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Model studies of colloidal silica precipitation using biosilica extracts from<Emphasis Type="Italic"> Equisetum telmateia</Emphasis>

Structural materials containing silicon are produced in single celled organisms through to higher plants and animals. Hydrated amorphous silica is a colloidal mineral of infinite functionality that is formed into structures with microscopic and macroscopic form. Proteins and proteoglycans are suggested to play a critical role in the catalysis of silica polycondensation and in structure direction during the formation of these magnificent structures. This article extends knowledge on the effect of protein containing biosilica extracts from Equisetum telmateia on the kinetics of silica formation and structure regulation. Utilising potassium silicon catecholate as the source of soluble silicon, bioextracts obtained from plant silica by dissolution of the siliceous phase with aqueous HF following extensive acid digestion of the plant cell wall were found to modify the kinetic rate constants for the formation of small silicic acid oligomers under circumneutral pH conditions and to modify the solubility of silicic acid in solution. Addition of the bioextracts at ca. 1 wt% to the reaction medium reduced the sizes and range of sizes of the fundamental silica particles formed and led to the formation of crystalline polymorphs of silica under conditions of ca. neutral pH, room temperature and in the absence of multiply charged cations, conditions assumed to be relevant to the biological mineralization environment. The ability of biological organisms to regulate the formation of silica structures with prevention of crystallinity is discussed as are the implications of this study in terms of the generation of new materials with specific form and function for industrial application.     

Norbornane: an investigation into its valence electronic structure using electron momentum spectroscopy, and density functional and Green's function theories

We report on the results of an exhaustive study of the valence electronic structure of norbornane (C(7)H(12)), up to binding energies of 29 eV. Experimental electron momentum spectroscopy and theoretical Green's function and density functional theory approaches were all utilized in this investigation. A stringent comparison between the electron momentum spectroscopy and theoretical orbital momentum distributions found that, among all the tested models, the combination of the Becke-Perdew functional and a polarized valence basis set of triple-zeta quality provides the best representation of the electron momentum distributions for all of the 20 valence orbitals of norbornane. This experimentally validated quantum chemistry model was then used to extract some chemically important properties of norbornane. When these calculated properties are compared to corresponding results from other independent measurements, generally good agreement is found. Green's function calculations with the aid of the third-order algebraic diagrammatic construction scheme indicate that the orbital picture of ionization breaks down at binding energies larger than 22.5 eV. Despite this complication, they enable insights within 0.2 eV accuracy into the available ultraviolet photoemission and newly presented (e,2e) ionization spectra, except for the band associated with the 1a(2) (-1) one-hole state, which is probably subject to rather significant vibronic coupling effects, and a band at approximately 25 eV characterized by a momentum distribution of "s-type" symmetry, which Green's function calculations fail to reproduce. We note the vicinity of the vertical double ionization threshold at approximately 26 eV.     

Inter-cycle variation in whole-body vibration exposures of operators driving track-type loader machines

Whole-body vibration (WBV) measurements are an important aspect of performing risk assessments for those exposed to vibration. A large array of variables affect the outcome of a vibration measurement and its extrapolation to a daily dose measure: e.g. variability in driving style, road surface roughness, loading. The variability in vibration emission is an inherent property for most vibrating environments and there is a risk that a vibration measurement might not be representative of the long-term exposures. It is important to acknowledge the variation inherent to WBV exposure to help understand how this variation will affect health risk assessments. A field investigation was conducted in order to characterise the variation of WBV magnitudes between work cycles of track-type loaders. Six different track-type loaders were measured at four different work sites. The vibrations were measured at the operators seat in three translational axes (x-, y-, and z-axis) in accordance with ISO 2631-1 (1997). The findings indicate the worst axis of vibration for the track-type loaders was predominantly the fore-and-aft (x-axis), for most operations. The most severe emission values were measured for machine C at site 2 (1.12 ms⁻² rms) and machine D at site 2 (1.03 ms⁻² rms). These machines would exceed the action value of the Physical Agents (Vibration) Directive within 2 h of exposure. All of the machines measured would exceed the exposure action value of the Directive within an 8 h working period. The lateral (y-axis) produced the greatest amount of variability between work cycles (coefficient of variation up to 20%). It is concluded that the inherent variability between work cycles and tasks reinforces the requirement to perform a full task analysis prior to measuring WBV exposures to ensure that all tasks are measured and that adequate cycles are measured to obtain a reliable indication of the vibration emission.     

Atomic and molecular ions in intense ultra-fast laser fields

The interaction of a 60 fs 790 nm laser pulse with beams of Ar⁺, C⁺, H₂ ⁺, HD⁺ and D₂ ⁺ are discussed. Intensities up to 10¹⁶ Wcm^-2 are employed. An experimental z-scanning technique is used to resolve the intensity dependent processes in the confocal volume.Received: 6 January 2003, Published online: 15 July 2003PACS: 32.80.Fb Photoionization of atoms and ions - 33.80.Rv Multiphoton ionization and excitation to highly excited states (e.g., Rydberg states) - 42.50.Hz Strong-field excitation of optical transitions in quantum systems; multiphoton processes; dynamic Stark shift