Combinatorial and noncommutative list-processing and associated graphs

Recently the authors have proposed a list-processing approach to the modeling of algebraic quantum field theory methods in quantum mechanics in which the noncommutative algebra of quantum-mechanical operators is emulated by lists. The processing produces reordered sequences of elements of a ring with a unit commutator and generates dynamic structures which, for some initial arrangements, correspond to partially ordered graphs characterized by recurrence relations and combinatorial identities. Likewise, in another list-processing application to physical problems, a simulation of Feynman diagrams hinged on predominantly combinatorial aspects and demanded explicit generation of certain combinatorial objects. This motivated an investigation into the combinatorial nature of noncommutative list-processing and of recursive algorithms for explicit construction of combinatorial lists, which we now present. The emphasis is also placed on the consideration of associated graphs and the graph-theoretic origin of the appearance of recurrence relations in the reordering theorems of the noncommutative algebra.     

Strong intramolecular secondary si.N bonds in trifluorosilylhydrazines

The simple silylhydrazines F(3)SiN(Me)NMe(2) (1), F(2)Si(N(Me)NMe(2))(2) (2), and F(3)SiN(SiMe(3))NMe(2) (3) have been prepared by reaction of SiF(4) with LiN(Me)NMe(2) and LiN(SiMe(3))NMe(2), while F(3)SiN(SnMe(3))NMe(2) (4) was prepared from SiF(4) and (Me(3)Sn)(2)NNMe(2) (5). The compounds were characterized by gas-phase IR and multinuclear NMR spectroscopy ((1)H, (13)C, (14/15)N, (19)F, (29)Si, (119)Sn), as well as by mass spectrometry. The crystal structures of compounds 1-5 were determined by X-ray crystallography. The structures of free molecules 1 and 3 were determined by gas-phase electron diffraction. The structures of 1, 2, and 4 were also determined by ab initio calculations at the MP2/6-311+G** level of theory. These structural studies constitute the first experimental proof for the presence of strong Si.N beta-donor-acceptor bonds between the SiF(3) and geminal NMe(2) groups in silylhydrazines. The strength of these non-classical Si.N interactions is strongly dependent on the nature of the substituent at the alpha-nitrogen atom of the SiNN unit, and has the order 3>4>1. The valence angles at these extremely deformed alpha-nitrogen atoms, and the Si.N distances are (crystal/gas): 1 104.2(1)/106.5(4) degrees, 2.438(1)/2.510(6) A; 3 83.6(1)/84.9(4) degrees, 2.102(1)/2.135(9) A; 4 89.6(1) degrees, 2.204(2) A.     

The quality of99mTc eluates

The possible effects of several protecting procedures on the quality of^99mTc eluates were investigated. The content of⁹⁹Mo in the eluates (⁹⁹Mo breakthrough) was expressed in (%) with respect to the total adsorbed⁹⁹Mo radioactivity and in () i.e. as the ratio of⁹⁹Mo and^99mTc radioactivities in each particular eluate. The radiochemical purity was expressed in (%) of^99mTc(VII) in the eluates. The content of Al³⁺ and Cu²⁺ as chemical impurities was also determined.     

Zur komplexometrischen Bestimmung des Natriums

Zusammenfassung Bei der Titration von Zink aus dem Niederschlag von Natrium-Zinkuranylacetat wird statt des früher vorgeschlagenen Indikators Eriochromschwarz T der Indikator Dithizon verwendet. Dadurch wird auch bei Titrationen mit 0,001-m Lösungen ein scharfer Umschlag erzielt.

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Summary Dithizone is used in place of Eriochrome black T previously suggested as indicator in the titration of zinc contained in the precipitate of sodium-zinc-uranyl acetate. A sharper change is thus observed even with 0.001M solutions.

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Résumé Lors du titrage du zinc dans le précipité d'acétate d'uranyle de zinc et de sodium, les auteurs emploient comme indicateur la dithizone au lieu du Noir Eriochrome T qui avait été précédemment recommandé. Il est ainsi possible d'obtenir un virage très net, même pour des titrages effectués avec des solutions 0,001M.

     

An ab initio study of the vibronic, spin-orbit, and magnetic hyperfine structure in the X2Pi electronic state of NCO

In the present study we give the results of the ab initio calculations on the vibronic, spin-orbit, and magnetic hyperfine structure in the X (2)Pi electronic state of the NCO radical. The calculations of the potential surfaces and the electronic mean values of the hyperfine coupling constants are carried out by means of the density functional theory approach (B3LYP functional combined with an atomic orbital basis set suitable for calculations of the hyperfine structure). The vibronic levels, spin-orbit splitting, and the vibronic mean values of the components of the hyperfine tensor in the vibronic species are calculated using a variational method. The results of the calculations are in good agreement with the available experimental data.     

The effect of ligand field on the excitation luminescence spectra of some complex compounds of manganese (II)

The excitation and emission luminescence spectra of the complex compounds of manganese (II) chloride with the hydrochlorides of pyridine, 2-methyl- and 2-ethylpiperidine have been studied. It has been established that the crystals of these complex compounds appear in tetrahedral and octahedral configurations. The excitation spectra in both configurations contain bands originating from the⁴G,⁴P,⁴D and⁴F terms, the position of which is determined by configuration. From the excitation spectra the Racah parametersB andC and the ligand field strength parameter 10Dq have been determined.The emission luminescence spectra also depend on configuration of the complex compound. The character of these spectra is expressed in terms of the following characteristic parameters: the position of the maximum of the functionG(v), the half-width of the emission luminescence band, and the constants andm. From the excitation and emission luminescence spectra it has been established that the emission in both configurations is due to the⁴T₁(G)⁶A₁ transition.     

Excitation of adsorbed molecule vibrations in low energy electron scattering

We develop a theory of low energy electron loss spectroscopy of vibrational modes of molecules adsorbed on metal surfaces. Differential and total cross sections are calculated in the Distorted Wave Born Approximation, assuming i) strong elastic scattering on the metal surface, ii) direct electron-molecule interaction via the electric dipole field associated with the molecular vibration. The angular distributions are calculated and discussed for molecules adsorbed at various distances above the metal surface and for several electron energies and impact angles. The influence of electronic screening of dipolar oscillations is discussed and the consequences of the classical induced image dipoles are explored. It is shown that the metal surface selection rule known in IR spectroscopy is only approximately valid in electron scattering. Finally, we give numerical estimates of the inelastic scattering cross sections for the stretching vibrations of CO molecule adsorbed on transition metal surfaces, in reasonable agreement with experiments.     

Needle-type colloidal copper (II)hydroxide particles

Stable dispersions of fine (< 0.05m) needle-type copper(II) hydroxide particles were prepared at room temperature by admixing sodium acetate and ammonia to copper sulfate solution. The particle length and width could be altered with the concentration of reactants. The rate of dissolution of copper(II) hydroxide particles in doubly distilled water at room temperature is time dependent, which is due in part to the formation of a mononuclear complex solute (CuOH⁺). After extended times (e.g., 18 h), the particles underwent phase transformation, resulting in longer needles of higher degree of crystallinity.Supported by the Griffin Corp., Valdosta, Georgia.     

The influence of chitosan on in vitro properties of Eudragit RS microspheres

Eudragit RS microspheres containing chitosan hydrochloride were prepared by the solvent evaporation method using acetone/liquid paraffin solvent system and their properties were compared with Eudragit RS microspheres without chitosan, prepared in our previous study. Different stirring rates were applied (400-1200 rpm) and drug content, Higuchi dissolution rate constant, surface and structure characteristics of the microspheres were determined for each size fraction. An increase in average particle size with a reduction of stirring rate appeared in limited interval in both series. The average particle size of microspheres without chitosan, prepared at the same stirring rate, was smaller. Pipemidic acid content increased with increasing fraction particle size, but not with increasing stirring rate as it was observed for microspheres without chitosan. We presume that high pipemidic acid content in larger microspheres is a consequence of cumulation of undissolved pipemidic acid particles in larger droplets during microspheres preparation procedure. Pipemidic acid release was faster from microspheres with chitosan and no correlation between Higuchi dissolution rate constant and stirring rate or fraction particle size was found, though it existed in the system without chitosan. Structure and surface characteristics of microspheres observed by scanning electron microscope (SEM) were not changed significantly by incorporation of chitosan. But in contrast with microspheres without chitosan, the surface of chitosan microspheres was more porous after three hours of dissolution. It is supposed that the influence of particle size fraction and stirring rate on release characteristics is expressed to a great extent through porosity and indirectly through total effective surface area, but the incorporation of highly soluble component i.e. chitosan salt hides these effects on drug release. In conclusion, changes in biopharmaceutical properties due to varying stirring rate and fraction particle size exhibited the same direction as those reported for the microspheres without chitosan, although they are less expressed because of increased experimental variability, likely caused by chitosan.     

Coulometric redox titrations of hydrazine,phenylhydrazine and isoniazid with electrogenerated lead(IV) acetate and manganese(III) acetate in acetic acid

Summary The conditions fox coulometric determination of small quantities of hydrazine, phenylhydrazine and isoniazid in glacial acetic acid with electrogenerated manganese(III) acetate and lead(IV) acetate were investigated. With the direct coulometric method at room temperature, good results were obtained in the determination of hydrazine and isoniazid with lead(IV) acetate and in the determination of phenylhydrazine with manganese(III) acetate. Hydrazine and isoniazid can also be determined by the coulometric back-titration method if the oxidation with manganese(III) acetate is performed at elevated temperature.

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Zusammenfassung Die Bedingungen für die coulometrische Bestimmung kleiner Mengen Hydrazin, Phenylhydrazin und Isoniazid mit elektrolytisch erzeugtem Mangan(III)-Acetat und Blei(IV)-Acetat in Eisessig wurden untersucht. Bei Zimmertemperatur wurden gute Resultate durch direkte coulometrische Titration des Hydrazins und Isoniazids mit Blei(IV)-Acetat und bei Titration des Phenylhydrazins mit Mangan(III)-Acetat erhalten. Durch coulometrische Rücktitration können bei höheren Temperaturen Hydrazin und Isoniazid mit Mangan(III)-Acetat erfolgreich bestimmt werden.