Reductive activation of nitrate reductases

Protein film voltammetry of Paracoccus pantotrophus respiratory nitrate reductase (NarGH) and Synechococcus elongatus assimilatory nitrate reductase (NarB) shows that reductive activation of these enzymes may be required before steady state catalysis is observed. For NarGH complementary spectroscopic studies suggest a structural context for the activation. Catalytic protein film voltammetry at a range of temperatures has allowed quantitation of the activation energies for nitrate reduction. For NarGH with an operating potential of ca. 0.05 V the activation energy of ca. 35 kJ mol-1 is over twice that measured for NarB whose operating potential is ca. -0.35 V.     

Ion chromatographic determination of nitrate and nitrite in vegetable and fruit baby foods

An ion chromatographic method was developed for the determination of nitrate and nitrite in vegetable and fruit baby foods. The introduction of nitrate or nitrite to food may be natural or artificial as a preservative. Because of the higher pH found in babies' stomachs, nitrate can act as a reservoir for the production of nitrite by nitrate-reducing bacteria that can be harbored in the intestinal tract. This problem does not exist in adults because of the lower pH of the adult stomach. Exposure to nitrite by infants can result in methemoglobinemia (blue baby syndrome). There are also indications that carcinogenic nitrosamines can be formed from nitrates at the higher pH. These gastric conditions disappear at approximately 6 months of age. In this method, nitrate and nitrite were separated on a hydroxide-selective anion exchange column using online electrolytically generated high-purity hydroxide eluant and detected using suppressed conductivity detection. Average recoveries of spiked nitrite residue ranged from 91 to 104% and spiked nitrate residue ranged from 87 to 104%. This method and the AOAC Official Method yield comparable results for samples containing incurred nitrate residue. In addition, this method eliminates the hazardous waste associated with the use of cadmium found in the AOAC Official Method.     

A comparison of two methods for the preparation of 3-Deazapurine ribonucleosides

The reaction of the trimethylsilyl derivative of 4,6-dichloroimidazo[4,5-c]pyridine with 2,3,5-tri-O-benzoyl- D -ribofuranosyl bromide gave four nucleosides-the α- and β-anomers of the 1-isomer and the α- and β-anomers of the 3-isomer (3.9:2.7:1.5:1). In contrast, the fusion reaction of 4,6-dichloroimidazo[4,5-c ]pyridine with 1,2,3,5-tetra-O-acetyl-β- D -ribofuranose gave a high yield of the 1-β-isomer, which was converted to the known 3-deazaadenosine (4-amino-l-β- D -ribofuranosylimidazo[4,5-c]pyridine).     

9,9-diphenyl-1,9,10,10a-tetrahydro-2H-phenaleno[1,9-bc]pyrans

Reaction between some naphtho[2,1-b]pyrans and 1,1-diphenylethene affords 9,9-diphenyl-1,9,10,10a-tetrahydro-2H-phenaleno[1,9-bc]pyrans.     

Amperometric method for determining the degree of complexation of polyelectrolytes with cationic surfactants

The complexation of sodium polystyrene sulfonate with monovalent cationic surfactants at a microsized liquid/liquid interface has been studied using electrochemistry. The method is based on measurement of surfactant ion transfer across the interface between two immiscible electrolyte solutions (ITIES). The complexation of various cationic surfactants (alkylpyridinium- and trimethylammonium-) with oligosized polystyrene sulfonate was measured. Binding isotherms were used to determine the degree of binding as a function of the surfactant chain length and type of head group. It was found that the hydrophobicity of the surfactant was the predominant factor. The effect of the polyelectrolyte chain length on the binding mechanism was studied using cetylpyridinium chloride as a complexing agent. It was found that binding affinity, as well as cooperativity of the binding process, decreases with decreasing polyelectrolyte chain length. Thermodynamics of surfactant binding was measured using titration microcalorimetry. The thermodynamic data obtained show that the enthalpy of surfactant binding is not dependent on polymer chain length, but an increase in chain length makes the binding process entropically more favorable.     

Clustering files of chemical structures using the fuzzy k-means clustering method

This paper evaluates the use of the fuzzy k-means clustering method for the clustering of files of 2D chemical structures. Simulated property prediction experiments with the Starlist file of logP values demonstrate that use of the fuzzy k-means method can, in some cases, yield results that are superior to those obtained with the conventional k-means method and with Ward's clustering method. Clustering of several small sets of agrochemical compounds demonstrate the ability of the fuzzy k-means method to highlight multicluster membership and to identify outlier compounds, although the former can be difficult to interpret in some cases.     

Unusual selectivity of unprotected aziridines in palladium-catalyzed allylic amination enables facile preparation of branched aziridines

Functionalized branched aziridines can be prepared in high yields and with high levels of regioselectivity using unprotected aziridines as nitrogen sources in palladium-catalyzed allylic amination. High levels of enantioselectivity can be achieved with BINAP on palladium. This methodology allows for strategic placement of an aziridine-containing fragment within a complex molecule environment for further elaboration.     

The first structural characterization of a phosphonium amide: synthesis, isolation and molecular structure of (Ph3PEt)(NPh2)

The first isolation of a phosphonium amide, (Ph₃PEt)⁺(NPh₂)⁻, obtained via the deprotonation of a secondary amine (diphenylamine) with a phosphorus ylide (triphenylphosphonium ethylide), is described. An X-ray crystal structure provides the first observation of an essentially ion-separated Ph₂N⁻ anion in the solid state, though weak association with Ph₃PEt⁺ cations take plac through C---H…N hydrogen bonding. Cryoscopic and NMR spectroscopic data suggest that this association is not maintained in benzene solution.     

Raman scattering study of the low temperature phase transitions in ammonium nitrate

The phase changes in polycrystalline ammonium nitrate and its fully deuterated analogue have been studied by Raman scattering. The phase V and IV transition was found to be associated with the softening and intensity decrease of a NO₃^? librational mode. The Raman line-width data suggest that the VII to V phase transition involves a change in the degree of orientational order of the ions without incurring a change in lattice structure.     

Strong intramolecular secondary si.N bonds in trifluorosilylhydrazines

The simple silylhydrazines F(3)SiN(Me)NMe(2) (1), F(2)Si(N(Me)NMe(2))(2) (2), and F(3)SiN(SiMe(3))NMe(2) (3) have been prepared by reaction of SiF(4) with LiN(Me)NMe(2) and LiN(SiMe(3))NMe(2), while F(3)SiN(SnMe(3))NMe(2) (4) was prepared from SiF(4) and (Me(3)Sn)(2)NNMe(2) (5). The compounds were characterized by gas-phase IR and multinuclear NMR spectroscopy ((1)H, (13)C, (14/15)N, (19)F, (29)Si, (119)Sn), as well as by mass spectrometry. The crystal structures of compounds 1-5 were determined by X-ray crystallography. The structures of free molecules 1 and 3 were determined by gas-phase electron diffraction. The structures of 1, 2, and 4 were also determined by ab initio calculations at the MP2/6-311+G** level of theory. These structural studies constitute the first experimental proof for the presence of strong Si.N beta-donor-acceptor bonds between the SiF(3) and geminal NMe(2) groups in silylhydrazines. The strength of these non-classical Si.N interactions is strongly dependent on the nature of the substituent at the alpha-nitrogen atom of the SiNN unit, and has the order 3>4>1. The valence angles at these extremely deformed alpha-nitrogen atoms, and the Si.N distances are (crystal/gas): 1 104.2(1)/106.5(4) degrees, 2.438(1)/2.510(6) A; 3 83.6(1)/84.9(4) degrees, 2.102(1)/2.135(9) A; 4 89.6(1) degrees, 2.204(2) A.