High-performance liquid chromatographic determination of tocopherols in infant formulas

A method for the simultaneous determination of alpha-tocopherol acetate and alpha-, delta-, and gamma-tocopherols by normal-phase high-performance liquid chromatography (HPLC) with a fluorescent detector in infant formula is proposed. The values obtained in the determination of the analytical parameters: linearity, precision, limit of detection and accuracy (analysis of a standard reference material, SRM 1846), confirm the quality of the method. The proposed method is useful for the determination of alpha-, delta-, and gamma-tocopherols and alpha-tocopherol acetate in infant formulas at a low cost and in a total time of 2 h.     

P680: what is it and where is it?

Electron and X-ray crystallography have provided intermediate structural models for photosystem II (PSII), the membrane located multisubunit complex which uses light energy to split water into its elemental constituents. This reaction is thermodynamically demanding and involves the production of redox potentials in excess of 1 V. Structural analyses have now shown that the primary oxidant, P680, is not a 'special pair' of chlorophylls, as in other types of photosynthetic reaction centres, but a tetramer of equally spaced chlorophyll a molecules. Its high redox potential, and the involvement of four weakly coupled isoenergetic monomers rather than a strongly excitonically coupled 'special pair', has implications for redox mechanisms which are unique to PSII, and therefore not found in any other photosynthetic system. The importance of these features is discussed.     

Anomalous solvent shift effect and observation of phosphorescence in bilirubin

Bilirubin IX-α has a large extinction coefficient but shows a weak blue-shift in solvents of increasing dielectric constant. A blue-shift is typical of an n → π^* transition, and is here interpreted in terms of the amide group present in the terminal pyrrole rings. Compounds undergoing n → π^* transitions usually form triplet states. With bilirubin, an emission is observed at 77 K; evidence is presented that this may be phosphorescence from an excited triplet state. The energy of this triplet level is 230 kJ mole^?1, thus bilirubin should be capable of sensitizing the formation of ¹Δ_g O₂.     

The Navruz experiment: Cooperative monitoring for radionuclides and metals in Central Asia transboundary rivers

Summary This paper presents the results of radioecological investigation of Central Asian rivers.<Emphasis Type=Bold><Emphasis Type=Italic> </Emphasis></Emphasis>This work was done as part of the Navruz Project, a cooperative, transboundary river monitoring project involving rivers and institutions in Kazakhstan, Kyrgyzstan, Tajikistan, and Uzbekistan, and facilitated by Sandia National Laboratories in the United States. The study of waterborne radionuclides and metals concentrations in Central Asia is of particular interest because of the history of nuclear materials mining, fabrication, transport, and storage there, when it was part of the Soviet Union. This development left a legacy of radionuclides and metals contamination in some Central Asian regions, which poses a clear health hazard to populations who rely heavily upon surface water for agricultural irrigation and direct domestic consumption.     

Designing liquid-crystalline dendronised hexa-adducts of [60]fullerene via click chemistry

ABSTRACT

Liquid-crystalline [60]fullerodendrimers were constructed via click chemistry based on the reaction between hexa-adducts of [60]fullerene (C₆₀) bearing 12 azide groups and alkyne-terminated cyanobiphenyl dendrons of first- and second-generation. The structure of all the new compounds was confirmed by IR, UV, ¹H and ¹³C NMR spectroscopies and mass spectrometry. The mesomorphic properties were studied by polarised optical microscopy, differential scanning calorimetry and small-angle X-ray scattering. The hexa-adduct of C₆₀ functionalised with the first-generation dendrons gave rise to the formation of a smectic A phase and a rectangular columnar phase (c2mm symmetry) while the hexa-adduct of C₆₀ decorated with the second-generation dendrons displayed only a rectangular columnar phase (c2mm symmetry). Our results show that the hexa-adduct of C₆₀ is a unique synthetic platform for the design of fullerodendrimers and dendronised materials.     

High–quality protein backbone reconstruction from alpha carbons using Gaussian mixture models

Coarse‐grained protein structure models offer increased efficiency in structural modeling, but these must be coupled with fast and accurate methods to revert to a full‐atom structure. Here, we present a novel algorithm to reconstruct mainchain models from C traces. This has been parameterized by fitting Gaussian mixture models (GMMs) to short backbone fragments centered on idealized peptide bonds. The method we have developed is statistically significantly more accurate than several competing methods, both in terms of RMSD values and dihedral angle differences. The method produced Ramachandran dihedral angle distributions that are closer to that observed in real proteins and better Phaser molecular replacement log‐likelihood gains. Amino acid residue sidechain reconstruction accuracy using SCWRL4 was found to be statistically significantly correlated to backbone reconstruction accuracy. Finally, the PD2 method was found to produce significantly lower energy full‐atom models using Rosetta which has implications for multiscale protein modeling using coarse‐grained models. A webserver and C++ source code is freely available for noncommercial use from: http://www.sbg.bio.ic.ac.uk/phyre2/PD2_ca2main/ . © 2013 Wiley Periodicals, Inc.     

New 1,2,4‐ and 1,3,4‐oxadiazole materials: synthesis,and mesomorphic and luminescence properties

The synthesis and liquid crystalline properties of new series of 1,2,4‐ and 1,3,4‐oxadiazole derivatives (2a–f and 5a–f respectively) are reported. These compounds contain only one terminal flexible alkoxy chain, the other terminal substituent is a protecting benzyl group. All compounds of series 2 exhibit an enantiotropic nematic phase. The homologue with the longest chain (2f) displays an enantiotropic dimorphism smectic A– nematic. None of the compounds of series 5 shows mesomorphism and only crystal–isotropic transitions were observed. The liquid crystalline properties were investigated by differential scanning calorimetry, polarizing optical microscopy and X‐ray measurements. Luminescence properties, in chloroform solution, of 2f and the series 5 compounds were evaluated. Good photoluminescence quantum yields for compounds of series 5 were observed. Compound 2f, incorporating the 1,2,4‐oxadiazole ring shows a very strong reduction in emissive properties.     

Columnar liquid crystalline benzenetrisamides with pendant 1,3,4-oxadiazole groups

Novel liquid crystal materials based on 1,3,5-benzenetrisamide derivatives with three pendant 2-phenyl-5-(mono-, di-, and/or tri-n-alkoxyphenyl)-1,3,4-oxadiazole arms (Ia–c, IIa–c) were prepared. The mesomorphic properties of these compounds were characterised and studied by differential scanning calorimetry, polarising optical microscopy and X-ray diffraction. The formation of a columnar mesophase was found to be dependent on the number of alkoxy side chains. The compounds Ib and IIb, with a total of six alkoxy chains, and compounds Ic and IIc, with nine alkoxy chains, exhibited an enantiotropic hexagonal columnar (Col_h ) phase with high isotropisation temperatures; however, compounds Ia and IIa with a total of three alkoxy chains formed a crystalline phase. Compounds IIb and c were room temperature liquid crystals.     

Surface characteristics and electrochemical behaviour of sputter-deposited NiTi thin film

Thin nanocrystalline amorphous NiTi film was deposited on Si substrate using DC magnetron sputtering. The as-deposited NiTi thin film was crystallized by heat treatment at 500 °C for 1 h. The crystal structure, surface morphology, microstructure and surface chemistry of the deposited films were studied using X-ray diffraction, atomic force microscopy, scanning electron microscopy and X-ray photoelectron spectroscopy (XPS), respectively. Corrosion behaviour was assessed in Ringer’s solution at 37 °C by open circuit potential (OCP), potentiodynamic polarization and electrochemical impedance spectroscopy as a function of exposure time. OCP values indicate that the tendency for the formation of a spontaneous oxide film is greater for the NiTi thin films than the bulk NiTi. Long time exposure to Ringer’s solution was found to have a great effect on the corrosion behaviour of the samples. Significantly low corrosion current density was obtained for the annealed NiTi film from the potentiodynamic polarization curves indicating a typical passive behaviour, but as-deposited film and bulk NiTi alloy exhibited breakdown of passivity at potentials approximately +1.4 V (vs. SCE). XPS showed that the oxide film formed on the annealed NiTi thin film mainly composed of Ti oxides, and no evidence of Ni was found up to 8.2 nm beneath the top surface, suggesting the excellent corrosion resistance of this sample in Ringer’s solution.