Coating of silica sand with aluminosilicate clay

The objective of this work was to coat aluminosilicate clays on an inert silica support, and to characterize the properties and stability of the clay-silica coating. Two polymers, polyacrylamide (PAM) and polyvinyl alcohol (PVA), were used to bind kaolinite, illite, and smectite onto silica grains. The clay-polymer composites were studied by X-ray diffraction, FTIR, and electrophoretic mobility. Clay coatings on silica grains were characterized by mass coverage, scanning electron microscopy, specific surface area, and pH stability. Silica sand was successfully coated with clays by using the two polymers, but with PVA, the clay coating had a greater mass coverage and was more stable against pH variations. Less polymer was needed for the clay coating using PVA as compared to using PAM. Clay-polymer complexes and pure clay minerals had similar cation exchange capacities and electrophoretic mobilities, indicating that overall surface charge of the clays was little affected by the polymers. Some decrease in hydrophilicity was observed for illite and smectite when clays where coated with the polymers. The methodology reported here allows the generation of a clay-based porous matrix, with hydraulic properties that can be varied by adjusting the grain size of the inert silica support.     

Metal-catalyzed oxidation and epoxidation of alpha-hydroxy vinyl and dienyl sulfoxides

Treatment of acyclic alpha-hydroxyalkyl alpha,beta-unsaturated sulfoxides with t-BuOOH/VO(acac)2 results in rapid oxidation to the unsaturated sulfones followed by an unusual regio- and stereoselective epoxidation at the unsaturated sulfones; this methodology has been applied to the preparation of carbohydrate-like fragments.     

Unusual fragmentation of CH2Cl2 by an Ir(III) centre bonded to a doubly metalated Tp(Ms) Ligand (Tp(Ms) = hydrotris(3-mesitylpyrazol-1-yl)borate)

The Ir(III) compound Tp(Ms')Ir(N2), that contains a pentadentate, doubly metalated 3-mesityl substituted tris(pyrazolyl)borate ligand, induces the cleavage of C-H and C-Cl bonds of CH2Cl2 to yield a highly electrophilic chlorocarbene Ir=C(H)Cl complex.     

Experimental preparation and UV/IR spectroscopic characterization of 1,3-dibutanal-1,2,4,5-tetroxane

We report the experimental preparation of the 1,3-butanal-1,2,4,5-tetroxane by oxidation of glutataldehyde with oxygen peroxide in presence of concentrated sulfuric acid, following the Bayer and Viller method modified by Jorge et al. The UV and IR spectra are studied from the experimental and theoretical standpoint. A rather complete vibrational assignment was performed and the nature of the electronic transitions was discussed in detail.     

Raman spectroscopic study of mellite--a naturally occurring aluminium benzenehexacarboxylate from lignite--Claystone series of the tertiary age

Raman spectra have been obtained for crystals of the organic mineral mellite, from three different sites. Mellite occurs in the frame of the Tertiary series including lignite and coaly slates at Artern (Thuringia), Tula (Russia) and Bílina (Northern Bohemia). Mellite, Al(2)C(6)(COO)(6) x 16H(2)O, can be considered as evidence of previous biological activity in the geological record, similar to other salts of carboxylic acids such as whewellite and weddellite. Assignments of the major Raman features of mellite are proposed on the basis of comparison with the parent, mellitic acid, C(6)(COOH)(6). During diagenesis and epigenesis, mellite is formed from the reaction between organic carbon rich solutions with aluminosilicates, hence, with the current interest in the adoption of Raman spectroscopy for incorporation into robotic instrumentation for space mission landers, it is important that organic minerals be included into a spectroscopic database for the recognition of biomolecular signatures for remote life-detection experiments.     

Palladium complexes of a phosphorus ylide with two stabilizing groups: synthesis, structure, and DFT study of the bonding modes

The phosphorus ylide ligand [Ph3P=C(CO2Me)C(=NPh)CO2Me] (L1) has been prepared and fully characterized by spectroscopic, crystallographic, and density functional theory (DFT) methods (B3LYP level). The reactivity of L1 toward several cationic Pd(II) and Pt(II) precursors, with two vacant coordination sites, has been studied. The reaction of [M(C/\X)(THF)2]ClO4 with L1 (1:1 molar ratio) gives [M(C/\X)(L1)]ClO4 [M = Pd, C/\X = C6H4CH2NMe2 (1), S-C6H4C(H)MeNMe2 (2), CH2-8-C9H6N (3), C6H4-2-NC5H4 (4), o-CH2C6H4P(o-tol)2 (6), eta3-C3H5 (7); M = Pt, C/\X = o-CH2C6H4P(o-tol)2 (5); M(C/\X) = Pd(C6F5)(SC4H8) (8), PdCl2 (9)]. In complexes 1-9, the ligand L1 bonds systematically to the metal center through the iminic N and the carbonyl O of the stabilizing CO2Me group, as is evident from the NMR data and from the X-ray structure of 3. Ligand L1 can also be orthopalladated by reaction with Pd(OAc)2 and LiCl, giving the dinuclear derivative [Pd(mu-Cl)(C6H4-2-PPh2=C(CO2Me)C(CO2Me)=NPh)]2 (10). The X-ray crystal structure of 10 is also reported. In none of the prepared complexes 1-10 was the C(alpha) atom found to be bonded to the metal center. DFT calculations and Bader analysis were performed on ylide L1 and complex 9 and its congeners in order to assess the preference of the six-membered N,O metallacycle over the four-membered C,N and five-membered C,O rings. The presence of two stabilizing groups at the ylidic C causes a reduction of its bonding capabilities. The increasing strength of the Pd-C, Pd-O, and Pd-N bonds along with other subtle effects are responsible for the relative stabilities of the different bonding modes.     

Frustration and hydrophobicity interplay in protein folding and protein evolution

A lattice model is used to study mutations and compacting effects on protein folding rates and folding temperature. In the context of protein evolution, we address the question regarding the best scenario for a polypeptide chain to fold: either a fast nonspecific collapse followed by a slow rearrangement to form the native structure or a specific collapse from the unfolded state with the simultaneous formation of the native state. This question is investigated for optimized sequences, whose native state has no frustrated contacts between monomers, and also for mutated sequences, whose native state has some degree of frustration. It is found that the best scenario for folding may depend on the amount of frustration of the native structure. The implication of this result on protein evolution is discussed.     

Effect of double bonds on the conducting properties of ciguatoxin 3C and tetrahydropyrane-based polymers: a theoretical study

The electronic structure of the ciguatoxin 3C is analyzed through the Kohn-Sham model by using two different kinds of basis sets: localized basis set (Gaussian functions) and nonlocalized basis set (plane wave functions). With the localized basis functions, two approximations are used for the exchange-correlation functional: the local density approximation and the generalized gradient approximation. With the nonlocalized basis set, just the local density approximation is used. The energy gap, obtained from the frontier molecular orbitals, for this molecule predicts that this system is a semiconductor, even when the number of double bonds is increased inside the structure. However, as large molecules built with the basic unit--the tetrahydropyrane--of the ciguatoxin 3C are found in nature, it suggests studying the gap in polymeric systems built with the basic unit of this molecule. It is demonstrated that the presence of double bonds reduces considerably the gap, indicating the possibility of forming conducting materials by introducing double bonds in this kind of molecular systems. Thus, molecules strongly linked with biological systems can be used as precursor to build electric conducting systems.     

Signal-to-noise ratio and frequency analysis of continuous loop averaging deconvolution (CLAD) of overlapping evoked potentials

In this study, a frequency domain formulation of continuous loop averaging deconvolution (CLAD) of overlapping evoked potentials is developed and applied for the extraction of transient responses from recordings obtained at high stimulation rates. This formulation allows for a faster execution of CLAD by using fast Fourier transform algorithms. The frequency characteristics of the deconvolution filter depends exclusively on the stimulus sequence and determines whether the noncoherent noise is amplified or attenuated in different frequencies. A formula for calculating the signal-to-noise ratio (SNR) achieved by the deconvolution process is developed. The newly developed theory and the methodology is applied to the extraction of the auditory brainstem and middle latency responses using various sequences. The effects of the sequence used and the number of sweeps averaged in ongoing acquisition on SNR are examined by using single sweep recordings. The results verify the deconvolution theory and the methodology and show its limitations. Depending on the frequency characteristics of the sequence, the deconvolution process can amplify or attenuate the EEG noise. Proper selection of the stimulus sequence can increase the SNR enhancement obtained with conventional averaging.