共查询到20条相似文献,搜索用时 15 毫秒
1.
The modulation of membrane fluidity by hydrogenation processes. II. Homogeneous catalysis and model biomembranes 总被引:2,自引:0,他引:2
A homogeneous catalyst, chlorotris (triphenylphosphine) rhodium (I) has been incorporated into model biomembrane structures in the form of lipid bilayer dispersions in water. This enables the hydrogenation of the double bonds of the unsaturated lipids within the bilayers to be accomplished. To decide the optimum conditions for efficient hydrogenation the reaction conditions have been varied. The effect of catalyst concentration, hydrogen gas pressure and lipid composition (with and without cholesterol) have all been studied. The partition of the catalyst into the lipid medium was checked by rhodium analysis. The results show that an increase of catalyst concentration or an increase of hydrogen gas pressure leads to increasing rates of hydrogenation. Successful hydrogenation was accomplished with different types of lipid dispersions (mitochondrial, microsomal and erythrocyte lipids). A selectivity of the homogeneous hydrogenation process is indicated. The polyunsaturated fatty acyl residues are hydrogenated at an earlier stage and at a faster rate than the monoenoic acids. Furthermore, an increase in the proportion of cholesterol to lipid within the bilayer structures causes a progressive decrease in the rate of hydrogenation. The fluidity of the lipid bilayers can be altered to such an extent by the hydrogenation process that new sharp endotherms corresponding to the order-disorder transition of saturated lipids occur at temperatures as high as 319 K. Some potential uses of hydrogenation for the modulation of cell membrane fluidity are discussed as well as the design of new types of catalyst molecules. 相似文献
2.
Nadal B Thetiot-Laurent SA Pin S Renault JP Cressier D Rima G Le Roux A Meunier S Wagner A Lion C Le Gall T 《Bioorganic & medicinal chemistry》2010,18(22):7931-7939
The synthesis of three types of pulvinic acid analogues, using a diversity-oriented strategy starting from a single compound, dimethyl l-tartrate, is described. Lacey-Dieckmann condensation, alcohol dehydration and Suzuki-Miyaura cross-couplings were employed in the course of the analogues syntheses. The evaluation of the antioxidant properties of the 28 synthesized analogues was carried out using antioxidant capacity assays (protection of thymidine and β-carotene) and free radical scavenging assays (DPPH radical and ABTS radical cation). This allowed to assess the relative influence of the groups bonded to the tetronic ring and to the exocyclic double bond on the activity, as well as the importance of this exocyclic double bond. It was shown that the presence of an electron-donating group on the 3-position of the tetronic ring had a beneficial effect. It was shown in several assays that the presence of the exocyclic bond was not crucial to the activity. 相似文献
3.
Colin J. Restall Patrick Williams Michael P. Percival Peter J. Quinn Dennis Chapman 《生物化学与生物物理学报:生物膜》1979,555(1):119-130
A method is reported for the in situ modification of the lipids of isolated spinach chloroplast membranes. The technique is based on a direct hydrogenation of the lipid double bonds in the presence of the catalyst, chlorotris(triphenylphosphine)rhodium (I). The pattern of hydrogenation achieved suggests that the catalyst distributes amongst all of the membranes. The polyunsaturated lipids within the membranes are hydrogenated at a faster rate and at an earlier stage than are the monoenoic lipids.Whilst addition of the catalyst to the chloroplast causes an initial 10–20% decrease in Hill activity, saturation of up to 40% of the double bonds present can be accomplished without causing further significant alterations in photosynthetic electron transport processes or marked morphological changes of the chloroplast structure as observed in the electron microscope. 相似文献
4.
C J Restall P Williams M P Percival P J Quinn D Chapman 《Biochimica et biophysica acta》1979,555(1):119-130
A method is reported for the in situ modification of the lipids of isolated spinach chloroplast membranes. The technique is based on a direct hydrogenation of the lipid double bonds in the presence of the catalyst, chlorotris(triphenylphosphine)rhodium (I). The pattern of hydrogenation achieved suggests that the catalyst distributes amongst all of the membranes. The polyunsaturated lipids within the membranes are hydrogenated at a faster rate and at an earlier stage than are the monoenoic lipids. Whilst addition of the catalyst to the chloroplast causes an initial 10--20% decrease in Hill activity, saturation of up to 40% of the double bonds present can be accomplished without causing further significant alterations in photosynthetic electron transport processes or marked morphological changes of the chloroplast structure as observed in the electron microscope. 相似文献
5.
The enantioselective hydrogenation of several α-keto acid derivatives with rhodium diphosphine catalysts has been investigated using a random screening approach. The neutral rhodium catalyst prepared in situ from bis(2,5-norbornadiene rhodium chloride) and NORPHOS has been found to be an excellent catalyst for preparing aliphatic α-hydroxy esters in high optical purities. The reaction parameters for the hydrogenation of ethyl 2-oxo-4-phenyl-butyrate, an intermediate for the ACE inhibitor Benazepril, were optimized and the best optical yields obtained were 96%. 相似文献
6.
C E Gomez-Sanchez D N Kirk R D Farrant L Milewich 《Journal of steroid biochemistry》1985,22(1):141-146
The isolation of 18-hydroxycortisol from the urine of patients with primary aldosteronism was recently described and no synthetic procedure was available for its preparation. The C-13 angular methyl group of prednisolone-17 alpha,21-acetonide-11 beta-nitrite was functionalized by photolysis in the presence of oxygen to give the product 18-hydroxy-prednisolone-17 alpha,21-acetonide-18-nitrate. The 18-nitrate was reduced with zinc and ammonium acetate to the corresponding 18-hydroxy compound, 18-hydroxy-prednisolone-17 alpha,21-acetonide. Homogeneous hydrogenation with Tris(triphenyl-phosphine)rhodium (I) chloride as catalyst resulted in the formation of 18-hydroxy-cortisol-17 alpha,21-acetonide. Acid hydrolysis of the latter compound gave 18-hydroxycortisol. Oxidation of 18-hydroxycortisol-17 alpha,21-acetonide with pyridinium dichromate followed by acid hydrolysis gave 18-hydroxycortisone. The 18-hydroxylated steroids exist as the 18,21-hemiacetals. Catalytic reduction with tritium gas with Tris(triphenyl-phosphine)rhodium (I) chloride of 18-hydroxyprednisolone-17 alpha,21-acetonide and acid hydrolysis gave [1,2(3)H]18-hydroxycortisol. 相似文献
7.
A new "CO2-philic" chiral rhodium diphosphinite complex was synthesized and applied as catalyst precursor in the asymmetric hydrogenation of dimethyl itaconate in scCO2, scC2H6 and various liquid organic solvents. Deuterium labeling studies and parahydrogen-induced polarization (PHIP) NMR experiments were used to provide the first detailed mechanistic insight into the activation and transfer of the dihydrogen molecule during hydrogenation in scCO2. Chemical interactions between CO2 and reactive intermediates of the catalytic pathway could be excluded as possible explanations for the experimentally verified difference in the catalytic behavior in scCO2 and hexane. 相似文献
8.
In the course of the purification of enone reductase participating to the reduction of pulegone, two reductases (NtRed-1 and NtRed-2) were isolated from cultured cells of Nicotiana tabacum. The partial amino acid sequences of the reductases revealed that NtRed-1 was allyl-alcohol dehydrogenase (Accession No. BAA89423) and NtRed-2 was malate dehydrogenase (Accession No. CAC12826). cDNA cloning and expression of these reductases in Escherichia coli were performed. Reduction with recombinant proteins was examined with cyclic α,β-unsaturated ketones, such as pulegone, carvone and verbenone, as substrates. It was found that the recombinant NtRed-1 catalyses the hydrogenation of the exocyclic C-C double bond of pulegone. 相似文献
9.
Rhodium and iridium complexes of trisulfonated triarylphosphanes, TPPTS (tris(3-sulfonatophenyl)phosphane), T(p-A)PTS (tris(3-sulfonato-4-methoxyphenyl)phosphane), T(2,4-X)TS (tris(2,4-dimethyl-5-sulfonatophenyl)phosphane), have been tested in biphasic hydrogenation of aldehydes. T(2,4-X)TS could not stabilize the rhodium complex under the applied conditions. Guanidium salt of T(2,4-X)TS has been characterized by X-ray crystallography, and Tolman cone angle of the phosphane has been determined from crystallographic data. The large cone angle (196°, 210°) explains the instability of the rhodium complex. Contrary to the T(2,4-X)TS/rhodium system, the T(2,4-X)TS/iridium catalyst has been found to be stable and effective in hydrogenation of benzaldehyde and caproaldehyde. 相似文献
10.
3,8-Divinyl-chlorophyll(Chl)-a possessing a phytyl ester was hydrogenated in acetone by rhodium catalyst on alumina to afford 3-vinyl-8-ethyl-, 3-ethyl-8-vinyl- and 3,8-diethyl-Chls. The ratio of produced 3-ethyl-8-vinyl- over 3-vinyl-8-ethyl-Chls was determined to be 1.2, indicating that the reactivity of the 3-vinyl group was slightly higher than that of the 8-vinyl group. Catalytic hydrogenation of divinyl-protochlorophyll-a possessing a porphyrin ??-skeleton (C17C18) instead of the above chlorin moiety (C17H-C18H) gave an equal amount of mono-reduced regioisomers. The slight (or no) selectivity is different from that in the enzymatic reduction of divinyl-(proto)chlorophyllides-a lacking a phytyl ester in the biosynthetic pathway of Chl-a where the sole 8-vinyl group is transformed to the ethyl group. 相似文献
11.
The chloroimide 3,3-dichloro-4-(dichloromethylene)-2,5-pyrrolidinedione, a tetrachloroitaconimide, is the principal mutagen produced by chlorination of simulated poultry chiller water. It is the second most potent mutagenic disinfection by-product of chlorination ever reported. Six of seven new synthetic analogs of this compound are direct-acting mutagens in Ames tester strain TA-100. Computed energies of the lowest unoccupied molecular orbital (E(LUMO)) and of the radical anion stability (DeltaH(f)(rad)-DeltaH(f)) from MNDO-PM3 for the chloroimides show a quantitative correlation with the Ames TA-100 bacterial mutagenicity values. The molar mutagenicities of these direct acting mutagenic imides having an exocyclic double bond fit the same linear correlation (lnM(m) vs. E(LUMO); lnM(m) vs. DeltaH(f)(rad)--DeltaH(f)) as the chlorinated 2(5H)-furanones, including the potent mutagen MX, 3-chloro-4-(dichloro-methyl)-5-hydroxy-2(5H)-furanone, a by-product of water chlorination and paper bleaching with chlorine. Mutagenicity data for related haloimides having endocyclic double bonds are also given. For the same number of chlorine atoms, the imides with endocyclic double bonds have significantly higher Ames mutagenicity compared to their structural analogs with exocyclic double bonds, but do not follow the same E(LUMO) or DeltaH(f)(rad)-DeltaH(f) correlation as the exocyclic chloroimides and the chlorinated 2(5H)-furanones. 相似文献
12.
I Z Zel'tser E L Balabanova A V Lapchinskaia R G Anufrieva S S Gerasimova 《Antibiotiki》1978,23(6):533-536
The acute toxicity parameters of oxytetracycline and its semisynthetic derivatives was determined on laboratory animals of various species. The three antibiotics were described as belonging to the group of low toxic compounds according to the classification adopted in industrial toxicology. However, the absolute values of LD50 indicated that doxycycline was 5.6 or 2.8 times more toxic than oxyteyracycline or methacycline respectively. In addition, doxycycline had the most pronounced hepatoxic effect. 相似文献
13.
Isolation of a naphthaquinone with partly hydrogenated side chain from Corynebacterium diphtheriae 总被引:2,自引:0,他引:2
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1. Corynebacterium diphtheriae contains relatively large amounts (6.6mumoles/g. dry wt.) of a naphthaquinone whose ultraviolet-absorption spectrum is that of a typical menaquinone (vitamin K(2)), the E(1%) (1 cm.) value corresponding with that of MK-8, but on reversed-phase paper chromatograms it runs with MK-9. 2. In the presence of Adams catalyst hydrogen uptake is 2 atoms/mol. less than that calculated for MK-8. 3. Hydrogenated samples of the Corynebacterium quinone and the hydrogenation product of authentic MK-8 ran together on reversed-phase chromatograms. 4. Infrared-absorption spectra indicated close relationship with the menaquinone series, and nuclear-magnetic-resonance measurements show that one, non-terminal, double bond of the side chain has been saturated. 5. The compound is thus designated MK-8(2H), indicating a menaquinone with eight isoprene units but only seven double bonds in the side chain. 相似文献
14.
- In US Pacific Northwest ponderosa pine forests the primary attraction order shown previously for red turpentine beetle, Dendroctonus valens (Coleoptera: Curculionidae: Scolytinae), is (−)-β-pinene+ethanol > (+)-3-carene+ethanol > (+)-α-pinene+ethanol. The monoterpenes are bicyclic C10H16 isomers containing one 6-carbon ring with one double bond. Both pinenes have a 4-carbon second ring and differ only by their endocyclic or exocyclic double bond. The (+)-3-carene second ring has 3-carbons; its double bond is endocyclic like (+)-α-pinene.
- Ring system and double bond influences on primary attraction were evaluated by hydrogenating (+)-3-carene and (+)-α-pinene to cis-carane and cis-pinane, respectively. Field test primary attraction strengths were (−)-β-pinene+ethanol > cis-carane+ethanol > cis-pinane+ethanol > ethanol.
- In combination with ethanol (i) a double bond is not required in either ring system to attract D. valens, (ii) the cis-carane bicyclic 3, 6-carbon ring system provides stronger beetle attraction than the cis-pinane 4, 6-carbon bicyclic ring system, and likely structural basis for stronger (+)-3-carene attraction over (+)-α-pinene, (iii) adding an exocyclic double bond to the 4, 6-carbon ring system elevates attraction above the 3, 6-carbon ring system with no double bond, and (iv) the 4, 6-carbon ring system is a much stronger attractant with an exocyclic rather than endocyclic double bond.
15.
A hydrocarbon that is widespread in Juniperus foliage was isolated from Juniperus erectopatens (Cheng and L. K. Fu) R. P. Adams and identified as (E,E,E)-1,7-dimethylcyclodeca-1,4,7-triene (pregeijerene B). Geometry of the disubstituted double bond was determined by IR and NMR spectroscopy, while that of the trisubstituted double bonds was proven by comparison of the products of selective hydrogenation of the title compound and of pregeijerene. Common biosynthesis of pregeijerene B and a germacrane sesquiterpenoid, 8alpha-acetoxyhedycaryol, is inferred from their co-occurrence in foliage of 24 Juniperus species. 相似文献
16.
Piero Frediani Luca Rosi Lorenza Cetarini Marco Frediani 《Inorganica chimica acta》2006,359(9):2650-2657
The catalytic activity of the rhodium complex cis-[Rh(bipy)2Cl2]Cl · 2H2O in the transfer hydrogenation of different unsaturated substrates is reported. This complex, if pre-activated, is very active in the transfer hydrogenation of ketones (i.e., cyclohexanone is reduced with a 38.1% conversion at 283 K and 100% at 313 K) while in the case of hex-1-ene, a 36.8% conversion was reached at 293 K. A cyclic olefin (cyclohexene) was also reduced with a lower, but still significant, conversion.It is interesting to note the catalytic activity of this complex in the transfer hydrogenation of a CN double bond belonging to imides or nitrogen-containing heterocycles. For instance, N-benzylidenaniline was hydrogenated to N-benzylaniline at 303 K with a conversion of 27.3%. Increasing the temperature to 353 K, the conversion rised to 91.8%. A nitrogen containing heterocycle, quinoline, was also reduced by transfer hydrogenation at 353 K with a 11.7% conversion giving 1,2,3,4-tetrahydroquinoline (selectivity of 96.6%). The conversion rised up to 54.2% with a still high selectivity (84.5%) when the temperature was 383 K. Almost the same activity was shown in the reduction of pyridine to pyperidine (conversion, 51.1% at 383 K), while 2-methylpyridine was hydrogenated with a 24.7% conversion. 相似文献
17.
The aerial parts of Piptolepis ericoides afforded in addition to known compounds two new germacranolides, a zexbrevanolide and piptolepolide, tentatively characterized as a germacranolide with a trans-disubstituted double bond. From the aerial parts of two Vanillosmopis species in addition to goyazensolide, a new isomer with an exocyclic double bond was isolated. 相似文献
18.
Cationic iridium complexes with chiral phosphinooxazoline ligands are efficient catalysts for the enantioselective hydrogenation of olefins. The complexes are readily prepared, air-stable, and easy to handle. In contrast to chiral rhodium- and ruthenium-phosphine catalysts, they do not require the presence of a polar coordinating group near the C=C bond. In the hydrogenation of unfunctionalized trisubstituted 1,2-diaryl-olefins, high enantioselectivities of >95% ee with full conversion and turnover frequencies of >7,000 h-1 can be achieved, using 0.1 mol% of catalyst with tetrakis[3, 5-bis(trifluoromethyl)phenyl]borate (TFPB or BARF) as the counterion. The corresponding hexafluorophosphate or tetrafluoroborate salts give low conversion due to deactivation of the catalyst during the reaction. Substrates with polar substituents such as allylic alcohols, on the other hand, afford better results with the hexafluorophosphate salts. 相似文献
19.
The performance of a catalyst used in asymmetric synthesis is likely to be dependent upon its stereoisomeric purity. An impurity was detectable by (31)P NMR in early development batches of the asymmetric hydrogenation catalyst [(S,S)-Me-BPE-Rh(COD)](+)BF(4) (-) made from the ligand bis((2S,5S)-2,5-dimethylphospholano)ethane [(S,S)-Me-BPE]. Its identity as a stereoisomer with one chiral and one meso-phospholane ring was deduced by comparison of the (31)P NMR spectra and GC traces of the ligand with a deliberately synthesized mixture of isomers. Interestingly, the impurity corresponded to a trans-meso isomer formed by thermal (200 degrees C) pyramidal inversion at phosphorus of the initially synthesized cis-meso-phospholane when the ligand was purified by distillation. Low levels of this trans-meso/chiral impurity do not significantly impair the enantioselectivity of the rhodium complex as an asymmetric hydrogenation catalyst, but high levels of stereochemical impurities resulted in a loss of both enantioselectivity and activity. Therefore it is indeed important to establish that a catalyst used in asymmetric catalysis is sufficiently stereoisomerically pure. Owing to strict control of the stereochemical purity of the key hexane-2,5-diol intermediate, the impurity is not detected in production batches. 相似文献
20.
Various conditions were tested in an attempt to hydrogenate the unsaturated fatty acids of living Tetrahymena mimbres with the homogeneous catalyst palladium di-(sodium alizarine monosulfonate) without causing serious damage to the cells. Using a low (20 micrograms/ml) catalyst concentration in the external medium, hydrogenation of greater than 20% of surface membrane lipid double bonds were obtained, but hydrogenation of intracellular membranes was minimal. When exposed to H2, cells preincubated with inactive catalyst for several hours and visibly loaded with the catalyst lost viability as soon as hydrogenation exceeded trace levels. Material secreted by Tetrahymena into their medium effectively inhibited hydrogenation of added oleic acid, normally a good substrate. Mucus secreted by the cells, soluble proteins isolated from cell homogenates, bovine serum albumin, and cysteine were also inhibitory, but the inhibition could be overcome by employing higher catalyst concentrations. Although some enzymatic retroconversion of saturated lipids back to unsaturated lipids appeared to take place, the scale of the conversion was small, and further experimentation will be required to understand the mechanism involved. The selective hydrogenation of surface membranes achieved by these methods may be especially useful to those interested in fluidity effects on plasma membrane properties. 相似文献