Selective Adsorption and Chiral Amplification of Amino Acids in Vermiculite Clay -Implications for the origin of biochirality

Smectite clays are hydrated layer silicates that, like micas, occur naturally in abundance. Importantly, they have readily modifiable interlayer spaces that provide excellent sites for nanochemistry. Vermiculite is one such smectite clay and in the presence of small chain-length alkyl-NH3Cl ions, forms sensitive, 1-D ordered model clay systems with expandable nano-pore inter-layer regions. These inter-layers readily adsorb organic molecules. N-propyl NH3Cl vermiculite clay gels were used to determine the adsorption of alanine, lysine and histidine by chiral HPLC. The results show that during reaction with fresh vermiculite interlayers, significant chiral enrichment of either L- and D-enantiomers occurs depending on the amino acid. Chiral enrichment of the supernatant solutions is up to about 1% per pass. In contrast, addition to clay interlayers already reacted with amino acid solutions resulted in little or no change in D/L ratio during the time of the experiment. Adsorption of small amounts of amphiphilic organic molecules in clay inter-layers is known to produce Layer-by-Layer or Langmuir-Blodgett films. Moreover atomistic simulations show that self-organization of organic species in clay interlayers is important. These non-centrosymmetric, chirally active nanofilms may cause clays to act subsequently as chiral amplifiers, concentrating organic material from dilute solution and having different adsorption energetics for D- and L-enantiomers. The additional role of clays in RNA oligimerization already postulated by Ferris and others, together with the need for the organization of amphiphilic molecules and lipids noted by Szostak and others, suggests that such chiral separation by clays in lagoonal environments at normal biological temperatures might also have played a significant role in the origin of biochirality.Comment: 17 Pages, 2 Figures, 4 Table

One – and Two-Step Resonance Energy Transfer Between Cyanine Dyes in Layered Silicates Colloidal Systems

Resonance energy transfer (RET) is of high interest for both the basic research and practical applications. It is a phenomenon of radiationless transmission of energy between donor and acceptor molecules. In this study single- and two-step (RET) was investigated between cyanine dye cations (NK1, NK2, NK3) in colloids of layered silicate, synthetic Sumecton saponite. In these systems the dye molecules played role of the energy donors (NK1) or energy acceptors (NK2, NK3) or both (NK2). The adsorption and formation of various types of dye species was studied using visible spectroscopy. The absorption spectroscopy did not detect any significant molecular aggregation of the dyes at the surface of saponite particles. The RET process was described by fluorescence spectroscopy. Both the single- and two-step RET were detected in saponite dispersion. Effects of various parameters on the efficiency of the RET process, such as dye concentrations, saponite properties the distances between co-adsorbed dye cations were found to be essential. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/3530

Unconventional order/disorder behaviour in Al–Co–Cu–Fe–Ni multi-principal element alloys after casting and annealing

The effect of Cu concentration on the order/disorder behaviour of the AlCoCuxFeNi (x = 0.6 to 3.0) multi-principal element alloys was investigated. BCC and/or FCC phases were observed in the microstructures of the alloys after casting and annealing at 1050 ◦C followed by slow cooling. Interesting is that the alloys form ordered structures after casting and disordered structures after annealing and slow cooling, while the opposite would be expected. The ordering in the as-cast state is explained by the strong affinity of Al to transition metals, which results in the formation of supercell structures having sublattices occupied by certain elements only. Disordering after annealing has two reasons. Either the phase is composed of nearly pure element (Cu) and is disordered by default or it is composed of randomly distributed nano-segregated regions within a single phase resulting in a uniform distribution of all elements in the sublattices and therefore appearing to be macroscopically disordered. The reason for the formation of such nano-segregated areas might reside in the reduction of Gibbs free energy due to the annealing by the interplay between enthalpy and entropy

Crystal architectures of a layered silicate on monodisperse spherical silica particles cause the topochemical expansion of the core-shell particles

Anisotropic structural changes in an expandable layered silicate (directed towards the c-axis) occurring on isotropic and monodisperse microspheres were detected by measurable increases in the grain size. The hierarchical changes were observed through pursing the sophisticated growth of expandable layered silicate crystals on monodisperse spherical silica particles with diameters of 1.0 mu m; the core-shell hybrids with a quite uniform grain size were successfully produced using a rotating Teflon-lined autoclave by reacting spherical silica particles in a colloidal suspension with lithium and magnesium ions under alkaline conditions at 373 K. The size distribution of the core-shell particles tended to be uniform when the amount of lithium ions in the initial mixture decreased. The intercalation of dioctadecyldimethylammonium ions into the small crystals through cation-exchange reactions expanded the interlayer space, topochemically increasing the grain size without any change occurring in the shapes of the core-shell particles. (C) 2015 Elsevier Inc. All rights reserved.ArticleMICROPOROUS AND MESOPOROUS MATERIALS. 215:168-174 (2015)journal articl