New titrants for perchlorate and fluoroborate

Three new titrants have been evaluated for the precipitation titration of perchlorate: cetylpyridinum chloride (CPC), cetyltrimethylammonium chloride (CETAC), and benzyldimethyltetradecylammonium chloride (BDTAC). CETAC yielded the highest precision and largest potentiometric break, closely followed by CPC. BDTAC produced considerably lower precision and smaller breaks. Fluoroborate was similarly determined with CPC and CETAC. Again CETAC yielded the highest precision and largest potentiometric break. Titrations were monitored with a fluoroborate ion-selective indicator electrode and a double-junction reference electrode. The perchlorate and nitrate ISEs may also be used for monitoring the emf. Both titrants are considerably less expensive than equivalent amounts of the commonly used tetraphenylarsonium chloride titrant.     

Collinear collision of an atom with a homonuclear diatomic molecule

The problem of collinear scattering of an atom from a homonuclear diatomic molecule is formulated in terms of a first-order nonlinear matrix differential equation for the variable coefficient of reflection. For a homonuclear molecule when the target Hamiltonian is invariant under the parity transformation, only transitions between even states or odd states are possible. This selection rule reduces the number of open or closed channels that contribute to the reflection and transmission coefficients. But for numerical calculation, under the conditions of the problem, one can approximate the target Hamiltonian by the Hamiltonian of a displaced harmonic oscillator. In this approximation, the reflectional symmetry of the Hamiltonian is not preserved and transitions between any two levels of the target are possible. To simplify the problem further, the interaction between the projectile and the target is assumed to be a sum of two Gaussian terms. For this combination of the potentials the many-channel interaction can be expressed analytically. By fitting the Lennard–Jones potential with a sum of two Gaussian potentials and solving the matrix differential equation, transition probabilities are obtained for the He? H₂ collision. The numerical results are compared with the results found by Secrest and Johnson, and by Clark and Dickinson.     

Comments on the approximate calculation of lattice potential

The potential of a charge distribution due to a lattice of point charges may be evaluated by the classical multipole expansion method. The leading terms in the resultant expressions are just those used in some of our previous calculations [1–3]. In addition, for cases where the leading terms vanish because of the effect of orthogonality of the basis functions upon the Mulliken expansion (this being especially serious in the case of a one-centre charge distribution), we have derived the first nonvanishing term, involving |r|. In other cases it may be necessary to proceed to still higher multipole terms before a non-zero contribution is obtained. The entire procedure is formulated in such a way that it can be easily applied to LCAO-MO calculations for polyatomic ions in ionic lattices.     

Tellurate and periodate solutions as media for paper electrophoresis of carbohydrates

Electrophoretic separations of sugars and other polyhydroxy compounds may be performed in 0.2M telluric acid media adjusted to pH 10 with sodium hydroxide, and in 0.07M sodium metaperiodate at pH 11. Oxidation by periodate appears to be only slight under these conditions. Migration rates of 21 compounds are reported relative to the movement of d-ribose. In both electrolytes the compounds form anionic complexes.     

Zur komplexchemie von 4-zentren-π-systemen : VIII. ESR-untersuchungen an heterobutadien-chelaten. I. Kalium-(diazabutadien-tetracarbonyl-metallate)

Glyoxal- and diacetyl-bis(imine)metal tetracarbonyls (RNCR′CR′NR)M(CO)₄ (M = Cr, Mo, W) are reduced with potassium in DME to give paramagnetic mono-anions. Their high-resolutior, ESR spectra show the hyperfine splittings of the magnetically active ligand atoms as well as the satellites of the metal isotopes ⁵³Cr,^95,97Mo and ¹⁸³W. The coupling constants are discussed with respect to π-bonding mechanisms.     

Modeling of ultralyophobicity: suspension of liquid drops by a single asperity

With the aim of understanding the underlying physical phenomenon associated with utlralyophobic (or super repellent) surfaces, model studies have been performed on single asperities of different size and shape. A small liquid drop was deposited on top of each model asperity, and liquid was sequentially added. If the advancing contact angle was sufficiently large, it was possible to suspend large drops atop asperities with an apparent contact angle approaching 180 degrees. If more and more liquid was added, eventually the suspended drops collapsed. Roughening the surface of the asperities further bolstered suspension. Using an analysis that accounts for both capillary forces and the influence of gravity, the critical suspension volume was correctly predicted for each liquid/asperity combination.     

Isotope exchange between U/III/ and U/IV/ in the HCl-TBP extraction system

The measurement of the isotope-exchange reaction between U/IV/ in the organic phase and U/III/ in the aqueous phase in the extraction systems: 7-8M HCl—5–40% TBP /aromatic diluent or CCL₄/ were made. The high rate of exchange with the rate constant >10²M^–1min^–1 was observed.     

Simultaneous determination of all-trans, 9-cis, 13-cis retinoic acid and retinol in rat prostate using liquid chromatography-mass spectrometry

Since retinoic acid (RA) and RA receptors are key developmental regulators during organogenesis, they might participate in the abnormal development of the prostate caused by early estrogen exposure. In order to test this assumption, a sensitive analytical method that can differentiate 9-cis, 13-cis, and all-trans RA in small tissue samples ( approximately 8 mg) is required. Since retinol is the metabolic precursor to RA, simultaneous quantification of retinol would also provide valuable information. Here, we report a liquid chromatography-mass spectrometry method for simultaneous determination of retinol and 9-cis, 13-cis, and all-trans RA in rat prostate. Mass spectrometric signal responses for RA were compared using positive ion atmospheric-pressure chemical ionization (APCI) and electrospray, as well as positive ion and negative ion APCI. Positive ion APCI was selected for all subsequent analysis for its better sensitivity, and to provide simultaneous determination of retinol and RA. Ventral prostate tissue samples were homogenized and extracted following simple protein precipitation without derivatization. Baseline separation of 9-cis, 13-cis, and all-trans RA standards was obtained by using a non-porous silica C18 column. Selected ion monitoring of the ions m/z 301 and m/z 269 was carried out for mass spectrometric quantitative analysis. The ion of m/z 301 corresponded to the protonated molecule of RA, whereas the ion of m/z 269 corresponded to loss of water or acetic acid from the protonated molecule of retinol or the internal standard retinyl acetate respectively. The method has a linear response over a concentration range of at least three orders of magnitude. The limit of quantitation was determined to be 702 fmol all-trans RA injected on-column. The method showed excellent intra- and inter-assay reproducibility and good recovery, and is suitable for analyzing RA and retinol in small tissue samples (approximately 8 mg).     

Über Bromierungen mit Dibromoisocyanursäure unter ionischen Bedingungen, 1. Mitt.: Monobromierungen

Zusammenfassung Dibromoisocyanursäure (DBI) — in konz. Schwefelsäure gelöst-zeichnet sich durch eine besondere Bromierungsfähigkeit von aromatischen Verbindungen mit stark desaktivierenden Gruppen (Substituenten 2. Ordnung) aus. Ihre Verwendbarkeit bei Monobromierungen sowie die Abhängigkeit der äußerst kurzen Reaktionszeiten von den Reaktionsbedingungen werden beschrieben. Ein Vergleich mit anderen Bromierungsmethoden bzw. Bromierungsmitteln (aus der Klasse der N–Br-Verbindungen) zeigt die große Überlegenheit derDBI.

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Dibromoisocyanuric acid (DBI) in conc. sulfuric acid has been found to be a powerful brominating agent for aromatic compounds having strongly deactivating substituents. The use ofDBI for monobromination and the dependence of the very high reaction rate on the reaction conditions is described. Comparison with other brominating methods and agents of the N–Br-type shows the superiority ofDBI.

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