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.     

New route to a face-to-face biscorrole free-base and the corresponding heterobimetallic copper(III)-silver(III) complex

A meso-aryl-substituted face-to-face biscorrole was synthesised in a two-step reaction and the corresponding homo- and heterobimetallic complexes were obtained and fully characterised.     

The millimeter-wave spectrum of chlorine nitrate (ClONO2): The ν6 vibrational state

The pure rotational spectrum of chlorine nitrate in its v₆ = 1 excited vibrational state has been studied. A total of 2901 lines, with K_a extending to 33 in the ³⁵Cl isotopologue and 30 in the ³⁷Cl isotopologue, respectively, have been recorded and assigned. This analysis, along with our recently reported study of the ν₅/ν₆ν₉ dyad and the improved energy levels of ν₉ reported in this paper, should make possible accurate simulation of the corresponding ν₆ band and its complex hot band structure near 435 cm⁻¹.     

Experimental and computational study on the reactivity of 2,3-bis[(3-pyridylmethyl)amino]-2(Z)-butene-1,4-dinitrile, a key intermediate for the synthesis of tribenzoporphyrazine bearing peripheral methyl(3-pyridylmethyl)amino substituents

Abstract  

An earlier developed alkylating path leading to tetraalkylated diaminomaleonitrile derivatives was explored. Attempts to explain the reactivity of the representative dialkylated diaminomaleonitrile 2,3-bis[(3-pyridylmethyl)amino]-2(Z)-butene-1,4-dinitrile during the alkylation reaction were performed using X-ray and density functional theory (DFT) studies. The condensed Fukui functions accompanied by softness indices were found to be useful in explaining its reactivity observed during the reaction. The values of the Fukui functions and condensed softness for electrophilic attack calculated from Mulliken, L?wdin, and natural population analyses closely corresponded to the experimental observations. When 2,3-bis[(3-pyridylmethyl)amino]-2(Z)-butene-1,4-dinitrile disodium salt was treated with dimethyl sulfate at lower temperatures the alkylation reaction prevailed, whereas at higher temperatures the alkylating agent acted as a hydride anion acceptor, which favored the elimination reaction. The tetraalkylated dinitrile 2,3-bis[methyl(3-pyridylmethyl)amino]-2(Z)-butene-1,4-dinitrile was used in the synthesis of tribenzoporphyrazine bearing methyl(3-pyridylmethyl)amino groups, which was subsequently subjected to solvatochromic and metallation studies. The changes observed during metallation seem to result from the coordination of the 3-pyridyl group by a palladium ion. This could influence the configuration of the methyl(3-pyridylmethyl)amino moiety, causing more effective donation of a lone pair of electrons from peripheral nitrogen to the macrocyclic ring.     

Directing Polymorphism in the Helical Nanofilament Phase

Herein, it is reported that the polymorphism in the helical nanofilament (HNF, B₄) liquid-crystalline phase depends on the fabrication methods, that is, UV-driven formation and template-assisted self-assembly in the nanoconfined geometry. As a result, uniaxially oriented HNFs with different helical structures were obtained, in which generation of the twisted-ribbon and cylindrical-ribbon polymorphs showed that even the molecular lattice has a different orientation. The detailed structures were directly observed by SEM and grazing-incidence X-ray diffraction with synchrotron radiation. The resultant polymorphs could be used in chiro-optical applications due to the capability for fine control of the helical structures.     

The lattice generated by <Emphasis Type="Italic">τ</Emphasis>-quasicontinuous functions

The lattices generated by the families of quasicontinuous and τ-quasicontinuous functions are described.     

Background current elimination in thin layer ion-selective membrane coulometry

A promising method for the elimination of undesired capacitive currents in view of realizing a potentially calibration free coulometric ion detection system is presented. The coulometric cell is composed of a porous polypropylene tube doped with a liquid calcium-selective membrane and a silver/silver chloride wire as an inner electrode, forming a thin layer sample between wire and tubing. The total charge passed through the system during potential controlled electrolysis of the thin layer sample is indeed found to be proportional to the amount of calcium present, but non-Faradaic processes do contribute to the obtained signal. We introduce here a multi-pulse procedure that allows one to perform a second excitation pulse at the same excitation potential after exhaustive ion transfer voltammetry of calcium has taken place. The intercept of the calibration curve after background subtraction is found as 20.6 ± 0.6 μC, significantly lower than the value of 54.1 ± 0.8 μC for the uncorrected curve. Changes in sample temperature (from 23 °C to 38 °C) did equally not affect the background corrected coulometric readings, supporting that the procedure renders the readout principle more robust.