Uno Mäeorg

Novel and sensitive high-performance liquid chromatographic method based on electrochemical coulometric array detection for simultaneous determination of catecholamines, kynurenine and indole derivatives of tryptophan.

A novel and simple method has been developed for the simultaneous quantification of tryptophan, kynurenine and indole derivatives as well as four catecholamines, including dopamine, noradrenaline, homovanillic acid and 3,4-dihydroxyphenylacetic acid. The method utilises isocratic reversed-phase high-performance liquid chromatography with electrochemical coulometric array detection. The influence of various parameters on chromatographic performance, such as the composition and the pH of the mobile phase and the detection potentials, was investigated. Separation of 13 compounds was achieved by a mobile phase consisting of 10% methanol in 50 mM sodium phosphate-acetate buffer, pH 4.10, containing 0.42 mM octanesulphonic acid. The calibration curve was linear over the range 12 pg to 300 ng on-column. The detection limits (SIN 3) depended on the working potential and were found to be between 10 and 100 pg injected. The method was reproducible with intra-day RSDs of 0.3 to 1.5% and inter-day RSDs of 0.5 to 4%.

Nanoporous carbon-based electrodes for high strain ionomeric bending actuators

Ionic polymer metal composites (IPMCs) are electroactive material devices that bend at low applied voltage (1–4 V). Inversely, a voltage is generated when the materials are deformed, which makes them useful both as sensors and actuators. In this paper, we propose two new highly porous carbon materials as electrodes for IPMC actuators, generating a high specific area, and compare their electromechanical performance with recently reported RuO2 electrodes and conventional IPMCs. Using a direct assembly process (DAP), we synthesize ionic liquid (Emi-Tf) actuators with either carbide-derived carbon (CDC) or coconut-shell-based activated carbon-based electrodes. The carbon electrodes were applied onto ionic liquid-swollen Nafion membranes using a direct assembly process. The study demonstrates that actuators based on carbon electrodes derived from TiC have the greatest peak-to-peak strain output, reaching up to 20.4 me (equivalent to>2%) at a 2 V actuation signal, exceeding that of the RuO2 electrodes by more than 100%. The electrodes synthesized from TiC-derived carbon also exhibit significantly higher maximum strain rate. The differences between the materials are discussed in terms of molecular interactions and mechanisms upon actuation in the different electrodes.

Phytochemical analysis of the essential oil of Thymus serpyllum L. growing wild in Estonia

Variations in the essential oil composition of Thymus serpyllum L., growing wild in Estonia (33 samples) and in some other countries (Russia, Latvia and Armenia, seven samples) were determined. The oil were obtained from Estonia (46 samples) in yields 0.6–4.4 and 1.9–8.2 mL kg–1 in other countries. The T. serpyllum herb grown in Estonia usually did not confirmed to the EP standard in the aspect of the essential oil contents (3.0 mL kg–1). Variations in the essential oil composition of wild thyme were studied using capillary gas chromatographic methods. A total of 94 components were identified. Thymol and carvacrol, mentioned in literature as principial components, are not the main components of the essential oil of wild thyme growing in Estonia. (E)-nerolidol, caryophyllene oxide, myrcene and borneol chemotypes of wild thyme drug are distinguishable. The chemical composition of samples from Russia, Latvia and Armenia is very variable.

Effect of glucose content on thermally cross-linked fibrous gelatin scaffolds for tissue engineering

Thermally cross-linked glucose-containing electrospun gelatin meshes were studied as possible cell substrate materials. FTIR analysis was used to study the effect of glucose on cross-linking reactions. It was found that the presence of glucose increases the extent of cross-linking of fibrous gelatin scaffolds, which in return determines scaffold properties and their usability in tissue engineering applications. Easy to handle fabric-like scaffolds were obtained from blends containing up to 15% glucose. Maximum extent of cross-linking was reached at nearly 20% glucose content. Cross-linking effectively resulted in decreased solubility and increased resistance to enzymatic degradation. Preliminary short-term cell culture experiments indicate that such thermally cross-linked gelatin-glucose scaffolds are suitable for tissue engineering applications.

Preparation of smooth siloxane surfaces for AFM visualization of immobilized biomolecules

Development of scanning probe microscopy (SPM) techniques during past decade has made possible to study bioprocesses at a molecular level. Common protocols for immobilization of biomolecules for SPM studies are based on their adsorption to alkylsiloxane monolayers on hydroxylated surfaces. The same procedure is also widely used for DNA chip and biosensor fabrication. For SPM studies of immobilized biomolecules smooth carrier surfaces are mandatory. Several studies refer to the lack of reproducibility in formation of smooth silanized surfaces. In this work a new method based on carrier treatment with linearly polymerized 3-aminopropyltrimethoxysilane for preparation of reproducibly smooth silanized surfaces is proposed.

Hydrazines and Azo-Compounds in the Synthesis of Heterocycles Comprising N-N Bond

Abstract – The synthesis of nitrogen containing heterocycles is of great importance in modern science, owing to their valuable biological properties, and endocyclic hydrazinocycles are no exception. There are methods that enable the transformation of amines to hydrazines, however the use of hydrazine derivatives and azo-compounds as starting materials is both logical and straightforward. In this review we aimed to summarize the methods that use simple hydrazines and azo-compounds for the synthesis of these heterocycles. We begin with simple stoichiometric alkylation of hydrazines and later on move to catalytic systems. Finally, we provide an overview of the advances in the field of azomethine imines chemistry.

Zn Mediated Regioselective Barbier Reaction of Propargylic Bromides in THF/aq. NH4Cl Solution

The reaction of substituted and unsubstituted propargylic bromides with butanal in presence of zinc power in THF/saturated aqueous NH4Cl solution gave corresponding allenic and propargylic alcohols with high selectivity.

Highly selective arylation of disubstituted hydrazines by pentavalent organobismuth reagents

Abstract The scope of a set of recently reported hydrazine reagents has been explored with respect to arylation. Compounds of type R1NHNHCOR2 can be selectively arylated under very mild conditions using triarylbismuth diacetates.

Selfcondensation of 2-methylpropanal with homochiral BINOL catalysts as a model asymmetric aldol–Tishchenko reaction

Abstract Binaphtholate catalysts were used to investigate the stereochemistry of 2-methylpropanal selfcondensation. Several steps of this condensation were found to be affected weakly or moderately by homochiral catalysts, but with opposite enantioselectivities.

Reduction of Acetylenic Compounds to (E)-Olefins by Alkali Metals – An Investigation of the Scope

Efficient procedures have been developed for the stereospecific reduction by alkali metals of disubstituted acetylenes with long carbon chains. Acetylenes containing two or more (isolated) triple bonds are reduced considerably more easily than are monoynes.