Concatenation of two molecular switches via a Fe(II)/Fe(III) couple

[reaction: see text] Modulation of the fluorescein fluorescence in the presence of spiropyran and ferric ion by light was observed. Such fluorescence modulation was due to the low oxidation potential of complex MC.Fe(2+), which made the electron transfer from MC.Fe(2+) to Flu(+)()(*)() thermodynamically favorable. As a result, the communication between two molecular switches based on fluorescein and spiropyan, respectively, was realized via the reversible Fe(III)/Fe(II) redox couple. The communicating behavior corresponds well to the function of an INHIBIT logic gate.     

A general method for the preparation of 4- and 6-azaindoles

Nitropyridines reacted with an excess of vinyl Grignard reagent to produce 4- or 6-azaindoles. Improved yields were obtained when a halogen atom was present at the position alpha to the nitrogen atom in the pyridine ring.     

Differentiation and quantitation of isomeric dipeptides by low-energy dissociation of copper(II)-bound complexes

Application of the kinetic method based on the dissociation of transition metal centered cluster ions is extended from chiral analysis (Tao, W. A.; Zhang, D.; Nikolaev, E. N.; Cooks, R. G. J. Am. Chem. Soc. 2000, 122, 10598) to quantitative analysis of isomeric mixtures, including those with Leu/Ile substitutions. Copper(II)-bound complexes of pairs of peptide isomers are generated by electrospray ionization mass spectrometry and the trimeric complex [CuII(ref)2(A) - H]+ (analyte A, a mixture of isomeric peptides; reference compound ref, usually a peptide) is caused to undergo collisional dissociation. Competitive loss of the neutral reference compound or the neutral analyte yields two ionic products and the ratio of rates of the two competitive dissociations, viz. the product ion branching ratio R is shown to depend strongly on the regiochemistry of the analyte in the precursor [CuII(A)(ref)2 - H]+ complex ion. Calibration curves are constructed by relating the branching ratio measured by the kinetic method, to the isomeric composition of the mixture to allow rapid quantitative isomer analysis.     

Novel construction of the brassinolide side chain

A stereoselective synthesis of brassinolide, which involves construction of the side chain by a highly stereoselective aldol reaction between 20S-6β-methoxy-3α,5-cyclo-5α-pregnane-20-carboxaldehyde 2 and ketone 3 or 4 catalyzed by l-proline, is described.     

Electronic density of levels in a disordered system

Three-, two-, and one-dimensional disordered systems with randomly distributed, purely repulsive scattering centers, known as Lorentz models, are studied in the low energy limit [1]. Using a functional integral representation and a version of the “replica trick”, we have found in the D-dimensional system the density of electronic levels of the form

$\text{n(E)=b}{}_0\text{Eγ}\text{exp}\text{(?b}{}_1\text{E}{}^{\mathrm{<mtext>?(</mtext><mtext>D</mtext><mtext>2</mtext><mtext>)</mtext>}}\text{+b}{}_2\text{E}{}^{\mathrm{<mtext>?(</mtext><mtext>D</mtext><mtext>2</mtext><mtext>)+1</mtext>}}\text{+·+b}{}_{\mathrm{D}}\text{E}{}^{\mathrm{<mtext>?(</mtext><mtext>1</mtext><mtext>2</mtext><mtext>)</mtext>}}\text{)(1+O(}\text{E}\text{))}$

and the constants b₀, b₁,…, b_D, and γ have been determined.     

Sorption and desorption of neptunium(V) on calcareous soil and its solid components: A comparative study

The sorption and desorption isotherms of untreated calcareous soil and three treated soils to remove CaCO₃, organic matter (OM) and both CaCO₃ and OM were determined and analyzed with the Freundlich equation at pH 7.8, moderate concentrations of NpO₂ ⁺ (~10^-5mol/l), in the presence of 0.01 mol/l CaCl₂ and under ambient aerobic conditions. The relative contribution of CaCO₃ and OM to the neptunium(V) sorption on calcareous soil and the sorption/desorption hysteresis is discussed. The effects of adding fulvic acid (FA) and carbonate in to the solution on the sorption of neptunium(V) on the soils were also studied. The sorption and desorption characteristics of NpO₂ ⁺, Zn²⁺, Sr²⁺ and Cs⁺ on the soils are compared.     

A Substituted Tetraazaporphyrinogen as an Electroactive Component for a Polymeric Membrane Anion-Selective Electrode

A novel anion-selective electrode has been prepared by usingtetraazaporphyrinogen as the electroactive component and o-nitrophenyloctylether as the plasticizer. The electrode exhibits almost Nernstian responsecharacteristics for Pic^-, ReO ₄ ^- ,SCN^-, ClO ₄ ^- and TPB^-. The linearresponse ranges towards the above-mentioned anions are 10^-6 10^-2, 10^-5 10^-2,10^-5 10^-2, 10^-5 10^-1, and 10^-5 10^-2mol/Land the corresponding slopes are -56.8, -57.1, -56.3, -56.1, and -59.9mV/decade with correlation coefficients of -0.99978, -0.99987, -0.99999,-0.99998, and -0.99998, respectively. The electrode shows an anti-Hofmeisterselectivity sequence: Pic^- > SCN^- >ReO ₄ ^- > ClO ₄ ^- > I^- >Br^- > BF ₄ ^- > Sal^->NO ₃ ^- > Cl^-. The unusual responsemechanism of the novel anion-selective electrode was investigated byexperimental observations and calculation with the MNDO method. Theelectrode was used as a TPB^- and a Pic^-sensitiveelectrode, respectively, and applied to the assay of levamisolehydrochloride tablets by potentiometric titration and Gran's methods. Theresults obtained are in excellent agreement with that determined by thestandard pharmacopoeia method based on nonaqueous titration.