Sensitised near-infrared luminescence from lanthanide(III) centres using Re(I) and Pt(II) diimine complexes as energy donors in d-f dinuclear complexes based on 2,3-bis(2-pyridyl)pyrazine

The luminescent transition metal complexes [Re(CO)(3)Cl(bppz)] and [Pt(CC-C(6)H(4)CF(3))(2)(bppz)] [bppz = 2,3-bis(2-pyridyl)pyrazine], in which one of the diimine binding sites of the potentially bridging ligand bppz is vacant, have been used as 'complex ligands' to make heterodinuclear d-f complexes by attachment of a {Ln(dik)(3)} fragment (dik = a 1,3-diketonate) at the vacant site. When Ln = Pr, Nd, Er or Yb the lanthanide centre has low-energy f-f excited states capable of accepting energy from the (3)MLCT excited state of the Pt(II) or Re(I) centre, quenching the (3)MLCT luminescence and affording sensitised lanthanide(III)-based luminescence in the near-IR region. UV/Vis and luminescence spectroscopic titrations allowed measurement of (i) the association constants for binding of the {Ln(dik)(3)} fragment at the vacant diimine site of [Re(CO)(3)Cl(bppz)] or [Pt(CC-C(6)H(4)CF(3))(2)(bppz)], and (ii) the degree of quenching of the (3)MLCT luminescence according to the nature of the Ln(III) centre. In all cases Nd(III) was found to be the most effective of the series at quenching the (3)MLCT luminescence of the d-block component because the high density of f-f excited states of the appropriate energy make it a particularly effective energy-acceptor.     

Dissociative Electron Attachment to Hexachlorobenzene

Gas phase molecules of hexachlorobenzene (C₆Cl₆) were investigated by means of dissociative electron attachment spectroscopy (DEAS). Three channels of molecular negative ions decay have been identified: abstraction of Cl⁻ and Cl₂⁻ as well as electron detachment (τ_a∼250 μs at 343 K). All three channels exhibit temperature dependence. The adiabatic electron affinity estimated using a simple but typically accurate Arrhenius model (EA_a=1.6–1.9 eV) turns out to be much higher than the quantum-chemical predictions (EA_a=0.9–1.0 eV). We discuss the possible reasons behind the observed discrepancy.     

Efficient spectral and pseudospectral algorithms for 3D simulations of whistler-mode waves in a plasma

Efficient spectral and pseudospectral algorithms for simulation of linear and nonlinear 3D whistler waves in a cold electron plasma are developed. These algorithms are applied to the simulation of whistler waves generated by loop antennas and spheromak-like stationary waves of considerable amplitude. The algorithms are linearly stable and show good stability properties for computations of nonlinear waves over tens of thousands of time steps. Additional speedups by factors of 10–20 (comparing single core CPU and one GPU) are achieved by using graphics processors (GPUs), which enable efficient numerical simulation of the wave propagation on relatively high resolution meshes (tens of millions nodes) in personal computing environment. Comparisons of the numerical results with analytical solutions and experiments show good agreement. The limitations of the codes and the performance of the GPU computing are discussed.     

Rogue wave early warning through spectral measurements?

We study the spectra of the Peregrine soliton and higher-order rational solutions of the nonlinear Schrödinger equation (NLSE), which we use as a model of the rogue waves in optics and in the deep ocean. We show that these solutions have specific triangular spectra that are certainly easily measurable in optical systems and which may be amenable to characterisation in ocean environments. As the triangular feature of the solutions appears at an early stage of their evolution, this raises the possibility of early detection and possible localized warning of the appearance of rogue waves. We anticipate that studying the characteristics of “early warning spectra” of rogue waves may become an important future field of research.     

Adsorption recovery and preconcentration of Ni(II), Zn(II), and Cd(II) on nitrocellulose membranes modified with <Emphasis Type="Italic">N</Emphasis>-acylamidophosphates

N-(Thio)phosphorylated (thio)carbamides and (thi o)amides are proposed as modifiers of polymer nitrocellulose membranes for the adsorption preconcentration of Ni(II), Zn(II), and Cd(II) from aqueous solutions. The binding constants of metalions with the immobilized reagents are 1.5–2.5 times higher than those with monomer ligands in solution. The preconcentration coefficients are 1950–3500. Aprocedure was developed for the adsorption preconcentration and recovery of Ni(II), Zn(II), and Cd(II) as complex compounds, using nitrocellulose membranes modified with N-(thio)phosphorylated thiocarbamides and thioamides.     

Structure and intramolecular mobility of N-(thio)phosphoryl(thio)amides: XV. Study of structure and intramolecular dynamics of N3-phenyl-N1-(diisopropoxythiophosphoryl)thiosemicarbazide in CD2Cl2 solution by 1H, 13C and 31P NMR spectroscopy

Structure and intramolecular transformations of N³-phenyl-N¹-(diisopropoxythiophosphoryl)-thiosemicarbazide in CD₂Cl₂ were studied by one- and two-dimensional ¹H, ¹³C and ³¹P NMR spectroscopy. The combined analysis of the data of NMR spectroscopy and calculation simulation confirmed a high lability of the studied compounds resulting in the formation of various conformational and tautomeric forms in solutions. The preference of Z,E-conformation of the amide form with cis- and trans-location of two N-H groups and the C=S group relatively to the two C-N bonds was revealed.     

Three-dimensional dynamical systems with four-dimensional Vessiot-Guldberg-Lie algebras

Dynamical systems attract much attention due to their wide applications. Many significant results have been obtained in this field from various points of view. The present paper is devoted to an algebraic method of integration of three-dimensional nonlinear time dependent dynamical systems admitting nonlinear superposition with four-dimensional Vessiot-Guldberg-Lie algebras $L_4.$ The invariance of the relation between a dynamical system admitting nonlinear superposition and its Vessiot-Guldberg-Lie algebra is the core of the integration method. It allows to simplify the dynamical systems in question by reducing them to \textit{standard forms}. We reduce the three-dimensional dynamical systems with four-dimensional Vessiot-Guldberg-Lie algebras to 98 standard types and show that 86 of them are integrable by quadratures.     

A Comparative Study of the Cyclic Chlorophosphites with C2-Symmetrical Organic Fragments as the Reagents for Enantiomeric Composition Control of the Chiral Alcholos

Abstract

The ³¹P NMR method is intensively used for enantiomeric composition control during the last years [1]. Among all other derivatizing agents the C₂-symmetrical ones have some advantages.     

The Relationship Between the TMDSC Curve of Frozen Sucrose Solutions and Collapse During Freeze-Drying

This study compares measurements of the collapse temperature of sucrose solutions by freeze drying microscopy with features of TMDSC curves both in the scanning and quasi-isothermal modes. The objective was to determine which feature of the TMDSC curve is predictive of collapse and to provide additional evidence for recent interpretations of the physical significance of the low temperature transitions for sucrose solutions. Interpretations based on the heat capacity signal and the kinetic heat flow using TMDSC are consistent with previous reports based on total heat flow measurement, where the lower temperature transition is the glass transition and the higher temperature transition is associated with the onset of ice melting. Quasi-isothermal experiments further support these conclusions, since additional crystallization of ice is observed only in the region of the lower temperature transition. Collapse of sucrose solutions during freeze-drying begins at the approximate midpoint between the end of the glass transition region and the onset of ice melting. This revised version was published online in July 2006 with corrections to the Cover Date.