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91.
To investigate the helical conformation of oligo(m-phenylene ethynylene)s, a pair of TEMPO spin labels were appended to the backbone. The two TEMPO radicals were separated by the four, five, and six repeating units. ESR spectra of the labeled oligomers were measured in chloroform and in ethyl acetate solvents in which the oligomers are disordered and folded, respectively. The measurement and analysis of ESR spectra revealed that six repeating units make one helical turn. 相似文献
92.
[reaction: see text] Boryl substitution on an olefin activates the olefinic double bond toward addition of an organozinc reagent. Addition of an allylic zinc reagent to an alkenylboronate thus takes place smoothly to afford a variety of gem-zincio/boryl species. Theoretical studies with density functional calculations on the reaction pathway revealed that the reaction proceeds via a zincio-ene reaction rather than a bora-Claisen rearrangement. 相似文献
93.
By the self-immolative asymmetric synthesis, optically pure key intermediate β-piperonyl-γ-lactone (R)-(+)- was found to be prepared in reasonable yield from the easily available chiral γ-lactone synthon () which had been also reported to give an antipode (S)-(-)-. The optically pure (R)-(+)- was shown to be converted successfully into several optically pure natural lignan lactones. 相似文献
94.
Transformation of arctiin to estrogenic and antiestrogenic substances by human intestinal bacteria 总被引:2,自引:0,他引:2
Xie LH Ahn EM Akao T Abdel-Hafez AA Nakamura N Hattori M 《Chemical & pharmaceutical bulletin》2003,51(4):378-384
After anaerobic incubation of arctiin (1) from the seeds of Arctium lappa with a human fecal suspension, six metabolites were formed, and their structures were identified as (-)-arctigenin (2), (2R,3R)-2-(3',4'-dihydroxybenzyl)-3-(3",4"-dimethoxybenzyl)butyrolactone (3), (2R,3R)-2-(3'-hydroxybenzyl)-3-(3",4"-dimethoxybenzyl)butyrolactone (4), (2R,3R)-2-(3'-hydroxybenzyl)-3-(3"-hydroxy-4"-methoxybenzyl)butyrolactone (5), (2R,3R)-2-(3'-hydroxybenzyl)-3-(3",4"-dihydroxybenzyl)butyrolactone (6), and (-)-enterolactone (7) by various spectroscopic means including two dimensional (2D)-NMR, mass spectrometry, and circular dichroism. A possible metabolic pathway was proposed on the basis of their structures and the time course of the transformation. Enterolactones obtained from the biotransformation of arctiin and secoisolariciresinol diglucoside (SDG, from the seeds of Linum usitatissium) by human intestinal bacteria were proved to be enantiomers, with the (-)-(2R,3R) and (+)-(2S,3S) configurations, respectively. Compound 6 showed the most potent proliferative effect on the growth of MCF-7 human breast cancer cells in culture among 1 and six metabolites, while it showed inhibitory activity on estradiol-mediated proliferation of MCF-7 cells at a concentration of 10 microM. These results indicate that the transformation of 1 by intestinal flora might be essential for the manifestation of the estrogenic and antiestrogenic activity of 1. 相似文献
95.
Improved separation of alpha chains of collagen type I (alpha 1 [I]2 alpha 2[I]), type III(alpha 1[III]3), and type V (alpha 1[V]alpha 3[V])was achieved by noninterrupted sodium dodecyl sulfate-polyacrylamide gel electrophoresis with a negatively charged reducer, thioglycolic acid. The thioglycolic acid, added to the running buffer of the cathodic reservoir, in the middle of electrophoresis quickly migrated in the gel anode, reducing interchain disulfide linkages in collagen type III and dissociating it into its alpha chain monomer, alpha 1[III], without an interruption of electrophoresis. The alpha chain, alpha 1[III], migrated more slowly than the alpha 1 [I] and alpha 2[I] chains of collagen type I, resulting in an excellent separation of alpha 1[III] from alpha 1[I]. The mobility of alpha 1[III] could be controlled by varying the time of thioglycolic acid addition to the running buffer. This enabled us not only to separate alpha 1[III] from alpha 1[I] and alpha 1[V], but also to precisely quantitate these alpha chains, even at low protein loading of mixed samples. 相似文献
96.
Hoteling AJ Kawaoka K Goodberlet MC Yu WM Owens KG 《Rapid communications in mass spectrometry : RCM》2003,17(14):1671-1676
Details of the optimization of the collision-induced dissociation (CID) process, using a collision cell on a matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometer, are described using poly(ethylene glycol) 1000 (PEG 1000) as a model analyte. The effects of collision gas identity (helium, air, and argon), as well as collision gas pressure, on the resulting MS/MS data were investigated. With PEG 1000, helium was found to give the best results with respect to signal-to-noise (S/N) ratio. The optimum pressure for each gas was found to be in the range where the precursor ion signal was attenuated to approximately 30-50% for helium and 40-60% for argon. The effect of cation choice (Li, Na, and K) on the CID of PEG was also studied. CID spectra were produced for each, but PEG cationized with lithium was found to produce the spectra with the highest S/N ratio. The MALDI-TOF CID spectra that were generated for PEG were compared with the high-energy and low-energy MS/MS spectra obtained from a sector mass spectrometer and from a triple quadrupole mass spectrometer, respectively. The results observed for PEG confirm that CID on a MALDI-TOF mass spectrometer is a high-energy MS/MS technique. 相似文献
97.
Itoh T Nagata K Yokoya M Miyazaki M Kameoka K Nakamura S Ohsawa A 《Chemical & pharmaceutical bulletin》2003,51(8):951-955
Chiral 1-substituted isoquinoline derivatives, which were obtained by the reaction using alanine derivatives as chiral auxiliaries, were transformed to (S)-2,3,9,10,11-pentamethoxyhomoprotoberberine (7) and a synthetic intermediate for O-methylkreysigine (9) in good yields and high stereoselectivity. The corresponding chiral allyl derivative of isoquinoline was transformed to a pyrrolidinoisoquinoline (16) in a highly enantioselective manner. 相似文献
98.
(+)-Steganacin was synthesized in a new and highly specific asymmetric pathway based on the novel application of chiral γ-lactone as a chiral synthon. By this synthesis the absolute stereochemistry of natural (?)-steganacin could be determined in unequivocal way. 相似文献
99.
Synthesis of diphenyl cucurbit[6]uril (CB[6]) has been achieved via co-oligomerization of diphenyl glycoluril and unsubstituted glycoluril. The unsymmetrically substituted CB[6], Ph(2)CB[6], was further converted to a rotaxane incorporating bis(dinitrophenyl)spermine. [reaction: see text] 相似文献
100.
Yoshinori Kadoma Takashi Toida Kenji Takeda Keikichi Uno Yoshio Iwakura 《Journal of polymer science. Part A, Polymer chemistry》1975,13(3):707-716
The polymerization of picryl (PMA), 2,4-dinitrophenyl (2,4-DNMA),2,6-dinitrophenyl (2,6-DNMA), 2-methyl-4,6-dinitrophenyl (MDNMA), and 2,6-dimethylphenyl methacrylates (DMMA) was carried out in benzene at 60°C. PMA, 2,6-DNMA, and MDNMA did not undergo radical homopolymerization, while 2,4-DNMA and DMMA did. The results suggest that the growing radical readily attacks the oxygen atom of the nitro group at the 2 position of the terminal phenyl group due to the steric effect of the substituent at the 6 position, resulting in chain termination. PMA formed a charge-transfer complex with 2-naphthyl methacrylate (NMA). The stoichiometric composition of this complex was shown to be 1:1 molar complex. PMA was readily copolymerized with NMA. The amount of solvent affected the composition of the copolymer obtained at a given same mole fraction in feed. The results suggest that charge-transfer interaction between the ester groups affects the copolymerization mechanism. 相似文献