Structural characterisation of a uracil containing hairpin DNA by NMR and molecular dynamics

Three-dimensional (3D) structure of a hairpin DNA d-CTAGAGGATCCTTTUGGATCCT (22mer; abbreviated as U4-hairpin), which has a uracil nucleotide unit at the fourth position from the 5' end of the tetra-loop has been solved by NMR spectroscopy. The H-1 resonances of this hairpin have been assigned almost completely. NMR restrained molecular dynamics and energy minimisation procedures have been used to describe the 3D structure of the U4 hairpin. This study establishes that the stem of the hairpin adopts a right handed B-DNA conformation while the T-12 and U-15 nucleotide stack upon 3' and 5' ends of the stem, respectively. Further, T-14 stacks upon both T-12 and U-15 while T-13 partially stacks upon T-14. Very weak stacking interaction is observed between T-13 and T-12. All the individual nucleotide bases adopt 'anti' conformation with respect to their sugar moiety. The turning phosphate in the loop is located between T-13 and T-14. The stereochemistry of U-15 mimics the situation where uracil would stack in a B-DNA conformation. This could be the reason as to why the U4-hairpin is found to be the best substrate for its interaction with uracil DNA glycosylase (UDG) compared to the other substrates in which the uracil is at the first, second and third positions of the tetra-loop from its 5' end, as reported previously.

Chemistry of dihydrogen complexes containing only phosphorus co-ligands

A series of new dicationic dihydrogen complexes of ruthenium of the type cis-[(dppm)(2)Ru(eta(2)-H-2)(L)][BF4](2) (dppm = Ph2PCH2PPh2; L = phosphite) have been prepared by protonating the precursor hydride complexes cis-[(dPPM)(2)Ru(H)(L)][BF4] using HBF4.Et2O. The precursor hydride complexes have been obtained from trans-[(dppm)(2)Ru(H)(L)][BF4][(L = phospfiite) via a rare acid-catalysed isomerization reaction in six coordinate species. The trans-[(dppm)(2)Ru(H)(L)][BF4] complexes (L = phosphine) upon protonation gave the isomerized derivatives, however, further addition of acid resulted in a five-coordinate species, [(dppm)(2)RuCl](+) presumably via an intermediate phosphine dihydrogen complex. The electronic as well as the steric properties of the co-ligands seem to strongly influence the structure-reactivity behaviour of this series of complexes.

Mechanical properties of Nylon-6/LDPE blends containing an epoxy resin compatibilizer

Binary and ternary blends of nylon-6/low density polyethylene (nylon-6/LDPE) and Nylon-6/LDPE/poly(ethylene-co-glycidyl methacrylate) were prepared by melt mixing. The blends exhibit two phase morphology with LDPE dispersed in the form of spherical domains in the nylon-6 matrix. The mechanical properties of the blends were measured by standard methods. It is shown that the use of the epoxy copolymer as a compatibilizer improves the impact strength of the blend as compared to nylon-6, which is attributed to better stress transfer across the interface due to the compatibilizer. The data for each mechanical property were also fitted into a best fit model equation and the method of steepest ascent was applied to arrive at the optimum composition of the blend for that property.

Slow orientational dynamics of water molecules at a micellar surface

The dynamics of water molecules near an aqueous micellar interface is studied in an atomistic molecular dynamics simulation of cesium pentadecafluorooctanoate (CsPFO) in water. The dipolar orientational time correlation function (tcf) and the translational diffusion of the water molecules are investigated. Results show that both the reorientational and the translational motion of water molecules near the micelle are restricted. In particular, the orientational tcf exhibits a very slow component in the long time which is slower than its bulk value by 2 orders of magnitude. This slow decay seems to be related to the slow decay often observed in experiments. The origin of the slow decay is analyzed.

Sulfates of organic diamines: hydrogen-bonded structures and properties

In order to investigate the supramolecular hydrogen-bonded networks and other structural features exhibited by compounds containing an organic cation and an inorganic anion, sulfates of the organic diamines, ethylenediamine (I), 1,3-diaminopropane (II), piperazine (III), and 1,4-diazabicyclo[2.2.2]octane (DABCO) (IV) have been prepared investigated by X-ray crystallography. While II, III, and IV crystallize in the centrosymmetric space group, Pbca, P2(1)/n, Pbcn, respectively, I crystallizes in the non-centrosymmetric space group, P4(1) exhibiting chirality and weak NLO properties. I-IV exhibit different types of supramolecular H-bonded networks involving the organic cation and the SO42- anion. The nature and strength of the H-bonding network vary from one compound to another, with the strongest network found in piperazinium sulfate, III, and the weakest in II. While in III, water molecules form part of the H-bonded network, they are present as guest molecules in the channels of IV. Thermal stability of the compounds as well as the infrared spectra reflect the stabilities of these H-bonded solids. (C) 2002 Editions scientifiques et medicales Elsevier SAS. All rights reserved.

Synthesis and structure of La14V6CuO36.5: a transparent Cu(I) vanadate containing [OCuO](3-) sticks

The title compound, La14V6CuO36.5, was prepared from a stoichiometric mixture of La2O3,V2O5, and CuO at 1050-1080 degreesC. The compound forms transparent, pale green crystals and was characterized by wavelength dispersive spectroscopy and single crystal X-ray diffraction. The structure contains isolated VO43- tetrahedra and [OCuO](3-) sticks dispersed in a lanthanum oxide network. Films of La14V6CuO36.5 were grown on R-plane sapphire by using pulsed laser deposition. Rutherford backscattering spectroscopic and X-ray diffraction analyses of the films showed oriented growth of the title phase, a similar to5 eV optical band gap and n-type conductivity. The compound is an example of a transparent copper(I) oxide.

Synthesis of acicular hydrogoethite (alpha-FeOOH center dot xH(2)O; 0.1 < x < 0.22) particles using morphology controlling cationic additives and magnetic properties of maghemite derived from hydrogoethite

A method for the preparation of acicular hydrogoethite (alpha -FeOOH.xH(2)O, 0.1 < x < 0.22) particles of 0.3-1 mm length has been optimized by air oxidation of Fe( II) hydroxide gel precipitated from aqueous (NH4)(2)Fe(SO4)(2) solutions containing 0.005-0.02 atom% of cationic Pt, Pd or Rh additives as morphology controlling agents. Hydrogoethite particles are evolved from the amorphous ferrous hydroxide gel by heterogeneous nucleation and growth. Preferential adsorption of additives on certain crystallographic planes thereby retarding the growth in the perpendicular direction, allows the particles to acquire acicular shapes with high aspect ratios of 8-15. Synthetic hydrogoethite showed a mass loss of about 14% at similar to 280 degreesC, revealing the presence of strongly coordinated water of hydration in the interior of the goethite crystallites. As evident from IR spectra, excess H2O molecules (0.1- 0.22 per formula unit) are located in the strands of channels formed in between the double ribbons of FeO6 octahedra running parallel to the c- axis. Hydrogoethite particles constituted of multicrystallites are formed with Pt as additive, whereas single crystallite particles are obtained with Pd (or Rh). For both dehydroxylation as well as H-2 reduction, a lower reaction temperature (similar to 220 degreesC) was observed for the former (Pt treated) compared to the latter (Pd or Rh) (similar to 260 degreesC). Acicular magnetite (Fe3O4) was prepared either by reducing hydrogoethite (magnetite route) or dehydroxylating hydrogoethite to hematite and then reducing it to magnetite (hematite- magnetite route). According to TEM studies, preferential dehydroxylation of hydrogoethite along < 010 > leads to microporous hematite. Maghemite (gamma -Fe2O3 (-) (delta), 0 < < 0.25) was obtained by reoxidation of magnetite. The micropores are retained during the topotactic transformation to magnetite and finally to maghemite, whereas cylindrical mesopores are formed due to rearrangement of the oxygen sublattice from hexagonal to cubic close packing during the conversion of hydrogoethite to magnetite and then to maghemite. Accordingly, three different types of maghemite particles are realized: strongly oriented multicrystalline particles, single crystalline acicular particles with micropores or crystallites having mesopores. Higher values of saturation magnetization ((s) = 74 emu g(-1)) and coercivity (H-c = 320 Oe) are obtained for single crystalline mesoporous particles. In the other cases, the smaller size of particles and larger distribution of micropores decreases sigma (s) considerably ( < 60 emu g(-1)) due to relaxation effects of spins on the surface atoms as revealed by Mossbauer spectroscopy.

Synthesis of phospholipids with fatty acid chains containing aromatic units at various depths

A series of diacyl phosphatidylcholine lipid derivatives, which contain aromatic units at various depths of their fatty acid chains, have been synthesized. These lipids produced stable aqueous suspensions. Electron microscopy revealed the presence of vesicular aggregates in the suspensions of these newly synthesized lipids. These membranes were oxidatively stable and maintained fluid character at ambient temperature making them ideal candidates for membrane protein reconstitution studies.

The effect of mischmetal addition on the structure and mechanical properties of a cast Al-7Si-0.3Mg alloy containing excess iron (up to 0.6 Pct)

The effect of Fe content (0.2 to 0.6 pct) on the microstructure and mechanical properties of a cast Al-7Si-0.3Mg (LM 25/356) alloy has been investigated. Further, 1 pct mischmetal (MM) additions (a mixture of rare-earth (RE) elements) were made to these alloys, and their mechanical properties at room and at elevated temperatures (up to 200 degreesC) were evaluated. A structure-property correlation on this alloy was attempted using optical microstructure analysis, fractographs, X-ray diffraction, energy-dispersive analysis of X-rays (EDX), and quantitative metallography by image analysis. An increase in Fe content increased the volume percentage of Fe-bearing intermetallic compounds (beta and pi phases), contributing to the lower yield strength (YS), ultimate tensile strength (UTS), percentage elongation, and higher hardness. An addition of 1 pct MM to the alloys containing 0.2 and 0.6 pct Fe was found to refine the microstructure; modify the eutectic silicon and La, Ce, and Nd present in the MM; form different intermetallic compounds with Al, Si, Fe, and Mg; and improve the mechanical properties of the alloys both at room and elevated temperatures.

The hydrolytic reactivities of N-methyl-N(methylthiomethyl)acetamide and N-acetyl-1,3-thiazolidine: the influence of the sulfur atom

The sulfur atom in the substrates leads to modest enhancements in the titled phenomena: these are essentially derived from favourable enthalpies of activation, the negative entropies of activation possibly indicating a measure of stereoelectronic control.

A layered chlorophosphate, Na-3[Cd4Cl3(HPO4)(2)(H2PO4)(4)], containing Na+ ions in the interlamellar space

Reaction between CdCl2.H2O and NaH2PO4.H2O Under hydrothermal conditions gives rise to a new cadmium chlorophosphate of the formula Na-3[Cd4Cl3(HPO4)(2)(H2PO4)(4)] I. This material crystallizes in the orthorhombic system with space group Fmm2(no. 42). I has macroanionic layers of [Cd4Cl3(HPO4)(2)(H2PO4)(4)](3-) with Na+ ions in the interlamellar space. The discovery of such compounds suggests that metathetic reactions carried out under hydrothermal conditions may provide a novel route for the synthesis of new open-framework structures.

Scalable weak aligning medium for enantiodiscrimination of water soluble chiral molecules

The study reports the first indication of a lyotropic liquid crystalline phase of an aqueous solution of polysaccharide xanthan gum, as a physical parameter dependent scalable and reversible weak alignment medium, for enantiodiscrimination of water soluble chiral molecules.

Identity, energetics, dynamics and environment of interfacial water molecules in a micellar solution

The structure and energetics of interfacial water molecules in the aqueous micelle of cesium perfluorooctanoate have been investigated, using large-scale atomistic molecular dynamics simulations, with the primary objective of classifying them. The simulations show that the water molecules at the interface fall into two broad classes: bound and free, present in a ratio of 9:1. The bound water molecules can be further categorized on the basis of the number of hydrogen bonds (one or two) that they form with the surfactant headgroups. The hydrogen bonds of the doubly hydrogen-bonded species are found to be, on the average, slightly weaker than those in the singly bonded species. The environment around interfacial water molecules is more ordered than that in the bulk. The surface water molecules have substantially lower potential energy, because of interaction with the micelle. In particular, both forms of bound water have energies that are lower by �2.5-4.0 kcal/ mol. Entropy is found to play an important role in determining the relative concentration of the species.

Properties of concrete containing ultra-fine fly ash

Fly ash and silica fume are two pozzolans that have been widely used for improved concrete strength and durability. Silica fume displays a greater pozzolanic reactivity than fly ash primarily due to its finer particle size. The reactivity of fly ash can be improved by reducing its particle size distribution. This paper discusses the fresh and hardened properties of concrete made with an ultra-fine fly ash (UFFA) produced by air classification. Durability testing for chloride diffusivity, rapid chloride permeability, alkali-silica reaction (ASR), and sulfate attack was also conducted It was found that at a given workability and water content, concrete containing UFFA could be produced with only 50% of the high-range water-reducer dosage required for comparable silica fume concrete. Similar early strengths and durability measures as silica fume concrete were observed when a slightly higher dosage of UFFA was used with a small reduction (10%) in water content.