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1.
The respective effects and interactions of supplementation with two conjugated linoleic acid (CLA) isomers and exercise on plasma metabolic profile, activity of lipogenic enzymes and cellularity in two adipose tissue sites, those of the liver and heart, were examined in adult Wistar rats. Rats that were either sedentary or exercise-trained by treadmill running were fed one of four diets: a diet without CLA; a diet with either 1% cis 9, trans 11 CLA or 1% trans 10, cis 12 CLA; or a mixture of both isomers (1% of each) for 6 weeks. We observed that the exercise decreased lipogenic enzyme activities in epididymal and perirenal adipose tissue. Plasma cholesterol, insulin, and leptin concentrations were lower in exercise-trained rats than in sedentary rats. The ingestion of either CLA mixture or the trans 10, cis 12 CLA increased lipogenic enzyme activities in epididymal tissue and more markedly in perirenal adipose tissue, especially in sedentary rats, and without affecting adipose tissue weight or cellularity. A similar effect of trans 10, cis 12 CLA was observed in regard to malic enzyme activity in the liver. In addition, this isomer decreased plasma lipid and urea concentrations and increased plasma 3-hydroxybutyrate levels. The ingestion of cis 9, trans 11 CLA increased fatty acid synthase activity in perirenal adipose tissue in sedentary rats and decreased plasma cholesterol and leptin concentrations. These results show that isomers of CLA decrease plasma lipids and stimulate adipose tissue lipogenesis without changing adipose weight in adult sedentary or exercise-trained rat, thus suggesting a stimulation of adipose tissue turnover. 相似文献
2.
A sensitive method was developed to determine permethrin extracted from phosphate buffer and cattle plasma by potassium cyanide catalyzed transesterification of this insecticide with refluxing ethanol and detection of the resulting ethyl esters by capillary gas chromatography with an electron capture detector. With a reflux time of 2 h and with 3-phenoxybenzyl 2-chlorobenzoate as an internal standard, linear calibration curves from buffer (5–250 ng) and plasma (5–100 ng) were obtained. Precision and accuracy of the method were 15%. The limit of detection was approximately 2.5 ng/ml ( cis) and 1 ng/ml ( trans) from buffer. In cattle sprayed along the back at 2 mg/kg, the concentration of cis- and trans-permethrin in plasma was below the detection limit (5 ng/ml). 相似文献
3.
In the search for a breast cancer prevention strategy which would avoid undesirable effects of orally administered tamoxifen, the percutaneous administration of the highly active metabolite 4OHTamoxifen (4OHTam) has been proposed. Percutaneous 4OHTam penetrates the skin to reach breast tissues. It, thus, avoids the hepatic first pass effect, and offers an optimal local/systemic effect. However, trans-4OHTamoxifen can spontaneously isomerize into the cis-isomer, which may have estrogen agonist action. The aim of this study was to examine the effect of cis-4OHTam on normal human breast epithelial (HBE) cells in culture. Spontaneous isomerization of trans- into cis-4OHTam occurred within 24–48 h, but stabilized rapidly at a trans/cis ratio of 70/30, whether in stock solution, culture medium or cultured cells. The cis-4OHTam did not stimulate HBE cell growth according to histometric cell counts and scanning electron microscopy analysis, but inhibited E2-induced cell growth, albeit two to three times less than trans-4OHTam. In conclusion, spontaneous isomerization of trans- to cis-4-OHTam is limited and 4OHTam retains a marked antiestrogenic effect. It may prove to be a useful alternative to tamoxifen in breast cancer prevention, especially if administered percutaneously. 相似文献
4.
The reaction of the monoalkyl complex trans-[Pt(DMSO) 2Cl(CH 3)] with a large variety of heterocyclic nitrogen bases L, in chloroform solution, leads to the formation of uncharged complexes of the type [Pt(DMSO)(L)Cl(CH 3)], containing four different groups coordinated to the metal center. Only two out of the three different possible isomers were detected in solution. These two trans(C,N) and cis(C,N) species can be unambiguously identified through 1H NMR spectroscopy. For the trans(C,N) isomers, average values of 2JPtH=75±4 Hz and 3JPtH=36±4 Hz have been observed for the coordinated methyl and DMSO ligands, respectively. In the case of the cis(C,N) isomers, these values increase to 2JPtH=83±2 Hz, and decrease to 3JPtH=26±3 Hz due to the mutual exchange of ligands in trans position to CH 3 and DMSO. In the case of bulky asymmetric ligands, such as quinoline, 2-quinolinecarboxaldehyde, 2-methylquinoline, 5-aminoquinoline, 2-phenylpyridine and 2-chloropyridine, slow rotation of the hindered group around the Pt---N bond makes the coordinated DMSO ligand prochiral. NMR experiments have shown that the first reaction product is the trans(C,N) isomer as a consequence of the very fast removal of one DMSO ligand by the nitrogen bases from the starting complex trans-[Pt(DMSO) 2Cl(CH 3)]. This trans kinetic product undergoes a geometrical conversion into the more stable cis(C,N) isomer through the intermediacy of fast exchanging aqua-species. The rate of isomerization and the relative stability of the two isomers depends essentially on the rate of aquation and on the steric congestion imposed by the new L ligand on the metal. 相似文献
5.
A method was developed for the assay of amitriptyline, amitriptyline-N-oxide, nortriptyline, desmethylnortriptyline and E ( trans) and Z ( cis) isomers of 10-hydroxyamitriptyline and of 10-hydroxynortriptyline in plasma and brain of animals, using high-performance liquid chromatography with ultraviolet detection (254 nm). Single extraction was performed at pH 10.5 from 0.25 ml of plasma or 1 ml of brain mixture. Chromatographic separations were achieved with a silica column and an aqueous methanol mobile phase containing ammonia. This procedure offers high sensitivity (8–10 ng/ml), high linearity ( r > 0.99) and acceptable precision (coefficient of variation ≤ 13.3%). The method was used to determine levels of amitriptyline and its major metabolites in mice 30 min after a single intraperitoneal administration of amitriptyline (20 mg/kg). 相似文献
6.
[10D- 3H; 3- 14C]- and [10L- 3H; 3- 14C]arachidonic acids were incubated with human polymorphonuclear leukocytes and with human platelets. Leukotriene B 4 and 5( S),12( S)-dihydroxy-6 trans,8 cis,10 trans,14- cis-eicosatetraenoic acid (5,12-DHETE) were isolated and the 3H/ 14C ratios determined. It could be concluded that the 10D ( pro-R)-hydrogen is eliminated in the conversion of 5( S)-hydroperoxy-6 trans,8 cis,11 cis,14 cis-eicosatetraenoic acid into leukotriene A 4 whereas in the conversion of arachidonic acid into 5,12-DHETE the 10L ( pro-S)-hydrogen is lost. Incubation of the doubly labeled arachidonic acids with human platelets confirmed and extended previous data on the stereochemistry of the hydrogen removal from C-10 during the conversion into 12( S)-hydroperoxy-5 cis,8 cis,10 trans,14 cis-eicosatetraenoic acid, i.e., the 10L ( pro-S)-hydrogen is eliminated and the 10D ( pro-R)-hydrogen retained. 相似文献
7.
Addition of Yb(fod) 3 to methyl oleate ( cis) and methyl elaidate ( trans) shifts the carboxylic lines of their 13C-NMR spectra to different extents; that of the cis isomer less than that of the trans isomer, as is to be expected. On the same theoretical ground it can be anticipated that the opposite will occur for C-17: an effect that has been confirmed experimentally. The method is thus proposed as a means of aiding in the assignment of the cis and trans configuration in esters of fatty acids with one double bond. 相似文献
8.
The endonuclease III from Escherichia coli is a repair enzyme which exhibits both a glycosylase and an endonuclease functions. The activity of the enzyme can be assayed by measuring the released targeted bases in solution from a sample of modified DNA. In the present study, gas chromatography–mass spectrometry was used together with an HPLC prepurification step in order to single out the released bases. The prepurification was found to enhance the specificity and the sensitivity of the assay. Thus, the overall method allowed us to analyze separately 5-hydroxy-5,6-dihydrothymine from the cis and trans isomers of 6-hydroxy-5,6-dihydrothymine. Examples of application of the assay are provided with the measurement of the E. coli endonuclease III-mediated excision of 5-hydroxy-5,6-dihydrothymine and 5,6-dihydrothymine from samples of γ-irradiated DNA in the presence of cysteine. 相似文献
9.
A series of 1,3-dioxolane-based ligands, bearing hydroxymethyl or ester functionalities, was synthesized and tested as potential muscarinic antagonists. The compounds display moderate to low affinity for the three receptor subtypes M 1-M 3, with some of them showing a significant selectivity for the M 3 subtype. The configurational and conformational properties were studied using NOE experiments and vicinal coupling constants. The 1H and 13C NMR chemical shifts show stereochemically dependent trends. Quantitative analysis of conformer populations showed that the exocyclic CH 2N +(CH 3) 3 group is prevalently in a pseudo-axial orientation in the cis isomers and in a pseudo-equatorial orientation in the trans isomers. 相似文献
10.
The reactions of singlet oxygen ( 1O 2) with cis and trans butenes-1,1,1-d 3, at—80°C in Freon-11, show a product isotope effect ( kH/ kD) of 1.38 and 1.25 respectively. Isomerization of the starting materials or formation of dioxetanes were not observed during the course of the photooxygenation. Together with the isotope effects on the reactions of tetramethylethylene-d 6 isomers with singlet oxygen, these results require the reversible formation of a perepoxide or charge transfer intermediate. 相似文献
11.
( S)-(−)- and ( R)-(+)-limonene was transformed to carvone via corresponding cis- and trans-carveol using Solanum aviculare and Dioscorea deltoidea plant cells. Both carveols and carvone formed were racemic in all biotransformations. 相似文献
12.
From a mixture of cis- and trans-Ru(SH) 2(dppm) 2 (4), formed from reaction of H 2S with trans-Ru(H)Cl(dppm) 2 (2), a crystal of cis-4 has been isolated and its structure determined by X-ray analysis. The mercapto protons are located within the centrosymmetric structure, although the S-atoms are partially disordered (S–H1.06 Å). The thiolate complexes, trans-Ru(H)SR(dppm) 2 (R=Ph, 5a; C 6F 5, 5b), have been isolated from reaction of trans-2 with 1 equiv. of RSH. trans-Ru(H)SH(dppm) 2 (3) has been isolated from reaction of H 2S with a mixture of cis- and trans-Ru(H) 2(dppm) 2 (1). An improved synthetic route for 1 is presented. 相似文献
13.
The dinuclear Pt---Si complex {(Ph 3P)Pt{μ-η 2-H---SiH(IMP)]} 2 ( trans-1a– cis-1b=3:1; IMP=2-isopropyl-6-methylphenyl) reacted with basic phosphines such as 1,2-bis(diphenylphosphino)ethane (dppe) and dimethylphenylphosphine (PMe 2Ph) to afford different dinuclear Pt---Si complexes with loss of H 2, {(P) 2Pt[μ-SiH(IMP)]} 2 [P=dppe, trans-2a (major), cis-2b (trace); PMe 2Ph, 3 ( trans only)]. Complexes 2 and 3 were characterized by multinuclear NMR spectroscopy and X-ray crystallography (2a). In contrast, the reaction of 1a,b with the sterically demanding tricyclohexylphosphine (PCy 3) afforded {(Cy 3P)Pt{μ-η 2-H---SiH(IMP)]} 2 ( trans-4a– cis-4b 2:1) analogous to 1a,b where the central Pt 2Si 2(μ-H) 2 core remains intact but the PPh 3 ligands have been replaced by PCy 3. Complexes 4a and 4b was characterized by multinuclear NMR and IR spectroscopies. 相似文献
14.
This report presents a comparison of the effects of cis- and trans-diamminedichloroplatinum complexes on in vitro platelet functions. Pretreatment of platelets with cis-platinum ( cisplatin) induced a slow, dose-dependent (0.1–0.45 mM), increase in the cytosolic Ca 2+ concentration, pleckstrin (47 kDa) phosphorylation and serotonin secretion, as well as a slight shape modification with emission of a few pseudopodia. All these effects were remarkably increased in platelets exposed to trans-platinum ( transplatin). The rise in cytosolic Ca 2+ concentration and serotonin secretion evoked by stimulation of platelets with thrombin were not significantly influenced by cellular exposure to cis-platinum, whereas they were enhanced and inhibited, respectively, by exposure to trans-platinum. Trans-platinum also inhibited thrombin-promoted platelet aggregation to a greater extent than the cis-isomer. While the viscosity of platelet rich-plasma tended to decrease in the presence of cis-platinum, it tended to increase in the presence of trans-platinum. Taken together, these results indicate that the effects on platelet functions of the efficacious antitumor complex cis-platinum is rather different from that of the inactive complex trans-platinum. Therefore, the in vitro tests of platelet functions employed in this study might provide an index of antitumor drug toxicity and serve as a preliminary indicator of therapeutic efficacy. 相似文献
15.
The aim of this study is to probe the glycerol backbone conformation of the substrate (or inhibitor) in the active site of Pseudomonas species lipase by the 1,2-cyclopentandiol analogues of the ethylene glycerol carbamate inhibitors. Cyclopentane-carbamates, cis-1,2-di- N- n- butylcarbamyl-cyclopentane (1) and trans-1,2-di- N- n-butylcarbamyl-cyclopentane (2), are the conformationally constrained analogues of 1,2-di- N- n-butylcarbamyl ethane (3). All carbamates are synthesized and characterized as the pseudo-substrate inhibitors of the enzyme. Cis-cyclopentane -di-carbamate (1) is a more potent inhibitor than both ethane-di-carbamate (3) and trans-cyclopentane-di-carbamate (2) probably because the glycerol backbone conformations of cis-cyclopentane-di-carbamate (1) are constrained by the cyclopentane ring and cis-cyclopentane-di-cabamate (1) is a meso compound but trans-cyclopentane-di-carbamate (2) is a racemate. 相似文献
16.
The enantiomers of cis- and trans-3-(4-propyl-cyclopent-2-enyl) propyl acetate, which are conformationally constrained analogues of (Z)-5-decenyl acetate (1), a sex pheromone component of the turnip moth, Agrotis segetum, have been synthesized and tested using the electrophysiological single-sensillum technique. The analogues mimic a cisoid and transoid conformation of 1, respectively. In addition, the enantiomers of each of the cis- and trans-isomers are conformationally constrained analogues of enantiomeric cisoid and transoid conformations of 1. Thus, the compounds prepared and tested are well suited to investigate the nature of the bioactive conformation of the natural pheromone component 1 and the chiral sense of its interaction with the receptor. Electrophysiological single-sensillum recordings show that the activity of the most active cis-isomer, which has a (1 S,4 R)-configuration, is more than two orders of magnitude higher than that of the most active trans-isomer. Furthermore, the (1 S,4 R)-isomer is at least 100 times more active than its enantiomer. These results strongly support a previously proposed cisoid bioactive conformation of 1. Furthermore, the (1 S,4 R)-configuration of most active stereoisomer identifies the chiral sense of the interaction between the natural pheromone component 1 and its receptor. 相似文献
17.
Conjugated linoleic acids (CLAs) comprise a family of positional and geometric isomers of linoleic acid (18:2 n − 6; LA) that are formed by biohydrogenation and oxidation processes in nature. The major dietary sources of these unusual fatty acids are foods derived from ruminant animals, in particular dairy products. The main form of CLA, cis-9, trans-11-18:2, can be produced directly by bacterial hydrogenation in the rumen or by delta-9 desaturation of the co-product vaccenic acid ( trans-11-18:1) in most mammalian tissues including man. The second most abundant isomer of CLA is the trans-10, cis-12-18:2 form. Initially identified in grilled beef as a potential anti-carcinogen a surprising number of health benefits have subsequently been attributed to CLA mixtures and more recently to the main individual isoforms. It is also clear from recent studies that the two main isoforms can have different effects on metabolism and cell functions and can act through different cell signalling pathways. The majority of studies on body compositional effects (i.e. fat loss, lean gain), on cancer and cardiovascular disease attenuation, on insulin sensitivity and diabetes and on immune function have been conducted with a variety of animal models. Observations clearly emphasise that differences exist between mammalian species in their response to CLAs with mice being the most sensitive. Recent studies indicate that some but not all of the effects observed in animals also pertain to human volunteers. Reports of detrimental effects of CLA intake appear to be largely in mice and due mainly to the trans-10, cis-12 isomer. Suggestions of possible deleterious effects in man due to an increase in oxidative lipid products (isoprostanes) with trans-10, cis-12 CLA ingestion require substantiation. Unresponsiveness to antioxidants of these non-enzymatic oxidation products casts some doubt on their physiological relevance. Recent reports, albeit in the minority, that CLAs, particularly the trans-10, cis-12 isomer, can elicit pro-carcinogenic effects in animal models of colon and prostate cancer and can increase prostaglandin production in cells also warrant further investigation and critical evaluation in relation to the many published anti-cancer and anti-prostaglandin effects of CLAs. 相似文献
18.
We used gel electrophoresis and mass spectrometry to investigate differences in protein expression in ovarian tissues from Babesia bovis-infected and uninfected southern cattle tick, Rhipicephalus ( Boophilus) microplus. Soluble and membrane proteins were extracted from ovaries of adult female ticks, and analyzed by isoelectric focusing (IEF) and one-dimensional or two-dimensional (2-D) gel electrophoresis. Protein patterns were analyzed for differences in expression between infected and uninfected ticks. 2-D separation of proteins revealed a number of proteins that appeared to be up- or down-regulated in response to infection with Babesia, in particular membrane/membrane-associated proteins and proteins in a low molecular mass range between 6 and 36 kDa. A selection of differentially expressed proteins was subjected to analysis by capillary-HPLC-electrospray tandem mass spectrometry (HPLC-ESI-MS/MS). Among the ovarian proteins that were up-regulated in infected ticks were calreticulin, two myosin subunits, an endoplasmic reticulum protein, a peptidyl-prolyl cis– trans isomerase (PPIase), a cytochrome c oxidase subunit, a glutamine synthetase, and a family of Kunitz-type serine protease inhibitors. Among the down-regulated ovarian proteins were another PPIase, a hemoglobin subunit, and a lysozyme. This study is part of an ongoing effort to establish a proteome database that can be utilized to investigate specific proteins involved in successful pathogen transmission. 相似文献
19.
A Brazilian strain of the bacteria Serratia rubidaea CCT 5742 quantitatively reduced 4- tert-butylcyclohexanone and 4-methylcyclohexanone to the less thermodynamically stable diastereoisomeric alcohols cis-4- tert-butylcyclohexanol and cis-4-methylcyclohexanol with a diastereoisomeric excesses (de) of 96% and 44%, respectively. 2-Methylcyclohexanone was also totally reduced to the corresponding alcohols affording the trans-(+)-(1 S, 2 S)-2-methylcyclohexanol with 78% of de and an enantiomeric excess (ee) of 80%. The cis-(+)-(1 S, 2 R)-2-methylcyclohexanol was obtained in 98% ee. 相似文献
20.
The complex [Ru(H 2)(H)(PMe 2Ph) 4]PF 6 (1) has been prepared by reaction of [Ru(H)(PMe 2Ph) 5] FP 6 (2) in THF with 1 atm H 2 and characterised by variable temperature 31P and 1H NMR. It undergoes four distinct fluxional processes listed in order of decreasing activation energy: (i) exchange of H 2 in solution with the dihydrogen ligand above 273 K; (ii) isomerisation of cis and trans isomers of 1 above 230 K; (iii) exchange of H atoms between H 2 and hydride in trans-1 above 180 K; (iv) rapid H 2/hydride exchange in cis-1 to below 180 K. A single crystal X-ray diffraction study of 1 at 173 K shows that the complex has the cis geometry in the solid state but does not clearly reveal the positions of the hydrogen ligands. Complex 1 starts out as a catalyst of high activity for the selective hydrogenation of 1-alkynes to 1-alkenes (RC≡CH; R= 11Bu, Ph) but it is rapidly deactivated, possibly because of formation of the enynyl complex [Ru( η3RC 3CHR)(PMe 2Ph) 4] +. Complex 1 efficiently catalyzes the hydrogenation of internal alkynes (3-hexyne, 2-pentyne) to internal cis-alkenes with little deactivation, although some isomerisation of the alkene produced is observed. These observations are consistent with those of Nkosi, Coville, Albers and Singleton who reported that complex 2 must dissociate one PMe 2Ph ligand to produce the species active for alkyne hydrogenation. Complex 2 catalyses these hydrogenations with slower initial rates than complex 1 but deactivates less readily. In contrast to 1, complex 2 does not appear to cause the isomerisation of internal alkenes. 相似文献
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