Synthesis and antiinflammatory activity of the sulfoxides of 4-[3-(dimethylamino)propyl] - 3,4- dihydro- 2-(1-hydroxyethyl)-3-phenyl-2H-1,4-benzothiazine

Oxidation of 4-[3-(dimethylamino)propyl]-3,4-dihydro-2-(1-hydroxyethyl)-3-phenyl-2H-1,4-benzothiazine, hydrochloride (I) with hydrogen peroxide yielded a mixture of two sulfoxides (II). Since this mixture exhibited antiinflammatory activity, the two components (Isomers A and B) were prepared in purified form by oxidation of I with N-chlorosuccinimide and hydrogen peroxide, respectively. Isomer A was more potent than Isomer B in the carrageenin-induced edema test.     

Characterization of dynamic and steady-state protein phosphorylation using a fluorescent phosphoprotein gel stain and mass spectrometry

Protein phosphorylation plays a vital role in the regulation of most aspects of cellular activity, being key to propagating messages within signal transduction pathways and to modulating protein function. Pro-Q Diamond phosphoprotein gel stain is suitable for the fluorescence detection of phosphoserine-, phosphothreonine-, and phosphotyrosine-containing proteins directly in sodium dodecyl sulfate (SDS)-polyacrylamide gels. The technology is especially appropriate for profiling steady-state and dynamic phosphorylation on a proteome-wide scale, as demonstrated through detection of the native phosphorylation of cardiac mitochondrial phosphoproteins and changes in this profile arising from the activity of a protein kinase. For example, Pro-Q Diamond phosphoprotein gel stain was employed to demonstrate that among the 46 subunits of the mitochondrial respiratory chain complex, NADH:ubiquinone oxidoreductase (complex I), a 42 kDa subunit is phosphorylated in the steady-state. However, exposure of mitochondria to cAMP-dependent protein kinase increases phosphorylation of this 42 kDa subunit and results in de novo phosphorylation of an 18 kDa subunit as well. Since Pro-Q Diamond dye binds to phosphorylated residues noncovalently, the staining technology is fully compatible with modern microchemical analysis procedures, such as peptide mass profiling by matrix assisted laser desorption/ionization-time of flight (MALDI-TOF) mass spectrometry and post-source decay analysis of peptide phosphorylation.     

Infrared intensities of the external modes of crystalline nitrous oxide

The absorption intensities of two infrared active lattice modes of crystalline N₂O have been measured. Both the frequencies and intensities of the external modes of N₂O have been found to be very similar to those of CO₂, and most of the differences between the spectra of CO₂ and N₂O can be explained by the differences in the quadrupole moments.     

Synthesis and structural characterization of acetatobis(triphenylphosphine)dicarbonylmanganese(I), (CH3CO2)Mn(CO)2[P(C6H5)3]2: An organometallic complex containing a chelating acetate ligand

The accidental but intriguing synthesis of acetatobis(triphenylphosphine)dicarbonylmanganese(I), (CH₃CO₂)Mn(CO)₂[P(C₆H₅)₃]₂, has been accomplished by the reaction of NaMn(CO)₅ with (CH₃)₃SiCl followed by the addition of triphenylphosphine and acetic acid. A three-dimensional single-crystal X-ray diffraction analysis has shown an octahedral-like molecule containing a symmetrically oxygen-chelating acetate group, the first such group to be reported in a metal carbonyl complex. The two triphenylphosphine ligands occupy mutually trans positions with the two carbonyl ligands possessing the remaining cis sites in the octahedral complex. The compound crystallizes with four molecules in a monoclinic unit cell of space group symmetry $\text{P}\text{2}{}_1\text{c}$ and of dimensions a = 17.744(2) Å, b = 9.692(1) Å, c = 20.004(2) Å, and β = 106.195(4)°. The relatively long MnO(acetate) bond lengths [2.066(6) and 2.069(7) Å] and the relatively short MnCO bond lengths [1.701(12) and 1.760(13) Å] and the relatively short MnP(C₆H₅)₃ bond lengths [2.260(3) and 2.275(3) Å], compared to the corresponding MnCO and MnP(C₆H₅)₃ bond lengths in other manganese carbonyl triphenylphosphine complexes, are rationalized on the basis that the acetate ligand in this molecule functions primarily as a σ-donor.     

Die Kristallstruktur des W3CoB3 und der dazu isotypen Phasen Mo3CoB3, Mo3NiB3 und W3NiB3

Zusammenfassung Mo₃CoB₃, Mo₃NiB₃, W₃CoB₃ und W₃NiB₃ kristallisieren in einem eigenen Typ (W₃CoB₃-Struktur). Das trigonal prismatische Bauelement [T ₆B]^* ist zu Ketten vereinigt, wobei B₃-Gruppen entstehen. Die Phasen sind vermutlich Bor-reicher als obiger Formel entspricht.

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The crystal structure of W₃CoB₃ and the isotypic phases Mo₃CoB₃, Mo₃NiB₃, and W₃NiB₃

Mo₃CoB₃, Mo₃NiB₃, W₃CoB₃, and W₃NiB₃ were found to possess a new type of crystal structure (W₃CoB₃-structure type). Trigonal prismatic groups [T ₆B]^* are linked together forming chains in such a way that B₃-groups occur. These borides do probably exist with a larger amount of boron as to compared with the formula.

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Mit 2 Abbildungen     

Konzentrationsabhängigkeit der Dipolmomente in n-Hexan-Lösungen normaler α, ω-dichlorierter Kohlenwasserstoffe

Zusammenfassung Es wurden die Dipolmomente der, -dichlorierten Kohlenwasserstoffe in Lösung mit Hexan über den ganzen Konzentrationsbereich bei 25 °C bestimmt. Untersucht wurden die Verbindungen dieser Reihe vom 1,2-Dichloräthan bis zum 1,10-Dichlordekan.Die Dipolmomente dieser Verbindungen ließen sich gut deuten, wenn ein Gemisch starrer Rotationsisomerer angenommen wurde. Dabei zeigten sich auch noch die durch eine Kohlenstoffkette von 10 C-Atomen getrennten Partialmomente deutlich in ihrer Richtung gegenseitig abhängig.Die Konzentrationsabhängigkeit der Dipolmomente wurde an Hand der durch dieKirkwood-Fröhlichsche Theorie gegebeneng-Faktoren diskutiert. Es ergab sich, daß dieg-Faktoren des 1,2-Dichloräthans weitgehend auf eine DK-abhängige Konformationsänderung von der unpolaren trans- in die polare gauche-Konformation zurückzuführen sind. Dies scheint eine grundsätzliche Eigenschaft von Verbindungen zu sein, die Partialmomente in 1,2-Stellung haben. Dieg-Faktoren der Verbindungen, deren Partialmomente weiter voneinander entfernt sind, wie bei den höheren Gliedern der Reihe, wurden nahezu ausschließlich auf zwischenmolekulare Ausrichtung der Partialmomente zurückgeführt.Ein Vergleich mit deng-Faktoren des Hexylchlorids und des 2,2-Dichlorpropans zeigte, daß bis zu einer Konzentration von 1 Mol/l in erster Linie dimere bzw. kettenartige antiparallele bzw. parallele Assoziate der Partialmomente zu erwarten sind. Nach höheren Konzentrationen weichen dieg-Faktoren von diesem Verhalten nach größeren Werten hin ab. Daraus wurde auf parallele Ausrichtung in höherer Koordinationszahl geschlossen.Für die Unterstützung dieser Arbeit sprechen wir der Deutschen Forschungsgemeinschaft unseren verbindlichsten Dank aus.Der Firma Bayer, Leverkusen, danken wir für die Hilfe bei Beschaffung einiger der Substanzen.     

Purification of 3-ethoxycarbonylquinuclidine and its conversion to 3-quinuclidinecarboxylic acid and 3-quinuclidinylmethanol

3-Ethoxycarbonylquinuclidine obtained by the Grob method is a mixture of 3-ethoxycarbonyl-1-azabicylo-[2.2.2]- and, according to ¹³C NMR data, 5-ethoxycarbonyl-5-azatricyclo[3.2.1.0^2,7]octanes (1621). 3-Ethoxy-carbonylquinuclidine was purified by recrystallization of the hydrochloride, hydrolyzed by water to 3-quinuclidinecarboxylic acid, and reduced by LiAlH₄ to 3-quinuclidinylmethanol.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, 1509–1512, November, 1992.     

Differentiation between dexamethasone and betamethasone in a mixture using multiple mass spectrometry

Direct gas chromatographic methods to analyse phenylurea pesticides are discouraged by the thermal instability of these compounds, that in conventional hot splitless inlet systems leads to extensive and irreproducible formation of isocyanates and amines. However a careful control of the operating conditions, like the inlet temperature, the pressure and the presence of suitable chemical additives (as acetic acid, low-molecular-mass amines, organic anhydrides) can either: (i) minimise the thermal decomposition enabling the direct GC-MS analysis of phenylureas, or (ii) lead to reproducible conversion to isocyanates. Experimental design was employed to study the effect of the experimental variables on the thermal transformation of phenylurea pesticides in splitless inlet system. Two strategies were alternatively optimised: (i) the minimisation of degradation reactions to increase the signal of phenylureas; (ii) the maximisation of the degradation to isocyanates that are in turn determined. The maximal yields in isocyanate were obtained with high inlet temperatures, low carrier flows in the injection phase and the presence of acetic anhydride. By contrast, the use of relatively low inlet temperatures, high carrier flows during the injection and the presence of an amine maximise the response of the parent compounds.     

Simultaneous determination of cefazolin in rat blood and brain by microdialysis and microbore liquid chromatography

A sensitive microbore liquid chromatographic method combined with the minimally invasive technique of microdialysis was devised for simultaneously and continuously monitoring the levels of unbound blood and brain cefazolin in rats. Microdialysis probes were inserted into the jugular vein and brain striatum for blood and brain sampling, respectively. Chromatographic conditions consisted of a mobile phase of methanol-acetonitrile-100 mM monosodium phosphoric acid (20:10:70, v/v, pH 4.5) pumped through a microbore reversed-phase column at a flow rate of 0.05 mL/min. The ultraviolet detection wavelength was set at 270 nm. An on-line design allowed direct and continuous analysis of protein-free samples in the dialysate. Microdialysis probes, being home-made, were screened for acceptable in vivo recovery. Chromatographic resolution and detection were validated for response linearity as well as intra-day and inter-day variabilities. This method was then applied to pharmacokinetic profiling of protein unbound cefazolin in both the blood and brain following intravenous administration (10 mg/kg, i.v., n = 6). Rapid appearance of cefazolin in the rat brain striatal dialysate following drug injection suggested good blood-brain barrier penetration. According to a non-compartmental pharmacokinetics model, the area under the concentration (AUC) vs time ratio of cefazolin in rat brain and blood was 6%.