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.     

A study of polyamine complex formation with H+, Cu(II), Zn(II), Pb(II), and Mg(II) in aqueous solution

Summary The composition and stability of the following biogenic amine complexes have been investigated: 1,4-diaminobutane(Put), 4-azaoctane-1,8-diamine(Spd), 4,9-diazadodecan-1, 12-diamine(Spm) as well as homologues such as 1,3-diaminopropane(Put3), 4-azaheptane-1, 7-diamine(Spd3,3) and 4,8-diazaundecan-1,11-diamine(Spm3,3,3) with H⁺, Cu(II), Zn(II), Pb(II) and Mg(II). A potentiometric method was used. The VIS technique enabled the determination of coordination mode in copper/amine systems. It was found that Mg(II) does not form coordination compounds with any of the studied polyamines in solution. An increase in the concentration of ligand and metal was found to result in a stronger tendency towards the formation of protonated compounds accompanied by a decrease in the concentration of hydroxocomplexes. At physiologicalpH (7.4) an increase in the concentration of protonated compounds by approximately 15% was observed within the ligand concentration range from 0.001 mol dm^–3 to 0.0001 mol dm^–3 at a Cu(II) concentration of 0.000177 mol dm^–3.

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Untersuchungen zur Komplexbildung von Polyaminen mit H⁺, Cu(II), Zn(II), Pb(II) und Mg(II) in wäßriger Lösung

Zusammenfassung Anhand einer Analyse von potentiometrischen Daten wurden Zusammensetzung und Beständigkeit folgender biogener Aminkomplexe untersucht: 1,4-Diaminobutan(Put), 4-Azaoktan-1,8-diamin(Spd), 4,9-Diazadodekan-1,12-diamin(Spm), sowie auch deren Homologen 1,3-Diaminopropan(Put3), 4-Azaheptan-1,7-diamin(Spd3,3) und 4,8-Diazaundekan-1,11-diamin(Spm3,3,3) mit H⁺, Cu(II), Zn(II), Pb(II) und Mg(II). Mit Hilfe der VIS-Technik wurde die Koordinationsweise in Kupfer/Amin-Systemen bestimmt. Es wurde festgestellt, daß Mg(II) keine Koordinationsverbindungen mit den untersuchten Polyaminen bildet. Eine höhere Konzentration von Ligand und Metall führte zu stärkerer Tendenz der Bildung protonierter Verbindungen, wobei die Konzentration von Hydroxokomplexen kleiner wurde. Bei physiologischempH (7.4) wurde im Bereich der Ligand-Konzentration von 0.001 mol dm^–3 bis 0.0001 mol dm^–3 bei einer Cu(II)-Konzentration von 0.000177 mol dm^–3 ein Anstieg der Konzentration protonierter Verbindungen um etwa 15% beobachtet.

     

Interferences in ultratrace speciation of organolead and organotin by gas chromatography with atomic spectrometric detection

Interferences in trace and ultratrace speciation analysis of organotin and organolead compounds in various samples by gas chromatography coupled with atomic absorption spectrometry (AAS) and/or microwave induced plasma atomic emission spectrometry (MIP AES) are investigated. Particular attention is given to the effects of matrix co-extractives and reagents impurities introduced during sample preparation. Their influence on the detection limits is discussed in terms of baseline noise level, blank value, formation of artefacts and signal suppression. Loss of column resolution during the analysis of some matrices is observed.     

Molecular tight-binding method. I. Many-electron method for hole bands of molecular crystals

A method for calculating ab initio electronic excitation energies of molecular crystals, based on a many-electron tight-binding approximation, is described. The method follows Frenkel's model for excitons and allows a many-electron treatment of the band-structure problem of molecular crystals. The case of hole bands is studied in detail and various versions of the method are considered. A computational scheme is proposed, in which approximate correlation corrections to the HFR matrix equations of the one-electron LCMO method are calculated. The main effects contributing to these corrections are the effect of relaxation of a molecular ion, the effect of intramolecular electronic-correlation change, and the effect of polarization of the remaining molecules in a crystal. The method developed in the present paper is applied to calculation of the hole bands of the HCP helium crystal.     

Formation and thermal decomposition of aluminium nitroxy compounds

During the reactions of lithium oxide with aluminium nitride, and of lithium nitride with aluminium oxide, the formation has been observed of a previously unknown compound, of composition Li₂AlNO. The course of its thermal decomposition has also been determined.

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Zusammenfassung Es wurde das Auftreten einer bisher unbekannten Verbindung der Zusammensetzung LiAlNO bei den Reaktionen von Lithiumoxid mit Aluminiumnitrid und Lithiumnitrid mit Aluminiumoxid beobachtet. Der Verlauf der thermischen Zersetzung dieser Verbindung wurde bestimmt.

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Li₂AlNO. .

     

Multidimensional gravitational waves. I. Purely radiative spacetimes

The concept of gravitational radiation in multidimensional Einstein gravity is studied. Due to technical difficulties the Petrov classification of the conformal tensor and the peeling off theorem cannot be generalized to spaces of dimensiond > 4. A multidimensionalpp wave is defined by analogy with that ford = 4. If the definition is supplemented by the Lichnerowicz condition for purely radiative spacetimes, the admitted solutions of the dimensionally reduced gravity theory describe a scalar (dilaton) and a gravitationalpp wave moving in the external spacetime in the same direction. The existence of the extra dimensions can be traced back by measuring the frequence of thepp wave in the external space. The condition is equally restrictive in a more general case of the internal space being a flat anisotropic manifold (i.e. an abelian group space).     

Miscibility of gramicidin A-ethyl nonadecanoate in langmuir monolayers in the presence of salts dissolved in the subphase

The behavior of binary mixed Langmuir monolayers from gramicidin A (GA) and ethyl nonadecanoate (EN), spread on aqueous subphases containing NaCl and CaCl2, was investigated on the basis of the analysis of surface pressure-average area per molecule (pi-A) isotherms complemented with Brewster angle microscopy (BAM) images. Compression modulus versus surface pressure (C(S-1)-pi) curves indicate the existence of interactions in the GA-EN mixed monolayers at low surface pressures (below 5 mN m(-1)). However, for mixtures in which the ester is the predominant component, both GA and EN are miscible within regions from fully expanded to collapse. To examine the interactions between both components in the studied system, values of the mean molecular area per molecule (A12) were plotted as a function of molar fraction of gramicidin A (X(GA)). A12-X(GA) plots exhibit negative deviations from ideality at high surface pressures, wherein beta-helices of GA are vertically oriented in respect to the interface. However, at surface pressures below the plateau transition, which is due to reorientation of GA, the binary system obeys the additive rule. Brewster angle microscopy (BAM) was applied for a direct visualization of the monolayers morphologies. The obtained images prove that for molar ratios of GA > or = 0.3 and at surface pressures above 5 mN m(-1), both components are immiscible at the interface. The observed negative deviations from the additively rule were attributed to the formation of a three-dimensional phase in the mixed film, which provokes its contraction at the interface.     

The vibrational spectra and normal coordinate analysis of tetracyclopropyllead

All the fundamental frequencies observed in IR and Raman spectra have been assigned to the normal modes of the molecule (C₃H₅)₄Pb (C₃H₅ = cyclopropyl). The calculated force field is compared to that of (C₃H₅)₂Hg and the Cmetal stretching force constants are discussed along with those of Me₄Pb and Me₂Hg; The similarity of the spectra of cyclopropyllead and cyclopropyl-mercury proves that the vibrations of cyclopropyl structural units are isolated in both molecules.     

Photochemical syn-anti isomerization reactions in N2-hydroxyisocytosines--an experimental matrix isolation and theoretical study

N2-hydroxyisocytosine and 1-methyl-N2-hydroxyisocytosine were studied using a matrix isolation technique combined with infrared absorption spectroscopy. For N2-hydroxyisocytosine isolated in an Ar matrix (at 10 K), two imino-oxo isomers, one with the hydroxyimino =N-OH group directed toward the N1-H group (the form called further anti) and the second with the =N-OH group directed toward N3-H (syn), were observed in the ratio 1.4:1. The syn isomer is converted totally to the anti form after UV (lambda > 295 nm) irradiation of the matrix. A small amount of the N(3)H-hydroxy-amino tautomer of N2-hydroxyisocytosine was also detected in the matrix. This form did not react photochemically. For 1-methyl-N2-hydroxyisocytosine, only the syn form of the imino-oxo tautomer was observed after deposition of the matrix. UV (lambda > 295 nm) irradiation induced a photoreaction converting this isomer into the anti form. After 15% of the starting material had been converted into the product, a photostationary state was achieved, and no further progress of the reaction was observed. Subsequent UV irradiation (lambda > 335 nm) caused a back reaction, leading to a disappearance of the anti form and to the recovery of the initial syn isomer. All isomers were identified by comparing their experimental IR spectra with the spectra theoretically calculated at the DFT(B3LYP)/6-31G(d,p) level, where DFT is the density functional theory. Good agreement between the observed and predicted patterns of the spectral lines allowed for reliable identification. The experimental IR spectra were interpreted and discussed. The relative energies of the 12 isomers of N2-hydroxyisocytosine were calculated at the MP2/6-31G(d,p) and MP4//MP2/6-31G(d,p) levels. For six isomers of 1-methyl-N2-hydroxyisocytosine, the calculations were carried out at the MP2/6-31G(d,p) level. The anti form of the imino-oxo tautomer of N-hydroxyisocytosine and the syn form of the imino-oxo tautomer of 1-methyl-N2-hydroxyisocytosine were predicted to be the most stable.     

Reaction of 4‐benzylidene‐2‐methyl‐5‐oxazolone with amines,Part 2: Influence of substituents in para‐position in the phenyl ring and a substituent on amine nitrogen atom on the reaction kinetics

An influence of a structure of the amine (benzylamine, N‐methyl‐benzylamine, N‐isopropyl‐benzylamine, N‐methyl‐butylamine, N‐ethyl‐butylamine, sec‐butylamine, and tert‐butylamine) on a rate constant of the ring‐opening reaction of 4‐benzylidene‐2‐methyl‐5‐oxazolone (Ox) was studied. The good correlation between logarithm of the rate constants and Charton's steric substituent constant ν as well as good correlation with a form of the simple branching equation indicate that there is a steric effect because of substitution at C1 carbon atom of nucleophile which decreases the reaction rate. Additionally, an influence of a structure of the benzylidene moiety of Ox on a rate of the oxazolone ring‐opening reaction was studied. The substituents (? OH, ? OCH₃, ? N(CH₃)₂, ? Cl, ? NO₂) in para‐position of the phenyl ring of Ox substantially modified the rate of the reaction with benzylamine in acetonitrile. The rate of the Ox ring‐opening reaction decreased with increase of the electron‐donating properties of the substituent. A good correlation between the rate constants of the reaction of 4‐(4′‐substituted‐benzylidene)‐2‐methyl‐5‐oxazolones with benzylamine and the electron density at the reaction center (carbon C5 of the oxazolone ring), calculated using ab initio method, and the Hammett substituent constants, and CR equation were established. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 148–155, 2002; DOI 10.1002/kin.10039