Effect of encaged aromatic guests on the shape and connectivity of molecular cavity in crystalline polystyrene evaluated by molecular simulations

The delta form of crystalline syndiotactic polystyrene is a clathrate molecular compound in which various aromatic molecules are encaged. We have investigated the size, shape, and connectivity of the molecular cavity in the crystal using a molecular dynamics simulation. The effects of the guest species on the cavity structure were investigated in detail. In order to systematically vary the guest structure, various aromatic guests, e.g., benzene, toluene, p-xylene, m-xylene, o and mesitylene were examined. The interstitial spaces between the guests and the polymer chains were analyzed by cluster analysis of the free volumes. The individual cavity volumes into which the guests are clathrated were also evaluated. It was found that the guest molecules can greatly affect not only the cavity size and shape but also the connectivity of the cavities. The transport of small molecules in the crystal is discussed in connection with the cavity structure.     

Attempts at Solvolytic Generation of Phenyl Cations

New substrates and reaction conditions which may be expected to yield phenyl cation intermediates have been investigated. The approaches used were: (a) solvolysis of PhX in fluorinated alcohols, where X = ? N (O) = NOTs (tosyloxyazoxy), ? N (O) = NONf (Nf = C₄F₉SO) and ? OSO₂\documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm N}\limits^{\rm + } $\end{document} (CH₃)₃ōTf (Tf=CF₃SO); (b) solvolysis of ArBr, PhOTf and PhOSO₂\documentclass{article}\pagestyle{empty}\begin{document}$ \mathop {\rm N}\limits^{\rm + } $\end{document}(CH₃)₃ōTf (phenyl ‘betylate triflate’) in super-acid solvents (FSO₃H · SbF₅, SbF₅, AgSbF₆). Analysis of the product mixtures provided no evidence for the intermediacy of phenyl cations as a major pathway in any of the reactions. This result is remarkable, since the ‘betylate’, for example, is a better leaving group by a factor of at least 10⁵ than the ‘super’ leaving group triflate in the solvolysis of alkyl sulfonates. These results are a further indication of the extremely low stability of phenyl cations, as well as of the very special properties of the nitrogen leaving group in arenediazonium ions.     

15β-Hydroxylation of Lithocholic Acid by cunninghamella sp.

The microbiological transformation of lithocholic acid (3α-hydroxy-5β-cholanic acid) into 3α, 15β-dihydroxy-5β-cholanic acid by Cunninghamella sp. is Investigated. The structure has been determined on the basis of two-dimensional ¹H-NMR.     

Isolation of new quinidine metabolites and simultaneous determination of quinidine and its metabolites in blood and urine by direct injection HPLC analysis

Summary New quinidine metabolites, including 10,11-dihydrodiol quinidine N-oxide, 10,11-dihydrodiol quinidine and their glucuronides, were found in human urine. A quinidine monitoring HPLC method including these metabolites, is proposed by the direct injection of body fluid samples onto the precolumn for deproteinization followed by reverse phase separation in the analytical column with a column switching technique. The recovery of spiked quinidine and its metabolites in plasma was quantitative (98–102%) with good reproducibility (C.V.: 1.6–4.0%). Several clinical samples such as whole blood and urine were analyzed by the present method.     

In situ monitoring of metal nanoparticle self-assembly on protein-functionalized glass by broadband optical waveguide spectroscopy

Broadband, time-resolved optical waveguide (OWG) spectroscopy has been used for in situ, real-time investigation into the self-assembly of metal nanoparticle monolayers. The OWG spectroscopy makes it possible to use the transverse electric (TE) and transverse magnetic (TM) modes to measure surface plasmon absorption of immobilized metal nanoparticles in two directions, parallel and normal to the waveguide surface. Therefore, this technique can provide direction-dependent information on the metal nanoparticles at the interface. In this paper, a 50-microm-thick glass plate was used as a slab waveguide and the kinetics of Au nanoparticle adsorption on a hemoglobin-functionalized glass substrate was examined in the early stage of self-assembly. The findings show that with the TE mode the surface plasmon resonance (SPR) behavior for immobilized Au nanoparticles is different from that with the TM mode.     

A new selective population transfer experiment using a double pulsed field gradient spin-echo

A new pulse sequence is proposed for the determination of scalar coupling correlation in small- and medium-sized organic compounds. The method uses a combination of the double pulsed field gradient spin-echo (DPFGSE) and the selective population transfer (SPT) techniques and is shown to be useful in the analysis of complex spectra with many overlapped signals. The usefulness of this method in the structural elucidation of natural substances is demonstrated using strychnine and digitoxin as examples.     

Isolation of xylose reductase gene ofPichia stipitis and its expression inSaccharomyces cerevisiae

Applied Biochemistry and Biotechnology - A NADPH/NADH-dependent xylose reductase gene was isolated from the xylose-assimilating yeast,Pichia stipitis. DNA sequence analysis showed that the gene...     

A Novel Production of γ-Butyrolactone Catalyzed by Homogeneous Ruthenium Complexes

γ-Butyrolactone (hereafter abbreviated GBL) is produced by the two-stage hydrogenation of maleic anhydride(MAH) in the liquid phase: the hydrogenation of MAH to succinic anhydride(SAH) in the first stage and the subsequent hydrogenation of SAH to GBL in the second stage. A novel ruthenium catalyst system consisting of Ru salts, trialkylphosphine and p-toluene sulfonic acid (p-TsOH) was found very effective for the hydrogenation of SAH affording GBL, which exhibited excellent catalyst performance, exceeding 97% selectivity for GBL and high activity.     

New butenolides in plantlets of Virola surinamensis (Myristicaceae)

A phytochemical investigation in plantlets of the Brazilian medicinal tree Virola surinamensis resulted in the isolation and structural determination of four new compounds: 3-hydroxy-4-methyl-2-(11'-piperonyl-n-undecyl)-butenolide; 3-hydroxy-4-methyl-2-(7'-piperonyl-n-heptyl)-butanolide; 9'-(3,4-methylenedioxy-phenyl)-nonanoic acid and 13'-(3,4-methylene-dioxyphenyl)-tridecanoic acid. Thirteen compounds previously isolated from seeds and adult plants were also reported.