Identification of the source of the crude drug Tu-zhu-ye using low-temperature plasma ashing

Tu-zhu-ye is a Korean crude drug for use as a diuretic but its plant source has not been identified. The present work has been attempted for identification of the original plant using specimens collected both at Seoul and Taegu, Korea, their mineral microstructures being examined after ashing the specimens by a low-temperature method with high-frequency oxygen plasma. A preliminary survey of the specimens with the naked eye suggested that the Tu-zhu-ye was near to Phyllostachys or its closely related bamboo species. Several specimens, namely, Phyllostachys heterocyclaMitf. var. pubescensOhwi, Phyllostachys nigraMunro var. henonisStapf, Phyllostachys bambusoidesSieb. et Zucc. and Bambusa multiplexRaeuschel were therefore ashed by the low-temperature method and the comparative microscopic studies with the resultant ashed tissues concluded that the “Tu-zhu-ye” from Seoul was perfectly identical with Phyllostachys nigraMunro var. henonisStapf. A further investigation is continued for the specimen from Taegu since it is different from any other specimens provided for the present work.     

Quadruple Decker [3.3][3.3][3.3]Orthocyclophane Acetal—An Orthocyclophane Ladder

Through clever bridging of orthocyclophanes (in this case by acetalization), molecules such as 1 can be formed with four benzene rings in a stacked face-to-face arrangement. UV/Vis spectroscopic and electrochemical properties of 1 are governed by π–π through-space interactions within the molecule.     

Second-generation synthesis of endogenous sperm-activating and attracting factor (SAAF) isolated from the ascidian Ciona intestinalis

Stereoselective synthesis of the chemoattractant sperm-activating and attracting factor (SAAF), isolated from the eggs of the ascidian Ciona intestinalis, was achieved via reductive 1,3-transposition of an allylic alcohol and the axial opening of an epoxide as key steps. This second-generation synthesis improved the total yield of SAAF over that of the first-generation synthesis and provided a key intermediate for synthesizing molecular probes of SAAF.     

Determination of thiodiglycol, a mustard gas hydrolysis product by gas chromatography-mass spectrometry after tert-butyldimethylsilylation

A method for determining thiodiglycol (TDG), a mustard gas hydrolysis product in water, serum and urine samples using gas chromatography-mass spectrometry (GC-MS) after tert-butyldimethylsilylation (TBDMS) is described. Quantitation of TDG was performed by measuring the respective peak area on the extracted ion chromatogram of m/z 293, using an internal standard, the TDG homologue, thiodipropanol, peak area of which was measured as m/z 321. The presence of salts in the sample solution not only suppressed the loss of TDG by vaporization during the evaporation of water, but also facilitated the rate of production of di-silylated derivative, bis(tert-butyldimethylsilyoxylethyl)sulfide (TDG-(TBDMS)2). Under the pretreatment conditions used, in which 0.5 ml of water sample supplemented with 100 microM potassium chloride was evaporated to dryness under reduced pressure, followed by reaction with N-methyl-N-(tert-butyldimethylsilyl)trifluoroacetamide at 60 degrees C for 1 h, TDG-(TBDMS)2 was reproducibly detected with about a 55% recovery and a limit of detection (LOD, scan mode, S/N = 3) of 5.4 ng/ml. TDG was also determined by GC-MS from a 0.5 ml serum sample (after perchloric acid deproteinization) and from a 0.1 ml urine sample, after TBDMS derivatization. The LOD was determined to be 7.0 and 110 ng/ml for serum and urine, respectively.     

Stereoselective synthesis of 1'-C-branched arabinofuranosyl nucleosides via anomeric radicals generated by 1,2-acyloxy migration

Stereoselective C-C bond formation at the anomeric position of uracil and adenine nucleoside has been accomplished through reaction of the anomeric radical, generated by 1,2-acyloxy migration, with a radical acceptor. The present method consists of the following steps: (1) electrophilic addition (bromo-pivaloyloxylation) to 3',5'-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-protected 1',2'-unsaturated nucleoside, (2) tin radical-mediated reaction of the resulting adduct with a radical acceptor. The use of allyl(tributyl)tin gave the 1'-C-allylated uracil nucleoside 14 in 66% yield together with the unrearranged 2'-C-allylated product 15 (6%). Radical acceptors such as styryl(tributyl)tin and 3-bromo-2-methylacrylonitrile can also be used in the reaction of 5, giving 16 (70%) and 17 (76%) without the formation of unrearranged product. The radical-mediated C-C bond formation of the adenine counterpart 12 was also investigated.     

Rhodium-complex-catalyzed addition reactions of chloroacetyl chlorides to alkynes

The addition reaction of chloroacetyl chloride derivatives with terminal alkynes was found to be catalyzed by Rh(acac)(CO)(AsPh(3)) to afford (Z)-1,4-dichloro-3-buten-2-one derivatives, which displayed diverse reactivities in synthetic elaboration.     

Two Beam Collection Mode Photon Scanning Tunneling Microscope

We studied the image deformation due to the surface inclination of objects in photon scanning tunneling microscopes (PSTM). A novel collection mode PSTM with two light sources is proposed to reduce the deformation and experimental results show that the PSTM system is effective.