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181.
A strategy for the stereoselective synthesis of all the possible diastereoisomers of the 2,6-diaryl-3,7-dioxabicyclo[3.3.0]octane (furofuran) lignans from a single dihydrofuran precursor is described. The key steps involve a diastereocontrolled templated cationic cyclization followed by stereoselective reduction of the resulting methyl glycoside. 相似文献
182.
Sternfeld T Thilgen C Hoffman RE Del Rosario Colorado Heras M Diederich F Wudl F Scott LT Mack J Rabinovitz M 《Journal of the American Chemical Society》2002,124(20):5734-5738
Reduction of the two "closed" [6,6] methanofullerenes, [6,6]C(61)H(2) (1) and [6,6]C(71)H(2) (5), to the corresponding hexaanions with lithium metal causes the bridgehead-bridgehead bonds to open, at least partially, and this change gives rise to diamagnetic ring currents in the resulting homoconjugated six-membered rings (6-MRs). These new ring currents shield the overlying hydrogen atoms on the methylene bridge and induce upfield shifts of 1.60 and 0.11 ppm in their (1)H NMR resonances, respectively. Analogous reduction of the already "open" [5,6]methanofullerenes, [5,6]C(61)H(2) (2) and [5,6]C(71)H(2) (3 and 4), only slightly enhances the shielding of the hydrogen atoms over the homoconjugated 6-MRs (upfield shifts of 0.13, 0.68, and 0.14 ppm, respectively) but leads to exceptionally strong diamagnetic ring currents in the homoconjugated five- membered rings (5-MRs), as evidenced by dramatic shielding of the hydrogen atoms situated over them (upfield shift of 5.01, 6.78, and 1.63 ppm, respectively). The strongest shielding is seen for the hydrogen atom sitting over the 5-MR at the pole of C(71)H(2)(6)(-) (delta = -0.255 ppm) indicating that the excess charge density is concentrated at the poles. 相似文献
183.
A new high-performance liquid chromatographic method has been developed for the determination of the beta-receptor blocker carvedilol in human cardiac tissue. After homogenizing tissue samples in a microdismembrator, carvedilol and the internal standard naftopidil are extracted with acetone. The extract is evaporated to dryness and reconstituted in a potassium acetate buffer of pH 3.5. Samples are cleaned up with solid-phase extraction columns. Carvedilol and the internal standard show recoveries of 69.8 +/- 12.2% and 63.9 +/- 9.34%, respectively. The linearity range for carvedilol is 0.01-0.35 ng/mg (parts per billion) tissue (wet weight), and the limit of quantitation is 0.01 ng/mg. The percentage coefficient of variation of the intra-assay varies between 1.45 and 5.38% and the interassay between 4.25 and 6.96%. To use as an application of the assay, the cardiac carvedilol tissue level in a patient on oral carvedilol therapy for congestive heart failure is reported. 相似文献
184.
We have studied the diffusion inside the silica network of sodium atoms initially located outside the surfaces of an amorphous silica film. We have focused our attention on structural and dynamical quantities, and we have found that the local environment of the sodium atoms is close to the local environment of the sodium atoms inside bulk sodo-silicate glasses obtained by quench. This is in agreement with recent experimental results. 相似文献
185.
Pál Tapolcsányi János Wélfling Erzs?bet Mernyák Gyula Schneider 《Monatshefte für Chemie / Chemical Monthly》2004,44(3):1129-1136
The Mitsunobu inversion reaction of 3-methoxyestra-1,3,5(10)-trien-17-ol is dramatically influenced by the acidic component. There appears to be a relationship between the dissociation constant of the electron-withdrawing substituent on the aryl acid and the overall effectiveness of the reaction, with more acidic species generally providing a higher yield of inverted product. 相似文献
186.
The antifolate methotrexate (MTX) is widely used in cancer chemotherapy. In this study, we show that MTX (MTX-Glu1) and MTX-polyglutamates (MTX-Glu2-5) strongly inhibited the growth of the leukemic cell line MOLT-4. This effect, however, was mitigated by ascorbic acid. We investigated whether ascorbic acid is able to reduce dihydrofolic acid (DHF) to tetrahydrofolic acid (THF) directly or by circumventing the MTX inhibition of dihydrofolate reductase (DHFR). The inhibition of this NADPH-dependent reduction of DHF by MTX-Glun in the absence or presence of ascorbate, was determined by analytical isotachophoresis. Using 0.01 M HCl/histidine, pH 6.0, as a leading electrolyte (L) and 0.005 M 2-(N-morpholino)ethanesulfonic acid (MES)/histidine, pH 6.0, as a terminating electrolyte (T), MTX-Glun derivatives including MTX-Glu1 could be easily separated, whereas the quantitative estimation of THF was not possible. A quantitative characterization of the DHFR reaction by measuring NADPH, NADP+ and ascorbate was achieved with another system (L: 0.01 M HCI/beta-alanine, pH 3.73; T: 0.01 M caproic acid, pH 3.27). Nanomolar concentrations of MTX-Glu1-5 inhibited consumption of NADPH and production of NADP+. Ascorbic acid was not able to reduce DHF, neither directly nor after inhibition of DHFR by MTX. However, ascorbic acid seemed to diminish the oxidation of THF and this may account for its capacity to reduce the inhibitory effect of MTX on MOLT-4 cells. 相似文献
187.
Alfred Kreutzberger Elfriede Kreutzberger Hans-Joachim Saltler Hayriye Aml Aysel Gürsoy 《Journal of heterocyclic chemistry》1982,19(4):753-755
The three-component reaction comprising the interaction of 2-amino-4-antipyrinyl-5-ethylthiazole (1) with s-triazine (2) and pyrrolidine leads to 4-anitpyrinyl-5-ethyl-2-[(4-pyrrolidinyl)methyleneamino]thiazole (5). Structure 5 is supported by 1H- and 13C-NMR spectroscopy. 相似文献
188.
Jzsef Reiter Lszl Pong Pter Krajcsi Klra Esses-Reiter Pl Sohr Hilda Molnr Pter Dvortsk 《Journal of heterocyclic chemistry》1987,24(4):927-930
The ring-closure of the 5-amino-1-(2-aminophenyl)-3-methylthio-1H-1,2,4-triazole derivatives 3 and 4 with different simple and cyclic C1 components lead to the formation of 1,2,4-triazolo[1,5-α]-1,3,5-benzotriazepines 5–6 , their 4,5-dihydro- 7 , different 5-spiro-homocyclic- 8–13 , and 5-spiro-heterocyclic- 14-15 analogues. The structure of the compounds obtained was proved with the use of their ir, uv, 1H-nmr and 13C-nmr spectra. 相似文献
189.
190.
This paper describes a novel approach for the surface modification of a cation-exchange membrane, bearing sulfonate groups, by a cationic layer. The modification procedure involved the chlorosulfonation of the sulfonate groups of the base membrane with thionyl chloride, followed by a reaction with a diamine to yield a sulfonamide bond and a terminal amine. The latter could be quaternized by reaction with methyl iodide or protonated by soaking in acidic media. The membranes were characterized in detail by attenuated total reflectance Fourier transform infrared and X-ray photoelectron spectroscopies as well as elemental analysis to confirm that the above reactions occurred. The selectivity of these membranes toward the electrochemically assisted transport of protons versus Zn2+ metallic cations was determined during an electrodialysis in a two-compartment electrochemical cell. The data indicate a significant decrease of the transport of the metallic cations following modification of the membrane with the cationic layer. The later allows for the transport of protons from the catholyte to the anolyte compartment with much improved selectivity since the divalent cations are excluded from the membrane due to the electrostatic barrier of the cationic layer. 相似文献