In situ measurement of conformational changes in proteins at liquid interfaces by circular dichroism spectroscopy

A new circular dichroism (CD) spectroscopy technique for studying conformational changes in proteins in situ at the air-water interface is described. By using this technique, conformations of four proteins, viz., beta-casein, bovine serum albumin (BSA), lysozyme, and fibrinogen in the adsorbed state at the air-water interface have been studied. beta-Casein, which is predominantly in a disordered state in solution, assumes a beta-sheet conformation at the air-water interface. On the other hand, lysozyme and fibrinogen, which are alpha+beta-type proteins in solution, become beta-type proteins by completely transforming their alpha-helix structure into beta-sheets. Bovine serum albumin, which is an alpha-type protein in solution, loses its alpha-helix and becomes a disordered protein at the air-water interface. The results indicated that during unfolding and film formation at the interface, structural changes in proteins, regardless of their initial native state, follow the course of increasing beta-sheet and disordered structure and decreasing alpha-helix content. Although this seems to be the general trend, the exceptional case of BSA suggests, however, that this is not universal.     

PHOTOCHEMISTRY OF FLAVINS—I. CONVENTIONAL AND LASER FLASH PHOTOLYSIS STUDY OF ALLOXAZINE

Abstract— The photobleaching of alloxazine in buffered aqueous solution has been studied by means of flash photolysis using conventional and laser excitation sources. Several transient species have been characterized. The alloxazine triplet state (Λ_max 420 nm and 550 nm, times; = 9 μs) was identified with the aid of low-temperature comparison experiments in ethanol. Transient absorption with Λ_max 440 nm, which appears after decay of the triplet state, and whose second-order decay is pH-dependent, is postulated to be due to the semiquinone radical (AH₂*) and a radical derived from alloxazine by addition of water and loss of a hydrogen atom (HAOH*), which are in equilibrium with their conjugate cation radicals. The results of experiments in the presence of oxygen indicate that these species are not primarily formed from the triplet state. The enhanced second-order decay of the flavin radicals in oxygen-containing solutions is interpreted in terms of their reaction with the peroxy radicals. The proposed mechanisms account for the production of hydroxylated alloxazines.     

Syntheses and spectral characteristics of 6-mono-, 3,6-di- and 3,5,6-trisubstituted-1,2,4-triazines

The reaction of acidhydrazides with α-substituted carbonyl compounds in the presence of metal acetates gives substituted 1,2,4-triazines. These cyclisations could be effected without any added acetate by refluxing in dimethyl formamide, pyridine/acetic acid or dimethyl sulfoxide Sixty five 3,5,6-tri-3,6-di and 6 monosubstituted-1,2,4-triazines (in 50–90% yields) with a wide variation in the C₃ substituent (alkyl, aryl or heteryl) and the C₆-substituent (aryl or heteryl) are reported. The mechanistic path followed in the formation of these compounds is discussed.     

Radiation chemical studies of nickel-glycine reaction with carbonate radical

Carbonate radical shows moderate reactivity (k₂=1.8·10⁶ M^–1 s^–1) with nickelglycine complex. As an oxidizing free radical, it may attack the ligand to form Ni(II) coordinated glycine radical or oxidize the metal center to form a Ni(III) glycine transient. Continuous -irradiation of the complex-bicarbonate mixture yields glyoxalic acid (G=1.7) as the major product. The reaction involves an attack of the ligand and precludes the oxidation of metal center.     

Synthesis and Structure of a Molecular Zinc Phosphate [(C12H8N2Zn)2(HPO4)(H2PO4)2]

A hydrothermal reaction of a mixture of ZnCO₃, phosphoric acid, 1, 10‐phenanthroline in H₂O gave rise to large plates of a new zinc phosphate, [(C₁₂H₈N₂Zn)₂(HPO₄)(H₂PO₄)₂], I . The structure consists of ZnO₃N₂ distorted trigonal‐bipyramidal and PO₄ tetrahedral units linked through their vertices to give rise to a zero‐dimensional molecular solid (monomer). The structure of the monomer appears to be similar to the secondary building unit (SBU) 4 = 1, commonly found in many fibrous zeolites. To our knowledge, this is the first time this building unit has been isolated. The structure, with a unique composition, is stabilized by hydrogen bond interactions between the terminal —OH groups forms a one‐dimensional molecular wire and also by strong π…π interactions between the 1, 10‐phenanthroline units. Photoluminescence studies show that there is a ligand‐to‐metal charge transfer (LMCT). Crystal data: orthorhombic, space group = Fdd2 (no. 43), a = 40.4669(1), b = 7.4733(2), c = 17.4425(5)Å, V = 5274.9(2)ų, Z = 8.     

Spectral investigations on 1,4-dimethylamino anthraquinone under laser excitation

Surface enhanced Raman spectrum of 1,4-dimethylamino anthraquinone (1,4-DMAAQ) adsorbed on silver particles has been analyzed to understand the interaction between the molecule and silver surface. By studying the band intensities, the orientation of the molecule is determined. The high intensity and frequency downshifted peak due to carbonyl stretching vibration plays a major role, which shows that the molecules are chemisorbed through coordinating sites. The new peaks observed due to C-N and N-H stretching vibrations also provide the evidence for adsorption through co-ordinating sites. Optical absorption and laser induced fluorescence spectra of this molecule have also been studied in different solvents to understand the effect of environment. Polarization and anisotropy measurements provide the change in orientation induced by solvent molecules between absorption and emission transition dipoles.     

Influence of post-deposition annealing on the structural,optical and electrical properties of Li and Mg co-doped ZnO thin films deposited by sol–gel technique

Lithium (Li) and magnesium (Mg) co-doped zinc oxide (ZnO) thin films were deposited by sol–gel method using spin coating technique. The films were deposited on glass substrates and annealed at different temperatures. The effects of annealing temperature on the structural, optical and electrical properties of the deposited films were investigated using X-ray diffraction (XRD), Ultraviolet–Visible absorption spectra (UV–VIS), photoluminescence spectra (PL), X-ray photo electron spectroscopy (XPS) and Hall measurements. XRD patterns indicated that the deposited films had a polycrystalline hexagonal wurtzite structure with preferred (0 0 0 2) orientation. All films were found to exhibit a good transparency in the visible range. Analysis of the absorption edge revealed that the optical band gap energies of the films annealed at different temperatures varies between 3.49 eV and 3.69 eV. Room temperature PL spectra of the deposited films annealed at various temperatures consist of a near band edge emission and visible emission due to the electronic defects, which are related to deep level emissions, such as oxide antisite (O_Zn), interstitial zinc (Zn_i), interstitial oxygen (O_i) and zinc vacancy (V_Zn) which are generated during annealing process. The influence of annealing temperature on the chemical state of the dopants in the film was analysed by XPS spectra. Ion beam analysis (Rutherford back scattering) experiments were performed to evaluate the content of Li and Mg in the films. Hall measurements confirmed the p-type nature of the deposited films.     

Invariants for E0-Semigroups on II1 Factors

We introduce four new cocycle conjugacy invariants for E ₀-semigroups on II ₁ factors: a coupling index, a dimension for the gauge group, a super product system and a C*-semiflow. Using noncommutative Itô integrals we show that the dimension of the gauge group can be computed from the structure of the additive cocycles. We do this for the Clifford flows and even Clifford flows on the hyperfinite II ₁ factor, and for the free flows on the free group factor ${L(F_\infty)}$ L ( F ∞ ) . In all cases the index is 0, which implies they have trivial gauge groups. We compute the super product systems for these families and, using this, we show they have trivial coupling index. Finally, using the C*-semiflow and the boundary representation of Powers and Alevras, we show that the families of Clifford flows and even Clifford flows contain infinitely many mutually non-cocycle-conjugate E ₀-semigroups.