Regularities of the photodestruction of acridine dyes in aqueous media

Acridine dyes were found to exhibit a low light fastness in oxygen-containing aqueous solutions because of photooxidation with the participation of molecular oxygen. The values of the quantum yield for the photooxidation of Acridine Yellow, Acridine Orange, and proflavin acetate at their initial concentration 2 × 10^?5 mol/l were determined to be 1.8 × 10^?3, 1.5 × 10^?3, and 0.8 × 10^?3, respectively. It was concluded that the photooxidation of these acridine dyes in dilute solutions results in the formation of primary photoproducts of peroxide nature. For proflav in acetate, as an example, it was demonstrated that the increase of the substrate concentration to 6 × 10^?4 mol/l results in a fourfold increase in the quantum yield, a behavior indicative of a change in the photodecomposition mechanism. The rate of the interaction between exited and unexcited proflavin molecules, the process responsible for the photodecomposition of this compound, was found to be ～4 × 10⁷ l/(mol s). The quantum yield for the photooxidation of the proflavin base was estimated to exceed that for the photooxidation of the proflavin monocation by more than an order of magnitude.     

The HLB dependency for detergent solubilization of hormonally sensitive adenylate cyclase.

The HLB dependency for the solubilization of membrane proteins and adenylate cyclase activity from a plasma membrane-enriched fraction from rat liver has been determined. The HLB (hydrophilic/lipophilic/balance) number of a detergent is an empirical measure of its relative hydrophobicity. Detergent HLB numbers vary systematically with the length of the ethylene oxide chain for a homologous series of detergents such as the Triton X series. These detergents have a constant hydrophobic moiety, octylphenyl, and a variable polar portion, polyethoxyethanol. Basal-NaF-epinephrine-, and glucagon-stimulated adenylate cyclase activities were solubilized in the HLB range of 16.8-17.4. Solubilization was most effective in 0.01 M Tris buffers at pH 7.5 containing 1-5 mM mercaptoethanol, 1 mM MgCl2, and 0.1% Triton X-305. The detergent to membrane protein ratio used in these studies was 3:1. Criteria for solubilization included lack of sedimentation at 100,000 X g, the absence of particulate material in the supernatant when examined by electron microscopy, and inclusion of hormonally sensitive adenylate cyclase activity in Sephadex G-200 gels. The apparent molecular weight of the solubilized enzyme was approximately 200,000 in the presence of Triton X-305. The solubilized enzyme was stimulated 5-fold by NaF, 7-fold by glucagon, and 20-fold by epinephrine compared to the particulate enzyme used in this study which was stimulated 10-fold, 3.4-fold, and 4-fold by NaF, epinephrine, and glucagon, respectively. The solubilized enzyme is stable for several weeks when stored at -60 degrees C.     

Alternative methods for titratable acidity determination

Methods for determination of titratable acidity, other than traditional titration, i.e. methods without titration, are considered. A number of them use analytical acid-base reagents which quickly convert a mixture of strong and weak acids into a new system. This conversion makes it possible to obtain directly the analytical signal (pH, optical density, etc.) for titratable acidity calculation. These methods in stationary conditions and in flow injection analysis are discussed. Methods not using acid-base reagent (iodide-iodate, chromatographic, spectroscopic and others) are also described. The advantages of the alternative methods such as the decrease labour-consumption and analysis time, simplicity of automation and others are shown.     

Hydrosilylation of allyl esters of monosaccharides

By hydrosilylation of 1-O-allyl-2,3,4,6-tetra-O-acetyl-β-D-glucopyranose and 1-O-allyl-2,3,4,6-tetra-O-acetyl-β-D-galactopyranose with 1,3-bis(dimethylsilyl)-2,2,4,4-tetramethylcyclodisilazane in the presence of the catalyst Co₂(CO)₈, we have obtained 1,3-di[3-(2,3,4,6-tetra-O-acetyl-β-D-glucopyranosyloxy)propyldimethylsilyl]-2,2,4,4-tetramethylcyclodisilazane and 1,3-di[3-(2,3,4,6-tetra-O-acetyl-β-D-galactopyranosyloxy)propyldimethylsilyl]-2,2,4,4-tetramethylcyclodisilazane. By deacetylation, we obtained 1,3-di[3-(β-D-glucopyranosyloxy)propyldimethylsilyl]-2,2,4,4-tetramethylcyclodisilazane. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1859–1862, December, 2005.     

Polyhydroxylated nortropanes starting from D-glucose: Synthesis of homochiral (+) and (−)-calystegines B2

The cycloheptano-isoxazoline 1, prepared from D-glucose, is converted to 6,7-dideoxy cycloheptitols which are suitable precursors for the synthesis of enantiomerically pure (+) and (−)-Calystegines B₂.     

Indolopyridines with a bridging heteroatom

Reaction of 2-acetylpyridine with 4-[2.2]paracyclophanyllithium or 4-acetyl[2.2]paracyclophane with 2-pyridllithium gives 1-([2.2]paracyclophan-4-yl)-1-(2-pyridyl)ethanol. Its molecular and crystalline structures have been studied by x-ray analysis. It was found that heating this alcohol in acid medium causes dehydration and heterocyclization to give 1-paracyclophanyl-1-pyridylethylene and 10-methyl[2.2]paracyclophano[4,5-bindolizine.For communication 9 see [1]. This report is also communication [5] in the series Synthesis, Structure, and Biological Activity of [2.2]Paracyclophanes (for communication 4 see [2]).Russian University of National Friendship, Moscow 117198. A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, Moscow 117813. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 793–800, June, 1997.     

New homochiralortho-palladated matrix bearing a bulky substituent at the carbon stereocenter

A new homochiral dimericortho-palladated complex bearing a bulkytert-butyl substituent at the carbon stereocenter was synthesized from optically activeN,N-dimethyl-α-tert-butylbenzylamine. Regioselective activation of only the aromatic C−H bond was shown to occur during the cyclometallation process proceeding under very mild conditions due to steric effects. Spectral characteristics of mononuclear derivatives of the new dimeric complex indicate that the five-membered palladacycle exists predominantly in one of two possible chiral conformations with the axial position of thetert-butyl substituent. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1375–1384, July, 1997.     

Reaction of K2PdCl4 with Synthetic and Natural Nucleic Acids

Circular dichroism was used to study reaction of K₂PdCl₄ with polydeoxyribonucleotides and calf thymus DNA. The optical and structural characteristics of the molecular components were determined to show that K₂PdCl₄ reacts with natural and synthetic acids, producing profound rearrangements in their structure.