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11.
Hong JW Benmansour H Bazan GC 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(14):3186-3192
Conjugated polymers and oligomers can serve as highly responsive fluorescent reporters for biosensor applications. However, their optical properties in aqueous media are highly dependent upon environmental conditions. The structure of the paracyclophane framework provides a platform for designing optical reporters that show little sensitivity to surfactants, and thus is well-suited for fluorescent assays. The permanent intramolecular delocalization through the paracyclophane core dominates intermolecular perturbations in spontaneously formed aggregates. 相似文献
12.
Water soluble paracyclophane chromophore dimers provide optical reporters that show little sensitivity to surfactants and thus are ideal for biosensor design. Strong intramolecular delocalization circumvents complications from intermolecular delocalization in spontaneously formed aggregates. The synthesis of 2 involves a novel TBAT deprotection/butane sultone ring-opening sequence, which should be general for the preparation of water-soluble conjugated oligomers and polymers. 相似文献
13.
Fauhl C Wittkowski R Lofthouse J Hird S Brereton P Versini G Lees M Guillou C 《Journal of AOAC International》2004,87(5):1179-1188
The aim of the present study was to provide the official wine control authorities with an internationally validated method for the determination of 3-methoxy-1,2-propanediol (3-MPD) and cyclic diglycerols (CycDs)-both of which are recognized as impurities of technical glycerol-in different types of wine. Because glycerol gives a sweet flavor to wine and contributes to its full-body taste, an economic incentive is to add glycerol to a wine to mask its poor quality. Furthermore, it is known that glycerol, depending on whether it is produced from triglycerides or petrochemicals, may contain considerable amounts of 3-MPD in the first case or CycDs in the second. However, because these compounds are not natural wine components, it is possible to detect glycerol added to wine illegally by determining the above-mentioned by-products. To this end, one of the published methods was adopted, modified, and tested in a collaborative study. The method is based on gas chromatographic/mass spectrometric analysis of diethyl ether extracts after salting out with potassium carbonate. The interlaboratory study for the determination of 3-MPD and CycDs in wine was performed in 11 laboratories in 4 countries. Wine samples were prepared and sent to participants as 5 blind duplicate test materials and 1 single test material. The concentrations covered ranges of 0.1-0.8 mg/L for 3-MPD and 0.5-1.5 mg/L for CycDs. The precision of the method was within the range predicted by the Horwitz equation. HORRAT values obtained for 3-MPD ranged from 0.8 to 1.7, and those obtained for CycDs ranged from 0.9 to 1.3. Average recoveries were 104 and 109%, respectively. 相似文献
14.
Janice M. Klunder 《Journal of heterocyclic chemistry》1995,32(6):1687-1691
Functionalization at the 3-position of the dipyridodiazepinone nevirapine ( 1 ) has been accomplished by Sommelet-Hauser rearrangement of an ylide derived from 1 . Treatment of N-cyanomethylpyrrolidinium salt 4 with potassium tert-butoxide in a mixture of dimethylsulfoxide and tetrahydrofuran at ?10°, followed by acid hydrolysis, afforded a mixture of compounds 5 and 6 in a ratio of 1:1.8. Upon treatment of 4 with sodium amide in liquid ammonia, 5 and 6 were obtained in a ratio of 1.5:1 and a combined yield of 83%. Compound 5 is the desired product resulting from Sommelet-Hauser rearrangement of 4 , whereas 6 derives from competing Stevens rearrangement and intramolecular cyclization of the aldehyde produced upon hydrolysis. Baeyer-Villiger oxidation of 5 afforded the 3-hydroxy derivative 2 , a recently identified metabolite of nevirapine. 相似文献
15.
Joseph C. P. Koo Janice S. W. Lam Gregory A. Chass Ladislaus L. Torday Andras Varro Julius Gy. Papp 《Journal of Molecular Structure》2003,620(2-3):231-255
The sidechain conformational potential energy hypersurfaces (PEHS) for the γL, βL, αL, and αD backbone conformations of N-acetyl-
-aspartate-N′-methylamide were generated. Of the 81 possible conformers initially expected for the aspartate residue, only seven were found after geometric optimizations at the B3LYP/6-31G(d) level of theory. No stable conformers could be located in the δL, L, γD, δD, and D backbone conformations. The ‘adiabatic’ deprotonation energies for the endo and exo forms of N-acetyl-
-aspartic acid-N′-methylamide were calculated by comparing their optimized relative energies against those found for the seven stable conformers of N-acetyl-
-aspartate-N′-methylamide. Sidechain conformational PEHSs were also generated for the estimation of ‘vertical’ deprotonation energies for both endo and exo forms of N-acetyl-
-aspartic acid-N′-methylamide. All backbone–sidechain (N–H−O–C) and backbone–backbone (N–HO=C) hydrogen bond interactions were analyzed. A total of two backbone–backbone and four backbone–sidechain interactions were found for N-acetyl-
-aspartate-N′-methylamide. The deprotonated sidechain of N-acetyl-
-aspartate-N′-methylamide may allow the aspartyl residue to form strong hydrogen bond interactions (since it is negatively charged) which may be significant in such processes as protein–ligand recognition and ligand binding. As a primary example, the molecular geometry of the aspartyl residue may be important in peptide folding, such as that in the RGD tripeptide. 相似文献
16.
Prater MR Gogal RM De Fabo EC Longstreth J Holladay SD 《Photochemistry and photobiology》2003,77(4):383-389
Exposure to ultraviolet radiation results in increased levels of intradermal cis-urocanic acid (cUCA) and alters cutaneous immunity by interfering with processing and presentation of antigen by Langerhans cells. Reports on effects of systemic immunotoxicity with 30 day cUCA exposure in laboratory rodents include thymic atrophy, thymic hypocellularity and decreased T-cell-mediated immunity; however, immune effects of single exposure or 5 day cUCA administration, which may better mimic human exposures, are poorly defined. The present study initially evaluated immune effects of single, 5 day, and 4 week cUCA exposure in C57BL/6N mice. Single administration of intradermal cUCA resulted in decreased splenocyte phagocytosis that persisted for 30 days after cUCA exposure. Five day consecutive cUCA exposure decreased numbers of phenotypically mature CD4(+)CD8(-) and CD4(-)CD8(+) (single positive) thymocytes, increased CD4(+)CD8(+) (double positive) immature thymocytes and increased splenocyte proliferation. Prolonged cUCA exposure (4 weeks) caused profound thymic hypocellularity and splenic hypercellularity and increased splenic macrophage chemiluminescence. Because of this apparent sensitivity of C57BL/6N mice to cUCA, thymic hypocellularity was compared between C57BL/6N and C3H/HeN mice dosed with cUCA, and was found to be more pronounced in the C57BL/6N strain. These results are an extension of previous conclusions on immune modulation caused by cUCA in the spleen and thymus. Further, the observed variation in sensitivity between the mouse strains is consistent with known genetic susceptibility of these strains to the immunomodulatory effects of exposure to sunlight. 相似文献
17.
Yao M Mantha S Shah VR Vachharajani NN Arnold ME Pursley JM Srinivas NR 《Biomedical chromatography : BMC》2002,16(3):175-182
A high performance liquid chromatographic-mass spectrometric (LC/MS) assay was developed and validated for the determination of BMS-204352 in dog K(3)EDTA plasma. A 0.5 mL aliquot of control plasma was spiked with BMS-204352 and internal standard (IS) and buffered with 1 mL of 5 mM ammonium acetate. The mixture was then extracted with 3 mL of toluene. After separation and evaporation of the organic phase to dryness using nitrogen at 40 degrees C, the residue was reconstituted in the mobile phase and 25 microL of the sample were injected onto a Hypersil C(18) column (2 x 50 mm; 3 microm) at a flow rate of 0.5 mL/min. The mobile phase was consisted of two solvent mixtures (A and B). Solvent A was composed of 5 mM ammonium acetate and 0.1% triethylamine in 75:25 v/v water:methanol, pH adjusted to 5.5 with glacial acetic acid, and solvent B was 5 mM ammonium acetate in methanol. A linear gradient system was used to elute the analytes. The mass spectrometer was programmed to admit the de-protonated molecules at m/z 352.7 (IS) and m/z 357.9 (BMS-204352). Standard curves of BMS-204352 were linear (r(2) > or = 0.998) over the concentration range of 0.5-1000 ng/mL. The mean predicted quality control (QC) concentrations deviated less than 5.1% from the corresponding nominal values (ie 4, 80, 400 and 2000 ng/mL); the within- and between-assay precision of the assay were within 5.5% relative standard deviation. Stability of BMS-204352 was confirmed after at least three freeze/thaw cycles and BMS-204532 was stable in dog plasma when stored frozen at or below -20 degrees C for at least 16 weeks in spiked QC samples and for at least 4 1/2 weeks for in vivo study samples. BMS-204352 and IS were stable in the injection solvent at room temperature for at least 24 h. The assay was applied to delineate the pharmacokinetic disposition of BMS-204352 in dogs following a single intravenous dose administration. In conclusion, the assay is accurate, precise, specific, sensitive and reproducible for the pharmacokinetic analysis of BMS-204532 in dog plasma. 相似文献
18.
19.
Donald E. Kiely Kathy Semk-gray James M. Riordan 《Journal of carbohydrate chemistry》2013,32(2):191-211
Abstract N,N'-Diacetyl-tri-O-acetylxylaramide (8) and N,N'-diacetyl-tri-O-acetylribaramide (20) were directly converted to the nitrogen heterocycle 6-acetamido-2,6-diacetyloxy-aza-1,4-cyclohexadlen-3-one (9) with sodium acetate in acetic anhydride. Treatment of tri-O-acetylxylaramide (7) or tri-O-acetylribaramide (19) with the same solvent-base combination gave the highly crystalline 2,3,5,6-tetraacetyloxypyridlne (30) as the principal product. Mechanistic considerations for the formation of these nitrogen heterocycles are presented. 相似文献
20.
Philip E. Morris Jr Donald E. Kiely Gerald S. Vigee Pavol Kòváč 《Journal of carbohydrate chemistry》2013,32(5):661-673
ABSTRACT The use of a phase transfer catalyst, benzyltriethylammonium chloride (BTEAC), is described in conjunction with the ruthenium dioxide/periodate : water/chloroform system for the oxidation of carbohydrate alcohols to the corresponding ketone, aldehyde, or carboxylic acid. The method was found to be applicable to carbohydrates appropriately protected as acetals, ethers, or containing a benzoyloxy group not positioned to readily undergo β-elimination. While the method was very suitable for the oxidation of carbohydrate secondary alcohols to ketones, it was found to be less suitable for the oxidation of a carbohydrate primary alcohol to the corresponding aldehyde or carboxylic acid. Evidence presented suggests that under the mildly basic conditions of the reaction, ruthenium tetraoxide is converted to ruthenate and perruthenate ions in the aqueous solution and then the perruthenate ion is carried by the phase transfer catalyst into the organic layer where oxidation of the substrate occurs. A number of examples illustrating the scope of the method are presented. 相似文献