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91.
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
92.
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
93.
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
94.
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
95.
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
96.
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
97.
Bazzicalupi C Bencini A Berni E Bianchi A Fornasari P Giorgi C Valtancoli B 《Inorganic chemistry》2004,43(20):6255-6265
Zn(II) binding by the dipyridine-containing macrocycles L1-L3 has been analyzed by means of potentiometric measurements in aqueous solutions. These ligands contain one (L1, L2) or two (L3) 2,2'-dipyridine units as an integral part of a polyamine macrocyclic framework having different dimensions and numbers of nitrogen donors. Depending on the number of donors, L1-L3 can form stable mono- and/or dinuclear Zn(II) complexes in a wide pH range. Facile deprotonation of Zn(II)-coordinated water molecules gives mono- and dihydroxo-complexes from neutral to alkaline pH values. The ability of these complexes as nucleophilic agents in hydrolytic processes has been tested by using bis(p-nitrophenyl) phosphate (BNPP) as a substrate. In the dinuclear complexes the two metals play a cooperative role in BNPP cleavage. In the case of the L2 dinuclear complex [Zn(2)L2(OH)(2)](2+), the two metals act cooperatively through a hydrolytic process involving a bridging interaction of the substrate with the two Zn(II) ions and a simultaneous nucleophilic attack of a Zn-OH function at phosphorus; in the case of the dizinc complex with the largest macrocycle L3, only the monohydroxo complex [Zn(2)L3(OH)](3+) promotes BNPP hydrolysis. BNPP interacts with a single metal, while the hydroxide anion may operate a nucleophilic attack. Both complexes display high rate enhancements in BNPP cleavage with respect to previously reported dizinc complexes, due to hydrophobic and pi-stacking interactions between the nitrophenyl groups of BNPP and the dipyridine units of the complexes. 相似文献
98.
Search on ruggedness of fast gas chromatography-mass spectrometry in pesticide residues analysis 总被引:1,自引:0,他引:1
Kirchner M Matisová E Otrekal R Hercegová A de Zeeuwb J 《Journal of chromatography. A》2005,1084(1-2):63-70
In this study, suitability of fast gas chromatography-mass spectrometry (GC-MS) on a narrow-bore column with a programmed temperature vaporizer for the analysis of pesticide residues in non-fatty food was evaluated. The main objectives were ruggedness and stability of chromatographic system with regards to co-extractives injected. The chromatographic matrix induced response enhancement was found to be strongly dependent on the concentration of residues and is reaching up to 700% compared to the pesticides solutions in a neat solvent. However, the responses of pesticides in matrix-matched standards at different concentration levels do not significantly change during 130 injections. Response enhancement/or decrease is influenced by the sample preparation technique. External calibration with matrix-matched calibration standards should, therefore, provide results with good precision also at the concentration level of 0.005 mg kg(-1). Special attention is given to the performance of the chromatographic column and retention gap with regards to peak widths, peak tailing and different sample preparation methods. During approximately 460 matrix sample injections, the performance of the analytical column was acceptable. GC-MS set-up with 0.15 mm i.d. column can be successfully utilized for the pesticide residues analysis. 相似文献
99.
Mario Bossa Elena Cervone Carmine Garzillo Andrea Peluso 《Journal of Molecular Structure》1997,390(1-3):101-107
The electronic absorption spectra of Ni, Zn and Mg hemiporphyrazine derivatives are presented and discussed together with theoretical results obtained by INDO/S computations. The absorption spectra of all the metal derivatives show marked red shifts of the lowest energy absorption bands with respect to those of the metal free hemiporphyrazine. The possible explanation that in metal derivatives low lying excited states with a fully conjugated π electron system are present is supported by theoretical computations. 相似文献
100.
Cocchi M Faeti V Manfredini M Manzini D Marchetti A Sighinolfi S 《Journal of AOAC International》2005,88(2):393-398
The presence of some essential and toxic metals in fat supplements for swine diet was investigated. Collected samples represented a relevant production of the Italian industry. In particular, some samples were enriched with antioxidants or waste cooking oils. The method for the determination of Ca, Cu, Cd, Fe, Mg, Mn, Ni, Pb, and Zn in fat samples was developed by means of a certified reference material (CRM 186) and a representative fatty sample (RFS). All samples were digested in closed vessels in a microwave oven and then analyzed by flame atomic absorption or graphite furnace atomic absorption spectrometry. The entire analytical method provided a satisfactory repeatability and reproducibility confirmed by agreement between the experimental recovery data obtained for the CRM 186 sample and, with the method of standard additions, for the RFS material. The samples generally showed a small amount of metals compared with the recommended daily intake for the essential elements. On the other hand, some samples contained a significant concentration, from an analytical point of view, of Cd, Ni, and Pb. Principal component analysis (PCA) was applied to inspect the experimental data obtained from samples analysis. Basically no differences were detected in terms of metal concentration among the fat supplements analyzed. 相似文献