Chemoenzymatic synthesis of phosphocarnitine enantiomers

Racemic phosphocarnitine 3 has been synthesized starting from diethyl 3-chloro-2-oxopropanephosphonate 4 in three steps involving reduction of 4 to the corresponding 2-hydroxyphosphonate 5, conversion of the latter to phosphonic acid 6, and final reaction with trimethylamine, affording the trimethylammonium salt of 3. Baker's yeast reduction of 4 and enzymatic kinetic resolution of (+/-)-5 afforded the enantiomerically pure precursors of phosphocarnitine, (R)-(+)-5 and (S)-(-)-5, which were converted to (S)-(-)- and (R)-(+)-phosphocarnitine 3, respectively.     

Methodological studies of the determination of 99Tc in matrix-rich environmental samples

A few experiments testing technetium behavior at different conditions for complex matrixes (soils, sediments) were performed. It was confirmed that the incineration of samples soaked with ammonia can be done without technetium losses. Next, for the precipitation of iron(III) hydroxide at different pH levels, the degree of co-precipitation of technetium was studied. It can be helpful during purification of very matrix-rich and massive samples. Finally the technetium and rhenium fractionation during separation of technetium from the environmental samples was studied. This test clearly showed limitations for using Re as yield tracer during ⁹⁹Tc analyses in case of mineral matrixes.     

Targeted Metabolomics of Dried Blood Spot Extracts

Dried blood spot (DBS) samples are already successfully used in newborn screening and pharmacological analyses. The application of DBS matrix to further metabolomic methods will considerably extend the analytical options for the diagnostics of metabolic diseases. We present an MS/MS based method for the simultaneous extraction and quantification of 188 metabolites from dried blood spots. We provide a sensitive and reproducible method that adapts the AbsoluteIDQ? p180 kit of Biocrates to the DBS matrix for the quantification of metabolites of different substance classes including amino acids, biogenic amines, free carnitine, acylcarnitines, hexoses, glycerophospholipids, lysophosphatidylcholines, phosphatidylcholines, and sphingolipids.     

Synthesis and characterisation of PEG-peptide surfaces for proteolytic enzyme detection

Peptide surfaces were obtained by the covalent immobilisation of fluorescently labelled pentapeptides carboxyfluorescein–glycine–arginine–methionine–leucine–glycine, either directly or through a poly(ethylene glycol) (PEG) linker on modified silicon wafers. Each step during the preparation of the peptide surfaces was confirmed by several surface characterisation techniques. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy were used to determine the surface composition, the wafers philicity was measured by contact angle and atomic force microscopy was used to investigate the surface morphology. Exposure of the peptide surfaces to trypsin resulted in the release of a fluorescently labelled peptide product, which allowed the kinetics of the enzymatic reaction to be followed with the aid of fluorescence spectroscopy. The electrospray ionisation mass spectrometry analysis of the post-digestion solution confirmed that the pentapeptides attached to the solid support undergo specific trypsin hydrolysis at the C-terminus of the arginine residues. Detailed surface analyses before and after the enzyme action was performed using ToF-SIMS. Because of the limited accessibility of the short peptide directly attached to the surface, a quantitative yield of enzymatic hydrolysis was observed only in case when the peptide was bound through the PEG linker. The insertion of the PEG linker increased the number of immobilised peptides and the rate of enzymatic digestion which consequently improved the quality of the enzyme assays. The described approach may be used for different peptide sequences designed for other proteases.

The role of Mg<Subscript>2</Subscript>FeH<Subscript>6</Subscript> formation on the hydrogenation properties of MgH<Subscript>2</Subscript>-FeF<Subscript>x</Subscript> composites

The hydrogenation properties of magnesium hydride mechanically milled with iron fluorides (FeF₂ and FeF₃), were investigated by Temperature Programmed Desorption (TPD) and volumetric methods using a Sieverts-type apparatus, as prepared upon dehydrogenation and finally upon subsequent hydrogenation. The activation energy of hydrogen desorption (E_a), calculated from the Kissinger formula using TPD measurements obtained with different heating rates, showed significant decreases of Ea in comparison to that of milled MgH₂ without any dopants. Moreover, the influence of these metal fluorides on the thermodynamics of the decomposition process was also examined. In the case of the FeF₂ dopant, rehydrogenation following desorption caused the complete decomposition of the iron fluoride to BCC iron and the formation of a predominant MgH₂ phase. In contrast to FeF₂, the addition of FeF₃ led to the formation of β-MgH₂ as a major phase coexisting with Mg₂FeH₆ and MgF₂ compounds. The presence of pure Fe in the MgH₂+FeF₂ composite, as opposed to MgH₂+FeF₃ containing Mg₂FeH₆ and MgF₂, did not cause any significant influence on the sorption properties of MgH₂. Moreover, the original material doped with FeF₃ predominantly showed iron in the Mg₂FeH₆ compound, while the FeF₂ dopant iron mostly showed the nearly pure BCC metallic phase      

Low-background,digital gamma-ray spectrometer with BEGe detector and active shield: commissioning,optimisation and software development

Journal of Radioanalytical and Nuclear Chemistry - This paper presents results of the development process of low-background, digital gamma-rays spectrometer equipped with Broad Energy Germanium...     

Synthesis,Spectral and Magnetic Properties,and Crystal Structures of Copper(II) Pyridinecarboxylate Adducts with N‐Heterocyclic Ligands

Synthesis and characterization of seven new complexes [Cu(2‐MeSnic)₂(CH₃OH)]₂ (where 2‐MeSnic is 2‐methylthionicotinate), [Cu(2‐MeSnic)₂L₂]₂ (where L is pyridine — py, ethylnicotinate — Etnic and butylnicotinate — Bunic), [Cu(2‐MeSnic)₂L₂(H₂O)₂] (where L is py and nicotinamide — nia) and [Cu(2‐MeSnic)₂(N‐Menia)₂(H₂O)₂]·2H₂O (where N‐Menia is N‐methylnicotinamide) are reported. The characterization were based on elemental analysis, infrared, electronic and EPR spectra, and magnetic susceptibility measurements over a temperature range of 1.8 — 300 K or 70 — 300 K. Three complexes of different type were studied by X‐ray analysis. The molecule of [Cu(2‐MeSnic)₂(CH₃OH)]₂ has dimeric paddle‐wheel cage structure with a tetragonal pyramidal arrangement around Cu^II. The dimer results from the fact that carboxyl groups of four 2‐MeSnic anions function as bridging in a syn‐syn arrangement. On the other hand [Cu(2‐MeSnic)₂(py)₂]₂ forms dimers with hexacoordinated Cu^II atoms in highly distorted coordination octahedra, each with two oxygen atoms of bridging carboxyl groups in an anti‐anti arrangement of two 2‐MeSnic anions, with two oxygen atoms of one asymmetrically chelating 2‐MeSnic anion and with two nitrogen atoms of two pyridine ligands. The temperature independent EPR spectrum for this complex exhibits an axial signal which corresponds to almost isolated S = ¹/₂ magnetic ions. Magnetic data for the dimer show a weak antiferromagnetic interaction between the two metal ions with J = —0.65 cm^—1. The Cu^II atom in complex [Cu(2‐MeSnic)₂(py)₂(H₂O)₂] is hexacoordinated in an elongated centrosymmetrical tetragonal‐bipyramidal arrangement (4 + 2). Based on the molecular structure the electronic, infrared, electron paramagnetic resonance spectra and magnetic properties are discussed and stereochemistry as well as the mode of ligand coordination in new solid complexes under study have been determined.     

4-isocyano-2,2,6,6-tetramethylpiperidin- 1-oxyl: a valuable precursor for the synthesis of new nitroxides

To enrich the limited set of isonitriles typically employed, 4-isocyano-2,2,6,6-teramethylpiperidin-1-oxyl (1) is proposed as an isonitrile bearing a nitroxyl moiety. Isocyanide 1 was used in some reactions characteristic of isonitriles. Isoselenocyanate, amides (products of Passerini and Ugi reactions), and tetrazole derivative were obtained. The EPR spectra of the urea derivative 5b and a product of an Ugi reaction 7 (both dinitroxides) were analyzed. [structure: see text]     

Expedient protocol for solid-phase synthesis of secondary and tertiary amines

[reaction: see text] An expedient solid-phase synthetic approach to secondary and tertiary amines was developed. The protocol employs conversion of resin-bound amino alcohols to the corresponding iodides, followed by iodide displacement with primary or secondary amines or with unprotected amino alcohols. This two-step procedure, affording products in good to excellent yields, is suitable for solid-phase synthesis of polyamines.