DNA Hydrolysis by Homo- and Heteronuclear Cu(II)–Ni(II) Complexes of Two Diester-type Ligands

Nucleolytic activities of novel mononuclear Cu(II), homo- and heterodinuclear Cu(II)–Ni(II) complexes with two diester-type ligands were investigated on pCYTEXP by neutral agarose gel electrophoresis. The analyses of the cleavage products obtained electrophoretically indicate that the examined complexes induce very similar conformational changes on supercoiled DNA by converting supercoiled form to nicked form. At concentrations greater than 100M, the complexes possessed effective nucleolytic activities for 10min of incubation time. However, their nucleolytic activities did not increase significantly with longer periods of incubation. The pH-nucleolytic activity profiles of the complexes differed significantly. Metal complex induced DNA cleavage was also tested for inhibition by various radical scavengers. It could be proposed from the data that diffusible intermediate oxidants are not involved in these reactions or they are not necessary for DNA cleavage since none of antioxidants inhibited DNA cleaving activities of the complexes.     

Novel design of a pentacyclic scaffold as structural mimic of saframycin A

The design, synthesis and evaluation of a pentacyclic scaffold, CWO-324 to mimic saframycin A is described. CWO-324 is readily synthesized in five steps from 1,4-diacetyl-piperazine-2,5-dione and 2,5-dimethoxybenzaldehyde. CWO-324 was found to scission DNA, binds to bases 69-83(5′-GCAGTCAGG CACCGT-3′) of Hind III/Rsa I from plasmid pBR322 DNA in a foot-printing study and possesses anti-tumor activity.     

Studies of physico-chemical properties of mixed adsorbent in the zeolite/SiO2 system

The paper presents physico-chemical properties of mixed adsorbents in the clinoptylolite (mordenite)/SiO₂ system containing 30, 50, 80 mass% zeolite. Adsorption capacity towards polar (water, butanol) and non-polar (n-octane) substances as well as total surface heterogeneity (energetic and geometrical) were determined. Desorption energy distribution functions as well as fractal dimensions were also determined and compared with the low-temperature nitrogen adsorption data. Irregular shapes of the curves q=f(E _d) as well as large values of volumetric fractal dimensions (D _f~2.6) revealed heterogeneous properties of the zeolite/SiO2 system surfaces. Addition of zeolite increases total heterogeneity of the material.     

Mechanistic Study on the Oxidation of Promazine and Chlorpromazine by Hexaimidazolcobalt(III) in Acidic Aqueous Media

The kinetics of the oxidation of promazine and chlorpromazine by hexaimidazolcobalt(III) were studied in the presence of a large excess of cobalt(III) and H⁺ ions using u.v.–vis. spectroscopy ([Co^III] = (1–6) × 10⁻³ m, [ptz] = (2.5–10) × 10⁻⁵ m, [H⁺] = 0.05–0.8 m, I = 1.0 m (H⁺, Na⁺, Cl⁻), T = 333–353 K, l = 1 cm). In each case, the reversible reaction leads to formation of cobalt(II) species and a stable cationic radical. A linear dependence of the pseudo-first-order rate constant (k_obs) on [Co^III] with a non-zero intercept was established for both phenothiazine derivatives. A marked difference in the observed reaction rate for promazine and chlorpromazine is associated with the difference in its ability to undergo oxidation and is consistent with a trend in the redox potential changes for these reductants. The activation parameters for reactions studied were determined. Mechanistic consequences of all the results are discussed.     

Mutual Solubilities of Water and Alkanes

Summary.  The evaluation of mutual solubility data for systems water with n-alkanes, isoalkanes, and cycloalkanes along the three phase line is reported and a formula for the prediction of solubility of alkanes in water is developed. Then a cubic equation of state with an added term, which accounts for hydrogen bonding is used for correlation of liquid–liquid equilibrium data and for prediction of solubility of water in hydrocarbons using alkane in water solubility data. Comparison of the predicted and experimental solubilities is performed using all accessible experimental data. With this approach it is possible to predict the solubilities of water in alkanes with good accuracy over the temperature range up to about 20 K below critical temperature. Solubility of alkanes in water can also be calculated using experimental data for solubility of water in alkanes but results of these calculations are more sensitive to experimental errors of the data. Corresponding author: E-mail: macz@ichf.edu.pl Received August 5, 2002; accepted (revised) September 13, 2002 Published online March 13, 2003 RID="a" ID="a" Dedicated to Prof. Dr. H. Gamsj?ger on the occasion of his 70^th birthday anniversary     

A Stopped-flow Study on the Kinetics and Mechanism of CO2 Uptake by the cis-[Cr(1,10-phenanthroline)2(OH2)2]3+ Complex Ion

The kinetics of the reaction between gaseous CO₂ and the cis-[Cr(phen)₂(OH₂)₂]³⁺ ion leading to the formation of the carbonato complex ion, have been studied over the pH and temperature ranges: 3 < pH < 6 and 5 < T < 25 °C, respectively, at a constant ionic strength of 1 m (NaClO₄). Investigations were carried out using the stopped-flow spectrophotometry technique in the UV–Vis range: 340–700 nm. The major reactant species in the pH range studied was cis-[Cr(phen)₂(OH)(OH₂)]²⁺ ion, which underwent reaction with CO₂ to form cis-[Cr(phen)₂(OH₂)(HCO₃)]²⁺ ion. Subsequently, slower ring closure of the latter species to form the bidentate carbonato chelate was observed. The possible mechanism has been discussed and the activation parameters ΔH^† and ΔS^† were also determined for the reaction studied.     

Determination of total heterogeneity and fractal dimensions of high-temperature superconductors

Using thermo-analytical and sorptometric methods physicochemical properties and especially surface heterogeneity of HgBa₂Ca₂Cu₃O₈₊, (Hg-1223) was investigated. The desorption energy distribution was derived from mass loss Q-TG and differential mass loss Q-DTG curves of thermodesorption in quasi-isothermal conditions of pre-adsorbed n-octane and water vapour. It is shown that the superconducting Hg-1223 phase is highly sensitive to water vapours. The mechanism of water adsorption depends largely on the activation time. By water vapour saturation in a period of 90 min, physisorption takes place. Prolonged periods result in a chemical decomposition. From nitrogen ad- and desorption isotherms the fractal dimension of superconductors were calculated. A new approach is proposed to calculate fractal dimension from Q-TG curves.This revised version was published online in November 2005 with corrections to the Cover Date.     

Triplet losses in dye lasers

The expression for losses due to triplet states in dye laser considered as a six-level system is given. It is shown that triplet losses depend on pumping parameters and photon number. Depending on molecular and cavity parameters two different behaviours of dye lasers are expected. Physical conditions are discussed in which triplet losses as well as photon number undergo a jump at the threshold.     

Synthesis and structural studies of (2E,3E)-3-[(6-{[(1E,2E)-2-(hydroxyimino)-1-methylpropylidene]amino}pyridin-2-yl)imino]butan-2-one oxime, ligand and its mono-, di- and trinuclear copper(II) complexes

A new dioxime ligand, (2E,3E)-3-[(6-{[(1E,2E)-2-(hydroxyimino)-1-methylpropylidene]amino}-pyridin-2-yl)imino]butan-2-one oxime, (H₂Pymdo) (3) has been synthesized in H₂O by reacting 2,3-butenedione monoxime (2) with 2,6-diaminopyridine. Mono-, di- and tri-nuclear copper(II) complexes of the dioxime ligand (H₂Pymdo) and/or 1,10-phenanthroline have been prepared. The dioxime ligand (H₂Pymdo) and its copper(II) complexes were characterized by ¹H-n.m.r., ¹³C-n.m.r. and elemental analyses, magnetic moments, i.r. and mass spectral studies. The mononuclear copper(II) complex of H₂Pymdo was found to have a 1:1 metal:ligand ratio. Elemental analyses, stoichiometric and spectroscopic data of the metal complexes indicated that the metal ions are coordinated to the oxime and imine nitrogen atoms (C=N). In the dinuclear complexes, in which the first Cu(II) ion was complexed with nitrogen atoms of the oxime and imine groups, the second Cu(II) ion is ligated with dianionic oxygen atoms of the oxime groups and are linked to the 1,10-phenanthroline nitrogen atoms. The trinuclear copper(II) complex (6) was formed by coordination of the third Cu(II) ion with dianionic oxygen atoms of each of two molecules of the mononuclear copper(II) complexes. The data support the proposed structure of H₂Pymdo and its Cu(II) complexes.     

Application of kinetic investigations for interpretation ofn-hexane and benzene adsorption on active carbon

Differencies between the mechanism ofn-hexane and benzene adsorption on active carbon were investigated on the ground of kinetic measurements. As it has been stated, the kinetic measurements show fundamental differencies between the mechanism of adsorption in spite of analogy existing in the state of adsorption equilibrium. Within the range investigated, only the adsorption ofn-hexane follows the model of volume filling of micropores. Existence of those differencies is also confirmed by measurements of effective diffusion coefficient values as well as changes of activation energy of the diffusion—adsorption process.

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Anwendung kinetischer Untersuchungen zur Interpretation des Adsorptionsverhaltens vonn-Hexan und Benzol an Aktivkohle

Zusammenfassung Mittels kinetischer Messungen untersuchte man die Unterschiede im Mechanismus des Adsorptionsverlaufes vonn-Hexan und Benzol an Aktivkohle. Man stellte fest, daß trotz der Analogie im Adsorptionsgleichgewichtszustand die kinetischen Messungen auf prinzipielle Unterschiede im Adsorptionsmechanismus hinweisen. Im untersuchten Bereich verläuft nur die Adsorption vonn-Hexane nach dem Modell der Mikroporenvolumenausfüllung. Die auftretenden Unterschiede wurden auch durch die Berechnungen der Werte der effektiven Diffusionskoeffizienten sowie Änderungen der Aktivierungsenergie des Diffusions-Adsorptionsprozesses bestätigt.