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31.
Syntheses of epigallocatechin trimer, (epigallocatechin)2-epicatechin and (epigallocatechin)2-catechin were achieved. The key condensation to form the proanthocyanidin trimer derivatives was accomplished in a one-pot procedure using a dimeric epigallocatechin electrophile, which was prepared in situ by self-condensation of an epigallocatechin derivative, and an epigallocatechin, epicatechin, or catechin derivative as the nucleophile in the presence of a Lewis acid. The epigallocatechin monomer to trimer compounds containing a pyrogallol group significantly suppressed cell proliferation in PC-3 prostate cancer cells.  相似文献   
32.
Nakatsuji H  Ueno K  Misaki T  Tanabe Y 《Organic letters》2008,10(11):2131-2134
We have developed a general, robust, and cost-effective method for the (E)- or (Z)-stereocomplementary enol tosylation of beta-ketoesters using TsCl- N-methylimidazole (NMI)-Et3N or LiOH. TsCl coupled with NMI formed a highly reactive N-sulfonylammonium intermediate. Stereocongested secondary alcohols were smoothly sulfonylated using Ts(Ms)Cl-NMI-Et3N. beta-Ketoesters underwent (E)-selective tosylation using TsCl-NMI-Et3N and (Z)-selective tosylation using TsCl-NMI-LiOH (total of 23 examples; 60%-99% yield). Stereoretentive Negishi and Sonogashira couplings using enol tosylates proceeded successfully to give trisubstituted alpha,beta-unsaturated esters.  相似文献   
33.
We have discussed the resolution of submicron photoluminescence (PL) imaging using a solid immersion lens (SIL), which collects an evanescent light field. We apply the SIL microscope to measure PL image of a strip-line-patterned GaAs quantum well structure at low temperature. An improved resolution beyond diffraction limit and high collection efficiency of PL are realized.This paper was originally presented at the 5th International Conference on NEAR FIELD OPTICS and RELATED TECHNOLOGIES (NFO-5), which was held on December 6–10, 1998 at Coganoi Bay Hotel, Shirahama, Japan, in cooperation with the Japan Society of Applied Physics and Mombusho Grant-in Aid for Scientific Research on Priority Areas “Nearfield Nano-optics” Project, sponsored by Japan Society for the Promotion of Science.  相似文献   
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Little is known about the chemical properties of carbide cluster metallofullerenes (CCMFs). Here we report the photochemical reaction of a newly assigned CCMF Sc(2)C(2)@C(2v)(5)-C(80) with 2-adamantane-2,3-[3H]-diazirine (AdN(2), 1), which provides a carbene reagent under irradiation. Five monoadduct isomers (2a-2e), with respective abundances of 20%, 40%, 25%, 5%, and 10%, were isolated and characterized with a combination of experimental techniques including unambiguous single-crystal X-ray crystallography. Results show that the two Sc atoms of the bent Sc(2)C(2) cluster tend to move in most cases, whereas the C(2)-unit is almost fixed. Accordingly, it is difficult to explain the addition patterns by considering the strain and charge density on the cage with a fixed cluster, and thus a moving cluster may account for the addition patterns. These results show that the situation of CCMFs is more complicated than those in other metallofullerenes. Furthermore, a thermal isomerization process from 2b to 2c was observed, confirming that the most abundant isomer 2b is a kinetically favored adduct. Finally, it is revealed that the electronic and electrochemical properties of pristine Sc(2)C(2)@C(2v)(5)-C(80) have been markedly altered by exohedral modification.  相似文献   
36.
The photoinduced changes of metal-ion complexing ability of crowned spirobenzopyran derivatives were studied by using electrospray ionization mass spectrometry (ESI-MS). Stability constants for the complexation with various metal ions in methanol under visible-irradiation conditions were determined for the first time by ESI-MS. It was found that the stability constants of crowned bis(spirobenzopyran) derivatives with metal ions are decreased dramatically by visible irradiation due to the disappearance of powerful ionic interaction between phenolate anion(s) of the merocyanine form of their spirobenzopyran moiety and a metal ion bound to their crown ether moiety, and the decrease in the stability constants is more pronounced for the multivalent metal-ion complexes. A theoretical consideration was also made to attain reliable values of stability complexes for metal-ion complexes of crown compounds.  相似文献   
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The effect of complex formation on stereoregulation in free-radical polymerization was studied. Complexes of methacrylonitrile with ZnCl2 and SnCl4 were prepared and their properties and structures examined. The complexes were polymerized by initiation of α,α′-azobisisobutyronitrile or by irradiation with γ-rays from a60Co source or ultraviolet rays either in solution or in bulk at various temperatures ranging from ?78 to 100°C. The triad tacticities of the resulting polymethacrylonitrile were determined by converting it to poly(methyl methacrylate) for NMR spectroscopy. The radicals in complexed forms were studied by ESR spectroscopy with the polymerization system in toluene irradiated with ultraviolet rays at ?120°C. The tacticities of the resulting polymers and their dependencies on the polymerization temperature were found to be characteristic of the complex species, i.e., the kind of metal chloride and the stoichiometry, being different from the tacticities and the dependencies, respectively, of the polymer obtained with pure methacrylonitrile. The 2:1 and the 1:1 complexes with SnCl4 were found to give an eleven-line and a nine-line spectrum, respectively. On the basis of the results of both the tacticities and the ESR spectra, it was estimated that the proportion of the intracomplex reaction was 40%, and that the probabilities of isotactic diad addition of intra- and intercomplex reaction were 0.70 and 0.48, respectively.  相似文献   
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Recently, air and ground water pollution and contamination of soil by toluene have been drawing increasing attention and became an urgently important problem in environmental pollution. Hence, the development of highly sophisticated removal techniques of toluene is required for the global environmental preservation. Since toluene is a highly volatile material, it is difficult to treat it by usual activated sludge water treatment. In this study, in order to prevent volatilization of toluene, randomly methylated β-cyclodextrin (RM-β-CD) was used to complex with toluene and by reason of that, facilitates the biodegradation of toluene by activated sludge. The enhanced effect of RM-β-CD for the biodegradation of toluene by activated sludge was studied in batch systems. The addition of RM-β-CD dominantly promoted proliferation of activated sludge. This implied that the addition of RM-β-CD prevented toluene from evaporating during treatment, and as a result, toluene was effectively decomposed by the activated sludge.  相似文献   
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