Laser-induced fluorescence and infrared spectroscopic studies on the specific solvation of tris(1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedionato)europium(III) in an ionic liquid

The extraction constant and the two-phase stability constant (K_D,Mβ₃) of tris(2-thenoyltrifluoroacetonato)europium(III) between 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C₄mim][Tf₂N]) as an ionic liquid and an aqueous phase were determined by considering the extraction equilibria including anionic tetrakis(2-thenoyltrifluoroacetonato)europate(III). Specific solute-solvent interactions between the neutral Eu(III) chelate and [C₄mim][Tf₂N] molecules were revealed from the relationships between the distribution constant of the enol form of 2-thenoyltrifluoroacetone (Htta) as a proton chelate and the distribution constant (K_D,M) of the neutral Eu(III) chelate because the [C₄mim][Tf₂N] system gave the high K_D,Mβ₃ value compared with those in conventional molecular solvents such as benzene and 1,2-dichloroethane. The coordination environment of Eu³⁺ in the neutral Eu(III) chelate in [C₄mim][Tf₂N] was investigated by time-resolved laser-induced fluorescence spectroscopy and infrared absorption spectroscopy. Both methods consistently indicated that not only the Eu(III) chelate extracted but also Eu(tta)₃(H₂O)₃ synthesized as a solid crystal were almost completely dehydrated in [C₄mim][Tf₂N] saturated with water. Consequently, the higher K_D,M or extractability of the neutral Eu(III) chelate in the [C₄mim][Tf₂N] system can be ascribed to the dehydration of the Eu(III) chelate, which is caused by the specific solvation with [C₄mim][Tf₂N] molecules.     

Determination of selenomethionine by high performance liquid chromatography-direct hydride generation-atomic absorption spectrometry

A simple, reliable, trace determination of selenomethionine (Semet) based on a direct hydride generation atomic absorption spectrometric method was developed using sodium tetrahydroborate (0.3% in 0.2% NaOH) and hydrochloric acid (3 M). The method excluded any chemical pretreatment prior to hydride generation (HG). The optimized HG system was successfully coupled with the HPLC system. The detection limit (3σ of blank; n=5), reproducibility (R.S.D. of three successive analyses/day, performed on three different days), and repeatability (R.S.D. of three successive analyses) of the method were 1.08 ng ml⁻¹, 9.8% for 9.04 ng ml⁻¹ and 2.1–9.5% for 30.0–1.27 ng ml⁻¹ Semet as Se (standards prepared in Milli-Q water). Calibration graph was linear up to 30 ng ml⁻¹. This HPLC-HG-AAS method is very promising and successfully determined Semet (spiked) in human urine.     

New studies on scattering properties of different kinds of soot and carbon-black

New polarization and brightness curves as a function of scattering angle are studied at λ=632.8 and 543.5 nm using PROGRA2 instruments (Propriétés Optiques des Grains Astronomiques et Atmosphériques) for four different kinds of soot and for two samples of carbon-black levitating in the cloud. The soot samples are also studied on the deposited surface. Two of the soot samples are issued from incomplete combustion of Toluene liquid solvent under two different combustion conditions. Two others are issued from a solid polymer. Polymethyl Methacrylate or PMMA under two different combustion conditions. These new studies are done using new more sensitive cameras than previous ones, allowing darker agglomerates to be detected.     

Ion implantation effects on the microhardness and microstructure of GaN

We study the effect of N⁺ and O⁺ implantation on the microhardness and the microstructure of epitaxially grown GaN. The microhardness is measured using a Knoop diamond indenter while information on the effect of implantation on the surface morphology, microstructure and electronic structure is provided by atomic force microscopy, cross-section transmission electron microscopy and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. It is demonstrated that implantation increases the surface microhardness. A possible mechanism for the surface hardening effect is based on the formation of N interstitials that pin the dislocations and prohibit the plastic deformation. In addition to the hardening effect, the implantation induced N interstitials introduce a characteristic resonance in the NEXAFS spectra, at 1.4 eV below the absorption edge.     

A probabilistic property of Katsuura's continuous nowhere differentiable function

Katsuura's example of a continuous nowhere differentiable function is based on a fixed-point method. In this paper we use probability theory to study the increments of Katsuura's function.     

Time‐resolved spectroscopy study of donor–acceptor‐type copolymers in a monodisperse system: The effect of ratio between the acceptor and the donor

The photoexcitation processes of two donor–acceptor‐type copolymers PCFBT with different ratios between the donor and the acceptor ( PCFBT_0.5 and PCFBT_0.1 ) in the solution system are systematically studied. If the number of the donor is equal to that of the acceptor in one repeat unit (such as PCFBT_0.5 ), intrachain charge transfer (ICT) can occur and participate in the relaxation of the excited state after photoexcitation. When the number of donors is much larger than that of acceptors (such as PCFBT_0.1 ) in one repeat unit, the ICT character can disappear, and the localized exciton decay process is dominant in the relaxation of the copolymer, which also involves an excitation intensity‐independent vibrational thermal relaxation process at the initial time. The results further the understanding of the basic structure‐property relationship. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 992–996     

Determination of Lead in Human Hair by High Resolution Continuum Source Graphite Furnace Atomic Absorption Spectrometry with Microwave Digestion and Solid Sampling

The content of lead in human hair was measured by high resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GFAAS) combined with microwave-assisted digestion (MAD) and direct solid sampling (DSS). Hair strands were washed, dried, and then cut into three parts (root, middle portion, and tip). For MAD-GFAAS assays, approximately 0.25 g of hair was completely digested using a mixture of concentrated nitric acid and hydrogen peroxide in a closed system. In the DSS-GFAAS assays, 0.1–0.2 mg of dried hair was directly introduced into a graphite furnace using a solid autosampler. The temperature programs were optimized and the effects of various added modifiers were compared. The results indicated that NH₄H₂PO₄ was the optimal modifier for analysis of Pb using GFAAS. Use of the optimal modifier and temperature program gave similar limits of detection for MAD-GFAAS and DSS-GFAAS of 1.16 ng/g and 0.82 ng/g, respectively. Both methods also produced satisfactory recoveries ranging from 98.69% to 103.14%. There was no significant difference observed between the Pb contents of hair strands determined by the MAD-GFAAS and DSS-GFAAS assays, which both indicated that the Pb levels increased along the hair strands. Comparison of the two methods revealed that DSS-GFAAS had several advantageous characteristics over MAD-GFAAS, including the need for much less sample material and having a less time-consuming procedure, lower sample blank absorbance, lower memory effect, and no risk of environmental pollution by digesting chemicals. The direct solid sampling technique can be employed as a good alternative to conventional wet digestion in AAS assays.