Studies on the copolymerization of unsaturated 1,3-dioxane derivatives—IV. Radical copolymerization of 2-furyl-5,5-dimethyl-1,3-dioxane with maleic anhydride

The copolymerization of 2-furyl-5,5-dimethyl-1,3-dioxane with maleic anhydride in the presence of a radical catalyst yields equimolar, alternating copolymers in which the furyl units have 2,5-linkage. It has been shown that 2-furyl-5,5-dimethyl-1,3-dioxane forms a charge transfer complex with maleic anhydride. The equilibrium constant for the complex was determined by NMR spectroscopy.     

Phospholipid mesophases at solid interfaces: in-situ X-ray diffraction and spin-label studies

In this work, we report on recent investigations, both on the global and on the local molecular architecture of supported phospholipid model membranes. A brief theoretical introduction explains how global structural information on supramolecular lipid ensembles can be retrieved from surface X-ray diffraction measurements as well as how spin-label electron paramagnetic resonance spectroscopy (EPR) provides complementary information on the local environment of probe molecules. The combination of especially designed X-ray cells with the technique of small- and wide-angle X-ray surface scattering makes it possible to explore various fields of lipid research and its applications. Examples for different physico-chemical conditions are presented: (i) in situ chemistry under excess of water conditions demonstrating how solid-supported lipid films sense salinity, (ii) the 3D electron density reconstruction of a vesicle-fusion intermediate under controlled humidity, and (iii) complementary temperature and pressure effects on oriented phospholipid samples. Further, special attention has been given to the influence of different film preparation techniques with respect to quality and the defect structure manifestation. To resolve the proportions and local properties of defects in a hydrated lipid-deposited surface, spin-label EPR was applied. The results from 9.6 GHz EPR as well as from 1.2 GHz EPR suggest the alignment to be in the range between 30% and 80%. In addition, slow time-dependent EPR measurements point to nano-structural rearrangements due to water flow and reduction of alignment quality.     

An efficient reagent for the phosphorylation of deoxyribonucleosides, DNA oligonucleotides, and their thermolytic analogues

[reaction: see text] The phosphoramidite 11 was prepared in three steps from methyl 2-mercaptoacetate and demonstrated efficiency in the synthesis of conventional 5'-/3'-phosphate/thiophosphate monoester derivatives of 2'-deoxyribonucleosides and DNA oligonucleotides. Moreover, the use of 11 has enabled the preparation of the dinucleoside phosphorothioate analogue 26 in high yields (>95%) with minimal cleavage (<2%) of the thermolytic thiophosphate protecting group.     

Variable coordination geometries at the diiron(II) active site of ribonucleotide reductase R2

The R2 subunit of Escherichia coli ribonucleotide reductase contains a dinuclear iron center that generates a catalytically essential stable tyrosyl radical by one electron oxidation of a nearby tyrosine residue. After acquisition of Fe(II) ions by the apo protein, the resulting diiron(II) center reacts with O(2) to initiate formation of the radical. Knowledge of the structure of the reactant diiron(II) form of R2 is a prerequisite for a detailed understanding of the O(2) activation mechanism. Whereas kinetic and spectroscopic studies of the reaction have generally been conducted at pH 7.6 with reactant produced by the addition of Fe(II) ions to the apo protein, the available crystal structures of diferrous R2 have been obtained by chemical or photoreduction of the oxidized diiron(III) protein at pH 5-6. To address this discrepancy, we have generated the diiron(II) states of wildtype R2 (R2-wt), R2-D84E, and R2-D84E/W48F by infusion of Fe(II) ions into crystals of the apo proteins at neutral pH. The structures of diferrous R2-wt and R2-D48E determined from these crystals reveal diiron(II) centers with active site geometries that differ significantly from those observed in either chemically or photoreduced crystals. Structures of R2-wt and R2-D48E/W48F determined at both neutral and low pH are very similar, suggesting that the differences are not due solely to pH effects. The structures of these "ferrous soaked" forms are more consistent with circular dichroism (CD) and magnetic circular dichroism (MCD) spectroscopic data and provide alternate starting points for consideration of possible O(2) activation mechanisms.     

Thermal analytical and infrared spectroscopic investigations on polymorphic organic compounds-II

At room temperature, three of the six polymorphic compounds described are not present in their highest melting-point form, owing to enantiotropy. These three are triphenyltin chloride (3 modifications), 1-(4,4-dimethyl-2-oxo-3-tetrahydrofuryl)thiourea (4 modifications), and 2-aminoethyl diphenylborinate (3 modifications). In the case of 4-amino-1-(2-phenylethyl)-1,2,4-triazoline-5-thione, in addition to the absolutely stable modificationI, a further six unstable crystal forms have been observed. The three modifications of,-dimethyl-[1,1-biphenyl]-4-methanol are also monotropic in character. 2,9-Dimethyl-1,10-phenanthroline, the three polymorphic forms of which are unstable, is a special case, since it absorbs water from the air and changes into a semi-hydrate.     

Determination of total carbon and total organic carbon from volatile air pollutants. Part I

Summary A new method of collection of representative air samples for the determination of TC and TOC from volatile air pollutants has been developed. The organic substances undergo combustion and only the carbon dioxide produced is concentrated on molecular sieve 5 A at ambient temperature. The CO₂ is subsequently liberated by thermal desorption at ca. 380°C in a stream of purified gas. Atmospheric CO₂ must be removed first and this can be done (at the sample flow rate of 700 ml/min) by a layer of Ascarite heated at 90° C. Organic compounds passing through the layer are then combusted by a dynamic method utilizing Körbl catalyst and the CO₂ formed is concentrated on a molecular sieve 5 A, followed by thermal desorption and final determination. Organic acids are also retained by the first CO₂ absorber. A diffusion cell for preparation of the mixtures of purified air with vapours of organic compounds is described.

---

Zusammenfassung Eine neue Anreicherungsmethode zur Gewinnung representativer Luftproben zur Bestimmung des Gesamtkohlenstoffgehaltes und des Gehaltes an organischem Kohlenstoff (TOC) aus flüchtigen Luftverunreinigungen wurde entwickelt. Während der Probenahme werden die flüchtigen Verunreinigungen verbrannt und nur das entstandene Kohlendioxid bei Zimmertemperatur am Molekularsieb 5A angereichert. Anschließend wird CO₂ bei ca. 380° C im gereinigten Gasstrom thermisch desorbiert. Bei der TOC-Bestimmung muß atmosphärisches CO₂ vorangehend aus dem Luftstrom entfernt werden und wird an einer auf 90° C erwärmten Ascariteschicht gebunden. Die durchfließenden organischen Verbindungen werden dann im dynamischen System am Körblkatalysator oxydiert, das entstandene CO₂ am Molekularsieb 5A angereichert, thermisch desorbiert und einer Endbestimmung zugeführt. Organische Säuren werden gleichfalls durch den ersten CO₂-Absorber gebunden. Eine Diffusionszelle zur Herstellung von Gemischen gereinigter Luft mit Dämpfen organischer Verbindungen wurde beschrieben.

     

Analytical control of silica glass production. Voltammetric determination of titanium and iron in raw materials and silica glass samples

Adsorptive stripping voltammetric (AdSV) methods are presented for the determination of titanium and iron in quartz and silica glass samples obtained after pressure decomposition. Mandelic acid and catechol were used as complexing agents for titanium and iron, respectively. The method for titanium determination is based on the catalytic effect of chlorate ions. An insoluble residue remaining after decomposition of quartz and silica glass samples in HF+H2SO4 mixture was checked by energy-dispersive X-ray analyses. ET-AAS was applied as a reference method to AdSV measurements.     

Principle of a new immunoassay based on electrophoretic mobility of poly(styrene/alpha-tert-butoxy-omega-vinylbenzyl-polyglycidol) microspheres: application for the determination of helicobacter pylori IgG in blood serum

The principle of a novel latex diagnostic test for the determination of antibodies against Helicobacter pylori in blood sera is described. The test is based on the measurement of the electrophoretic mobility of the microspheres with immobilized H. pylori antigens. The electrophoretic mobility of these microspheres depends on the concentration of the antibodies against H. pylori in suspending medium. Particles with hydrophilic polyglycidol in the surface layer were used for the test. The microspheres were obtained by an emulsifier-free emulsion copolymerization of styrene and alpha-tert-butoxy-omega-vinylbenzyl-polyglycidol macromonomer (D(n) = 220 nm, diameter polydispersity factor D(w)//D(n) = 1.02). Activation of polyglycidol hydroxyl groups with cyanuric chloride allowed for covalent immobilization of H. pylori antigens. The fraction of H. pylori not specifically adsorbed onto the microspheres was negligible. Changes of the electrophoretic mobility of the microspheres with the surface concentration of the covalently immobilized H. pylori antigens Gamma = (1.6 +/- 0.3) . 10(-3) g m(-2) were suitable for the detection of the antibodies in the sera of patients with titer in the range (determined by the indirect ELISA test) from 1:500 to 1:32 000.     

Zinc-catalyzed Williamson ether synthesis in the absence of base

Zinc powder was found to be a highly efficient catalyst for the synthesis of aromatic ethers using microwave heating in the presence of N,N-dimethylformamide as well as under stirring in an oil-bath using tetrahydrofuran as solvent without any inorganic base. This method can be used for selective mono-, di- or tri-O-alkylations.     

Mechanistic Study on the Oxidation of Promazine and Chlorpromazine by Hexaimidazolcobalt(III) in Acidic Aqueous Media

The kinetics of the oxidation of promazine and chlorpromazine by hexaimidazolcobalt(III) were studied in the presence of a large excess of cobalt(III) and H⁺ ions using u.v.–vis. spectroscopy ([Co^III] = (1–6) × 10⁻³ m, [ptz] = (2.5–10) × 10⁻⁵ m, [H⁺] = 0.05–0.8 m, I = 1.0 m (H⁺, Na⁺, Cl⁻), T = 333–353 K, l = 1 cm). In each case, the reversible reaction leads to formation of cobalt(II) species and a stable cationic radical. A linear dependence of the pseudo-first-order rate constant (k_obs) on [Co^III] with a non-zero intercept was established for both phenothiazine derivatives. A marked difference in the observed reaction rate for promazine and chlorpromazine is associated with the difference in its ability to undergo oxidation and is consistent with a trend in the redox potential changes for these reductants. The activation parameters for reactions studied were determined. Mechanistic consequences of all the results are discussed.