Amino wagging and inversion in hydrazine: K′ = 1 levels in the first excited state of the antisymmetric wagging vibration

The infrared absorption spectrum of NH₂NH₂ vapor has been observed in the region 899–1077 cm^?1, where the antisymmetric wagging band (v_a = 1 ← 0) appears, by the use of a Fourier transform spectrometer with a practical resolution of 0.003 cm^?1. In the region 925.0–925.6 cm^?1, the spectrum was also observed with a tunable diode laser, and a component, β, of the ^pQ₂ cluster has been further resolved. Most of the absorption lines assignable to β-^pP₂(J″), γ-^pP₂(J″), β-^pQ₂(J″), γ-^rQ₀(J″), β-^rR₀(J″), and γ-^rR₀(J″), where J″ = 2 ～ 15, have been identified. From these observed transition frequencies, in combination with the ground state energy levels given by microwave spectroscopy, the energy level structure of the K′ = 1 rotational states was determined. From this, the following molecular parameters for the v_a = 1 state were determined: molecular asymmetry, B′-C″ = 0.00017 cm^?1; a parameter q₅ describing an umbrella motion Coriolis interaction (q₅K) about the a axis, q₅ = ?0.0030 cm^?1; its J(J + 1) variation, q_5j = 0.00014 cm^?1; and a parameter describing an umbrella-motion K-type doubling g₅J(J + 1), g₅ = 0.000021 cm^?1.     

A photo-induced redox reaction by visible light via a charge transfer complex

The reduction of tropylium cation (Tr⁺) with the concomitant oxidation of O,O′-dialkyldithiophosphate anions (dtp^?) have been achieved by visible irradiation of their acetonitrile solution in presence of a bipyridinium dication ; the later via its charge transfer complex with dtp^? acts as a light-harvest and as an electron relay.     

Degenerate Dirichlet Problems Related to the Invariant Measure of Elasto-Plastic Oscillators

A stochastic variational inequality is proposed to model a white noise excited elasto-plastic oscillator. The solution of this inequality is essentially a continuous diffusion process for which a governing diffusion equation is obtained to study the evolution in time of its probability distribution. The diffusion equation is degenerate, but using the fact that the degeneracy occurs on a bounded region we are able to show the existence of a unique solution satisfying the desired properties. We prove the ergodic properties of the process and characterize the invariant measure. Our approach relies on extending Khasminskii’s method (Stochastic Stability of Differential Equations, Sijthoff and Noordhoff, 1980), which in the present context leads to the study of degenerate Dirichlet problems with nonlocal boundary conditions. This research was partially supported by a grant from CEA, Commissariat à l’énergie atomique and by the National Science Foundation under grant DMS-0705247.     

Influence of femtosecond laser marking on the corrosion resistance of stainless steels

Marking is of prime importance in the field of biomaterials to allow the identification of surgical tools as well as prostheses. Nowadays, marking is often achieved by means of laser beam, which may modify the characteristics of the treated surfaces. The use of laser devices delivering nanosecond pulses is known to induce dramatic corrosion degradations during sterilization or decontamination processes of the biomaterials. The aim of the present study is to investigate the ability of femtosecond (pulse duration in the 10⁻¹⁵ s range) laser treatments to avoid preferential corrosion processes of the marked areas, in order to extend the durability and the reliability of biomaterials. Experiments have been performed on martensitic Z30C13 and austenitic 316L stainless steels. Electrochemical measurements (cyclic polarization curves) were carried out to determine the passive state of samples before and after engraving, their corrosion rate and their susceptibility to localized corrosion. Further protracted immersion tests were also carried out to evaluate the natural long-term degradation of engraved parts. The electrochemical behavior is then explained on the basis of surface characterizations. Femtosecond laser marking is shown to provide an electrochemical ennoblement. Moreover, the chemical composition is not affected so that the passive character of both stainless steels is maintained, even improved if we consider the susceptibility to localized corrosion.     

Camphor-derived sulfonylhydrazines: catalysts for Diels-Alder cycloadditions

Camphor-derived sulfonylhydrazines proved to be very active for organocatalyzed Diels-Alder cycloadditions with cyclopentadiene. Good chemical yields and enantiomeric excesses up to 89% and 88% are obtained for endo/exo adducts.     

Influence of water on localized and delocalized molecular mobility of cellulose

The influence of hydration on cellulose molecular mobility is investigated by two dielectric methods at different molecular scale. The mobility of side groups, assigned to γ mode, for dried cellulose increases. The water molecules have an anti-plasticizer effect on γ mode due to the water–polymer hydrogen bonding. For the β relaxation mode, only observed by the Thermo Stimulated Current technique, the hydration plays a role of plasticizer. The α relaxation mode assigned to the delocalized cooperative mobility of long chain segments of cellulose is plasticized by water. The study of activated parameters deduced from fractional polarization procedure, shows an increase of the activation enthalpy range with dehydration. It permits to conclude that reduction of hydrogen bonds density leading to a more extended cooperative mobility.     

Instability of mercury in specimens of human urine for external quality assessment

An under-recovery of inorganic mercury added to urine and a wide range of results is observed in quality assessment schemes (EQAS) for trace elements. Furthermore, the under-recoveries are inconsistent suggesting features associated with the urine matrix may make the mercury unavailable for measurement. To investigate the instability of mercury in urine the following experiments were set up: (1) a sample of Hg²⁺ in water with various ‘stabilizers’ added was sent to UK external quality assessment scheme participants. (2) Urine was collected from volunteers who also completed a 3-day food diary. Hg, Ca, Mg, Se, uric acid, phosphate, creatinine, reducing substances and protein were measured. Inorganic mercury was spiked into the urine, stabilizers were added and the mercury determined following storage. The results confirmed under-recovery of mercury in association with the urine matrix. Further investigations of how urinary components affect the measurement of mercury are necessary.     

Synthesis of new boron analogues of cyclic carboxylic α-amino acids using ring-closing metathesis reactions

Ruthenium catalyzed ring-closing metathesis has been used as a key step for the synthesis of cyclic α-aminoboronic esters as, for example, boron-containing mimics of pipecolic, 2-azepanecarboxylic acid or baikiain.     

Polymorphism of Anhydrous Cadmium Iodate Structure of ε‐Cd(IO3)2

The investigation of CdCl₂‐HIO₃ system, in aqueous and HNO₃ solutions, revealed that anhydrous cadmium iodate presents a marked polymorphism. No less than four new Cd(IO₃)₂polymorphs have been isolated and characterized, two of which showing second harmonic generation activity. Single crystals of ε‐Cd(IO₃)₂ are obtained by slowly evaporating, at 60 °C, a saturated solution of γ‐Cd(IO₃)₂ in 30 % nitric acid. This compound crystallizes in the orthorhombic space group Pca2₁ [a = 17.581(2), b = 5.495(2), c = 11.163(2) Å]. The basic structural unit can be described as the connection of two cadmium polyhedrons with a short metal – metal distance of 3.88Å. These units are further linked through two other iodate bridges resulting in layers parallel to the (100) plane. The 3D linkage is ensured by short bonds of the fourth iodate group.