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121.
In the presence of trifluoroacetic acid, N-phenyl-N′-phenoxyurea (1a) rearranges to N-(4′-hydroxy-2-biphenylyl)urea (2a) and N-carbamoyl-2-hydroxy-diphenylamine (3a). The rearrangement is an intramolecular reaction, and the transition state of the breakage of the N-O bond is deduced to be polarized in the form Nδ- --- Oδ+. The reaction is entirely new and constitutes a fundamental aromatic rearrangement. 相似文献
122.
Large-scale separation of metallic and semiconducting single-walled carbon nanotubes 总被引:6,自引:0,他引:6
Maeda Y Kimura S Kanda M Hirashima Y Hasegawa T Wakahara T Lian Y Nakahodo T Tsuchiya T Akasaka T Lu J Zhang X Gao Z Yu Y Nagase S Kazaoui S Minami N Shimizu T Tokumoto H Saito R 《Journal of the American Chemical Society》2005,127(29):10287-10290
In the applications of single-walled carbon nanotubes (SWNTs), it is extremely important to separate semiconducting and metallic SWNTs. Although several methods have been reported for the separation, only low yields have been achieved at great expense. We show a separation method involving a dispersion-centrifugation process in a tetrahydrofuran solution of amine, which makes metallic SWNTs highly concentrated to 87% in a simple way. 相似文献
123.
K Ichimura H Yamanaka K Chiba T Shinozuka Y Shiki K Saito S Kusano S Ameniya K Oyama Y Nozaki 《Journal of chromatography. A》1986,374(1):5-16
Until now, there has been little work covering all of the main native adrenal-cortical steroids in blood. We therefore established a method for the simultaneous quantitative measurement of 14 native adrenal-cortical steroids, which involves capillary column gas chromatography-mass spectrometry (GC--MS). Serum steroids were purified from serum with the Extrelut mini-column and then converted into stable derivatives for GC-MS by a combination of boronic cyclization and trimethylsilyl and methyloxime derivatization. The sensitivities (with a signal-to-noise ratio greater than or equal to 7) of our GC-MS method ranged from 0.1 to 1.0 ng/ml of serum, and the coefficients of variation of intra- and inter-assays were less than 19% for each steroid. Our newly devised method involving a capillary column GC-MS system has been proven to be a simple and suitable method for a diagnosis requiring simultaneous detection of many native adrenal steroids in clinical practice. The analysis time is only 4 h. 相似文献
124.
To study the role of glycine residues in stabilizing the collagen triple helix, the glycine residues in the polytripeptide (Pro-Ala-Gly)n were partially replaced by alanine. The proline content was kept constant. The stability of the helical conformation of these polypeptides was studied by IR- and X-ray measurements in the solid state and by ORD, CD and viscometry in solution. The renaturation was followed as a function of time. All the polytripeptides studied, with the exception of (-Pro-Ala-Ala-)n attained the polyproline II conformation. However the stability decreased with increasing alanine content. Obviously the molecules of (-Pro-Ala-Gly-) are highly associated by intermolecular hydrogen bonds and one may therefore suppose that a triple-stranded helix aggregation occurs. The results of the refolding process show that the stability of the helices seems to also affect the refolding rate in terms of the optical rotation, Two transitions appeared: the first one is responsible for a rapid reversible change in conformation and the second one for a further slow and irreversible change in the hydrodynamic shape. The latter seems to be due to the partial helical nature, leading to higher chain mobility. 相似文献
125.
[reaction: see text] Chiral C(4)-substituted (E)- or (Z)-1-alkynyl-1-trimethylsilyloxy-2-butene systems provide anti-(Z) or syn-(Z) conjugated dienyne, with a very high level of stereocontrol, on treatment with BF(3).OEt(2) in CH(2)Cl(2) at -50 degrees C in the presence of allyltrimethylsilane. The Cieplak conformation for (E)-substrates and neighboring-group participation for (Z)-substrates are considered to be responsible for the stereochemical consequences. 相似文献
126.
Shuji Saito 《Journal of polymer science. Part A, Polymer chemistry》1970,8(1):263-271
The effects of various alkylammonium thiocyanates (ethyl, butyl, hexyl, and octyl) on aqueous solutions of polyvinylpyrrolidone (PVP) and poly(vinyl alcohol–acetate) copolymer (PVA-Ac) were studied and compared with the effects caused by the respective chlorides. Whereas the PVP solution was hardly affected by the chlorides, it was precipitated by n-octylammonium thiocyanate (OASCN) at dilute concentrations and dissolved at higher concentrations. On taking the effects of ammonium chloride and thiocyanate on the solubility of PVA-Ac as references, with increasing of alkyl chain length, alkylammonium chlorides raised the polymer solubility steadily; on the contrary, the thiocyanates at dilute concentrations, except for ethylammonium thiocyanate, lowered it, and OASCN at dilute concentrations, except for ethylammonium thiocyanate, lowered it, and OASCN at dilute concentrations was a particularly strong salting-out agent. The amount of binding of OASCN to the polymers in the precipitated systems was measured. The precipitation was attributed to ion-pair binding of OASCN to the polymers, and the mechanism was discussed in terms of the interaction between the water structure-breaking SCN? and the water structure-making hydrophobic groups. 相似文献
127.
For evaluation of a chiral C2-symmetric bis(oxazoline) ligand, its Lewis acid complexes-catalyzed asymmetric 1,3-dipolar cycloaddition reactions of nitrones with electron-deficient dipolarophiles, 3-(2-alkenoyl)-1,3-oxazolidin-2-ones, have been investigated and it was found that the cycloadditions using a Cu(II)-bis(oxazoline) complex under optimized reaction conditions induced extremely high enantioselectivity. 相似文献
128.
M Saito S Kataoka A Nasu N Yamaji A Ichikawa 《Chemical & pharmaceutical bulletin》1991,39(12):3207-3210
A series of adenosine 3',5'-cyclic monophosphoramidates (3, cAMP amidates), including long-chain alkyl amidates, were synthesized from adenosine 3',5'-cyclic monophosphate (1, cAMP) by means of a one-pot reaction. This reaction proceeded by the treatment of cAMP tributylammonium salt (2) with phosphorus pentachloride (PCl5) and alkylamine in N,N-dimethylformamide (DMF). Compounds 3 synthesized were investigated to determine their cytotoxic activities on the growth of mouse mastocytoma P-815 cells, mouse mammary tumor FM3A cells, and human mammary tumor ZR-75 cells in culture. It was found that compounds 3h-m showed significant cytotoxic activities against these cell lines, and that cAMP decylamidate (3j) was the most cytotoxic compound (the concentration required for 50% inhibition of cell growth, ID50 = 6.0, 15.0, 2.2 microM, respectively); the antitumor effect on P-815 cells by a total packed cell volume method showed 81.8% inhibition. The cytotoxic activity of 3 increased with the increase in alkyl chain length up to 10 carbon atoms and decreased in compounds having longer alkyl chain. 相似文献
129.
Tohru Nishinaga 《Tetrahedron》2004,60(15):3375-3382
A series of hexadehydro[18]annulenes fused with different numbers of p-benzoquinone, 4-6, were synthesized by stepwise transformation of the p-dimethoxybenzene moiety of the precursor dehydroannulene 3 fused with three 3,6-dimethoxy-4,5-dimethylbenzene units at 1,2-positions into p-benzoquinone using ceric ammonium nitrate. The UV-vis spectra of compounds 4 and 5, which have both electron-donating p-dimethoxybenzene unit(s) and electron-accepting p-benzoquinone unit(s) in the π-systems, showed the maximum absorption bands bathochromically shifted in comparison with 3 having only p-dimethoxybenzene units and 6 having only p-benzoquinone units. However, the solvatochromism expected for 4 and 5 was found to be quite weak possibly because the HOMO and LUMO (B3LYP/6-31G(d)) are not localized but rather delocalized over the whole π-systems. 相似文献
130.
Poly(1,4-dimethyl-6-vinylnaphthalene) and poly(1,2,4-trimethyl-6-vinylnaphthalene) react with singlet oxygen to give corresponding endoperoxide polymers which on warming generate singlet oxygen efficiently. Singlet oxygenations by the use of these polymers have been described. 相似文献