Structure and magnetic properties of a non-heme diiron complex singly bridged by a hydroxo group

The synthesis of the first singly bridged non-heme diiron complex with a mu-hydroxo bridging ligand, [{(salten)Fe}2(OH)][B(C6H5)4].(CH3CN)x.(H2O)y (1) [H2salten = 4-azaheptane-1,7-bis(salicylideneiminate)], is reported. The complex has been characterized with X-ray crystallography, FTIR, magnetic susceptibility measurements, and M?ssbauer spectroscopy. The data have been compared with the results of DFT calculations on both 1 and a model with an unsupported mu-oxo bridge (2) to verify the formulation of the complex as a mu-hydroxo-bridged species. The X-ray structure [Fe-O(H) = 1.997(1) A and Fe-O(H)-Fe = 159 degrees ] is consistent with the DFT-optimized geometry of 1 [Fe-O(H) = 2.02 A and Fe-O(H)-Fe = 151 degrees ]; the Fe-O(H) distance in 1 is about 0.2 A longer than the Fe-O separations in the optimized geometry of 2 (1.84 A) and in the crystallographic structures of diiron(III) compounds with unsupported mu-oxo bridges (1.77-1.81 A). The formulation of 1 as a hydroxo-bridged compound is also supported by the presence of an O-H stretch band in the FTIR spectrum of the complex. The magnetic susceptibility measurements of 1 reveal antiferromagnetic exchange (J = 42 cm(-1) and H(ex) = JS(1).S(2)). Nearly the same J value is obtained by analyzing the temperature dependence of the M?ssbauer spectra (J = 43 cm(-1); other parameters: delta = 0.49 mm s(-1), DeltaE(Q) = -0.97 mm s(-1), and eta = 0.45 at 4.2 K). The experimental J values and M?ssbauer parameters agree very well with those obtained from DFT calculations for the mu-hydroxo-bridged compound (J = 46 cm(-1), delta = 0.48 mm s(-1), DeltaE(Q) = -1.09 mm s(-1), and eta = 0.35). The exchange coupling constant in 1 is distinctly different from the value J approximately 200 cm(-1) calculated for the optimized mu-oxo-bridged species, 2. The increased exchange-coupling in 2 arises primarily from a decrease in the Fe-O bond length.     

Quadruplex-based molecular beacons as tunable DNA probes

Molecular beacons (MBs) are fluorescent nucleic acid probes with a hairpin-shaped structure in which the 5' and 3' ends are self-complementary. Due to a change in their emissive properties upon recognition with complementary sequences, MBs allow the diagnosis of single-stranded DNA or RNA with high mismatch discrimination, in vitro and in vivo. Whereas the stems of MB hairpins usually rely on the formation of a Watson-Crick duplex, we demonstrate in this report that the preceding structure can be replaced by a G-quadruplex motif (G4). Intramolecular quadruplexes may still be formed with a central loop composed of 12 to 21 bases, therefore extending the sequence repertoire of quadruplex formation. G4-MB can efficiently be used for oligonucleotide discrimination: in the presence of a complementary sequence, the central loop hybridizes and forms a duplex that causes opening of the quadruplex stem. The corresponding G4-MB unfolding can be detected by a change in its fluorescence emission. We discuss the thermodynamic and kinetic opportunities that are provided by using G4-MB instead of traditional MB. In particular, the intrinsic feature of the quadruplex motif facilitates the design of functional molecular beacons by independently varying the concentration of monovalent or divalent cations in the medium.     

Electrical conductivity of low-temperature carbons as a function of frequency

The electrical conductivity of anthracene carbon samples, heat treated to temperatures of 600, 650, 730 and 800°C is measured at variable frequency up to 100 MHz. The carbons heat-treated to 600 and 650°C have a specific behaviour of amorphous solids, whereas the carbons HTT 730° and 800°C have an electrical conductivity independent of the frequency. The experimental results are correctly explained by means of the equations developed by Pollak and Geballe. Analysis of the results points to the conclusion that a hopping conduction between localized states could be a possible process of conduction in such solids.     

Spin fluctuations in metals: Application to the actinides

We present here a review of the spin fluctuation theory and of its applications to transition and actinide systems, with a particular emphasis to the latter where some very anomalous properties find an explanation in terms of spin fluctuation effects. Firstly, we summarize the development of the spin fluctuation model which had been initially applied to transition metals and alloys such as palladium or Pd–Ni alloys. Then, we present the extension of the paramagnon model to nearly magnetic actinide systems by taking into account explicitly the temperature dependence of the Stoner susceptibility, because the 5f-band of actinides is much narrower than the d-band of transition metals. As a result the paramagnon contribution to the resistivity departs from the usual T ² and T power laws at temperatures higher than the spin fluctuation one and saturates at high temperatures, with eventually the presence of a maximum at intermediate temperatures. We present also the calculation of the other properties of actinide systems, namely the thermal resistivity, the thermoelectric power, the magnetic susceptibility, the specific heat capacity and the NMR relaxation rate, which are generally enhanced by the presence of paramagnons. Finally, we have introduced the concept of ‘antiferromagnetic-like’ spin fluctuations which have a maximum of the q-dependent susceptibility _χ(q) at a q value different from q =0, in contrast to the regular ferromagnetic spin fluctuations; both types of spin fluctuation give the same resistivity behaviour, while they yield a markedly different behaviour of the magnetic susceptibility, in agreement with experiment. The spin fluctuation theory is applied successfully to the different properties of neptunium and plutonium metals and of many nearly magnetic compounds such as UAl₂.     

Multi-mJ pulse compression in hollow fibers using circular polarization

We develop a numerical model to explore the polarization-dependent compression of multi-mJ laser pulses in a gas-filled hollow fiber. We show how losses and instabilities due to cycling of pulse energy between fiber modes can be efficiently minimized using circularly polarized light and adjusting simple experimental parameters such as pulse energy, chirp and gas pressure. This should help scale the peak power of few-cycle pulses available for high-field experiments using standard hollow fiber compressors. We also discuss the limits of this approach.     

In-situ SEOP polarizer and initial tests on a high flux neutron beam

Polarized ³He has shown its unique characteristics in many areas of polarized neutron scattering, its ability to polarize neutrons at short wavelengths, accept wide-angle and divergent beams and low backgrounds enable new classes of experiments. While polarized ³He is not a steady state solution as commonly applied, the benefits have been shown to offset the drawbacks of polarizing and refreshing the polarization in the neutron spin filter cells. As an extension of this work, in-situ polarization using the spin-exchange optical pumping (SEOP) method was explored as a means to construct a system which could be used to polarize ³He in the state used for an effective neutron spin filter to constant polarization while on the neutron beam. An in-situ SEOP polarizer was constructed. This device utilized many devices and principles developed for neutron spin filters which are polarized off the beam line using either SEOP or metastability exchange optical pumping (MEOP) under the same research program. As a collimation of this work effects of extremely high neutron capture flux density incident on the in-situ polarizer were explored.     

Preparation and characterization of “furanoradialene” (tetramethylene - tetrahydrofuran)

Tetramethylene-tetrahydrofuran has been prepared by flash vacuum thermolysis. This compound is stable in solution below ?50° C, and was characterized by NMR and mass spectrometry.