Cytotoxic activity of polyacetylene compounds in Panax ginseng C. A. Meyer

The effects of the three polyacetylene compounds, panaxynol, panaxydol and panaxytriol, on in vitro-cell growth were studied. These compounds are much different in their water-solubility. In order to increase water-solubility, solid complexes of polyacetylene compounds with alpha-cyclodextrin (CD) were prepared. Accurate concentrations of the active compounds in a culture medium were determined by gas chromatography. All of these CD-complexes inhibited the growth of various kinds of cultured cell lines in a dose-dependent fashion. The cell growth inhibitory activity of these complexes was much stronger against malignant cells than against normal cells. A continuous contact between the compounds and target cells was not necessarily required for growth inhibition. And the inhibition was cytotoxic at high concentrations and cytostatic at low concentrations. These findings indicate that these polyacetylene compounds' mode of action is more dose-dependent than time-dependent. The panaxynol, panaxydol and panaxytriol contents in red ginseng powder were 250, 297 and 320 micrograms/g, respectively.     

Method of computer algebraic calculation of the matrix elements in the second quantization language

An automated method by the algebraic programming language REDUCE3 for specifying the matrix elements expressed in second quantization language is presented and then applied to the case of the matrix elements in the TDHF theory. This program works in a very straightforward way by commuting the electron creation and annihilation operators (a^? and a) until these operators have completely vanished from the expression of the matrix element under the appropriate elimination conditions. An improved method using singlet generators of unitary transformations in the place of the electron creation and annihilation operators is also presented. This improvement reduces the time and memory required for the calculation. These methods will make programming in the field of quantum chemistry much easier. © 1995 John Wiley & Sons, Inc.     

Single-crystal growth of Tl2Ru2O7 pyrochlore using high-pressure and flux method

Single crystals of the thallium ruthenium pyrochlore have been grown by flux method under high oxygen pressure. The growth conditions were determined by direct observations using in situ powder X-ray diffraction (XRD) method under high pressure and high temperature. The crystals were grown using NaCl-KCl flux at 1350 °C and B₂O₃ flux at 1150 °C. High growth temperature of 1350 °C for the NaCl-KCl flux caused Pt contamination from the crucible and oxygen deficiency for the crystals obtained. The crystal growth using B₂O₃ flux proceeded at lower temperature by grain growth with material transfer through B₂O₃. The crystal obtained was characterized by single-crystal XRD method, and was found to have a stoichiometric composition, Tl₂Ru₂O_7−δ (δ=0), with a structural phase transition around 120 K. The grain growth technique with B₂O₃ is efficient for high-temperature single-crystal growth under high pressure.     

Novel radical compounds bearing mesogenic cores with long alkyl substituents

Series of aminoxyl radicals (TEMPO or nitronyl nitroxide radicals) bearing phenyl benzoate, troponoid, or biphenylcarbonitrile as mesogenic cores with long alkyl substituents were prepared. Although most aminoxyl radicals showed only weak antiferromagnetic interactions due probably to the remote spin centers as clarified by the X-ray analysis of 4a and no appreciable mesogenic phase was observed in each compound, an unusual magnetic transition from an original Curie-Weiss phase to another magnetic phase well-expressed by a singlet-triplet (ST) model was disclosed through the thermal transition in the 4'-undecyloxy-4-biphenylcarbonitrile derivative with oxocarbonyl-TEMPO 12b.     

Synthesis of optically active forms of (Z)-14-methylhexadec-8-enal : The pheromone of female dermestid beetle

The both enantiomers of (Z)-14-methylhexadec-8-enal were synthesized starting from (R)-(+)-citronellol. The (R)-(?)enantiomer (1) was about 250 times more active than its antipode (1') when tested on dermestid beetle.     

A practical synthesis of (+)-biotin from L-cysteine

Alpha-amino aldehyde 4, which is readily derived from L-cysteine through cyclization and elaboration of the carboxy group, was subjected to the Strecker reaction, which, via sodium bisulfite adduct 16, afforded alpha-amino nitrile 5 with high diastereoselectivity (syn/anti=11:1) and in high yield. Amide 6, derived from 5, was converted to thiolactone 8, a key intermediate in the synthesis of (+)-biotin (1), by a novel S,N-carbonyl migration and cyclization reaction. The Fukuyama coupling reaction of 8 with the zinc reagent 21, which has an ester group, in the presence of a heterogeneous Pd/C catalyst allowed the efficient installation of the 4-carboxybutyl chain to provide 9. Compound 9 was hydrogenated and the protecting groups removed to furnish 1 in 10 steps and in 34 % overall yield from L-cysteine.     

Photoinduced reaction on quantized GaAs nanocrystals prepared by wet process

Gallium arsenide nanocrystals of 1.5 to 9.0 nm were prepared in triethylene glycol dimethylether (triglyme), and photoinduced reduction of methylviologen (MV²⁺) on the nanocrystals was investigated. The rate of MV+ production determined for an initial stage of photoinduced reduction of MV²⁺ was found to be low compared to that determined for bulk GaAs particles of 0.4 mm, if the rate was evaluated for unit surface area of the semiconductor particles. To account for this finding, the apparent association constant of MV²⁺ to GaAs was determined, which suggested that molecular species which worked as stabilizing agents for the GaAs nanocrystals retarded the adsorption of MV²⁺ onto the particle surfaces.     

Chemistry and biology of khafrefungin. Large-scale synthesis, design, and structure-activity relationship of khafrefungin, an antifungal agent

Large-scale synthesis, design, and structure-activity relationships of khafrefungin are reported. Khafrefungin is an antifungal agent that inhibits inositol phosphorylceramide (IPC) synthase, an enzyme involved in fungal sphingolipid biosynthesis. Unlike other inhibitors that inhibit the corresponding enzyme in fungi and mammals to the same extent, khafrefungin does not impair sphingolipid synthesis in mammals. We have developed an efficient method for large-scale synthesis of khafrefungin, and various khafrefungin derivatives were synthesized based on this method. While most of the khafrefungin derivatives lost antifungal activity, a lactone-type derivative had almost the same activity as khafrefungin. We also designed and synthesized derivatives which contain a five- or six-membered ring at the central part of the structure based on NOE experiments of khafrefungin. A macrocyclic khafrefungin derivative was also synthesized, but the antifungal activity was lost. These results suggest that the structure of khafrefungin might be strictly recognized in fungi.     

O-(N-succinimidyl)-1,1,3,3-tetramethyluronium tetrafluoroborate-N-hydroxysuccinimide-CuCl2: a facile and reliable system for racemization-free coupling of peptides having a carboxy-terminal N-methylamino acid

Simultaneous use of N-hydroxysuccinimide (HOSu) and CuCl2 with a HOSu-based uronium coupling reagent, O-(N-succinimidyl)-1,1,3,3-tetramethyluronium tetrafluoroborate, has been found to eliminate the racemization of the carboxy-terminal N-methylamino acid residue during the segment condensation.