Structure and lithium mobility of Li<Subscript>4</Subscript>Pt<Subscript>3</Subscript>Si

The lithium-rich silicide Li₄Pt₃Si was synthesised from the elements by high-temperature synthesis in a sealed niobium ampoule. Its structure was refined on the basis of single-crystal X-ray diffraction data: R32, a = 693.7(2), c = 1627.1(4) pm, wR2 = 0.0762, 525 F² values and 21 variables. The striking structural motifs of the Li₄Pt₃Si structure are silicon atoms with a slightly distorted trigonal prismatic platinum coordination with short Si–Pt distances (238–246 pm). Always two trigonal prisms are condensed via a common Pt₃ triangle, and these double units built up a three-dimensional network by condensation via common corners. The channels left by this prismatic network are filled by two crystallographically independent lithium sites in a 3:1 ratio. The single crystal X-ray data were fully confirmed by neutron powder diffraction and ⁷Li magic-angle spinning (MAS)–nuclear magnetic resonance (NMR) results. The two distinct lithium sites are well differentiated by their ⁷Li isotropic chemical shift and nuclear electric quadrupolar interaction parameters. MAS-NMR spectra reveal signal coalescence effects above 300 K, indicating chemical exchange between the lithium sites on the millisecond timescale. The spectra can be simulated with a simple two-site exchange model. From the resulting temperature-dependent correlation times, an activation energy of 50 kJ/mol is extracted.     

Sodium dodecyl sulfate-modified electrochemical paper-based analytical device for determination of dopamine levels in biological samples

We report the development of an electrochemical paper-based analytical device (ePAD) for the selective determination of dopamine (DA) in model serum sample. The ePAD device consists of three layers. In the top layer, SU-8 photoresist defines a hydrophilic sample application spot on the filter paper. The middle layer was made from transparency film and contained two holes, one for sample preconcentration and the other for the surfactant to allow transfer to the third layer. A screen-printed carbon electrode formed the bottom layer and was used for electrochemical measurements. In the absence of the anionic surfactant, sodium dodecyl sulfate (SDS), the oxidation peaks of DA, ascorbic acid (AA) and uric acid (UA) overlapped. With the addition of SDS, the DA oxidation peak shifted to more negative values and was clearly distinguishable from AA and UA. The oxidation potential shift was presumably due to preferential electrostatic interactions between the cationic DA and the anionic SDS. Indeed, whilst the SDS-modified paper improved the DA current five-fold, the non-ionic Tween-20 and cationic tetradecyltrimethylammonium bromide surfactants had no effect or reduced the current, respectively. Furthermore, only the SDS-modified paper showed the selective shift in oxidation potential for DA. DA determination was carried out using square-wave voltammetry between −0.2 and 0.8 V vs. Ag/AgCl, and this ePAD was able to detect DA over a linear range of 1–100 μM with a detection limit (S/N = 3) of 0.37 μM. The ePAD seems suitable as a low cost, easy-to-use, portable device for the selective quantitation of DA in human serum samples.     

Binuclear cyclopentadienylcobalt sulfur and phosphinidene complexes Cp2Co2E2 (E = S, PX): Comparison with their Iron carbonyl analogues

Density functional theory studies on a series of Cp₂Co₂E₂ derivatives (E = S and PX; X = H, Cl, OH, OMe, NH₂, NMe₂) predict global minimum butterfly structures with one Co-Co bond for the “body” of the butterfly and four Co-E bonds at the edges of the “wings” of the butterfly. Tetrahedrane structures with both Co-Co and E-E bonds are higher in energy for Cp₂Co₂S₂ and Cp₂Co₂(PH)₂ and are not found in the other systems. This differs from the corresponding Fe₂(CO)₆S₂ and Fe₂(CO)₆(PX)₂ derivatives where tetrahedrane structures are predicted to be the lowest energy structures for all cases except X = NR₂ and OH and such a tetrahedrane structure is found experimentally for Fe₂(CO)₆S₂. The butterfly structures for the Cp₂Co₂E₂ derivatives are of two types. For Cp₂Co₂(PX)₂ (X = H, OH, OMe, NH₂, NMe₂) the lowest energy structures are unsymmetrical butterflies Cp₂Co₂(P)(PX₂) with two X groups on one phosphorus atom and a lone pair on the other (naked) phosphorus atom. Related low-energy unsymmetrical butterfly Fe₂(CO)₆(P)(PX₂) structures, not observed in previous theoretical studies, are now found for the corresponding Fe₂(CO)₆(PX)₂ derivatives. Symmetrical butterfly singlet diradical structures with one X group on each phosphorus atom in relative cis or trans positions are also found for the Cp₂Co₂(PX)₂ derivatives and are the global minima for Cp₂Co₂(PCl)₂ as well as Cp₂Co₂S₂. In all cases the cis structures are of lower energy than the corresponding trans structures. Rhombus structures having neither Co-Co nor E-E bonds are also found for all of the Cp₂Co₂(PX)₂ derivatives but always at higher energies than the butterfly structures, ranging from 17 to 29 kcal/mol above the global minima.     

Stability of Plasma Treated Non-vulcanized Polybutadiene Surfaces: Role of Plasma Parameters and Influence of Additives

Surface modification studies of non-vulcanized BR elastomers (butadiene rubber) by low-pressure air plasma treatment and the effect on ageing and adhesion performances are presented in this paper. In particular, the influence of discharge power and distance from the glow discharge, and impact of antioxidant molecules in the BR formulation were examined. To characterize the changes to the BR surface, XPS spectroscopy, contact angle measurements, AFM nanoindentation experiments and tack measurements were utilized. Oxidation and crosslinking were the main mechanisms observed on the polymer chains regardless of the plasma conditions used. Beyond a certain threshold of plasma energy (in our case, discharge power of ~60 W and exposure time of ~30 s), a steady state was reached irrespective of the distance from the glow discharge. The presence of antioxidant molecules considerably reduced crosslinking phenomena while maintaining oxidation processes on polymer chains and increasing the nitrogen content in the near surface region. The mechanisms responsible for these differences have been identified. Interestingly, the COOH/C=O ratio changed according to the balance between oxidation and crosslinking. The hydrophobic recovery rate was mainly driven by temperature-dependent dynamics and varied according to the degree of crosslinking in the surface region. It was found to be lower in air atmosphere in the presence of antioxidant molecules. Finally, the presence of antioxidant molecules in the BR formulation allowed the adhesion performances after plasma exposure to significantly increase.     

Coordination Chemistry of Lipoic Acid and Related Compounds V [1]. New Heteroditopic Ligands Derived from Monoazacrown Ethers and Lipoic Acid

Summary.  Lipoyl imidazolide reacts with aza-15-crown-5 (1,4,7,10-tetraoxa-13-azacyclopentadecane) or aza-18-crown-6 (1,4,7,10,13-pentaoxa-16-azacyclooctadecane) to afford new N-lipoylated azacrown compounds in good yields. These compounds can be transformed into 1,3-dithiols and amines by reduction with complex hydrides of the disulfide and/or amide group of the lipoyl chain. The new pendant-arm macrocycles react as heteroditopic ligands by forming dithiolate and disulfide complexes with the ‘soft’ metal ions Ni²⁺ and Pd²⁺, respectively, and an amine complex with the ‘hard’ Li⁺ ion. Semiempirical and DFT calculations on the complexation of a lithium ion give a most favourable structure in which the azacrown and two solvent molecules are in contact with the metal but not the pendant arm. Received January 29, 2002; accepted (revised) March 25, 2002     

Acid digestion of geological and environmental samples using open-vessel focused microwave digestion

The application of open vessel focused microwave acid digestion is described for the preparation of geological and environmental samples for analysis using inductively coupled plasma-mass spectrometry (ICP-MS). The method is compared to conventional closed-vessel high pressure methods which are limited in the use of HF to break down silicates. Open-vessel acid digestion more conveniently enables the use of HF to remove Si from geological and plant samples as volatile SiF4, as well as evaporation-to-dryness and sequential acid addition during the procedure. Rock reference materials (G-2 granite, MRG-1 gabbros, SY-2 syenite, JA-1 andesite, and JB-2 and SRM-688 basalts) and plant reference materials (BCR and IAEA lichens, peach leaves, apple leaves, Durham wheat flour, and pine needles) were digested with results comparable to conventional hotplate digestion. The microwave digestion method gave poor results for granitic samples containing refractory minerals, however fusion was the preferred method of preparation for these samples. Sample preparation time was reduced from several days, using conventional hotplate digestion method, to one hour per sample using our microwave method.