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181.
Pter Molnr Jzsef Deli Zoltn Matus Gyula Tth Andrea Steck Hanspeter Pfander 《Helvetica chimica acta》1997,80(1):221-229
β-Cryptoxanthin ( 1 ) was acetylated and then epoxidized with monoperoxyphthalic acid. After hydrolysis, repeated chromatography, and crystallization, (3S,5R,6S)-5,6-epoxy-β-cryptoxanthin ( 3 ), (3S,5S,6R)-5,6-epoxy-β-cryptoxanthin ( 4 ), (3R,5′R,6′R)-5′,6′-epoxy-β-cryptoxanthin ( 5 ), (3S,5R,6S,5′R,6′S)-5,6:5′,6′-diepoxy-β-cryp-toxanthin ( 6 ), and (3S,5S,6R,5′S,6′R)-5,6:5′,6′-diepoxy-β-cryptoxanthin ( 7 ) were isolated as main products and characterized by their UV/VIS, CD, 1H- and 13C-NMR, and mass spectra. The comparison of the carotenoid isolated from yellow, tomato-shaped paprika (Capsicum annuum var. lycopersiciforme flavum) with 3–5 strongly supports the structure of 3 for the natural product. 相似文献
182.
Methyl triazone (4,4',4'-[1,3,5-triazine-2,4,6-triyltriimino]tris-trimethyl benzoate) has been included in mesoporous MCM-41 (Mobil's composition of matter-41) silica, and its fluorescence emission has been compared in solution and in the solid state. Although inclusion does not affect significantly the absorption properties, a fluorescence emission shift and a behavior similar to the solid state has been observed by increasing the loading. It is believed that this observation reflects molecular aggregation inside the MCM-41 channels. The potential of formulations of this type for sunscreen applications is discussed. 相似文献
183.
Alexander Standler Andrea Schatzl Christian W. Klampfl Wolfgang Buchberger 《Mikrochimica acta》2004,148(3-4):151-156
A method for the determination of the new insect repellent Bayrepel in bathing lakes and public pools is presented. Sample preconcentration is performed either by solid-phase extraction (SPE) or stir bar sorptive extraction (SBSE). Analysis of the enriched analyte using gas chromatography-mass spectrometry (GC-MS) led to almost identical limits of detection (LOD) of 25ngL–1 for Bayrepel with both extraction methods. Because of the slightly reduced handling effort involved, the method based on preconcentration by SBSE was finally chosen for the analysis of real samples. 相似文献
184.
Gaul C Njardarson JT Shan D Dorn DC Wu KD Tong WP Huang XY Moore MA Danishefsky SJ 《Journal of the American Chemical Society》2004,126(36):11326-11337
The first asymmetric total synthesis of (+)-migrastatin (1), a macrolide natural product with anti-metastatic properties, has been accomplished. Our concise and flexible approach utilized a Lewis acid-catalyzed diene aldehyde condensation (LACDAC) to install the three contiguous stereocenters and the trisubstituted (Z)-alkene of migrastatin (2 + 3 --> 21). Construction of the two remaining stereocenters and incorporation of the glutarimide-containing side chain was achieved by an anti-selective aldol addition of propionyl oxazolidinone 28 to angelic aldehyde 27, followed by a Horner-Wadsworth-Emmons (HWE) coupling of 32 with glutarimide aldehyde 5. Finally, the assembly of the macrocycle was realized by a highly (E)-selective ring-closing metathesis (35 --> 37). Utilizing the power of diverted total synthesis (DTS), a series of otherwise inaccessible analogues was prepared and evaluated for their potential as tumor cell migration inhibitors in several in vitro assays. These studies revealed a dramatic increase in activity when the natural motif was considerably simplified, presenting macrolactones 45 and 48, as well as macrolactam 55, macroketone 60, and CF(3)-alcohol 71 as promising anti-metastatic agents. 相似文献
185.
The isoquinuclidines 7 and 8 were synthesised and tested as inhibitors of hexosaminidases from jack beans and from bovine kidney. These isoquinuclidines mimick the 1,4B‐conformer of a N‐acetyl‐glucosamine‐derived β‐d‐ glucopyranoside; they are competitive inhibitors with Ki values from 0.014 to 0.30 μM . The strong inhibition of these enzymes agrees with the hypothesis that the enzymatic hydrolysis of 2‐acetamido‐2‐deoxy‐β‐d‐ glucopyranosides proceeds via a boat‐like conformer with a pseudo‐axial scissile glycosidic bond and a pseudo‐axial acetamido substituent optimally oriented to effect an intramolecular substitution of the aglycon. 相似文献
186.
G. S. M. Moore 《Journal of Thermal Analysis and Calorimetry》1993,40(1):115-120
The bacground to the supposed development of the ‘Beilby layer’ on fine-grinding quartz is briefly reviewed. It is shown, using single crucible thermal analysis and sub-milligram DTA, that grinding quartz can cause a dispersion of the α-β inversion over a temperature range of several degrees; this is a crystallographic effect rather than an impurity effect. The sub-milligram DTA apparatus used is described and some thermal effects, such as impurity zoning, are illustrated. 相似文献
187.
Matthias Bhm Edwige Lorthiois Muthuppalaniappan Meyyappan Andrea Vasella 《Helvetica chimica acta》2003,86(11):3787-3817
Racemic and enantiomerically pure manno‐configured isoquinuclidines were synthesized and tested as glycosidase inhibitors. The racemic key isoquinuclidine intermediate was prepared in high yield by a cycloaddition (tandem Michael addition/aldolisation) of the 3‐hydroxy‐1‐tosyl‐pyridone 10 to methyl acrylate, and transformed to the racemic N‐benzyl manno‐isoquinuclidine 2 and the N‐unsubstituted manno‐isoquinuclidine 3 (twelve steps; ca. 11% from 10 ). Catalysis by quinine of the analogous cycloaddition of 10 to (?)‐8‐phenylmenthyl acrylate provided a single diastereoisomer in high yield, which was transformed to the desired enantiomerically pure D ‐manno‐isoquinuclidines (+)‐ 2 and (+)‐ 3 (twelve steps; 23% from 10 ). The enantiomers (?)‐ 2 and (?)‐ 3 were prepared by using a quinidine‐promoted cycloaddition of 10 to the enantiomeric (+)‐8‐phenylmenthyl acrylate. The N‐benzyl D ‐manno‐isoquinuclidine (+)‐ 2 is a selective and slow inhibitor of snail β‐mannosidase. Its inhibition strength and type depends on the pH (at pH 4.5: Ki=1.0 μM , mixed type, α=1.9; at pH 5.5: Ki=0.63 μM , mixed type, α=17). The N‐unsubstituted D ‐manno‐isoquinuclidine (+)‐ 3 is a poor inhibitor. Its inhibition strength and type also depend on the pH (at pH 4.5: Ki=1.2?103 μM , mixed type, α=1.1; at pH 5.5: Ki=0.25?103 μM , mixed type, α=11). The enantiomeric N‐benzyl L ‐manno‐isoquinuclidine (?)‐ 2 is a good inhibitor of snail β‐mannosidase, albeit noncompetitive (at pH 4.5: Ki=69 μM ). The N‐unsubstituted isoquinuclidine (?)‐ 2 is a poor inhibitor (at pH 4.5: IC50=7.3?103 μM ). A comparison of the inhibition by the pure manno‐isoquinuclidines (+)‐ 2 and (+)‐ 3 , (+)‐ 2 /(?)‐ 2 1 : 1, and (+)‐ 3 /(?)‐ 3 1 : 1 with the published data for racemic 2 and 3 led to a rectification of the published data. The inhibition of snail β‐mannosidase by the isoquinuclidines 2 and 3 suggests that the hydrolysis of β‐D ‐mannopyranosides by snail β‐mannosidase proceeds via a distorted conformer, in agreement with the principle of stereoelectronic control. 相似文献
188.
Julian M. Menter George D. Williamson Kimberly Carlyle Cyril L. Moore Isaac Willis 《Photochemistry and photobiology》1995,62(3):402-408
Although previous studies have demonstrated that the predominant photochemistry of type I collagen under 254 nm irradiation may be attributed either to direct absorption by tyrosine/phenylalanine or to peptide bonds, direct collagen photochemistry via solar UV wavelengths is much more likely to involve several age- and tissue-related photolabile collagen fluorophores that absorb in the latter region. In this study, we compare and contrast results obtained from irradiation of a commercial preparation of acid-soluble calf skin type I collagen in solution with UVC (primarily 254 nm), UVA (335–400nm) and broad-band solar-simulating radiation (SSR; 290^1–00nm). Excitation spectroscopy and analysis of photochemically induced disappearance of fluorescence (fluorescence fading) indicates that this preparation has at least four photolabile fluorescent chromophores. In addition to tyrosine and L-3,4-dihydroxyphenylalanine, our sample contains two other fluorophores. Chromophore I, with emission maximum at 360 nm, appears to be derived from interacting aromatic moieties in close mutual proximity. Chromophore II, with broad emission at430–435 nm, may be composed of one or more age-related molecules. Collagen fluorescence fading kinetics are sensitive to excitation wavelength and to conformation. Under UVC, chromophore I fluorescence disappears with second-order kinetics, indicating a reaction between two proximal like molecules. Adherence to second-order kinetics is abrogated by prior denaturation of the collagen sample. A new broad, weak fluorescence band at400–420 nm, attributable to dityrosine, forms under UVC, but not under solar radiation. This band is photolabile to UVA and UVB wavelengths. Amino acid analysis indicates significant destruction of aromatic amino acids under UVC, but not under UVA or SSR. When properly understood, collagen fluorescence fading phenomena may act as a sensitive molecular probe of structure, conformation and reactivity. 相似文献
189.
The cyclopentadienes 3a/b/c, 8b/c, 12a/b/d , and 16a/b/d were prepared as mixtures of regioisomers from the D -mannitol-derivatives 1,6,10 , and 14 and transformed into the ferrocenes 17, 18 , and 19 (73%; 38:17:45), 23, 24 , and 25 (70%; 6:42 :52), 26 (31%), and 27 (27%), respectively. Deprotection of 17–19 with HCl/MeOH gave the H2O-soluble ferrocenes 20–22 ; chloromercuration and iodination of 17 via 29 led to the C2-symmetric diiodo-ferrocene 30 . The mono(chloromercurio) derivative 28 , obtained as a by-product, was also transformed into 29 . The structure of the ferrocenes 18 and 19 , and of the bis(chloromercurio)ferrocene 29 has been established by X-ray analysis. The starting cyclopentadienes 3 were obtained in 50% yield from 1 by dialkylation of CpNa, followed by thermolysis of the spiro-annulated 2 . Similarly, dimesylate 6 (from 4 ) gave the spiro-annulated diene 7 and the annulated dienes 8 in about equal amounts; thermolysis transformed 7 into 8 (62%). The dienes 12 were prepared in 15% yield from the ditriflate 10 via 11 , the dimesylate 9 proving insufficiently reactive, and the dienes 16 (49%) from 14 via 15 . 相似文献
190.
Pb2(OH)2[p‐O2C‐C6H4‐CO2]: Synthesis and Crystal Structure Single crystals of Pb2(OH)2[p‐O2C‐C6H4‐CO2] ( 1 ) were obtained by hydrothermal reaction of terephthalic acid and PbCO3 at 180 °C (10 days). 1 crystallizes in the monoclinic space group P21/c with Z = 2 (a = 1115.6(2) pm, b = 380.10(4) pm, c = 1141.3(2) pm, β = 93.39(1)°, V = 0.4831(1) nm3). The crystal structure is characterized by ladder‐type Pb(OH)3/3 double chains, which are connected to a three‐dimensional framework by terephthalate dianions. 相似文献