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121.
Hanamoto T Hashimoto E Miura M Furuno H Inanaga J 《The Journal of organic chemistry》2008,73(12):4736-4739
N-Methylation by sequential treatment of 5-tributylstannyl-4-fluoro-1H-pyrazole 1 with LDA and iodomethane regioselectively afforded the compound 2a in high yield. The addition reaction of 5-lithiated-4-fluoro-1H-pyrazole generated from 2a with a wide range of electrophiles allowed a facile introduction of different substituents at position 5 in good yields. The adduct 3d was efficiently converted to N-methyl-chromeno[2,3-d]pyrazol-9-one 9 in 3 steps. 相似文献
122.
Inukai J Miyatake K Ishigami Y Watanabe M Hyakutake T Nishide H Nagumo Y Watanabe M Tanaka A 《Chemical communications (Cambridge, England)》2008,(15):1750-1752
A luminescent porphyrin dye film has been coated onto a transparent separator on the cathode side of a direct methanol fuel cell (DMFC) to visualise clearly oxygen distribution under operating conditions by analysing emission from the dye. 相似文献
123.
The phospholipid molecule is a typical component of the cell membrane. In particular, the phosphorylcholine polar group is an electrically neutral head group. 2-Methacryloyloxyethyl phosphorylcholine (MPC) comprising a phosphorylcholine group side chain was designed with the cell membrane as an inspiration. Versatile polymers comprising MPC could be synthesized, and their specific biofunctions were evaluated. Establishing an ultimate biointerface with multiple functions is important from the viewpoint of biomaterials science. Nonspecific protein adsorption is essential for achieving versatile biomedical applications. Simultaneously, bioconjugation and retention of its biofunction are crucial for a high-performance biointerface. In this review article, a tunable biointerface comprising MPCs was introduced. In particular, the use of nanoparticles and polymer brushes as biointerfaces was described along with the perspective versatility of their biological applications. 相似文献
124.
Sakurai J Oguchi T Watanabe K Abe H Kanno S Ishikawa M Katoh T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(3):829-837
Biologically important and structurally unique marine natural products avarone (1), avarol (2), neoavarone (3), neoavarol (4) and aureol (5), were efficiently synthesized in a unified manner starting from (+)-5-methyl-Wieland-Miescher ketone 10. The synthesis involved the following crucial steps: i) Sequential BF(3)Et(2)O-induced rearrangement/cyclization reaction of 2 and 4 to produce 5 with complete stereoselectivity in high yield (2 --> 5 and 4 --> 5); ii) strategic salcomine oxidation of the phenolic compounds 6 and 8 to derive the corresponding quinones 1 and 3 (6 --> 1 and 8 --> 3); and iii) Birch reductive alkylation of 10 with bromide 11 to construct the requisite carbon framework 12 (10 + 11 --> 12). An in vitro cytotoxicity assay of compounds 1-5 against human histiocytic lymphoma cells U937 determined the order of cytotoxic potency (3 > 1 > 5 > 2 > 4) and some novel aspects of structure-activity relationships. 相似文献
125.
We report an FTIR method to measure the accessibility and the size of cellulose microfibrils from the cell wall of Valonia ventricosa. This method is similar to the conventional deuteration technique for measuring the accessibility of cellulosic materials;
however, the difference in our method is that the hydroxyl groups O2H, O3H, and O6H in the crystalline region were initially
completely deuterated. The sample was then rehydrogenated by soaking in water at 25 °C, so that the OD groups on the surface
were rehydrogenated. The ratio of OH to OD absorbance was used to calculate the number of surface vs. core cellulose chains
in a microfibril. The obtained experimental ratio of 0.934 was consistent with the value calculated for a previously published
33 × 38 chain Valonia model (Sugiyama et al. 1984). The rehydrogenation process was further investigated by immersing the sample in water at elevated temperatures. At temperatures
above 120 °C, rehydrogenation was more efficient, and the efficiency plots vs. rehydrogenation temperature showed two inflection.
These points may correspond to the temperature where the cleavage of inter-chain hydrogen bonds and/or crystalline-phase transition
would have been occurred. 相似文献
126.
Ishizaka T Okada S Tokuyama E Mukai J Uchida T 《Chemical & pharmaceutical bulletin》2008,56(10):1389-1394
The objective of the study was to evaluate the bitterness, grittiness and uniformity of drug loading as measures of the quality of 12 formulations of clarithromycin dry syrup (CAMDS), comprising one branded and 11 generic products. Some of the generic CAMDS formulations were more bitter than the branded product while others had similar bitterness when tested as aqueous suspensions. Only one generic product was less bitter than the branded product when tested as a suspension in acidic sports drink. The usual dissolution test described in JP XV could not be used to evaluate the bitterness of the products. A brief dissolution test using only 12.5 ml of water was used to evaluate the bitterness of the products in aqueous suspensions. There were considerable variances in the grittiness of the various products, which were independent of particle size. Changes in grittiness level seemed to be correlated with changes in the intensity of bitterness due to the disintegration of the formulation. Finally, there was less variation in the uniformity of drug loading for the branded product than for the generic products. These data may be useful when selecting which CAMDS formulation to prescribe. 相似文献
127.
The effect of peripheral halogenation is examined based on analytical transmission electron microscopy and thermal analyses of two chemical family structures, specifically the vanadyl-phthalocyanine family (VOPcX: X = H16, F14.5) and the copper-phthalocyanine family (CuPcX: X = H16, F16, Cl16, Cl8Br8), focusing on the process of molecular changes and crystalline disintegrations. To clarify the molecular transformations, electron energy-loss spectroscopy (EELS) is applied to two fluorinated phthalocyanines (VOPcF14.5 and CuPcF16), by monitoring mass changes as well as energy loss near edge structures (ELNES). The elemental mass of both VOPcF14.5 and CuPcF16 remain constant up to 0.5 C x cm(-2), except in the case of mass reduction attributed to oxygen loss occurring in VOPcF14.5. It is expected that the released oxygen will induce higher radiation damage in VOPcF14.5. Although mass variation is not observed in CuPcF16, it is found from ELNES that the pi resonant system of nitrogen is more radiation sensitive than that of carbon. These results imply that the electron sensitivity in VOPcX is triggered by eliminated oxygen or, thus, an induced larger empty space, whereas the sensitivity of CuPcX is dominated only by a large intermolecular empty space resulting in the following bond alterations. It is also found that the decomposition temperature (Td) measured by thermal analyses and the characteristic dose (D1/e) are exponentially correlated to the "effective molecular occupancy" (Oe) evaluated as a volume function of molecules in unit cells. By measuring Td and/or Oe, we discuss the durability of peripheral halogenation with respect to the radiation damage. 相似文献
128.
129.
o-Formyl-substituted beta,beta-difluorostyrenes readily react with NH(2)OH.HCl or NH(4)OAc to afford 3-fluoroisoquinoline derivatives in good yield via (i) the formation of the corresponding oximes or imines and (ii) subsequent intramolecular replacement of a vinylic fluorine by the sp(2) nitrogen of the iminomethyl group (HON=CH- or HN=CH-). Beta,beta-Difluorostyrenes bearing an o-diazenyl group (HN=N-), generated by reduction of the corresponding diazonium ions, undergo a similar substitution to afford 3-fluorinated cinnolines. 相似文献
130.
An attempt to carry out a total synthesis of kulokekahilide-2 (1) by macrolactonization of a seco acid prepared from a suitably protected hexapeptide and a dioxy acid moiety unexpectedly resulted in the formation of the 43-epimer (1a) of the cytotoxic depsipeptide, for which structure 1b has previously been proposed. A second attempt involving macrolactamization of the corresponding amino acid gave the target product, 1b, but the spectral data of the product did not match those of natural 1. Furthermore, neither 1a nor 1b showed any cytotoxicity, from which it is concluded that the structure of natural 1 is incorrect and should be re-examined. 相似文献