Crystal and molecular structure of β-piperidinopropioamidoxime monochloroacetate and hydrochlorides of its O-benzoylation products

The structures of -piperidinopropioamidoxime monochloroacetate and O-benzoyl- and O-para-toluyl--piperidinopropioamidoxime hydrochlorides have been determined. The geometry of these compounds is analyzed. The N-O bond is in the syn-planar position in -piperidinopropioamidoxime monochloroacetate, but adopts an anti-orientation relative to the C(2)-C(3) bond of the propioamidoxime fragment in the other two compounds. In -piperidinopropioamidoxime monochloroacetate crystals, the cation-anion pairs are joined by intermolecular hydrogen bonds into chains; the latter are linked by van der Waals contacts. The crystals of the O-benzoyl- and O-para-toluyl--piperidinopropioamidoxime hydrochlorides are characterized by the same system of hydrogen bonds; the cations and anions are linked by hydrogen bonds into layers, and the latter make van der Waals contacts in the structure.Original Russian Text Copyright © 2004 by K. M. Beketov, J. T. Welch, P. Toskano, L. A. Kayukova, A. L. Akhelova, and K. D. PralievTranslated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 3, pp. 535–543, May–June 2004.     

Computational study of conformations and of sulfinyl oxygen-induced pentacoordination at silicon in 4-chloro-4-silathiacyclohexane 1-oxide and 4,4-dichloro-4-silathiacyclohexane 1-oxide

Second-order Møller-Plesset theory (MP2) and density functional theory (B3LYP) with the 6-311G(d,p) and 6-311+G(d,p) basis sets have been used to calculate the equilibrium geometries and relative energies of the chair, twist, and boat conformations of 4-chloro-4-silathiacyclohexane 1-oxide and 4,4-dichloro-4-silathiacyclohexane 1-oxide. The chair conformers of the axial sulfoxides are lower in energy than the chair conformers of the corresponding equatorial sulfoxides. MP2/6-311+G(d,p) predicted the chair conformer of axial trans-4-chloro-4-silathiacyclohexane 1-oxide (4a) to be 6.12, 0.44, and 0.45 kcal/mol, respectively, more stable than the corresponding 1,4-twist (4b), 2,5-twist (4c) and 1,4-boat (4d) conformers and 6.93 kcal/mol more stable than the 2,5-boat transition state ([4e]^‡). Structures 4c and 4d are stabilized by intramolecular coordination of the sulfinyl oxygen with silicon that results in trigonal bipyramidal geometry at silicon. The 1,4-boat conformer (7d) of axial 4,4-dichloro-4-silathiacyclohexane 1-oxide is also stabilized by transannular coordination of the sulfinyl oxygen with silicon. The energy difference (E_rel = 4.23 kcal/mol) between the chair conformer (7a) and 7d is larger than that between 4a and 4d. The relatively lower stability of the 1,4-boat conformer (7d) of axial 4,4-dichloro-4-silathiacyclohexane 1-oxide (7a) may be due to repulsive interactions of the axial halogen and sulfinyl oxygen atoms. The relative energies and structures of the conformers and transition states of cis- and trans-4-chloro-4-silathiacyclohexane 1-oxide and 4,4-dichloro-4-silathiacyclohexane 1-oxide are discussed in terms of hyperconjugative interactions, orbital interactions, nonbonded interactions, and intramolecular sulfinyl oxygen-silicon coordination.     

New routes to transition metal-carbido species: synthesis and characterization of the carbon-centered trigonal prismatic clusters [W(6)CCl(18)](n)(-) (n = 1, 2, 3)

Simultaneous reduction of WCl6 and CCl4 with bismuth metal at 400 degrees C affords a black solid, from which the new cluster [W6CCl18]2- is extracted into aqueous HCl. The cluster is isolated in 34% yield as (Bu4N)2[W6CCl18] and features a metal-metal bonded W6 trigonal prism centered by a carbon atom and surrounded by 12 edge-bridging and 6 terminal chloride ligands. A cyclic voltammogram of [W6CCl18]2- in DMF shows the cluster undergoes two reduction and two oxidation processes, suggesting five chemically accessible redox states. Consistent with this extensive electrochemistry, DFT calculations on the diamagnetic [W6CCl18]2- species reveal closely spaced frontier orbitals, with an a2' ' HOMO situated 0.61 and 0.71 eV below unoccupied e' ' and e' orbitals, respectively. Oxidation of the cluster by a single equivalent of NO+ gives [W6CCl18]1-, which, as expected on the basis of the [W6CCl18]2- HOMO character, possesses a less elongated W6 trigonal prism. Reduction of [W6CCl18]2- with a single equivalent of cobaltocene affords [W6CCl18]3-, wherein population of a low-lying e' orbital leads to a significant Jahn-Teller distortion.     

Chromatographic resolution of closely related species: Drug metabolites and analogs

In this study, we investigate the separation of a variety of mixtures of drugs, metabolites, and related analogs including representatives of the carbamazepine, methylated xanthine, steroid hormone, nicotine, and morphine families using several automated chromatographic method development screening systems including ultra high performance liquid chromatography, core–shell HPLC, achiral supercritical fluid chromatography (SFC), and chiral SFC. Of the 138 column and mobile phase combinations examined for each mixture, a few chromatographic conditions afford the best overall performance, with a single achiral SFC method (4.6 × 250 mm, 3.0 μm GreenSep Ethyl Pyridine, 25 mM isobutylamine in methanol/CO₂) affording good separation for all samples. Four of these mixtures were also resolved by achiral SFC on the Luna HILIC and chiral SFC Chiralpak IB columns using methanol or ethanol with 25 mM isobutylamine as polar modifiers. Modifications of standard chromatography screening conditions afforded fast separation methods (from 1 to 5 min) for baseline resolution of all components of each of these challenging sets of closely related compounds.     

On successors of Jónsson cardinals

We show that, like singular cardinals, and weakly compact cardinals, Jensen's core model K for measures of order zero [4] calculates correctly the successors of Jónsson cardinals, assuming does not exist. Namely, if is a Jónsson cardinal then , provided that there is no non-trivial elementary embedding . There are a number of related results in ZFC concerning in V and inner models, for a Jónsson or singular cardinal. Received: 8 December 1998     

Further development of a graduate program in nuclear and radiochemistry at the University of Texas

Over the last three years we have developed a very robust nuclear and radiochemistry program at The University of Texas at Austin. The cornerstone of support was the DOE Radiochemistry Educational Award Program (REAP) that was awarded from 2002–2005. A second award for the period of 2005–2008 was just received. This award has enabled us to support many educational activities from vanguard classroom instruction, to laboratory enhancements, to research activities at the graduate and undergraduate levels. Both traditional radiochemistry and advanced topics in nuclear instrumentation have been supported. Various DOE university programs, national lab funding and IAEA fellowship grants, have allowed the Nuclear and Radiation Engineering Program at the University of Texas to be at the forefront of nuclear and radiochemistry educational and research activities and help secure the next generation of needed expertise.     

Are Real-Time Displays of Benefit in the Singing Studio? An Exploratory Study

This article reports on an exploratory research project to evaluate the usefulness or otherwise of real-time visual feedback in the singing studio. The primary purpose of the work was not to optimize the technology for this application, but to work alongside teachers and students to study the impact of real-time visual feedback technology use on the students' learning experiences. An action research methodology was used to explore the benefit of real-time displays over an extended period. The experimental phase of the work was guided by a Liaison Panel of teachers and academics in the areas of singing, pedagogy, voice science, speech therapy, and linguistic science. Qualitative data were collected from eight students working with two professional singing teachers. The teachers and students acted as co-researchers under the action research paradigm. Teachers and students alike kept journals of their teaching and learning experiences. Singing lessons were observed regularly by the research team, coded for teacher and student behaviors, and all co-researchers were interviewed at the mid- and endpoint of the project. The use of technology had a positive impact on the learning process, and this is evidenced through case study data.