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901.
Ann M. Huff Howard L. Hall Melanie J. Smith Sheila A. O'Grady Frank C. Waters Richard W. Fengl Jeffery A. Welsh Charles F. Beam 《Journal of heterocyclic chemistry》1985,22(2):501-504
C(α),O-Dilithiooximes, C(α), N-dilithiophenylhydrazones, or C(α), N-dilithioacylhydrazones were prepared in an excess of lithium diisopropylamide (LDA) and condensed with a variety of esters followed by acid-cyclization to give substituted isoxazoles and pyrazoles. 相似文献
902.
In this report, we outline a highly enantio- and diastereoselective one-pot method for the efficient synthesis of synthetically useful acyclic epoxy alcohols and allylic epoxy alcohols. Our method takes advantage of a highly enantioselective C-C bond-forming reaction to set the initial chirality. The resulting allylic zinc alkoxide intermediate is then epoxidized in situ using either dioxygen or TBHP in the presence of a titanium tetraalkoxide. Epoxy alcohols with up to three contiguous stereocenters are formed in one pot with excellent enantio- and diastereoselectivity. In cases where the zinc alkoxide intermediates contain two different allylic olefins, the more electron-rich double bond is chemoselectively epoxidized to afford an allylic epoxy alcohol. This method represents a highly efficient, stereoselective, and chemoselective approach to the synthesis of a wide range of useful epoxy alcohol and allylic epoxy alcohol products that were previously difficult to access. 相似文献
903.
Dehouck P Jaggavarapu PK Desmedt A Van Schepdael A Hoogmartens J 《Electrophoresis》2004,25(18-19):3313-3321
We describe an intermediate precision study on a capillary electrophoretic (CE) method for chlortetracycline. It is shown how in one setup the influence of the factors time, analyst, and equipment on the precision can be investigated. As different types of CE equipments were included, the transferability of the method could be examined. Both the qualitative and quantitative aspect of the method were investigated. It was shown that small adaptations in method conditions can have a large influence on the method transferability. Although the method could be transferred to different types of CE equipments, the precision of the method was found poor when the between-equipment variability was taken into account. Despite the use of an internal standard, the between injection variability was found rather high. 相似文献
904.
Roberts JE Kukielczak BM Hu DN Miller DS Bilski P Sik RH Motten AG Chignell CF 《Photochemistry and photobiology》2002,75(2):184-190
The process of sight (photostasis) produces, as a by-product, a chromophore called 2-[2,6-dimethyl-8-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1E,3E, 5E,7E-octatetraenyl]-1-(2-hydroxyethyl)-4-[4-methyl-6-(2,6,6-trimethyl-1-cyclohexen-1-yl)-1E, 3E, 5E-hexatrienyl]-pyridinium (A2E), whose function in the eye has not been defined as yet. In youth and adulthood, A2E is removed from human retinal pigment epithelial (h-RPE) cells as it is made, and so it is present in very low concentrations, but with advanced age, it accumulates to concentrations reaching 20 microM. In the present study we have used photophysical techniques and in vitro cellular measurements to explore the role of A2E in h-RPE cells. We have found that A2E has both pro- and antioxidant properties. It generated singlet oxygen (phiso = 0.004) much less efficiently than its precursor trans-retinal (phiso = 0.24). It also quenched singlet oxygen at a rate (10(8) M(-1) s(-1)) equivalent to two other endogenous quenchers of reactive oxygen species in the eye: alpha-tocopherol (vitamin E) and ascorbic acid (vitamin C). The endogenous singlet oxygen quencher lutein, whose quenching rate is two orders of magnitude greater than that of A2E, completely prevented light damage in vitro, suggesting that singlet oxygen does indeed play a role in light-induced damage to aged human retinas. We have used multiphoton confocal microscopy and the comet assay to measure the toxic, phototoxic and protective capacity of A2E in h-RPE cells. At 1-5 microM, A2E protected these cells from UV-induced breaks in DNA; at 20 microM, A2E no longer exerted this protective effect. These results imply that the role of A2E is not simple and may change over the course of a lifetime. A2E itself may play a protective role in the young eye but a toxic role in older eyes. 相似文献
905.
A capillary zone electrophoresis method has been developed for the detection of 0.1% of (R)-levochlorpheniramine maleate in samples of (S)-dexchlorpheniramine maleate. Using 1.5 mM carboxymethyl-beta-cyclodextrin in an acidic background electrolyte, resolution values of more than 10 were obtained. Under these conditions the R-enantiomer is migrating in front of the bulk S-enantiomer. The assay was validated for linearity (2-10 microg/ml; R2 = 0.9992), selectivity [(RS)-pheniramine maleate and (RS)-brompheniramine maleate], limit of detection (0.25 microg/ml), limit of quantification (0.75 microg/ml), analytical precision (intra- and inter-day variability), repeatability of the method (RSD = 5.0%) and accuracy. In samples of dexchlorpheniramine maleate from two different manufacturers, concentrations of, respectively, 0.15% and 1.95% (m/m) of levochlorpheniramine maleate were detected. The method was compared to the HPLC method described in the European Pharmacopoeia III monograph. 相似文献
906.
Govaerts C Orwa J Van Schepdael A Roets E Hoogmartens J 《Journal of chromatography. A》2002,976(1-2):65-78
A selective reversed-phase liquid chromatography-tandem mass spectrometry method is described for the characterization of related substances in the colistin complex. Mass spectral data were acquired on an LCQ ion trap mass spectrometer equipped with an electrospray ionization probe operated in the positive ion mode. The main advantage of this technique is the characterization of novel related substances without time-consuming isolation and purification procedures. Using this method seven new related substances were partially identified in colistin bulk sample and tablets. Four components were assigned as isomers of the main components of colistin. 相似文献
907.
Equilibrium structures and both harmonic and anharmonic stretching force constants have been calculated ab initio for the four cyanides HCN, LiCN, FCN, and C1CN, and the four isocyanides HNC, LiNC, FNC, and ClNC, using several basis sets of about triple-zeta quality. The CN and NC bond lengths, as well as diagonal stretching force constants, are nearly the same throughout both series. Trends in the off-diagonal stretching force constants are discussed, and dipole moment values are correlated with the structural type, XCN and XNC, and the electronegativity of the ligand X. 相似文献
908.
Smoukov SK Kopp DA Valentine AM Davydov R Lippard SJ Hoffman BM 《Journal of the American Chemical Society》2002,124(11):2657-2663
The binding of ethanol and 1,1,1-trifluoroethanol (TFE) to both the H(mv) and H(ox) forms of soluble methane monooxygenase (sMMO) in solution has been studied by Q-band (35 GHz) CW and pulsed ENDOR spectroscopy of (1)H, (2)H and (19)F nuclei of exogenous ligands. As part of this investigation we introduce (19)F, in this case from bound TFE, as a new probe for the binding of small molecules to a metalloenzyme active site. The H(mv) form was prepared in solution by chemical reduction of H(ox). For study of H(ox) itself, frozen solutions were subjected to gamma-irradiation in the frozen solution state at 77 K, which affords an EPR-visible mixed-valent diiron center, denoted (H(ox))(mv), held in the geometry of the diiron(III) state. The (19)F and (2)H ENDOR spectra of bound TFE together with (1,2)H ENDOR spectra of bound ethanol indicate that the alcohols bind close to the Fe(II) ion of the mixed-valence cluster in H(mv) and in a bridging or semi-bridging fashion to H(ox). DMSO does not affect the binding of either of the ethanols or of methanol to H(ox), nor of ethanol or methanol to H(mv). It does, however, displace TFE from the diiron site in H(mv). These results provide the first evidence that crystal structures of sMMO hydroxylase into which product alcohols were introduced by diffusion represent the structures in solution. 相似文献
909.
Lee Ann Applegate Alexandre Noël Glenn Vile Edgar Frenk Rex M. Tyrrell 《Photochemistry and photobiology》1995,61(3):285-291
Abstract— Activation of expression of the heme oxygenase (HO) gene appears to be involved in a cellular defense system in mammalian cells. We now demonstrate that while HO-1 mRNA levels are strongly inducible in dermal fibroblasts they are barely inducible in human epidermal keratinocytes following oxidative stress (UVA radiation and hydrogen peroxide). Paralleling this result was the observation that HO-2 mRNA levels were low in dermal fibroblasts but were high in epidermal keratinocytes. In neither case was the HO-2 gene inducible. The expression of the two HO genes led to enzymatic activity in both types of skin cells with an approximately 2.5-fold higher level of enzymatic activity present in keratinocytes compared with fibroblasts derived from the same biopsy. In addition, ferritin levels, which have been found to be augmented via the HO-dependent release of iron from endogenous heme sources, were two- to three-fold higher in keratinocytes compared with matching fibroblasts. This higher ferritin pool would result in an enhancement of cellular iron sequestering capacity that may confer increased resistance to oxidative stress. Indeed, keratinocytes showed less UVA radiation-dependent cell membrane damage than fibroblasts. These results are consistent with the hypothesis that HO expression in human epidermis and dermis is related to cellular defense mechanisms that operate in human skin. 相似文献
910.
Musk ambrette (4-tert-butyl-3-methoxy-2,5-dinitrotoluene), a common component of perfumes, soaps, and some food flavorings, can cause cutaneous photosensitization reactions including photoallergy. These may be mediated through free radicals formed during photolysis. When musk ambrette was photolyzed under nitrogen in basic methanol, two distinct nitro anion radicals were identified by electron spin resonance. One radical was centered on a nitro group in the plane of the aromatic ring, while the other was centered on a nitro group twisted out of the plane of the ring due to steric hindrance by bulky substituents on either side of the group: the two radicals appeared to interconvert and maintain an equilibrium concentration ratio. Two closely related compounds which are also used in perfumes, but have not been reported to cause photosensitizing reactions, also produced free radicals during photolysis. Musk xylene (2,4,6-trinitro-1,3-dimethyl-5-tert-butylbenzene) generated two nitro anion radicals, both of which were centered on twisted nitro groups, while musk ketone (3,5-dinitro-2,6-dimethyl-4-tert-butylacetophenone) produced only one nitro anion radical, which is also twisted. Athough these nitro anion radicals are probably the first step in the photolysis of these nitroarornatic molecules, it seems likely that in vivo they will undergo further reduction to produce more reactive species including the corresponding nitroso and hydroxylamine derivatives. In addition, autoxidation of the nitro anion radical intermediate forms superoxide. 相似文献