Electrochemical study of 18-crown-6-Tl+ complexes in binary solvent mixtures

Summary The formation constants,K _S, of the 18-crown-6 complex with thallium(I) ion were studied by polarographic measurements in binary mixtures of acetonitrile, acetone, tetrahydrofuran, and dimethylsulfoxide with water, as a function of the solvent mole fraction. In all the cases, the variation of the stability constant can be described by the empirical relation logK _S=a[(–1)/(2+1)]+b where stands for relative permittivity of a given mixture anda andb mark the regression coefficients. The values ofa calculated for four series of binary mixtures showed correlation with the Gutmann donor numbers of the neat organic solvents which form the mixture.On leave from the Department of Chemistry, Jingzhou Teacher's College, Jingzhou, Hubei, China     

A Mountain Pass-type Theorem for Vector-valued Functions

The mountain pass theorem for scalar functionals is a fundamental result of the minimax methods in variational analysis. In this work we extend this theorem to the class of \(\mathcal{C}^{1}\) functions \(f:\mathbb{R}^{n}\rightarrow\mathbb{R}^{m}\), where the image space is ordered by the nonnegative orthant \(\mathbb{R}_{+}^{m}\). Under suitable geometrical assumptions, we prove the existence of a critical point of f and we localize this point as a solution of a minimax problem. We remark that the considered minimax problem consists of an inner vector maximization problem and of an outer set-valued minimization problem. To deal with the outer set-valued problem we use an ordering relation among subsets of \(\mathbb{R}^{m}\) introduced by Kuroiwa. In order to prove our result, we develop an Ekeland-type principle for set-valued maps and we extensively use the notion of vector pseudogradient.     

Diels-alder reaction of 2-chloro-2-nitrosopropane with 1,3-cyclohexadiene

3-(2-Chloropropyl)-2-oxa-3-azabicyclo[2.2.2]oct-5-ene and 2-oxa-3-azabicyclo[2.2.2]oct-5-ene hydrochloride have been prepared by cycloaddition of 2-chloro-2-nitrosopropane to 1,3-cyclohexadiene and their structure determined by nmr, using a ¹H nmr shift reagent.     

The effects of cross-generational and cross-dialectal variation on vowel identification and classification

Cross-generational and cross-dialectal variation in vowels among speakers of American English was examined in terms of vowel identification by listeners and vowel classification using pattern recognition. Listeners from Western North Carolina and Southeastern Wisconsin identified 12 vowel categories produced by 120 speakers stratified by age (old adults, young adults, and children), gender, and dialect. The vowels /?, o, ?, u/ were well identified by both groups of listeners. The majority of confusions were for the front /i, ?, e, ?, ?/, the low back /ɑ, ?/ and the monophthongal North Carolina /a?/. For selected vowels, generational differences in acoustic vowel characteristics were perceptually salient, suggesting listeners' responsiveness to sound change. Female exemplars and native-dialect variants produced higher identification rates. Linear discriminant analyses which examined dialect and generational classification accuracy showed that sampling the formant pattern at vowel midpoint only is insufficient to separate the vowels. Two sample points near onset and offset provided enough information for successful classification. The models trained on one dialect classified the vowels from the other dialect with much lower accuracy. The results strongly support the importance of dynamic information in accurate classification of cross-generational and cross-dialectal variations.     

Laurdan and Prodan as Polarity-Sensitive Fluorescent Membrane Probes

The steady-state and dynamic fluorescence spectral properties of 2-dimethylamino-6-lauroylnaphthalene (LAURDAN) and several other naphthalene derivatives are summarized to illustrate their sensitivity to the polarity of the environment. Results obtained both in solvents of different polarity and in phospholipid vesicles in two phase states are presented. The emission red shift observed in polar solvents and in the phospholipid liquid–crystalline phase is explained on the basis of dipolar relaxation of solvent molecules surrounding the fluorescent naphthalene moiety of these probes. In phospholipid environments, experimental evidence is shown that excludes the intramolecular relative reorientation of the dimethylamino and carbonyl groups in the naphthalene and the reorientation of the entire fluorescent moiety. The solvent dipolar relaxation observed for LAURDAN and PRODAN in phospholipid bilayers has been attributed to a small number of water molecules present at the membrane interface. A comparison between LAURDAN emission in phospholipid vesicles prepared in D₂O and in H₂O is also presented. The definition and the derivation of the generalized polarization function are also discussed.     

Insight into the mechanism of three component condensation leading to aminomethylenebisphosphonates

Three-component reaction of a primary amine, diethyl phosphite and triethyl orthoformate followed by acid hydrolysis of the adduct provides N-substituted aminomethylenebisphosphonic acids in good yields. Being extremely versatile, it is commonly utilized for preparation of compounds possessing potential antiosteoporotic, antibacterial, anticancer, antiparasitic or herbicidal activity. However, the mechanism of the reaction remains unknown. p-Nitroaniline has been found an interesting tool to shed light on this matter. Its use allowed to separate and identify four intermediates, both non-phosphorus and phosphorus containing, and subsequently suggest the mechanism of the whole process. The acquired knowledge was helpful in explanation the route and the final product structure obtained for more complex reaction proceeding with the use of 4-aminopyridine. Additional alkylation of the pyridine nitrogen atom, leading to unexpected N-(1-alkylpyridinium-4-amino)methylenebisphosphonic acids was unambiguously proved.     

Positive cooperativity in substrate binding of human prostatic acid phosphatase entrapped in AOT-isooctane-water reverse micelles

The kinetics of 1-naphthyl phosphate and phenyl phosphate hydrolysis, catalyzed by human prostatic acid phosphatase (PAP) entrapped in AOT-isooctane-water reverse micelles, has been studied over surfactant hydration degree (w0) range 5 to 35. Continuous spectrophotometric acid phosphatase assays, previously prepared, were employed. PAP was catalytically active over the whole w0 studied range. In order to determine steady-state reaction constants the experimental data were fitted to Hill rate equation. Positive cooperativity in substrate binding was observed, as it was earlier found in aqueous solutions. The extent of cooperativity (expressed as the value of the Hill cooperation coefficient h) increased from 1 to 4, when the micellar water-pool size was growing, at fixed enzyme concentration. In the plots of catalytic activity (kcat) versus w0, the maxima have been found at w0=10 (pH 5.6) and 23 (pH 3.8). It is suggested that catalytically active monomeric and dimeric PAP forms are entrapped in reverse micelles of w0=10 and 23, respectively.