Silk-silica composites from genetically engineered chimeric proteins: materials properties correlate with silica condensation rate and colloidal stability of the proteins in aqueous solution

The aim of the study was to determine the extent and mechanism of influence on silica condensation that is presented by a range of known silicifying recombinant chimeras (R5: SSKKSGSYSGSKGSKRRIL; A1: SGSKGSKRRIL; and Si4-1: MSPHPHPRHHHT and repeats thereof) attached at the N-terminus end of a 15-mer repeat of the 32 amino acid consensus sequence of the major ampullate dragline Spindroin 1 (Masp1) Nephila clavipes spider silk sequence ([SGRGGLGGQG AGAAAAAGGA GQGGYGGLGSQG](15)X). The influence of the silk/chimera ratio was explored through the adjustment of the type and number of silicifying domains (denoted X above), and the results were compared with their non-chimeric counterparts and the silk from Bombyx mori. The effect of pH (3-9) on reactivity was also explored. Optimum conditions for rate and control of silica deposition were determined, and the solution properties of the silks were explored to determine their mode(s) of action. For the silica-silk-chimera materials formed there is a relationship between the solution properties of the chimeric proteins (ability to carry charge), the pH of reaction, and the solid state materials that are generated. The region of colloidal instability correlates with the pH range observed for morphological control and coincides with the pH range for the highest silica condensation rates. With this information it should be possible to predict how chimeric or chemically modified proteins will affect structure and morphology of materials produced under controlled conditions and extend the range of composite materials for a wide spectrum of uses in the biomedical and technology fields.     

Experiences with Using Expert Systems in O.R.

Increased awareness of expert systems technology, and the availability of relevant software, has tempted many O.R. groups to investigate the expert systems approach. This paper considers the strategies open to O.R. groups interested in employing expert systems, reviews some of the relevant software, and discusses what those O.R. groups who have already investigated the use of expert systems methods are actually doing.Some of the authors' experience of developing expert systems is discussed. The development of an expert system that helps bankers analyse company accounts is presented. The use of expert system methods as vehicles for decision analysis, and the possibilities for producing systems that act as O.R. consultants are also discussed.     

C CPMAS studies of plant cell wall materials and model systems using proton relaxation-induced spectral editing techniques

The solid state ¹³C CPMAS NMR spectra of plant cell walls are often complex owing to superposition of resonances from different polysaccharides and the heterogeneity of the cell wall assembly. In this paper, we describe the application of a set of proton relaxation-induced spectral editing (PRISE) experiments which combine ¹H relaxation properties (T₁, T_1ρ, T₂) with ¹³C high resolution spectroscopy (CPMAS) to relate the dynamics of the plant cell walls and model systems to their domain structural details. With PRISE it has been found that in plant cell wall materials, cellulose is always associated with the long components of spin–lattice relaxation in both the laboratory and rotating frames whereas non-cellulose polysaccharides (pectin and hemicellulose) are associated with the short ones. For the proton T₂ relaxation, cellulose is only associated with the short component (below 20 μs), pectin contributes to both the short component and the long one.     

The effects of morphology and exchange on proton N.M.R. relaxation in agarose gels

The effects of morphology and exchange on N.M.R. relaxation times in agarose gels are interpreted within a unified theoretical framework based on the generalized Bloch equations. By acknowledging the spacial dependence of the N.M.R. parameters it is shown how the relaxation behaviour depends on the distance scale characterizing the heterogeneity of the gel. If this distance scale is sufficiently small to allow complete diffusive averaging we recover the traditional results based on the Bloch-McConnell equations describing relaxation in a homogeneous system. This is the case for fresh agarose gels which show monoexponential relaxation and has been widely interpreted in terms of the rapid exchange of protons between populations of ‘free’ and ‘bound’ water. Conversely, if the distance scale characterizing the heterogeneity is sufficiently large to prevent complete diffusive averaging our model predicts multiexponential relaxation. This is the case with the transverse magnetization in agarose gels that have been slowly frozen then thawed. These results show how it is possible to probe the degree of microheterogeneity in gel samples using N.M.R. For the purpose of deriving simple analytical expressions for the N.M.R. relaxation times we only consider one-dimensional solutions to our model. More realistic morphologies can be treated using numerical methods.     

Some Self-Adjoint Quantum Semimartingales

It is proved that the quantum stochastic gauge integral preservesself-adjointness of vacuum-adapted processes. This fact, togetherwith bounded perturbations and the link between the Hudson–Parthasarathycalculus and vacuum-adapted theory, is used to produce manyself-adjoint quantum semimartingales. 2000 Mathematics SubjectClassification 81S25, 47D06, 47A56.     

The effects of restricted diffusion in nuclear magnetic resonance microscopy

A stochastic computer simulation is used to investigate the effects of restricted diffusion in NMR microscopy. It is shown that diffusion contributes to a loss of interfacial resolution through two main mechanisms. The first applies to spatial regions bound by impermeable interfaces and involves diffusive averaging of the frequency differences set up by the applied field gradients. This effect can be made arbitrarily small by increasing the magnitude of the field gradient. The second mechanism involves diffusion through permeable membranes or interfaces defining the sample morphology. This effect can, in principle, be reduced by multiple echo imaging with short pulse spacings. The possibility of imaging diffusive flow through a permeable interface is discussed.     

Putrescine homologues control silica morphogenesis by electrostatic interactions and the hydrophobic effect

A systematic model study on the role(s) of putrescine homologues on silicification is presented and it is proposed that electrostatic forces between additive and silicic acid, and the hydrophobic behaviour of the additives are both important in silicification.