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) . - . . , .

     

Buffers for the Physiological pH Range: Thermodynamics of the Second Dissociation of N-(2-Hydroxyethyl)piperazine-N′-2-hydroxypropanesulfonic Acid From 5 to 55°C

The second acidic dissociation constants pK ₂ of the ampholyte N-(2-hydroxyethyl) piperazine-N-2-hydroxypropanesulfonic acid (HEPPSO) have been determined at seven temperatures from 5 to 55°C from emf measurements utilizing hydrogen and silver–silver chloride cells without liquid junction. The thermodynamic quantities, G°, H°,S°, and C _p ^o have been calculated from the temperature coefficient of pK ₂. At 25°C, the pK ₂ = 8.042 and at 37°C, pK ₂ = 7.876; hence, buffer solutions of HEPPSO and NaHEPPSOate are important for pH control in the region close to that of clinical fluids (blood serum). Conventional pH values from 5 to 55°C as well as those obtained from liquid junction correction at 25 and 37°C have been reported for three buffer solutions with the compositions (molality scale): (1) equimolal mixture of HEPPSO (0.04 m) + NaHEPPSOate (0.04 m) + NaCl (0.12 m); (2) HEPPSO (0.08 m) + NaHEPPSOate (0.08 m); and (3) HEPPSO (0.08 m) + NaHEPPSOate (0.08 m) + NaCl (0.08 m).     

Purification and characterization of a solvent stable protease from Pseudomonas aeruginosa PseA

A solvent tolerant Pseudomonas aeruginosa PseA strain was isolated from soil. It secreted a novel alkaline protease, which was stable and active in the presence of range of organic solvents, thus potentially useful for catalysis in non-aqueous media. The protease was purified 11.6-fold with 60% recovery by combination of ion exchange and hydrophobic interaction chromatography using Q-Sepharose and Phenyl Sepharose 6 Fast Flow matrix, respectively. The apparent molecular mass based on the sodium dodecyl sulphate-polyacrylamide gel electrophoresis (SDS-PAGE) was estimated to be 35,000 Da. The enzyme was stable in the pH range of 6.0-9.0, the optimum being 8.0. The Km and Vmax towards caseinolytic activity were found to be 2.7 mg/ml and 3 micromol/min, respectively. The protease was most active at 60 degrees C and characterized as a metalloprotease because of its sensitivity to EDTA and 1,10-phenanthroline. It was tested positive for elastase activity towards elastin-orcein, thus appears to be an elastase, which is known as pseudolysin in other strains of P. aeruginosa. The protease withstands range of detergents, surfactants and solvents. It is stable and active in all the solvents having log P above 3.2, at least up to 72 h. These two properties make it an ideal choice for applications in detergent formulations and enzymatic peptide synthesis.     

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).     

Synthesis of novel fullerene amino acids and their multifullerene peptides

[60]-Fullerene functionalized amino acids with 4-6 methylene spacers from α-carbon to the nitrogen atom of fulleropyrolidine and corresponding multifullerene peptides have been synthesized.     

N-halogeno-compounds. Part 9 [1]. Azoxy- and azo-arenes derived from 4-(dichloroamino)tetrafluoropyridine; crystal structure of trans-2,3,5,6-tetrafluoro-4-(2,4,6-trimethylphenyl-onn-azoxy)pyridine

The nitrosoarenes ArNO (Ar = C₆H₅, 2-MeC₆H₄, 2,4,6- Me₃C₆H₂ and C₆F₅) have been condensed with 4-(dichloroamino)- tetrafluoropyridine to provide the azoxy-compounds py_FN$\text{N}\text{+}$($\text{N}\text{-}$)Ar (py_F = 2,3,5,6-tetrafluoro-4-pyridyl); de-oxygenation of the first three with triphenylphosphine or triethyl phosphite gave the corresponding azo-compounds, and the reverse reaction was achieved in the case of py_FNNC₆H₂Me₃-2,4,6 using peroxytrifluoroacetic acid. Thermolysis of 4-azidotetrafluoropyridine in the presence of pentafluoronitrosobenzene provided the perfluorinated azoxy-compound py_FN$\text{N}\text{+}$($\text{O}\text{-}$)C₆F₅. X-Ray methods have been used to determine the molecular geometry of py_FN$\text{N}\text{+}$($\text{O}\text{-}$)C₆H₂Me₃-2,4,6.     

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.     

Novel perturbation expansion for the Langevin equation

We discuss the randomly driven systemdx/dt= -W(x) +f(t), wheref(t) is a Gaussian random function or stirring force withf(t)f(t)=2(t–t), andW(x) is of the formgx ¹⁺². The parameter is a measure of the nonlinearity of the equation. We show how to obtain the correlation functionsx(t)f(t)···x(t( n)) _f as a power series in. We obtain three terms in the expansion and show how to use Padé approximants to analytically continue the answer in the variable. By using scaling relations, we show how to get a uniform approximation to the equal-time correlation functions valid for allg and.     

Determining theCP-violating phase γ

The weak phase γ is conventionally probed by theB _s→ρ ⁰ mode. The predicted rate is tiny. Even if aB _s→ρ ⁰ K _s rate difference could be established, it would not be clear that sin 2γ had been measured, because amplitudes with other weak phases may contribute significantly. Non-CP eigenstates, such asB _s →D _s ^± K ^?, have a two-fold advantage overB _s→ρ ⁰ K _s. Their rates are orders of magnitude above that forB _s→ρ ⁰ K _s, and they probe theCP-violating phase γ, without any contamination from other weak phases. Detailed time-dependent studies of non-CP eigenstates remove possible final-state phases and extract the weak phase γ.