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131.
Fukuda T Makarova EA Luk'yanets EA Kobayashi N 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(1):117-133
Benzene- or 2,3-naphthalene-ring-expanded tetraazachlorins (TACs), tetraazabacteriochlorins (TABCs), and tetraazaisobacteriochlorins (TAiBCs) have been synthesized by using tetramethylsuccinonitrile as a source of hydrogenated sites. The derived compounds were characterized by using NMR spectroscopy, X-ray crystallography, electronic and magnetic circular dichroism (MCD) spectroscopy, and electrochemical and spectroelectrochemical methods. X-ray analysis revealed that the benzene-fused TAiBC deviates slightly from planarity at the hydrogenated sites as a result of the presence of sp(3) carbons, which prefer a nonplanar tetrahedral conformation. The spectral data were analyzed by using a band deconvolution technique. In the electronic absorption spectra of TAC and TABC species, the Q band splits into two intense components and smaller splittings were observed for the 2,3-naphthalene-fused derivatives relative to the benzo-fused species. In contrast, in the case of TAiBCs, the Q band splitting was apparently not observed in absorption spectra, as expected from the C(2v) molecular symmetry. However, MCD signals of the Q band in TAiBCs showed Faraday B terms, implying that the accidental degeneracy of the LUMO and LUMO+1 was broken even for adjacently ring-fused species. Relative molecular orbital energies were estimated by using cyclic and differential pulse voltammetry. The first reduction potentials were close for TACs and TABCs, although those of TAiBCs shifted to more negative potentials. In contrast, although TABCs and TAiBCs exhibited similar first oxidation potentials, those of TACs appeared at more positive potentials. These properties were reproduced and rationalized by molecular orbital and configuration interaction calculations within the framework of the ZINDO/S Hamiltonian. DFT-level frequency calculations have succeeded in reproducing the IR spectra for low-symmetry tetraazaporphyrin (TAP) derivatives for the first time. The relationship between structures and spectral features is discussed. 相似文献
132.
The iron-catalyzed Kirmse reaction was used to generate neopentyl alpha-silyl thioethers that were elaborated to meroterpenes using two complementary routes: one route involved a sila-Pummerer rearrangement, and the other route involved a Peterson olefination. While severe eclipsing interactions undermined the efficiency of the stereospecific sila-Pummerer rearrangement, they made it possible to stereoselectively generate E olefins without isolation or separation of syn- and anti-beta-silyl alkoxides. Addition of a neopentyl alpha-silyl alkyllithium intermediate to an aryl aldehyde generated a mixture of syn- and anti-beta-silyl alkoxides. The syn-beta-silyl alkoxide eliminated stereospecifically at -78 degrees C to give an E olefin, whereas the anti-beta-silyl alkoxide was unreactive. The reaction mixture was then acidified and heated to induce stereospecific elimination of the anti isomer to give the same E olefin via a complementary cationic pathway. This route was used to complete the first synthesis of the meroterpene (+/-)-3-hydroxybakuchiol. In addition, we synthesized another meroterpene corresponding to the natural product corylifolin and offer evidence that the structure of corylifolin was misassigned. 相似文献
133.
Therapeutic drug monitoring of anti-inflammatory drugs is necessary for the identification of the agents that cause toxic events and for the decision on the treatment for intoxication. Recently, capillary electrophoresis (CE) has been developed for the simple and rapid analyses of a variety of chemical agents. Micellar electrokinetic chromatography (MEKC) can separate acidic, neutral and basic anti-inflammatory drugs in serum. Furthermore, serum samples are directly applied to the CE system without any pretreatments, and some anti-inflammatory drugs can be separated from serum albumin in the MEKC analysis. On the other hand, capillary zone electrophoresis (CZE) enables us to determine a few microg/mL levels of acidic anti-inflammatory drugs with simple running buffer and stacking technique. A rapid and simultaneous determination of several analgesic anti-inflammatory agents, including ibuprofen, acetaminophen, indomethacin, and salicylic acid in human serum has been developed by using CZE. Therefore, the CZE and MEKC analysis may become a potentially useful alternative to high-performance liquid chromatography (HPLC) and fluorescence polarization immunoassay (FPIA) for therapeutic drug monitoring, particularly in serum of patients suffering from intoxication by overdosage of nonsteroidal anti-inflammatory agents. 相似文献
134.
Kimiko Makino Junya Tabata Tatsuya Yoshioka Minoru Fukuda Masahiko Ikekita Hiroyuki Ohshima Hiroshi Terada 《Colloids and surfaces. B, Biointerfaces》2003,29(4):277-284
The purpose of this work is to know the effect of surface properties of liposomes on their phagocytic uptake by macrophages. For this, liposomes were prepared by the Bangham technique from the mixture of phosphatidylcholine (PC) and cholesterol (Chol) incorporated either with phosphatidylserine (PS), phosphatidylethanolamine (PE) or phosphatidic acid (PA). The liposomes thus prepared had diameters in the range between 150 and 260 nm. Electric surface properties of the liposomes and the macrophages differentiated from HL-60RG cells were determined by measuring their electrophoretic mobilities. The phagocytic uptake of liposomes with different contents of PS, PE and PA by macrophage-like HL-60RG cells was investigated by measuring oxygen consumption associated with phagocytic uptake. The phagocytic activity was found to be the highest with the PC–Chol liposomes containing 7 mol% PS, but no significant effects were observed with PA- and PE-containing PC–Chol liposomes. As the uptake was independent of the electric surface property of liposomes, PS was concluded to be specifically important for phagocytic activity of macrophages. 相似文献
135.
A HPLC method is described in order to separate and identify 4 phenolic compounds including lithospermic acid B, 3,4-dihydroxyphenyllactic acid (danshensu), rosmarinic acid, and protocatechuic aldehyde as well as 3 lipophilic ones (tanshinone I, tanshinone II(A) and cryptotanshinone) from the roots of Salvia miltiorrihiza or the herbal product containing S. miltiorrihiza available in Chinese or Japanese market. The influence of extractive conditions, such as method, solvents and time, on the 4 phenolic marker components in S. miltiorrihiza is well discussed. In order to investigate the stability of lithospermic acid B, the preparation samples of an injection and a granule were analyzed after being stored at 4 degrees C, 20 degrees C and 40 degrees C for up to six months. 相似文献
136.
Yoshimatsu K Kiuchi F Shimomura K Makino Y 《Chemical & pharmaceutical bulletin》2005,53(11):1446-1450
A rapid and reliable solid-phase extraction method for HPLC analysis of opium alkaloids from Papaver plants was established. Fifty mg of dried and powdered plant sample was extracted with 5 ml of 5% acetic acid for 30 min under sonication. After centrifugation, 3 ml of the supernatant was loaded on a reversed-phase cation-exchange solid-phase extraction cartridge. After seriate washings with 0.1 M hydrochloric acid and methanol, alkaloids were eluted with a mixture of 28% ammonia and methanol (1:19). The eluate was concentrated under nitrogen stream at 40 degrees C and the residue was dissolved in 50% aqueous methanol for high performance liquid chromatographic analysis. With this solid-phase extraction method, the recovery of morphine, codeine, oripavine, thebaine, papaverine, noscapine and sanguinarine was from 99.94 to 112.18% when the standard alkaloids were added to the plant samples. Opium alkaloids of a variety of genus Papaver plants cultivated in a field and phytotron were analyzed by this method. 相似文献
137.
Separation of the enantiomers and diastereomers of ephedrines was investigated for impurity profiling of methamphetamine. We describe a method for the analysis of (1S,2R)-(+)-ephedrine, (1R,2S)-(-)-ephedrine, (1S,2S)-(+)-pseudoephedrine and racemic methylephedrine in bulk methamphetamine by HPLC using two different columns: a phenyl-beta-cyclodextrin-type column and an ODS-type column. The analytes were detected by UV absorbance measurement at 210 nm. As little as 0.05% of each ephedrine in bulk methamphetamine could be determined. In the impurity profiling of methamphetamine, the identification of ephedrines may provide valuable information about the precursor. This method was confirmed to be sufficiently sensitive to identify trace amounts of (1R,2S)-(-)-ephedrine and (1S,2S)-(+)-pseudoephedrine in bulk methamphetamine synthesized by the Emde method. 相似文献
138.
Takuji Ishikawa Tesuhiro Kodani Tsukasa Moriya Minoru Toriumi Hirokazu Aoyama Takamitsu Furukawa Kiyoshi Fujii 《Journal of fluorine chemistry》2004,125(11):1791-1799
We have synthesized various main-chain fluorinated polymers and studied base-resin properties, such as transparency at 157 nm, solubility in a standard alkaline developer, and lithographic performance. Main-chain-fluorinated polymers were synthesized by copolymerization of tetrafluoroethylene (TFE) with cyclic monomers, especially newly synthesized norbornene derivatives. We studied the correlation between pKa(OH) and the solubility of the copolymers of TFE and functional (fluoroalkyl alcohol group) norbornenes. Their solubility depends on the pKa value of the fluoroalkyl alcohol groups.We studied the impact of the polymerization initiators on base-resin properties. High transparency was obtained by using the fluorocarbon initiator. It was also confirmed that the monocyclic component improves dry-etch resistance and that fluorination at the terminal groups improves alkaline solubility.In addition, we found that the development characteristics of TFE/norbornene copolymers were significantly improved by the stereoselective (endo versus exo) partial protection of the hydroxyl groups in the fluoroalkyl alcohol moiety attached to norbornene unit. The polymer protected only in the exo position of the norbornene unit in the copolymer had a higher Rmax and a higher contrast. Positive-working resists based on these fluoropolymers were developed and 55 nm dense lines could be delineated by exposure at 157 nm wavelength with an alternating phase shift mask on a 0.9 NA 157 nm exposure tool. 相似文献
139.
A gold electrode modified with copper complexes containing a tridentate aromatic amine compound (bis(6-methyl-2-pyridylmethyl)amine ethyl sulfide, which is a model for the nitrite reduction centre of copper-containing nitrite reductase, catalyzed electrochemically the reduction of nitrite to nitrogen monoxide under acidic conditions. 相似文献
140.
A novel bisnorkaurenic acid-type diterpenelactone, named mikanialactone (1), was isolated along with five known kaurenic acid-type diterpenes (2-6) from the aerial parts of Mikania hirsutissima DC (Compositae). The structure of the new bisnorditerpene was determined by spectroscopic means. 相似文献