Determining the effect of Ru substitution on the thermal stability of CeFe4−xRuxSb12

The ternary, rare-earth filled (RE) Skutterudites (REM₄Pn₁₂; M = Fe–Os; Pn = P–Sb) have been proposed for use in high-temperature thermoelectric devices to convert waste heat to useful power. CeFe₄Sb₁₂ has been one of the most popular materials proposed for this application; however, it oxidizes at relatively low temperatures. The thermal stability of Skutterudites can be enhanced by selective substitution of the constituent elements and Eu(Fe,Ru)₄Sb₁₂ variants have been found to oxidize at temperatures above that of CeFe₄Sb₁₂. Unfortunately, these materials have poor thermoelectric properties. In this study, the thermal stability of CeFe_4−xRu_xSb₁₂ was examined depending on the value of x. (These compounds have similar thermoelectric properties to those of CeFe₄Sb₁₂.) It has been found by use of TGA and XANES that the temperature at which point CeFe_4−xRu_xSb₁₂ oxidizes increases with greater Ru substitution. XANES was also used to confirm the general charge assignment of Ce³⁺Fe_4−x²⁺Ru_x²⁺Sb₁₂¹⁻.     

PHOTOCHEMICAL LINKAGE OF ANTIBODIES TO SILICON CHIPS

Antibodies and antigen binding fragments thereof were photochemically immobilized on surface-modified silicon chips of 5 × 5 mm size. Silicon surface-grafted diazirines and benzophenones formed covalent bonds with the immunoreagents on light activation. Photolithographic immobilization of monoclonal antibodies in aqueous media was achieved on silicon chips by activating surface-grafted benzophenones. The presence of bovine serum albumin during irradiation reduced nonspecific adsorption of the immunoreagents and retained the immunoactivity of the photoimmobilized molecules.     

Fast immobilization of probe beads by dielectrophoresis-controlled adhesion in a versatile microfluidic platform for affinity assay

The use of probe beads for lab-on-chip affinity assays is very interesting from a practical point of view. It is easier to handle and trap beads than molecules in microfluidic systems. We present a method for the immobilization of probe beads at defined areas on a chip using dielectrophoresis (DEP)-controlled adhesion. The method is fast, i.e., it takes between 10 and 120 s--depending on the protocol--to functionalize a chip surface at defined areas. The method is versatile, i.e., it works for beads with different types of probe molecule coatings. The immobilization is irreversible, i.e., the retained beads are able to withstand high flow velocities in a flow-through device even after the DEP voltage is turned off, thus allowing the use of conventional high-conductivity analyte buffers in the following assay procedure. We demonstrate the on-chip immobilization of fluorescent beads coated with biotin, protein A, and goat-antimouse immunoglobulin G (IgG). The number of immobilized beads at an electrode array can be determined from their fluorescence signal. Further, we use this method to demonstrate the detection of streptavidin and mouse IgG. Finally, we demonstrate the feasibility of the parallel detection of different analyte molecules on the same chip.     

Reaction of Hydroxymethyl- and Alkyl-Substituted Azulenes with Manganese Dioxide

It is shown that the 2-(hydroxymethyl)-1-methylazulenes 6 are being oxidized by activated MnO₂ in CH₂Cl₂ at room temperature to the corresponding azulene-1,2-dicarbaldehydes 7 (Scheme 2). Extension of the MnO₂ oxidation reaction to 1-methyl- and/or 3-methyl-substituted azulenes led to the formation of the corresponding azulene-1-carbaldehydes in excellent yields (Scheme 3). The reaction of unsymmetrically substituted 1,3-dimethyl-azulenes (cf. 15 in Scheme 4) with MnO₂ shows only little chemoselectivity. However, the observed ratio of the formed constitutionally isometric azulene-1-carbaldehydes is in agreement with the size of the orbital coefficients in the HOMO of the azulenes. The reaction of guaiazulene ( 18 ) with MnO₂ in dioxane/H₂O at room temperature gave mainly the expected carbaldehyde 19 . However, it was accompanied by the azulene-diones 20 and 21 (Scheme 5). The precursor of the demethylated compound 20 is the carbaldehyde 19 . Similarly, the MnO₂ reaction of 7-isopropyl-4-methyalazulene ( 22 ) as well as of 4,6,8-trimethylazulene ( 24 ) led to the formation of a mixture of the corresponding azulene-1,5-diones and azulene-1,7-diones 20 / 23 and 25 / 26 , respectively, in decent yields (Schemes 6 and 7). No MnO₂ reaction was observed with 5,7-dimethylazulene.     

CO<Subscript>2</Subscript> laser-photoacoustic analysis of smoke emitted during minimal invasive electro-knife surgery

Smoke samples produced by colorectral laparoscopic operations have been studied with a ¹³CO₂ laser-based photoacoustic spectrometer. The most difficult problem was the existence of almost 100% CO₂ present in the sample. The PA measurements were complemented with broad range FTIR spectra. An important result is the striking difference between sample spectra taken from different operations and patients. Apart from dominating CO₂, a first spectral analysis revealed the existence of ~100 ppm water vapor and of unknown compounds that could not yet be identified but that are not identical with compounds found in related studies.     

Tetrathiafulvalene-based lanthanide coordination complexes: Synthesis,crystal structure,optical and electrochemical characterization

The explorative lanthanide coordination chemistry of 4′,5′-bis-(propylthio)tetrathiafulvenyl[i]dipyrido[3,2-a:2′,3′-c]phenazine (TTF-dppz) is described. Thereby, four new Ln(III) complexes, [Ln(NO₃)₃(TTF-dppz)₂] with Ln(III) = Nd (1), Eu (2), Gd (3), Tb (4), have been prepared and characterized. An X-ray crystallographic study of [Gd(NO₃)₃(TTF-dppz)₂] (3) shows that the Gd(III) ion is coordinated to six oxygen atoms from three bidentate nitrate ligands and four nitrogen atoms from two bidentate TTF-dppz molecules forming a distorted bicapped square antiprism coordination geometry. The UV-vis spectra of the four Ln(III) complexes show very strong absorption bands in the UV region consistent with ligand centred electronic π-π* transitions and an intense broad absorption band in the visible region corresponding to a spin-allowed electronic π-π* ¹ILCT transition from the TTF-dppz ligand. Upon coordination, the ¹ILCT band of the free TTF-dppz ligand is bathochromically shifted. The electrochemical studies reveal that all complexes undergo two reversible oxidation and one (quasi)reversible reduction processes, ascribed to the successive oxidations of the TTF moiety and the reduction of the dppz unit, respectively. Moreover, the magnetic properties of complexes 3 and 4 are discussed.     

Chemical analysis of surgical smoke by infrared laser spectroscopy

The chemical composition of surgical smoke, a gaseous by-product of some surgical devices??lasers, drills, vessel sealing devices??is of great interest due to the many toxic components that have been found to date. For the first time, surgical smoke samples collected during routine keyhole surgery were analyzed with infrared laser spectroscopy. Traces (ppm range) of methane, ethane, ethylene, carbon monoxide and sevoflurane were detected in the samples which consisted mostly of carbon dioxide and water vapor. Except for the anaesthetic sevoflurane, none of the compounds were present at dangerous concentrations. Negative effects on the health of operation room personnel can be excluded for many toxic compounds found in earlier studies, since their concentrations are below recommended exposure limits.     

S-wave spin-triplet order in superconductors without inversion symmetry: Li2Pd3B and Li2Pt3B

We investigate the order parameter of noncentrosymmetric superconductors Li2Pd3B and Li2Pt3B via the behavior of the penetration depth lambda(T). The low-temperature penetration depth shows BCS-like behavior in Li2Pd3B, while in Li2Pt3B it follows a linear temperature dependence. We propose that broken inversion symmetry and the accompanying antisymmetric spin-orbit coupling, which admix spin-singlet and spin-triplet pairing, are responsible for this behavior. The triplet contribution is weak in Li2Pd3B, leading to a wholly open but anisotropic gap. The significantly larger spin-orbit coupling in Li2Pt3B allows the spin-triplet component to be larger in Li2Pt3B, producing line nodes in the energy gap as evidenced by the linear temperature dependence of lambda(T). The experimental data are in quantitative agreement with theory.