Analyse von Kernresonanzspektren in Einkristallen niedriger Symmetrie. I

Zusammenfassung Es wird ein Verfahren beschrieben, das die Tensoren der Kernquadrupolkopplung und der paramagnetischen Hyperfeinstruktur in Einkristallen beliebiger Symmetrie aus Kernresonanz-messungen in mittleren Magnetfeldern zu bestimmen gestattet. Mögliche Anwendungen des Verfahrens in der paramagnetischen Elektronenresonanz werden diskutiert.

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A method is given, to determine the tensors of nuclear quadrupole coupling and paramagnetic hyperfine structure in single crystals of any symmetry from nuclear magnetic resonance measurements in intermediate fields. Possible applications in electron paramagnetic resonance are discussed.

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Résumé On décrit une méthode pour calculer les tenseurs de couplage quadripolaire nucléaire et de la structure hyperfme paramagnétique dans les monocristaux de toute symétrie, étant mesurées les résonances nucléaires dans les champs moyens. On discute l'application éventuelle de cette méthode a la résonance paramagnétique électronique.

     

Chloridionenübergänge in Phenylphosphoroxychlorid, 1. Mitt.: Spektrophotometrische Untersuchungen an Eisen (III)-chlorid-Lösungen

Zusammenfassung FeCl₃ liegt in PhPOCl₂ als roter solvatisierter Komplex, in Gegenwart von polaren Chloriden als gelbes [FeCl₄]^–-Ion vor. BCl₃, SnCl₄, TiCl₄, PCl₅ und wahrscheinlich auch HgCl₂ und SbCl₃ geben an FeCl₃ je 1 Chloridion ab, ZnCl₂ gibt beide Chloridionen und AlCl₃ zwei Chloridionen fast vollständig und ein drittes in geringem Umfang ab. Die Donorstärke nimmt in der Reihe KClEt₄NCl>1/2 AlCl₃>-TiCl₄>PCl₅>1/2 ZnCl₂>BCl₃ SnCl₄[AlCl]⁺⁺>HgCl₂>SbCl₃ ab. Als Chloridionenakzeptor ist nur SbCl₅ dem FeCl₃ ebenbürtig, die oben genannten Chloride sind wesentlich schwächere Akzeptoren.Mit 4 AbbildungenHerrn Professor Dr.L. F. Audrieth zum 60. Geburtstag gewidmet.     

Screening for metal ligands by liquid chromatography--ligand-exchange--electrospray mass spectrometry

Electrospray ionization mass spectrometry is applied for the selective detection of metal ligands after a post-column continuous-flow ligand-exchange reaction. The detection is based on the specific release of a reporter ligand from a metal-reporter ligand complex by a high affinity ligand. Constant infusion and direct-injection experiments are performed to optimize the method. The on-line coupling of a liquid chromatographic separation prior to the continuous flow ligand-exchange reaction enables the screening for high affinity ligands in complex samples. The feasibility of the method is demonstrated by using several ligands with a different affinity for either Cu(II) or Zn(II) ions. The selectivity of the ligand-exchange detection method can be tuned by the choice of the reporter ligand. This is demonstrated by using either 2,2'-bipyridyl or 5-methyl-1,10-phenanthroline as reporter ligands.     

Public education in nuclear science at the Kyushu Museum of Energy in Japan

The Kyushu Museum of Energy, funded by the Kyushu Electric Power Company, Inc., was opened in September 1982. The planning and design were done by Dentsu, Inc., and the actual construction was shared among several construction and manufacturing companies. I was retained as the principal scientific advisor for the museum, both prior to its construction, throughhout the planning of the exhibits, and afterwards when it was opened to the public. This is an educational museum, which shows how people have developed and depended on energy and energy sources since the discovery of fire in prehistory. There are four major sections, devoted to fire itself, electricity, nuclear power by fission, and nuclear power by fusion. In addition, the museum will track visitors through the exhibits, in terms of The History of Energy as a beginning point for their tour, lead them through Present Energy Needs and Uses, and thence to Future Energy Developments and Needs. The museum is of a hands-on active display type design, with many large and attractive display panels, working models, pleasant mixes of sound, light, and images, and educational levels that encompass general public interest to semitechnical explanations that will satisfy the undergraduate with a technical, background. Visitors can not only operate the models themselves, but join in a variety of games based on energy consumption, usage, and needs. It is very much a participatory museum, and visitors are exposed to the many facets of day-to-day energy generation and consumption, as well as the estimated needs for the future, and possible ways to supply these needs. To date, there have been well over 200,000 visitors recorded. *** DIRECT SUPPORT *** A0653119 00004     

Pd-catalyzed selective addition of heteroaromatic C-H bonds to C-C triple bonds under mild conditions

Simple heteroarenes such as pyrroles and indoles undergo addition reactions to C-C triple bonds in the presence of a catalytic amount of Pd(OAc)(2) under very mild conditions, affording cis-heteroarylalkenes in most cases. The cleavage of aromatic C-H bonds is the possible rate-determining step in CH(2)Cl(2), and the addition of heteroaromatic C-H bonds to C-C triple bonds is in a trans-fashion.     

Möbius aromaticity in [12]annulene: cis-trans isomerization via twist-coupled bond shifting

Density functional and coupled cluster calculations show that facile thermal configuration change in [12]annulene occurs via a twist-coupled bond-shifting mechanism. The transition state for this process is highly aromatic with M?bius topology. At the CCSD(T)/cc-pVDZ//BH&HLYP/6-311+G** level, the isomerization of tri-trans-[12]annulene 1a (CTCTCT) to its di-trans isomer 2 (CCCTCT) via such a mechanism has a barrier of 18.0 kcal/mol, in good agreement with earlier experiments. Two other aromatic M?bius bond-shifting transition states were located that result in configuration change for other [12]annulene conformers. This mechanism contrasts sharply with diradical configuration change for acyclic polyenes and with planar bond-shifting mechanisms generally assumed for annulenes. This constitutes evidence that neutral M?bius aromatic annulenes play a role in the dynamic processes of neutral [4n]annulenes.     

Novel annulene dications from methylated [2.2]metacyclophane monoenes and [e]-ring benzannelated dimethyldihydropyrene

Tetramethyl- and hexamethyl-substituted [2.2]metacyclophane monoenes (10 and 11) are transformed into their corresponding trans-dimethyldihydroethanophenanthrenium dications (14(2+) and 15(2+)) in FSO(3)H x SbF(5) (4:1) and FSO(3)H x SbF(5) (1:1) with SO(2)ClF or SO(2) as the solvent; these 10 pi-dications are equivalent to the C-4/C-5 diprotonated dications of the 2,7-dimethyl derivative of trans-DMDHP, 3a. The trans-12c,12d-dimethyl-12c,12d-dihydrobenzo[e]pyrene (6) reacts with FSO(3)H/SO(2)ClF under surprisingly mild conditions to give initially a persistent diprotonated dication (6H(2)(2+)) and, subsequently, the oxidation dication (6(2+)); the 6(2+):6H(2)(2+) ratio reaches 4:1 after 1 week at low temperature. Protonation of the anti-metacyclophane (13) was also examined. Charge delocalization mode and tropicity in the resulting dications are gauged via detailed NMR studies at 500 MHz.     

Evaluation and application of liquid chromatographic columns coated with 'intelligent' ligands: (I) acylcarnitine column

Unique stationary phases of octadecylsilica (ODS) coated with acylcarnitines have been developed for liquid chromatographic columns. The ODS column coated with acylcarnitine was readily prepared by recycling the solution containing acylcarnitine through an ODS column in a closed loop. Acylcarnitine was adsorbed on the ODS surfaces by hydrophobic interaction between the acyl group of acylcarnitine and the octadecyl group of the ODS phases. The ODS column coated with stearoylcarnitine (CN-18 column) was the most stable among the four columns coated with acylcarnitines of various acyl chain lengths (decanoylcarnitine, lauroylcarnitine, myristoylcarnitine, and stearoylcarnitine) under the condition of delivery of the mobile phase, indicating that adsorption of acylcarnitine on the ODS surfaces depended on the length of acyl chains. The CN-18 column was usable for delivering the mobile phase contained less than 20% (v/v) acetonitrile, retaining almost the same separation efficiency as the intact ODS column. The retention behavior of ionic solutes on the CN-18 column could be explained by both ionic and electrostatic interactions between the solutes and the stationary phase. The CN-18 column enabled efficient separation of inorganic anions, nicotinic acids, amino acids, and nucleotides. The chiral ODS column coated with enantiomer of stearoylcarnitine, L-stearoylcarnitine (L-CN-18 column) could achieve direct enantiomeric separation of DL-tryptophan, alpha-methyl-DL-tryptophan and DL-3-indolelactic acid using 100% water as the mobile phase. The L-CN-18 column could also separate enantiomers of amino acids and alpha-hydroxycarboxylic acids by ligand-exchange chromatographic mode using a mobile phase containing copper(II) ion. The chiral recognition is discussed for enantiomeric separation on the L-CN-18 column.     

Instrumental neutron activation analysis of tree rings for dendrochemical studies

Instrumental neutron activation analysis (INAA) was employed to determine zinc, cadmium and potassium concentrations in the growth rings of ponderosa pine (Pinus ponderosa Dougl.) trees growing along the shores of Lake Roosevelt in Washington State, U.S.A. where mineral processing activities have resulted in high burdens of zinc and cadmium in the lake sediments. The tree growing along the contaminated waterway display elevated concentrations of zinc in its growth rings relative to a tree growing along an uncontaminated tributary of Lake Roosevelt. Cadmium concentrations in the growth rings from both sites are similar from 1988 to 1993. Water quality data indicate an increased concentration of cadmium in the lake from 1984 to 1988. The increased concentrations of cadmium in the lake water were reflected in apparent increases in concentrations of cadmium in individual rings of the tree sampled at the contaminated site. This suggests that translocation of cadmium in the sapwood of heartwood-forming species does not occur in the short term, and thus may not be a limiting factor in using trees as environmental monitors for cadmium. In addition, five-year tree ring segments were analyzed and subsequently reanalyzed as individual single-year ring segments. The analytical data obtained for the pooled individual rings are essentially the same as for the five-year segments, demonstrating the utility of NAA for dendrochemical studies.     

Complex formation equilibria between 1-hydroxy-7-sulpho-2-naphthoic or 1-hydroxy-4,7-disulpho-2-naphthoic acid and iron(III) in 0.1M NaClO4 medium

The equilibria for formation of iron(III) complexes with 1-hydroxy-7-sulpho-2-naphthoic and 1-hydroxy-4,7-disulpho-2-naphthoic acids in aqueous 0.1M sodium perchlorate medium at 25 degrees have been studied by spectrophotometric and potentiometric methods. The data are well described in terms of a series of stepwise complexes, FeL((3-rn)+)(r) in both systems (L(n-) denotes the unprotonated ligand anion).