₆H₃₄, c-C₁₆H₃₂ and methyl-anthracene, respectively. All diluents lead for a constant crystal thickness to melting point depressions in agreement with Raoult's law. On the other hand, the effect of the diluents on the thickness of the crystals formed at a fixed crystallization temperature varies. While in the presence of the two alkanes thicker crystals form, no effect arises for the methyl-anthracene—as was previously found for the octene-co-units. We consider these observations as a further support for our view that polymer crystallization follows a multi-stage route which includes a passage through an intermediate mesomorphic phase. Under such conditions crystal thicknesses would only be affected if the diluent is still present in the mesomorphic phase and stay invariant if the diluent molecules are already rejected when this intermediate phase forms.     

Adsorption of hydrophobic polyelectrolytes onto oppositely charged surfaces

We present a scaling theory for the adsorption of a weakly charged polyelectrolyte chain in a poor solvent onto an oppositely charged surface. Depending on the fraction of charged monomers and on the solvent quality for uncharged monomers, the globule in the bulk of the solution has either a spherical conformation or a necklace structure. At sufficiently high surface charge density, a chain in the globular conformation adsorbs in a flat pancake conformation due to the Coulombic attraction to the oppositely charged surface. Different adsorption regimes are predicted depending on two screening lengths (the Debye screening length monitored by the salt concentration and the Gouy-Chapman length monitored by the surface charge density), on the degree of ionization of the polymer and on the solvent strength. At low bulk ionic strength, an increase in the surface charge density may induce a transition from an adsorbed necklace structure to a uniform pancake due to the enhanced screening of the intra-chain Coulombic repulsion by the counterions localized near the surface. Received 12 April 2001     

Methods for correlating T1rho and FID components in wideline 1H NMR studies of motionally heterogeneous polymer systems

We address the problem of correlating the observed FID and T_1ρ components in wideline ¹H relaxation measurements of motionally heterogeneous polymers, and show that different methods of data treatment can highlight different aspects of the correlations present. For a sample of polypropylene we find that the T_1ρ relaxation behaviour is driven by relaxation associated with the intermediate FID component, which strongly suggests a motionally inhomogeneous amorphous region in the sample.     

Thermal diffusion and bending kinetics in nematic elastomer cantilever

Vertically aligned monodomain nematic liquid-crystal elastomers contract when heated. If a temperature gradient is applied across the width of such a cantilever, inhomogeneous strain distribution leads to bending motion. We modelled the kinetics of thermally induced bending in the limit of a long thin strip and the predicted time variation of curvature agreed quantitatively with experimental data from samples with a range of critical indices and nematic-isotropic transition temperatures. We also deduced a value for the thermal diffusion coefficient of the elastomer.