Determination of trace metals at concentrations above the linear calibration range by electrothermal atomic absorption spectrometry

Difficulties encountered in the determinations of various metals (Cd, Pb, Cu, Fe, Cr, Ni, Co, Zn, Mn) in the graphite furnace are investigated. The most serious is the inconsistency often observed below the upper linear calibration limit. Because of that, and also to avoid the extra work and contamination resulting from dilution, formulae are given that afford a precise way of estimating the concentration within a range 5 to 25 times wider than the linear calibration range. The same computing technique may be employed with equal success when a flame is used, again avoiding dilution.     

The first rare earth organometallic complex of 1,4,7-trithiacyclononane: a precursor to unique cationic ethylene and alpha-olefin polymerisation catalysts supported by an all-sulfur donor ligand

[Sc([9]aneS3)(CH2SiMe3)3], the first rare earth organometallic complex of 1,4,7-trithiacyclonane, is a precursor to ethylene and alpha-olefin polymerisation catalysts upon activation with BAr(F)3 or [CPh3][BAr(F)4](Ar(F) = C6F5); these are the first cationic rare earth organometallic catalysts supported by an all-sulfur donor ligand.     

Single-component and mixed ferrocene-terminated alkyl monolayers covalently bound to Si(111) surfaces

Self-assembled ferrocene monolayers covalently bound to monocrystalline Si(111) surfaces have been prepared from the attachment of an amine-substituted ferrocene derivative to a pre-assembled acid-terminated alkyl monolayer using carbodiimide coupling. This derivatization strategy yielded nanometer-scale clean, densely packed monolayers, with the ferrocene units being more than 20 A from the semiconductor surface. The amount of immobilized electroactive units could be varied in the range 2 x 10(-11) to approximately 3.5 x 10(-10) mol cm(-2) by diluting the ferrocene-terminated chains by inert n-decyl chains. The highest coverage obtained for the single-component monolayer corresponded to 0.25-0.27 bound ferrocene per surface silicon atom. The electrochemical characteristics of the mixed n-decyl/ferrocene-terminated monolayers were found to not depend significantly on the surface coverage of ferrocene units. The reversible one-electron wave of the ferrocene/ferrocenium couple was observed at E degrees ' = 0.50 +/- 0.01 V vs SCE, and the rate constant of electron transfer kapp was about 50 s(-1).     

MRI methodological development of intervertebral disc degeneration: a rabbit in vivo study at 9.4 T

Intervertebral disc (IVD) degeneration is a complex process characterized by biochemical and structural changes in both the nucleus pulposus and the anulus fibrosus. In this study, we were able to obtain in vivo magnetic resonance (MR) images of the rabbit spine, with several MR imaging (MRI) contrasts (ρ, T₁ and T₂). We quantified several parameters (T₂, apparent diffusion coefficient, disc height and area) to differentiate between healthy and degenerative IVDs and to characterize the degeneration process. To our knowledge, there has not been any previous in vivo study of rabbit IVDs at high-field MRI (9.4 T).A custom radio frequency (RF) coil for 9.4 T was designed to match rabbit IVD morphology, to study the degeneration in vivo on a model of human lumbar disease. Our new probe, a custom half-birdcage-type coil, obtains the necessary exploration depth while meeting the requirements for signal homogeneity and sensitivity of the study. This design addresses some of the difficulties with constructing RF coils at high field strengths.     

Über das 2, 4, 6-Trichlor-3-Bromphenol und das 2-Chlor-4, 6-Dibromphenol

Ohne Zusammenfassung     

A disymmetric terpyridine based ligand for the formation of luminescent di-aquo lanthanide complexes

The synthesis of ligand H3 based on a disymmetrically substituted terpyridine core functionalised by a carboxylic acid in the 6-position and a bis(carboxymethyl)aminomethyl function in the 6'-position is described. The coordination behaviour of this heptadentate (4N/3O) ligand with lanthanide cations (Ln=Eu, Gd and Tb) was studied in solution showing the formation of complexes with [Ln] stoichiometry. Complexes with general formula [Ln(H2O)2] were isolated from neutral water solutions containing equimolar amounts of cations and ligands, and the complexes were characterized in the solid state (elemental analysis, IR) and in solution (mass spectrometry). The photo-physical properties of the luminescent complexes of Eu and Tb were studied in water solution by means of absorption, steady state and time-resolved emission spectroscopies. Evolution of the luminescence lifetimes of the Eu and Tb complexes in H2O and D2O reveals the presence of two water molecules coordinated in the first coordination sphere of the cations. Despite this important hydration number, the overall luminescence quantum yields of the complexes remained elevated, especially in the case of Tb (Phi=22.0 and 6.5% respectively for Tb and Eu). Upon crystallisation the Gd complex formed dimeric species in which two gadolinium atoms are each heptacoordinated by one ligand, the coordination sphere being completed by a single water molecule and a bridging carboxylate function, pointing to different behaviours in the solid and liquid states.     

Unprecedented Biodegradable Cellulose-Derived Polyesters with Pendant Citronellol Moieties: From Monomer Synthesis to Enzymatic Degradation

Levoglucosenone (LGO) is a cellulose-derived molecule that is present commercially on a multi-ton/year scale. Taking advantage of the α,β-conjugated ketone of LGO, a new citronellol-containing 5-membered lactone (HBO-citro) was synthesized through a one-pot two-step pathway involving oxa-Michael addition and Baeyer-Villiger oxidation. The solvent-free treatment of HBO-citro with NaBH₄ at room temperature led to the full reduction of the lactone moiety which gave a novel fully renewable triol monomer having a citronellol side chain (Triol-citro). Noticeably, by simply changing the reducing agent, temperature and reaction duration, the partial reduction of HBO-citro can be achieved to yield a mixture of 5- and 6-membered Lactol-citro molecules. Triol-citro was chosen to prepare functional renewable polyesters having citronellol pendant chains via polycondensation reactions with diacyl chlorides having different chain lengths. Good thermal stability (T_d5% up to 170 °C) and low glass transition temperatures (as low as −42 °C) were registered for the polyesters obtained. The polymers were then hydrolyzed using a commercial lipase from Thermomyces lanuginosus (Lipopan^® 50 BG) to assess their biodegradability. A higher degradation profile was found for the polyesters prepared using co-monomers (acyl chlorides) having longer chain lengths. This is likely due to the decreased steric hindrance around the ester bonds which allowed enhanced accessibility of the enzyme.     

2,2,3,3,11,11,12,12-Octamethyl-1,4,7,10,13-pentaoxacyclohexadecane: improved synthesis and crystal structure with NaSCN

An efficient synthesis of 2,2,3,3,11,11,12,12-octamethyl-1,4,7,10,13-pentaoxacyclohexadecane (1, OM16C5) is described, which affords over an order of magnitude improvement in yield over the previously reported method. The first X-ray crystal structure of 1, as a complex with NaSCN, is also reported.     

Novel polyisoprenylated benzophenone derivatives from Garcinia paucinervis

Four novel polyisoprenylated benzophenone derivatives, paucinones A-D (1-4), were isolated from the leaves of the plant Garcinia paucinervis. Paucinones A-C (1-3) contained an unexpected cyclohexane-spiro-tetrahydrofuran moiety. A 1-methylene-3,3-dimethylcyclohexane group never reported before was found in the structure of paucinone D (4). The structures of these compounds were elucidated with spectroscopic evidences. The relative stereochemistries of 1-4 were determined by NOESY correlations. These compounds showed significant cytotoxicities against HeLa cells.