Photooxidation of Histidine by 3,3′,4,4′-Benzophenone Tetracarboxylic Acid in Aqueous Solution: Time-Resolved and Field-Dependent CIDNP Study

The photooxidation reaction between 3,3′,4,4′-benzophenone tetracarboxylic acid (TCBP) and l-histidine (His) has been investigated in neutral aqueous solution using the technique of chemically induced dynamic nuclear polarization (CIDNP). Relative values of ¹³C isotropic hyperfine couplings in the TCBP and His radicals were obtained from the ¹³C-time-resolved CIDNP spectrum, recorded during the photoreaction of TCBP with His at natural abundance of the magnetic isotope ¹³C. Good agreement was found for the hyperfine coupling constants of the TCBP ketyl radical calculated using methods of density functional theory, and those obtained from the ¹³C-time-resolved CIDNP spectrum. The mechanism of the quenching reaction of triplet-excited TCBP by His in neutral aqueous solution was established. ¹H CIDNP field dependencies for the photoreaction of TCBP with His were obtained and the g-factor of the histidyl radical was found.     

Effect of doping with nickel ions on the structural state of a zinc oxide crystal

The fine structure of a hexagonal zinc oxide crystal doped with nickel ions of the composition Zn_{1 − x} Ni _x O has been studied using neutron diffraction and magnetic measurements. It is established that even at very low doping levels (x = 0.0004), the crystal undergoes local distortions in basal planes of the initial hexagonal lattice. The local distortions are assumed to be sources of the formation of ferromagnetism in compounds of this class.     

Surface bound states in the continuum

We introduce a novel concept of surface bound states in the continuum, i.e., surface modes embedded into the linear spectral band of a discrete lattice. We suggest an efficient method for creating such surface modes and the local bounded potential necessary to support the embedded modes. We demonstrate that the surface embedded modes are structurally stable, and the position of their eigenvalues inside the spectral band can be tuned continuously by adding weak nonlinearity.     

N‐Methylbenzoazacrown ethers with the nitrogen atom conjugated with the benzene ring: the improved synthesis and the reasons for the high stability of complexes with metal and ammonium cations

An improved method for the synthesis of formyl derivatives of N‐methylbenzoazacrown ethers is proposed. They are prepared in up to 68% yields over fewer steps and with a much shorter time required for the last step. The stability constants of complexes formed by N‐methylbenzoazacrown ethers and their structural analogs with alkali metal, alkaline‐earth metal and ammonium cations were determined by ¹H NMR titration in CD₃CN. High stability of complexes of N‐methyl derivatives of benzoazacrown ethers is demonstrated, comparable with or even exceeding the stability of benzocrown‐ether complexes and markedly exceeding the stability of complexes of phenylazacrown ethers with the same macrocycle size. The structures of azacrown ethers and their complexes with Ba(ClO₄)₂ were studied by X‐ray diffraction. A high degree of pre‐organization of N‐methylbenzoazacrown ethers toward the formation of complexes with metal and ammonium cations was noted, which is due to the clear‐cut pyramidal geometry of the nitrogen atom and the orientation of the lone electron pairs (LEPs) of most heteroatoms towards the centre of the macroheterocycle. Copyright © 2009 John Wiley & Sons, Ltd.     

Structure of trans-1,4-polybutadiene synthesized with a new catalyst system

Abstract

The structure, phase composition, and temperature behavior of two trans-1,4-polybutadienes (TPBs) were studied by means of x-ray scattering and differential scanning calorimetry (DSC) techniques. The two samples examined were (1) PB synthesized using an immobilized titanium-magnesium catalyst and (2) a random copolymer based on PB prepared with a homogeneous vanadium-containing catalyst used as a reference material. It was found that the nascent structure of the first PB involves three phases: crystalline, mesomorphic (low-temperature form), and amorphous. In the vicinity of 65°C, a first-order phase transition occurs. The system becomes biphasic and contains the high-temperature form of the mesophase, as well as the amorphous phase, component. Above 165°C, the polymer melts to form a single-phase isotropic melt with a structure typical of liquids. The lateral dimension of crystallites reversibly changes at the crystal-mesophase transition. It is suggested that during annealing of the mesophase formed by cooling of the isotropic melt, the chains acquire an extended conformation. Loss of regularity of the structure of macromolecules of TPB causes a reduction of phase transition temperatures, an increase of the imperfection of the crystalline phase, and a contraction of the temperature range of existence of the mesophase.     

Self-collimation and beam splitting in low-index photonic crystals

We study self-collimation and beam splitting in low-refractive-index photonic crystals created within chalcogenide glass. We propose a beam splitter structure that allows direct experimental verification of photonic-crystal effects at optical wavelengths in a straightforward and definitive manner. The beam splitter provides angular separation of 90° using a highly compact spatial footprint, thus delivering direct application in highly integrated photonic devices.     

Observation of nonlinear self-trapping in triangular photonic lattices

We experimentally study light self-trapping in triangular photonic lattices induced optically in nonlinear photorefractive crystals. We observe the formation of two-dimensional discrete and gap spatial solitons originating from the first and second bands of the linear transmission spectrum.     

Self-written waveguides in photopolymerizable resins

We study the optically induced growth and interaction of self-written waveguides in a photopolymerizable resin. We investigate experimentally how the interaction depends on the mutual coherence and the relative power of the input beams and suggest an improved analytical model that describes the growth of single waveguides and the main features of their interaction in photosensitive materials.