Skorostʹ i napravlenie vetra v Krymu 4-go i︠u︡li︠a︡ 1926 goda

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Purification and Properties of l-4-Hydroxymandelate Oxidase from Pseudomonas convexa

An inducible membrane-bound l-4-hydroxymandelate oxidase (decarboxylating) from Pseudomonas convexa has been solubilized and partially purified. It catalyzes the conversion of l-4-hydroxymandelic acid to 4-hydroxybenzaldehyde in a single step with the stoichiometric consumption of O2 and liberation of CO2. The enzyme is optimally active at pH 6.6 and at 55 oC. It requires FAD and Mn2+ for its activity. The membrane-bound enzyme is more stable than the solubilized and purified enzyme. After solubilization it gradually loses its activity when kept at 5 oC which can be fully reactivated by freezing and thawing. The Km values for DL-4-hydroxymandelate and FAD are 0.44 mM and 0.038 mM respectively. The enzyme is highly specific for DL-4-hydroxymandelic acid. DL-3,4-Dihydroxymandelic acid competitively inhibited the enzyme reaction. From the Dixon plot the Ki for DL-3,4-dihydroxymandelic acid was calculated to be 1.8 × 10−4 M. The enzyme is completely inactivated by thiol compounds and not affected by thiol inhibitors. The enzyme is also inhibited by denaturing agents, heavy metal ions and by chelating agents.

Temperature dependence of chlorine NQR in 2-chloro 5-nitrobenzoic acid and 4-chloro 3-nitrobenzoic acid

Temperature dependence of chlorine nuclear quadrupole resonance in 2-chloro 5-nitrobenzoic acid and 4-chloro 3-nitrobenzoic acid has been investigated in the region 77° K to room temperature. No phase transition has been observed. The results are analysed to obtain the torsional frequencies and their temperature dependence. A nonlinear temperature dependence is obtained for the torsional frequencies.

Infrared and Raman spectra of 2,4-dithiobiuret and its normal vibrations

The infrared spectra of 2,4-dithiobiuret(DTB), N-deuterated dithiobiuret(DTB-d5) and the laser Raman spectrum of DTB are reported. Normal coordinate treatments of DTB and DTB-d5 have been carried out to aid the assignment of the vibrational frequencies. A trans—cis conformation is favoured for DTB molecule in the solid state.

Purification and properties of Image -mandelate-4-hydroxylase from Pseudomonas convexa

An inducible Image -mandelate-4-hydroxylase has been partially purified from crude extracts of Pseudomonas convexa. This enzyme catalyzed the hydroxylation of Image -mandelic acid to 4-hydroxymandelic acid. It required tetrahydropteridine, NADPH, Fe2+, and O2 for its activity. The approximate molecular weight of the enzyme was assessed as 91,000 by gel filtration on Sephadex G-150. The enzyme was optimally active at pH 5.4 and 38 °C. A classical Michaelis-Menten kinetic pattern was observed with Image -mandelate, NADPH, and ferrous sulfate and Km values for these substrates were found to be 1 × 10−4, 1.9 × 10−4, and 4.7 × 10−5 Image , respectively. The enzyme is very specific for Image -mandelate as substrate. Thiol inhibitors inhibited the enzyme reaction, indicating that the sulfhydryl groups may be essential for the enzyme action. Treatment of the partially purified enzyme with denaturing agents inactivated the enzyme.

Venäjän politiikka ja perustuslaki : Tutkimus Venäjän perustuslakikäsitteistön kehityksestä 1900-luvulla

Constitutional politics in Russia, a conceptual history study of the constitutional rhetoric in the 20th century In April 2006 the Russian Constitution had its 100th anniversary. Following its late start, five constitutions have been adopted. The great number of constitutions is partly explained in my work by the fact that Russia s political system has changed many times, from one state system to another. From a monarchical state power, it changed first, with the October revolution, into the Russian Socialist Federal Soviet Republic, and after that, in 1924, into the Union of Soviet Socialist Republics. In 1991, the Russian Federation was established. The great number of constitutions can also be explained by the fact that in a one-party system, constitutional concepts became one of the most important instruments for introducing political programmes. When the political unity of the state was not only restricted by the Constitution, but also by the party ideology, the political debates concerning constitutional concepts were the key discussions for all the reformative pursuits of Soviet politics. It can be said that, in the Soviet Union, almost all political discourses dealt with constitutional concepts. In the context of restricted unity, the constitutional concepts were the most important tools to argue and create a basis for a new presentation and new political programmes. Thus, the basic feature of the Soviet political discourses has been a continuous competition regarding the constitutional concepts. By defining the constitutional concepts, a new, the political elites wanted especially to redefine, their own way, the traditional meanings of the October 1917 Revolution, and to differentiate them from those of the preceding period of power. From a methodological point of view, I argue that the Russian constitutional concepts make a conceptual historical approach very suitable, and change the focus on history. This approach studies history in contemporary contexts which follow after each other, and whose texts are the main research target. The picture of history is created through the interpretation of the original sources of contemporary contexts. Focusing on the dynamic and traditional characteristic of Russian constitutional concepts, I refer to a certain kind of value and the task of these concepts to justify and define the political and societal unity in every situation. This is done by combining the pursued future orientation of constitutional unity with the new acts of preservation of the traditional principles of the revolution. The different time layers of the constitutional concepts, the past, the present and the future, are the key aspects of storytelling in justifying the continuity and redefining the constitutional unity for the sake of reform. These aspects of constitutional concepts, in addition to all the other functions, have been the main elements of the argumentative structure of acting against opponents.

Knoevenagel condensation of 2-carbethoxycyclohexanone and malononitrile: Synthesis of 4-cyano-3-ethoxy-1-hydroxy-5,6,7,8-tetrahydroisoquinoline, an isomer of the abnormal product

The structure of the abnormal product 1a formed in the Knoevenagel condensation of 2-carbethoxycyclohexanone and malononitrile has been further confirmed. Oxidation of the tetrahydroisoquinoline 3b using Na2Cr2O-AcOH-H2SO4 gave the keto isoquinoline 3d and the isoquinoline-1-carboxylic acid 5a. The acid chloride of 5a was condensed with diethyl ethoxymagnesiomalonate to afford after decarbethoxylation the methyl ketone 5d which on Baeyer-Villiger oxidation gave a mixture of the acetate 1g and the title compound 1b. The unambiguous synthesis of 1b confirms the structure assigned earlier to the title compound also formed during the partial hydrolysis of the diethoxy compound 1c. Condensation of 2-acetylcyclohexane-1,3-dione with malononitrile gave the quinoline derivative 4c which on ethylation yielded the ketoquinoline 4d. The present studies have confirmed that the quinoline compound 4a is also formed in the condensation of 2-acetylcyclohexanone and cyanoacetamide.

Bromination of Intermolecular Chelate Linkage Isomers of 3-Oximino-4,9-Dimethyl (or 4,7,9-Trimethyl)-5,8-Diazadodeca-4,8-Diene-2,11-Dionato Nickel(II)

The reaction of the title complexes (FIG. 1) with N-bromosuccinimide or bromine in chloroform yields isomeric bromo complexes on substitution of the γ-CH carbon proton by bromine. The brominated products have been characterised by ir, pmr, electronic absorption spectra, conductivity and magnetic susceptibility measurements. The linkage isomerisation of the brominated products in chloroform has been shown to depend on the diamine residue.

Inhibition of Human Two-Pore Domain K+ Channel TREK1 by Local Anesthetic Lidocaine: Negative Cooperativity and Half-of-Sites Saturation Kinetics

TWIK-related K+ channel TREK1, a background leak K+ channel, has been strongly implicated as the target of several general and local anesthetics. Here, using the whole-cell and single-channel patch-clamp technique, we investigated the effect of lidocaine, a local anesthetic, on the human (h) TREK1 channel heterologously expressed in human embryonic kidney 293 cells by an adenoviral-mediated expression system. Lidocaine, at clinical concentrations, produced reversible, concentration-dependent inhibition of hTREK1 current, with IC50 value of 180 mu M, by reducing the single-channel open probability and stabilizing the closed state. We have identified a strategically placed unique aromatic couplet (Tyr352 and Phe355) in the vicinity of the protein kinase A phosphorylation site, Ser348, in the C-terminal domain (CTD) of hTREK1, that is critical for the action of lidocaine. Furthermore, the phosphorylation state of Ser348 was found to have a regulatory role in lidocaine-mediated inhibition of hTREK1. It is interesting that we observed strong intersubunit negative cooperativity (Hill coefficient = 0.49) and half-of-sites saturation binding stoichiometry (half-reaction order) for the binding of lidocaine to hTREK1. Studies with the heterodimer of wild-type (wt)-hTREK1 and Delta 119 C-terminal deletion mutant (hTREK1(wt)-Delta 119) revealed that single CTD of hTREK1 was capable of mediating partial inhibition by lidocaine, but complete inhibition necessitates the cooperative interaction between both the CTDs upon binding of lidocaine. Based on our observations, we propose a model that explains the unique kinetics and provides a plausible paradigm for the inhibitory action of lidocaine on hTREK1.

Purification, properties and induction of a specific benzoate-4-hydroxylase from Aspergillus niger (UBC 814)

An inducible benzoate-4-hydroxylase has been partially purified from crude extracts of the mycelial felts of Aspergillus niger. This enzyme catalyzes the transformation of benzoate to p-hydroxybenzoate with equimolar consumption of NADPH and O2. It requires tetrahydropteridine as a prosthetic group. The optimum activity was found at pH 6.2 with a Km value at 30°C of 1.6 · 10−4 M for NADPH and 1.3 · 10−4 M for benzoate. Fe2+ (iron) is required for the enzyme activity. The enzyme is stabilized by the inclusion of benzoate, EDTA and glutathione in the extracting buffer. The enzyme is specific for benzoate as substrate. Sulfhydryl group(s) are essential for enzyme activity as indicated by p-chloromercuri-benzoate and N-ethylmaleimide inactivation. Benzoate-4-hydroxylase activity is decreased in the mycelial felts of Aspergillus niger grown in the presence of higher concentrations of benzoate. Maximum activity of the enzyme was observed at 36 h after inoculation.

Degradation of (+/-)-synephrine by Arthrobacter synephrinum. Oxidation of 3,4-dihydroxyphenylacetate to 2-hydroxy-5-carboxymethyl-muconate semialdehyde.

1. Cell-free extracts of Arthrobacter synephrinum catalyse the oxidation of 3,4-dihydroxy-phenylacetate. 2. The product of oxidation was characterized as 2-hydroxy-5-carboxymethylmuconate semialdehyde from its chemical behaviour as well as from nuclear-magnetic-resonance spectra. 3. A 3,4-dihydroxyphenylacetate 2,3-dioxygenase (EC 1.13.11.15) was partially purified from A. synephrinum. 4. The enzyme had a Km of 25 micrometer towards its substrate and exhibited typical Michaelis-Menten kinetics. 5. The enzyme also catalysed the oxidation of 3,4-dihydroxymandelate and 3,4-dihydroxyphenylpropionate, at reaction rates of 0.5 and 0.04 respectively of that for 3,4-dihydroxyphenylacetate. 6. The enzyme was sensitive to treatment with thiol-specific reagents. 7. The molecular weight of the enzyme as determined by Sephadex G-200 chromatography was approx. 282000.

In-plane normal vibrations of 1,2,5-oxa-, thia- and selena-diazoles, 1,3,4-oxa- and thia-diazoles and 1,2,3,4-thiatriazoles

In-plane vibration modes of 1,2,5- and 1,3,4-oxa- and thia-diazoles, and 1,2,5-selenadiazole have been assigned on the basis of detailed normal coordinate analysis employing data on several deuterated species. In-plane vibration frequencies of two 1,2,3,4-thiatriazole derivatives have been calculated and compared with observed values.

Zeeman effect of NQR in 4,6-dichloropyrimidine and 6-chloro 2,4-dimethoxypyrimidine

Zeeman (35Cl) NQR studies in polycrystalline samples of 4,6-dichloropyrimidine and 6 chloro 2,4 dimethoxypyrimidine show that the asymmetry at the four chemically inequivalent chlorine sites in the former is about 10%, while in the latter (one line) the asymmetry is almost zero. Using a valence-bond picture, C-Cl bonds in 4,6-dichloropyrimidine have been characterised, and the results are also compared with those in a corresponding benzene compound using a simple molecular orbital calculation. The axial symmetry of C-Cl bond in the second compound has been attributed to mesomeric effects.

The Crystal and Molecular Structure of 4-Aza-5-oxo-tricyclo[4.4.0.03,8]decane (Aza-twistanone)

Die kristalline Struktur von Aza-twistanon wurde durch eine Röntgenstruktur-analyse untersucht. Die Kristalle gehören zur monoklinen Raumgruppe P21/n mit den Zelldimensionen a = 6,662(6), b = 13,36(2), c = 8,606(9) Å, = 98,97(2)°, V = 757 Å3, Z = 4. Die Struktur wurde mit Direktmethoden gelöst und bis zu R = 0,035 verfeinert (mittlere (c) = 0,003 Å3).Die cis-Amidgruppe ist relativ stark deformiert und hat einen Torsionswinkel C -C -N-C von 14,5(4)° (Deformation aus der Ebene c = 5,0(5)° und N = 13,5(4,0)°). Die gegenüberliegende äthylenbrücke weist einen Torsionswinkel von 25,1(5)° auf. Die entsprechenden Winkel in Twistan betragen je 20°. Das tricyclische Gerüst von Aza-twistanon hat approximative.

Complexes of lanthanide iodides with 4-methylpyridine-1-oxide and 2-methylpyridine-1-oxide

Complexes of lanthanide iodides with 4-methylpyridine-1-oxide and 2-methylpyridine-1-oxide of the formulae Ln(4-MePyO)8I3.xH2O (x=0 or 2) and Ln(2-MePyO)5I3.xH2O (x=0, 1 or 3) have been prepared and characterized by analyses, conductance, infrared and proton NMR data. Infrared spectra of the complexes indicate that the coordination of the ligand to the metal ion takes place through the oxygen of the N-O group of the ligand. Proton NMR data for the paramagnetic complexes indicate that both contact and pseudocontact interactions are responsible for the isotropic shifts. Proton NMR spectra of the 2-methylpyridine-1-oxide complexes indicate a restricted rotation of the ligand about the N-O group.