Metal island coated polymer sensor for direct determination of the volume effect of chaotropic agents

A new optical sensor is presented, based on the analyte reaction resulting in swelling and shrinking of a thin polymer layer. Changing the concentration of ions in a new bisazide photo-cross-linked poly(vinylpyrrolidone) polymer results in a concentration-dependent volume change of the hydrated gel. The volume response of the sensor induced by different ions is fully reversible over more than 250 cycles. The response of the device depends on the type, the charge and the concentration of the ions. The sensor material is part of an optical thin film system which transforms the variations in volume of the polymer into spectral information. The steady state of the sensor response is obtained within 60 s. The response time is mainly limited by the pump rate, the back pressure and the total volume of the system but not by the swelling of the sensor polymer. A comparative study of ion effects has demonstrated a fundamental correlation of the polymer swelling properties with the Hofmeister series of chaotropic agents. Thus it is concluded that the photopolymer, which is solubilized in aqueous solutions by the interaction of its amide structure with the solvent, behaves like the backbone amide structure of proteins.     

Enantiomeric resolution of anti-HIV agents on a cellulose derivative chiral stationary phase

Summary Anti-HIV enantiomeric 1H, 3H-thiazolo[3, 4-a] benzimidazoles have been stereospecifically analyzed by elution on a column of cellulose tris-(4-methyl-phenylbenzoate)ester adsorbed on macroporous silica (Chiralcel^R OJ).The enantiomeric resolution of the compounds examined is linked to a complex and competitive contribution of different factors.     

Surface modified precipitated calcium carbonates at a high degree of dispersion

Calcium carbonates of different degrees of surface hydrophobicity were obtained when sorbic acid or polyoxyethylene glycol were present during the precipitation. In the presence of trace amounts of divalent cations carbonates with high surface hydrophilicity and improved monodisperse character are obtained. Surface modification of the calcium carbonates by several proadhesive compounds can markedly improve the chemical affinity of the carbonates to polymers. Very effective are isostearoyl titanate and two polyoxyethylene compounds. Precipitated calcium carbonates modified with 2 to 3 percent (wt/wt) of isostearoyl titanate increased the tensile strenght of butadiene-styrene rubber by approximately 100%. Polyurethane is only strengthened when 30 wt/wt of a filler are introduced independently of the type proadhesive compounds. The best strength and hysteresis of polyurethanes are obtained with calcium carbonate modified with 2 percent (wt/wt) of polyoxyethylene glycol.     

Resistance to Surfactant and Protein Fouling Effects at Conducting Diamond Electrodes

Boron‐doped diamond thin‐film electrodes display negligible fouling effects in the presence of high levels of surface‐active materials, including proteins. Dramatic improvements in the stability of the analyte response (compared to common glassy carbon and carbon paste electrodes) are illustrated using bovine serum albumin (BSA), gelatin, and Triton X‐100 in connection with repetitive square‐wave voltammetric (SWV) measurements. The voltammetric response of ascorbic acid at the diamond electrode exhibits negligible shifts in peak potentials and minimal depressions of current signals over a wide range of surfactant concentrations (0–750 ppm). For example, the diamond electrode exhibited 70, 50 and 60 mV potential shifts for 10 repetitive voltammetric scans in the presence of 100 ppm BSA, gelatin and Triton X‐100, respectively, compared to 120, 190, and 280 mV shifts observed at the glassy carbon electrode. Furthermore, only 4.3 and 6.2% of the initial current decays were observed in the presence of 100 ppm Triton X‐100 and gelatin, respectively (compared to 45.2 and 34.4% diminutions at the glassy carbon electrode). Such improved performance was also confirmed from the SWV measurements of uric acid, dihydroxyphenylacetic acid, and catechol. The greatly improved resistance to surfactant interference reflects the fact that the as‐grown diamond thin film, composed of oxide‐free and hydrogen‐terminated surface, has a relatively lower surface energy and minimal electrostatic attributes, either specific or general, so that little adsorption of surface‐active agents occurs. The topographic AFM images of the diamond electrode surface confirm a negligible BSA fouling effect after repetitive SWV measurements. Such enhanced antifouling features make diamond electrodes very attractive for numerous real‐life electroanalytical applications.     

Synthesis of some novel substituted quinolines as potent analgesic agents

Summary 2-Chloroquinoline-3-carbaldehyde and 2-chloro-4-methylquinoline-3-carbaldehyde have been prepared from acetanilide and acetoacetanilidevia a Vilsmeier-Haack reaction. Upon reaction with phenyl hydrazine, hydroxylamine, urea, and thiourea in presence of acetic acid, these chloroaldehydes afforded the title compounds which exhibit a several times higher analgesic activity than noramidopyrine (NAP).

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Synthese einiger neuer substituierter Chinoline als stark analgetisch wirkende Substanzen

Zusammenfassung 2-Chlorchinolin-3-carbaldehyd und 2-Chlor-4-methylchinolin-3-carbaldehyd wurden, ausgehend von Acetanilid und Acetylacetanilid, über eineVilsmeier-Haack-Reaktion hergestellt. Reaktion dieser chlorsubstituierten Aldehyde mit Phenylhydrazin, Hydroxylamin, Harnstoff und Thioharnstoff ergab die Titelverbindungen, deren analgetische Aktivität jene von Noramidopyrin (NAP) um ein Mehrfaches übertrifft.

     

Oxazoline chemistry. Part 12: A metal-mediated synthesis of DMU-212; X-ray diffraction studies of an important anti-cancer agent

An improved synthesis of the anti-cancer agent DMU-212 (trans-3,4,5,4′-tetramethoxystilbene) is described. The methodology involves the use of a Pd-oxazoline catalyst as a mediator of a regio-selective (Heck) C-C bond formation reaction. A simple isolation step is then used to obtain the title material. The compound has been further characterised in the solid-state by X-ray diffraction methods.     

Synthetic tanning agents. Characterization,control of synthesis and assessment of correlations between product composition and taning properties by reversed-phase high performance liquid chromatography

Summary Gradient elution RP-HPLC has been applied to the separation of the constituents of synthetic tanning agents. Information obtained from the chromatographic results was used to assess the possibility of optimizing the conditions of synthesis, to find out the number of species formed and to make a start at correlating the composition of the tanning agents and their properties.     

Protease sensors for bioimaging

Optical imaging of specific molecular targets and pathways in vivo has recently become possible through continued developments in imaging equipment, reconstruction algorithms, and more importantly the availability of imaging reporter molecules. These reporter molecules encompass photoproteins expressed in vivo and exogenously administered probes detectable by fluorescence and/or bioluminescence imaging. One particularly enticing aspect of optical imaging is the ability to design activatible probes with inherent amplification. This review summarizes our experience in developing novel near-infrared fluorescent (NIRF) imaging agents that report on protease activities. These agents are designed to be biocompatible, highly activatible, and able to produce bright NIRF following protease cleavage.     

Direct capillary electrophoretic determination of three chemotherapeutic drugs in human urine

Summary Capillary zone electrophoresis (CZE) has been used for direct determination of 6-thioguanine, methotrexate, and 5-fluorouracil in human urine, by use of a fused-silica capillary (60.2 cm×75 μm i.d.). Separation was performed after hydrodynamic injection for 7 s; the separation potential and capillary temperature were 25 kV and 35°C, respectively. A 45mm borate buffer solution (pH 9.2) was used as separation electrolyte. Under these conditions the analysis takes approximately 10 min and interday precision of migration times and corrected peak areas is satisfactory. A linear response over the concentration range 3.0–20.0 mg L¹ was observed for the three chemotherapeutic drugs in diluted human urine. Detection limits (s/n=3) for 6-thioguanine and methotrexate were approximately 1.60 mg L¹ in diluted human urine; that for fluorouracil was 2.60 mg L¹. A 2-ml volume of human urine was diluted with 2-mL of water and introduced directly into the electrophoresis system. CZE was shown to be a good method with regard to simplicity, satisfactory precision, and sensitivity. This method resulted in especially excellent recoveries for determination of methotrexate in all the different urine samples analysed (n=10).     

Surface modification of highly dispersed rubber fillers and pigments by titanate proadhesive and hydrophobic compounds

A method of modifying silicate and carbonate fillers with titanate coupling agents and proadhesive agents was worked out. The modification aimed at hydrophobization of filler surface by introduction to the surface of functional groups with chemical affinity to polymers. Optimum amounts of modifying substances and appropriate conditions for performing the modification process were established. The obtained fillers showed a high degree of hydrophobicity.The modified fillers were applied in rubber mixtures based on butadienestyrene or natural rubber, in polyurethanes, in PVC, and as pigments in oil dyes of high corossive resistance.