Hydrogen bonding in redox-modulated molecular recognition. An experimental and theoretical investigation

Two receptors, a diaminotriazine derivative (DAT) and diamidopyridine (DAP), are complementary to the electroactive naphthalimide (N) through three-point hydrogen bonding. The association constants of the two receptors were evaluated for both the fully oxidized and the radical anion forms of N. In the oxidized state, the two receptors displayed identical binding constants. Diamidopyridine, however, lowers the reduction potential of naphthalimide to a far greater extent than does diaminotriazine, indicating a greater affinity for diamidopyridine by naphthalimide in the radical anion form. This behavior was mirrored by EPR experiments that showed small deviations from the hyperfine coupling pattern of N(red) in the presence of DAT, with greater effects seen for the N(red).DAP complex. Computational simulations using the UB3LYP/6-311+G(d,p)//UHF/6-31G(d) hybrid gave theoretical hyperfine constants in good quantitative agreement with the experimental results. Using this correlation, we determined that electrostatics and hydrogen bond polarizability play key roles in controlling redox-modulated molecular recognition.     

Solid support flame synthesis of 1-D and 3-D tungsten-oxide nanostructures

In this paper we report the growth of 1-D and 3-D tungsten-oxide nanostructures on tungsten wire probes inserted in an opposed-flow oxy-fuel flame. The probe diameter and oxygen content in the oxidizer were varied to study their influence on the growth of tungsten-oxide nanostructures. The introduction of a 1-mm diameter W probe into the flame environment with an oxidizer composition of 50%O₂ + 50%N₂, resulted in the formation of 1-D nanorods on the upper surface of the probe. The formation of triangular, rectangular, square, and cylindrical 3-D channels with completely hollow or semi-hollow morphology was achieved by reducing the probe diameter to 0.5 mm. Whereas, the increase of the O₂ content to 100% and the employment of a 1-mm probe resulted in the growth of ribbon-like micron-sized structures. The lattice spacing of ∼0.38 nm measured for the 1-D W-oxides closely matches a monoclinic WO₃ structure. X-ray photoelectron spectroscopy analysis revealed that the larger 3-D structures also consist of WO₃ confirming that the chemical composition of the structures remains the same while varying the probe and flame parameters. The proposed growth mechanism states that the 3-D WO₃ structures are formed through the lateral coalescence of 1-D W-oxide nanorods.     

Aerodynamic levitation and laser heating:

Aerodynamic levitation is an effective way to suspend samples which can be heated with CO₂ lasers. The advantages of this containerless technique are the simplicity and compactness of the device, making it possible to integrate it easily in different kinds of experiments. In addition, all types of materials can be used, including metals and oxides. The integration of aerodynamic levitation at synchrotron and neutron sources provides powerful tools to study the structure and dynamics of molten materials. We present here an overview of the existing techniques and of the developments made at the CEMHTI in Orléans, as well as a few examples of experimental results already obtained.     

Trialkyltetrathiafulvalene-sigma-tetracyanoanthraquinodimethane [R(3)TTF-sigma-TCNAQ] diads: synthesis, intramolecular charge-transfer properties, and X-ray crystal structure.

We report the use of the electron-donating 4,5-dipentyl-4'-methyl-TTF (TTF = tetrathiafulvalene) moiety in combination with the electron acceptor 11,11,12,12-tetracyanoanthraquinodimethane (TCNAQ) unit in the novel D-sigma-A diad molecules 11, 17, and 18. These compounds display a weak, broad, low-energy intramolecular charge-transfer (ICT) band in the UV-vis spectra (lambda(max) 430-450 nm). Cyclic voltammetric studies show two reversible one-electron oxidation processes for the R(3)TTF moiety, and a reversible two-electron reduction process for the TCNAQ moiety. The electron affinity of TCNAQ is significantly enhanced by the electron-withdrawing sulfonamide and sulfonic ester groups (compounds 17 and 18, respectively). Simultaneous electrochemistry and EPR (SEEPR) experiments show no significant intramolecular interaction between the R(3)TTF and TCNAQ moieties in compounds 11 and 18. X-ray crystallographic data are presented for 5, 11, and 20. The structure of 5 reveals hydrogen-bonded dimers. In molecule 11 the bond lengths and conformations of both donor and acceptor moieties are typical for neutral species. Compound 20 is an unusual calcium complex of TCNAQ derivative obtained by dicyanomethylation of anthraquinone-2-carboxylic acid.     

Validation of an HPLC method for the determination of *-dichlorobenzene and naphthalene in mothrepellents

 The determination of dichlorobenzene and naphthalene in commercial repellents used in Spain has been validated. This was done using an isocratic regime, to test the reverse -phase HPLC system with acetonitrile: water 65 : 35 (v: v) as the mobile phase, at 20  °C. This technique is proposed for the modular validation of the HPLC system . The results obtained with this method show good agreement with the results provided by the manufacturers of the mothrepellents. Received: 21 December 1998 / Accepted: 4 May 1999     

Glass fragility and atomic ordering on the intermediate and extended range

The relation between the fragility of glass-forming systems, a parameter which describes many of their key physical characteristics, and atomic scale structure is investigated by using neutron diffraction to measure the topological and chemical ordering for germania, or GeO(2), which is an archetypal strong glass former. We find that the ordering for this and other tetrahedral network-forming glasses at distances greater than the nearest neighbor can be rationalized in terms of an interplay between the relative importance of two length scales. One of these is associated with an intermediate range, the other with an extended range and, with increasing glass fragility, it is the extended range ordering which dominates.     

Crystal and magnetic structure of the system Li0.5+0.5xFe2.5-1.5xTixO4 (x=0.16, 0.44, and 0.72)

The influence of thermal treatment on the structure of lithium titanium ferrite spinels of general formula Li(0.5+0.5x)Fe(2.5-1.5x)Ti(x)O4 (x=0.16, 0.44, and 0.72) has been studied by X-ray and neutron diffraction and analysed by the Rietveld method. The results allow us to conclude the presence of an ordered phase (space group P4(3)32) at room temperature for the sample with x=0.16; this phase does not appear for the remaining compositions. The magnetic properties evidence a ferrimagnetic ordering in the structures when a random cation distribution (space group Fd3 m) is obtained. An exhaustive study carried out by neutron diffraction measurements on these samples shows a different behaviour when the titanium content is increased, concluding that the lower substituted phase (x=0.16) exhibits a Neel's collinear ferrimagnetic structure, with the higher substituted structures being noncollinear (x=0.44 and 0.72).     

Energy spectra for decaying 2D turbulence in a bounded domain

We use results derived in the framework of the replica approach to study the liquid-glass thermodynamic transition. The main results are derived without using replicas and applied to the study of the Lennard-Jones binary mixture introduced by Kob and Andersen. We find that there is a phase transition due to the entropy crisis. We compute both analytically and numerically the value of the phase transition point T(K) and the specific heat in the low temperature phase.     

Klein–Gordon and Dirac Equations in de Sitter Space–Time

We present and discuss the Klein–Gordonand Dirac wave equations in the de Sitter universe. Toobtain the Dirac wave equation we use the factorizationof the second-order invariant Casimir operatorassociated to the Fantappie–de Sitter group. Boththe Klein–Gordon and Dirac wave equations arediscussed in terms of the spherical harmonics with spinweight. A particular case of Dirac wave equation issolved in terms of a new class of polynomials.     

Mössbauer Spectroscopy, Dilatometry and Neutron Diffraction Detection of the ɛ-Phase Fraction in Fe–Mn Shape Memory Alloys

The results of a Mössbauer spectroscopy (MS) and a neutron diffraction (ND) study carried out on a set of Fe–Mn alloys quenched from high temperatures are reported. Upon quenching the high temperature stable phase FCC (γ) together with metastably retained HCP-(?) phase are formed. The lattice parameters obtained using ND are in excellent agreement with previous results of the literature. The phase fractions obtained from MS are coincident, within experimental errors, with those extracted from ND, with exception of the case of an alloy with the lowest Mn content (16.8 at.% Mn). That situation can be associated with the occurrence of a high density of stacking faults (SF) in the γ phase or to the presence of a paramagnetic γ phase. ? phase fractions obtained from MS and ND decrease smoothly with Mn content but are always larger than the values reported in literature resulting from dilatometry.