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41.
Y Hayashi S Fukushima S Kishimoto M Nakano 《Chemical & pharmaceutical bulletin》1990,38(10):2874-2876
The release profiles of a free polyunsaturated fatty acid, alpha-linolenic acid, from solutions in an oily lymphographic agent Lipiodol-Ultra-Fluid (Lipiodol), to rabbit and human plasma, phosphate buffer solution (PBS), and PBS containing bovine serum albumin (BSA) were examined in vitro. The times required for 50% release of alpha-linolenic acid from Lipiodol were about 1 and 1.5 h in the rabbit and human plasma, respectively. Although only a slight amount of alpha-linolenic acid was released from Lipiodol to PBS after 24 h incubation at 37 degrees C, release was markedly enhanced by the addition of BSA to PBS. The amount of alpha-linolenic acid released from Lipiodol into PBS containing 5% BSA increased as the alpha-linolenic acid content in Lipiodol was increased. In all experiments, the release had stopped before all alpha-linolenic acid had been released. The prolongation of alpha-linolenic acid release from Lipiodol is considered a requisite for a selective anticancer effect of Lipiodol containing a free fatty acid on liver cancer. 相似文献
42.
A new kinetic-catalytic method by the initial rate procedure for the determination of nanogram level of iron(III) is developed, which is based on its catalytic effect on the oxidative coupling of 3-methyl-2-benzothiazolinone hydrazone (MBTH) with N,N-dimethylaniline (DMA) to form an indamine dye (λmax=590 nm) in the presence of hydrogen peroxide. Iron(II) is also determined, being oxidized to iron(III) by hydrogen peroxide. Calibration graphs obtained by the initial rate method are linear in the range 1–1000 ng ml−1 Fe and as low as 10−8 M Fe(II, III) can easily be determined. The relative standard deviations are 6.6, 2.5 and 1.5% for ten determinations of 1, 20 and 60 ng ml−1 of Fe(III), respectively. The method is applicable to the determination of iron in natural waters without preconcentration and separation. 相似文献
43.
Chiral cationic palladium[bond]phosphinooxathiane complexes have been found to be effective catalysts for enantioselective Diels-Alder (DA) reaction of cyclopentadiene with acyl-1,3-oxazolidin-2-ones to give the corresponding DA adducts in good yield and high enantioselectivity up to 93% ee. 相似文献
44.
Miyoshi D Matsumura S Nakano S Sugimoto N 《Journal of the American Chemical Society》2004,126(1):165-169
Because of the importance of telomere DNAs, the structures of these DNAs in vivo are currently of great research interest in the medical, pharmaceutical, chemical, and industrial fields. To understand the structure of biomolecules in vivo, their properties studied in vitro are extrapolated to the in vivo condition, while the condition in a living cell is inherently molecularly crowded and a nonideal solution contains various biomolecules. We investigated the effect of molecular crowding, which is one of the most important cellular environmental conditions, on the structure and stability of the telomere and G-rich and C-rich DNAs using circular dichroism (CD) spectra, CD melting curves, and isothermal titration calorimetry (ITC). The CD spectra and CD melting curves of G-rich DNA, C-rich DNA, and the 1:1 mixture of G-rich and C-rich DNAs showed that each G-rich DNA, C-rich DNA, and the 1:1 mixture form the antiparallel G-quadruplex, I-motif, and duplex, respectively, in the noncrowding condition as previously considered. On the contrary, the G-rich and C-rich DNAs individually form the parallel G-quadruplex and I-motif, respectively, in the molecular crowding condition, and the 1:1 mixture folds into the parallel G-quadruplex and I-motif but does not form a duplex. The ITC measurements indicated that the thermodynamic stability (DeltaG degrees (20)) of the duplex formation between the G-rich and C-rich DNAs in the noncrowding condition was -10.2 kcal mol(-)(1), while only a small heat change was observed in the ITC measurements in the molecular crowding condition. These ITC results also demonstrated that the molecular crowding condition prevents any duplex formation between G-rich and C-rich DNAs. These results indicate that a structural polymorphism of the telomere DNAs is induced by molecular crowding in vivo. 相似文献
45.
Okuyama Y Nakano H Takahashi K Hongo H Kabuto C 《Chemical communications (Cambridge, England)》2003,(4):524-525
Easily prepared, chiral sulfideoxathiane ligands are described which give excellent enantioselectivity (up to 99% ee) in the Pd-catalyzed allylic alkylation of 1,3-diphenyl-2-propenyl acetate with a range of alkyl malonate nucleophiles. 相似文献
46.
We have applied cavity ring-down spectroscopy to a kinetic study of the reaction of NO3 with CH2I2 in 25–100 Torr of N2 diluent at 298 K. The rate constant of reaction of NO3 + CH2I2 is determined to be (4.0 ± 1.2) × 10−13 cm3 molecule−1 s−1 in 100 Torr of N2 diluent at 298 K. The rate constant increases with increasing pressure of buffer gas below 100 Torr. The reaction of CH2I2 with NO3 has the potential importance at nighttime in the atmosphere. 相似文献
47.
Harayama T Akiyama T Nakano Y Nishioka H Abe H Takeuchi Y 《Chemical & pharmaceutical bulletin》2002,50(4):519-522
A palladium-assisted coupling reaction of aryl triflate with arene was investigated, and a novel Pd reagent prepared from equimolar Pd(OAc)2, 1,3-Bis[diphenylphosphino]propane (DPPP), and Bu3P was developed. This method is useful for intramolecular biaryl coupling reactions, not only between aryl triflate and arene (triflate-amide), but also between aryl halide and arene (halo-amide). 相似文献
48.
H Harada K Iizuka T Kamijo K Akahane R Yamamoto Y Nakano A Tsubaki T Kubota I Shimaoka H Umeyama 《Chemical & pharmaceutical bulletin》1990,38(11):3042-3047
The experimental details for the synthesis of human renin inhibitors are described. In order to avoid metabolic degradation of the Phe-His (P3-P2) amide bond in transition-state analogs, structurally modified acyl residues (P4-P3) were incorporated into the inhibitors. Compound 1a, which contained 2-(1-naphthylmethyl)-3-(N-phenethylcarbamoyl)propionyl residue (P4-P3) with a retro-inverso amide bond, L-histidine, and norstatine isoamylamide residue (P1-P1) as a transition-state mimic, had potent human renin inhibitory activity, and it lowered blood pressure when administered orally to common marmosets. 相似文献
49.
Reversed-phase high-performance liquid chromatography (HPLC) was used to determine the levels of nucleosides, bases and their metabolites in perchloric acid extracts of gastrointestinal mucosa. By comparing the levels of these compounds in the normal portion with the neoplastic portion of mucosa resected from malignant cancer patients, it was found that there was significant elevation of the uracil level in the neoplastic mucosa of all eight patients with colorectal cancer (2.7-fold in normal mucosa), but only in the neoplastic mucosa of one out of four patients with gastric cancer. The levels of hypoxanthine and uridine in the colorectal cancer mucosa samples and the inosine in gastric cancer samples were also significantly higher than those in normal mucosa. The urinary modified nucleosides were prefractionated with a boronate affinity gel column, and their levels were determined by the same HPLC method. There was no significant difference in the concentrations of pseudouridine, 1-methylguanosine N2-methylguanosine and N2,N2-dimethylguanosine between urine samples taken before and after surgery from eight patients with malignant colorectal cancer. Contrary to other reports, no significant differences in modified nucleoside levels were observed between urine samples from patients with colorectal cancer and those from normal subjects. 相似文献
50.
The asymmetric hydroformylation of 2‐ and 3‐vinylfurans ( 2a and 2b , resp.) was investigated by using [Rh{(R,S)‐binaphos}] complexes as catalysts ((R,S)‐binaphos = (11bS)‐4‐{[1R)‐2′‐phosphino[1,1′‐binaphthalen]‐2‐yl]oxy}dinaphtho[2,1‐d:1′,2′‐f][1,3,2]dioxaphosphepin; 1 ). Hydroformylation of 2 gave isoaldehydes 3 in high regio‐ and enantioselectivities (Scheme 2 and Table). Reduction of the aldehydes 3 with NaBH4 successfully afforded the corresponding alcohols 5 without loss of enantiomeric purity (Scheme 3). 相似文献