填充式方钴矿化合物CeOs4Sb12近藤相互作用的非弹性中子散射研究

CeOs4Sb12晶体中由于导电电子与Ce3+ 4f1电子之间存在c-f杂化作用导致费米面附近存在能量间隙.这种c-f近藤相互作用和能量间隙是理解CeOs4Sb12物理性质,如近藤绝缘体行为、Ce3+磁矩在低温下猝灭以及重费米性等电、磁性质的关键.当用LAM-D中子谱仪对粉末CeOs4Sb12进行测量时,可以得到不同温度下CeOs4Sb12的非弹性中子散射谱.结果表明CeOs4Sb12中存在近藤相互作用,其作用强度为3.1 meV,证实了CeOs4Sb12为近藤绝缘体.中子测量得出CeOs4Sb12德拜温度为317 K.     

填充式方钴矿化合物CeOs4Sb12近藤相互作用的非弹性中子散射研究

CeOs₄Sb₁₂晶体中由于导电电子与Ce³⁺ 4f¹电子之间存在c-f杂化作用导致费米面附近存在能量间隙.这种c-f近藤相互作用和能量间隙是理解CeOs₄Sb₁₂物理性质，如近藤绝缘体行为、Ce³⁺磁矩在低温下猝灭以及重费米性等电、磁性质的关键.当用LAM-D中子谱仪对粉末CeOs₄Sb₁₂进行测量时，可以得到不同温度下CeOs₄Sb₁₂的非弹性中子散射谱.结果表明CeOs₄Sb₁₂中存在近藤相互作用，其作用强度为3.1 meV，证实了CeOs₄Sb₁₂为近藤绝缘体.中子测量得出CeOs₄Sb₁₂德拜温度为317 K. 关键词： 非弹性中子散射 填充式方钴矿 近藤绝缘体     

Lasting chemiluminescence of 3-indoleglyoxylyl chloride and its enhancement.

The chemiluminescence (CL) intensities of various indole derivatives substituted with a glyoxylyl group at the 3-position and a hydroxyl group at the 5-position of the indole ring were compared upon the addition of H2O2 in alkaline media. The CL intensities of 3-indoleglyoxylyl chloride, 3-indoleglyoxylic acid, 5-hydroxyindole and 5-benzyloxyindole in CH3CN were 5.9-, 48-, 5.9- and 3.3-fold stronger than that of 3-methylindole. A lasting CL of 3-indoleglyoxylyl chloride was found. Under appropriate conditions, the CL emission reached a maximum within 10 min after the addition of H2O2 in the presence of NaOH, and the intensity was retained for 25 min. One of the final products via the CL reaction of 3-indoleglyoxylyl chloride was indole-3-carboxylic acid. 3-Indoleglyoxylyl chloride emitted light by decompositions via both dioxetane and dioxetanedione. An enhancement effect of beta-cyclodextrin and bovine serum albumin on the CL of 3-indoleglyoxylyl chloride was also found.     

Structure and enantioselective synthesis of polyamine toxin MG30 from the venom of the spider Macrothele gigas

A novel polyamine toxin, named MG30, was isolated from the venom of the spider, Macrothele gigas, and its structure was elucidated by two-dimensional NMR and mass analysis. In addition, the enantioselective synthesis of MG30 was achieved to assign its absolute stereochemistry.     

Synthesis of endogenous sperm-activating and attracting factor isolated from ascidian Ciona intestinalis

A chemoattractant candidate named sperm-activating and attracting factor (SAAF) from the eggs of ascidian Ciona intestinalis, was synthesized from chenodeoxycholic acid in 16 steps. The present synthesis led to the unambiguous structure determination of SAAF to be (3R,4R,7R,25S)-3,4,7,26-tetrahydroxycholestane-3,26-disulfate. The synthetic pure specimen was also used to confirm the dual sperm-activating and attracting activity.     

Enantioselective spiro ene-carbocyclization of 1,6-enynes catalyzed by tropos rhodium(I) complex with skewphos ligand

A tropos rhodium(I) complex having skewphos ligand is shown to be a highly enantioselective catalyst for asymmetric ene-type carbocyclization of 1,6-enynes with tri-substituted olefins to control quaternary stereogenic centers or spiro-rings.     

Microchannel-assisted thermal-lens spectrometry for microchip analysis

We present a new method for homocysteine quantitation in human plasma based on in-capillary reaction of homocysteine with 2,2′-dipyridyl disulfide. Homocysteine is in this so-called thiol-exchange reaction quantitatively transformed in mixed disulfide concomitantly with formation of an equimolar amount of 2-thiopyridone that is further separated by micellar electrokinetic chromatography and determined specifically at 343 nm. The concentration of homocysteine is thus estimated indirectly from the result of 2-thiopyridone determination. The linear detection range for concentration versus peak area for the assay was from 0.03–3 mM (correlation coefficient 0.994) with a detection limit of 6 μM and a limit of quantitation 20 μM. The inter-day reproducibility of the peak area and the migration time were 1.37% and 0.05%, respectively. The method is simple, relatively rapid and can be easily automated. Moreover the common capillary electrophoresis apparatus with a UV detector can be used to distinguish between normal and pathological hyperhomocysteinemia plasma samples.     

HPLC determination of (+)-pseudoephedrine and (-)-ephedrine in Japanese herbal medicines containing Ephedra herb using solid-phase extraction

We developed a rapid and simple HPLC method combined with solid-phase extraction (SPE) for quantitative analysis of (+)-pseudoephedrine (PEP) and (-)-ephedrine (EP) in Japanese herbal (Kampo) medicines such as Kakkon-to, Sho-seiryu-to, Goshaku-san and Bofu-tsusho-san. SPE was performed on TOYOPAK IC-SP M containing propylsulfonic groups. Determination of PEP and EP was carried out using ion-pair reversed-phase HPLC with sodium dodecyl sulfate. N-Benzyldiethylamine was used as an internal standard. The analytical procedure was validated with regard to specificity, linearity, accuracy, and precision. These data suggest that the analytical method developed in this study is useful for quantitative analysis of PEP and EP in various formulations of Kampo medicine containing Ephedra herb.