Micellar effect of sodium dodecyl sulfate on the reactions between iron(II) and p-benzoquinone, and iron(III) and hydroquinone

The micellar effet of sodium dodecyl sulfate (SDS) on the initial stages of the reaction between (1) Fe(II) and p-benzoquinone, and (2) Fe(III) and hydroquinone have been investigated. In the former case acceleration was observed, the rate-[surfactant] profile showing a maximum. SDS has an inhibitory effect on the latter reaction. Kinetic analysis has been carried out using Berezin's approach.

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() 1) Fe(II) 2) Fe(III) . - . . , .

     

A family of oxorhenium(v) complexes incorporating chelated monoanionic ONN reduced Schiff base and dianionic ONNO tetradentate ligands: synthesis, spectroscopic and electrochemical studies

The green colored complexes of the type Re(V)O(L(SB))Cl(2), 1, have been synthesised by reacting NBu(4)[ReOCl(4)] with HL(SB) in dry ethanol. Here, L(SB)(-) are the deprotonated forms of N-(2-hydroxybenzyl)-2-picolylamine (HL(SB)(1)); N-(2-hydroxybenzyl)-N',N'-dimethylethylenediamine (HL(SB)(2)) and N-(2-hydroxybenzyl)-N',N'-diethylethylenediamine (HL(SB)(3)). Similarly, NBu(4)[ReOCl(4)] reacted with N,N-bis(2-hydroxybenzyl)-2-picolylamine (H(2)L(1)); N,N-bis(2-hydroxybenzyl)-N',N'-dimethylethylenediamine (H(2)L(2)); N,N-bis(2-hydroxybenzyl)-N',N'-diethylethylenediamine (H(2)L(3)); [N-(2-hydroxybenzyl)-N-(2-pyridylmethyl)]-2-aminoethanol (H(2)L(4)); [N-(2-hydroxybenzyl)-N-(2-pyridylmethyl)]-2-methyl-2-amino-1-propanol (H(2)L(5)); N,N-bis(1-hydroxyethyl)-2-picolylamine (H(2)L(6)), to give the monochloro complexes Re(V)O(L)Cl, 2. The X-ray structures of the complexes are reported. The molecular structures observed in the solid state are preserved in solution ((1)H NMR). In acetonitrile solution the Re(V)O(L)Cl, 2, display a one-electron couple, Re(VI)O(L)Cl(+)-Re(V)O(L)Cl, near 1.0 V vs SCE. The electrogenerated hexavalent complexes [Re(VI)O(L)Cl]ClO(4), 3, are paramagnetic and display sextet EPR spectra in solution at room temperature (A(av) approximately 417 (G), g approximately 1.914).     

X-band e.p.r. spectra of mixed-ligand copper(II) complexes

E.p.r. spectra of [Cu(et2dtc)2], Na[Cu(asp/glut)(et2dtc)] and Na2[Cu(asp/glut)(et2dtc)2] in the polycrystalline state have been recorded and discussed. The complexes display an antiferromagnetic exchange interaction, increasing in the order: Na2[Cu(asp/glut)(et2dtc)2] < Na[Cu(asp/glut)(et2dtc)] < [Cu(et2dtc)2] This revised version was published online in June 2006 with corrections to the Cover Date.     

Extractive spectrophotometric determination of molybdenum as a thiocyanate-2-acetylpyridinethiosemicarbazone complex

A new spectrophotometric method for the determination of molybdenum is based on the extraction of the orange red molybdenum thiocyanate-2-acetylpyridinethiosemicarbazone complex into chloroform from hydrochloric acid. The complex has an absorption maximum at 470 nm with a molar absorptivity of 1.7 × 10⁴ liters mol^?1 cm^?1. Beer's law is valid from 0.1 to 6.5 ppm of molybdenum. The equilibrium shift method indicated a 1:4:2 complex. The method has been used successfully for the determination of molybdenum in molybdenum steels.     

A Highly stereospecific and efficient synthesis of homopentafluoro- phenylalanine

A short and efficient synthesis of homopentafluorophenylalanine (6) from oxazolidine aldehyde 1 in 57% overall yield and in > 98% ee is described. The enantiomeric excess of the product was determined by 19F NMR analysis of the coupling product derived from 5 and L-Ser(O-t-Bu)-OCH3, by comparison to a dipeptide obtained from racemic 5.     

Structure of 4-[4-(Dimethylamino)-Phenylazo] Benzeneboronic Acid and Its Cyclic Esters with D-Glucose: A Computational Study

We present results from a computational study of 4-[4-(dimethylamino)-phenylazo] benzene boronic acid (DABBA) (the 4'-boronic acid isomer of the aminoazobenzene dye N,N-dimethylaminoazobenzene) and its associated anion, as well as, several cyclic esters formed from these azoborates and various conformers of D-glucose. Azo dyes that also contain one or more boronic acid functional groups are of practical importance in the development of chemical sensors for saccharide recognition because of their ability to induce a visible color change upon binding. The lowest-energy DABBA:D-glucose esters found in this investigation consistently involved at least one of the exocyclic hydroxymethyl groups on the D-glucose moiety rather than vicinal cis or trans diol arrangements of hydroxyl groups on the ring.     

Spectrophotometric determination of aromatic primary amines and nitrite by flow injection analysis

Aromatic primary amines are determined by injection into dilute hydrochloric acid carrier which merges sequentially with 4-N-methylaminophenol and dichromate. The purple-red color formed by oxidative coupling of amines with 4-N-methylaminophenol is measured at 530 nm. In contrast to the manual procedure, the flow-injection procedure avoided errors arising from the instability of the coupling intermediate, oxidation of the amine, and too great an excess of the oxidant. The method improves the selectivity for certain amines in the presence of those which are sterically hindered or have an electron-deficient aromatic nucleus. Nitrite is determined by diazotization of sulfanilamide and quantifying the residual sulfanilamide by oxidative coupling. The sample thourghout for the assay of amines (0.05–20 μg ml^?1 NH₂-N) and nitrite (1–10 μg ml^?1 NO₂^--N) was 120 h^?1. A system for the consecutive determination of aromatic primary amines and nitrite is decribed.     

Nucleation of β-hairpin structure in a pyrrole amino acid containing peptide

Synthesis and conformational studies of two short peptides containing pyrrole amino acids (1, Paa), Boc-Paa-Paa-d-Pro-Gly-Xaa-Paa-Paa-OMe (2: Xaa=Ala; 3: Xaa=Val), were carried out in which it was established that replacement of Ala in 2 with a Val residue helps peptide 3 to adopt a well-defined β-hairpin conformation in a nonpolar solvent, like CDCl₃.     

Stereochemical applications of mass spectrometry: 1—The utility of electron impact and chemical ionization mass spectrometry in the differentiation of stereoisomeric benzoin oximes and phenylhydrazones

A study of the electron impact and chemical ionization (H₂, CH₄, and iso-C₄H₁₀) mass spectra of stereoisomeric benzoin oximes and phenylhydrazones indicates that while the former can be distinguished only by their chemical ionization mass spectra the latter are readily distinguishable by both their electron impact and chemical ionization mass spectra. The electron impact mass spectra of the isomeric oximes are practically identical; however, the chemical ionization spectra show that the E isomer forms more stable [MH]⁺ and [MH? H₂O]⁺ ions than the Z isomer for which both the [MH]⁺ and [MH? H₂O]⁺ ions are relatively unstable. In electron impact the Z-phenylhydrazone shows a lower [M]⁺˙ ion abundance and more facile loss of H₂O than does the E isomer. This more facile H₂O loss also is observed for the [MH]⁺ ion of the Z isomer under chemical ionization conditions.