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.     

How adiabatic is activated adsorption/associative desorption?

Using density-functional theory we calculate friction coefficients describing the damping of nuclear motion into electron-hole pair excitation for the two best-known examples of activated adsorption: H2 dissociation on a Cu(111) surface and N2 dissociation on a Ru(0001) surface. In both cases, the frictions increase dramatically along the reaction path towards the transition state and can be an order of magnitude larger there than typical in the molecularly adsorbed state. In addition, the frictions for N2/Ru(0001) are typically an order of magnitude larger than for H2/Cu(111). We rationalize these trends in terms of the electron structure as the systems proceed to dissociation along the reaction paths. Combining these friction coefficients with the potential-energy surface in quasiclassical dynamics allows first-principles studies of the importance of the breakdown in the Born-Oppenheimer approximation in describing the chemistry. We find that nonadiabatic effects are minimal for the H2/Cu(111) system, but are quite important for N2/Ru(0001).     

Theoretical evidence for nonadiabatic vibrational deexcitation in H2(D2) state-to-state scattering from Cu(100)

Dynamical calculations are presented for electronically nonadiabatic vibrational deexcitation of H2 and D2 in scattering from Cu(111). Both the potential energy surface and the nonadiabatic coupling strength were obtained from density functional calculations. The theoretically predicted magnitude of the deexcitation and its dependence on incident energy and isotope are all in agreement with state-to-state scattering experiments [on Cu(100)], and this gives indirect evidence for a nonadiabatic mechanism of the observed deexcitation. Direct evidence could be obtained by measuring the chemicurrent associated with the deexcitation, and its properties have been predicted.