By selecting solvents with a very weakly concentration-dependent interaction parameter χ with poly(dimethylsiloxane) (PDMS) and using experimental values of the elastic modulus of dry, end-linked PDMS networks, the Flory-Rehner theory and the phantom network assumption we obtained good agreement between the values of χ from equilibrium swelling and those obtained from intrinsic viscosity measurements on solutions of linear chains. The solvents used were 2,3-dimethylpentane and 2,2,4-trimethylpentane at 25°C. 相似文献
The present study was designed to investigate the metabolism of the n−3 olyunsaturated fatty acids (PUFA) in adipose tissue
and its dependence upon dietary factors. Changes in the positional distribution of the fatty acids in triacylglycerols from
retroperitoneal adipose tissue were studied as a function of time on rats fed for 4 wk a diet enriched with fish oil. The
stereospecific analysis of triacylglycerols was based on random formation ofrac-1,2-diacylglycerols by Grignard degradation. This was followed by synthesis ofrac-phosphatidic acids and treatment with phospholipase A2. In the triacylglycerols of the fish oil diet, 57% of the total n−3 fatty acids were in position 3,i.e., two-thirds of 22∶5n−3 and 22∶5n−3 were esterified insn-3 position, whereas 22∶6n−3 was equally distributed in positions 2 and 3. After 4 wk of feeding fish oil, the fatty acid
composition of adipose tissue triacylglycerols reached a steady state. Half of the n−3 fatty acids were found in position
3, namely 75% of 22∶5n−3, 50% of 20∶5n−3 and 18∶4n−3 and 45% of 22∶6n−3, the latter being equally distributed in positions
2 and 3. This pattern of distribution resembled that found in triacylglycerols of the fish oil diet, except for a higher proportion
of 20∶5n−3 in adipose tissue in position 1 at the expense of position 3. Throughout the 4-wk period of fish oil feeding, the
distribution pattern of minor n−3 fatty acids (18∶4n−3 and 22∶5n−3) in adipose tissue triacylglycerols remained unchanged.
On the other hand, at the onset of fish oil feeding, 20∶5n−3 and 22∶6n−3 became concentrated in position 3, but thereafter
20∶5n−3 was progressively incorporated into position 1 and 22∶6n−3 into position 2. We thus conclude that n−3 fatty acids
are differentially esterified in triacylglycerols of white adipose tissue. Despite the complex sequence of hydrolysis and
acylation steps involved, the positional distribution of n−3 fatty acids was found to be similar in both the fish oil diet
and the stored fat, in contrast to what was observed for nonessential fatty acids. 相似文献
Synchronized catalysis in native enzyme : We used a photoactive nanotrigger (NT) to study the initial electron transfer to FAD in native neuronal NOS catalysis. Modeling and fluorescence spectroscopy showed that selective NT binding to NADPH sites is able to override Phe1395 regulation, thus permitting ultrafast injection of electrons into the protein electron pathway. That NT initiation of flavoenzyme catalysis led to the formation of NO is promising for time‐resolved X‐ray and other cellular applications.
In this work, different procedures, namely carbonate coprecipitation and modified solid–solid diffusion, were used to prepare hexaaluminate samples, unsupported or supported onto θ-Al2O3. These samples were used as catalyst for the methane total oxidation as synthesized or after impregnation of 1 wt% Pd. It was observed that the modified solid–solid diffusion procedure is an efficient method to obtain the hexaaluminate structure. At a theoretical ratio x of hexaaluminate onto Al2O3 less than 0.6 (xLa0.2Sr0.3Ba0.5MnAl11O19 + (1−x)·Al2O3, with x = 0.25, 0.60), samples with high specific surface area and θ-Al2O3 structure are then obtained. Large differences in catalytic activity can be observed among the series of sample synthesized. All the pure oxide samples (i.e. without palladium) present low catalytic activity for methane total oxidation compared to a reference Pd/Al2O3 catalyst. The highest activity was obtained for the samples presenting a θ-Al2O3 structure (with x = 0.60) and a high surface area. Impregnation of 1 wt% palladium resulted in an increase in catalytic activity, for all the solids synthesized in this work. Even if the lowest light-off temperature was obtained on the reference sample, similar methane conversions at high temperature (700 °C) were obtained on the stabilized θ-Al2O3 solids (x = 0.25, 0.60). Moreover, the reference sample is found to strongly deactivate with reaction time at the temperature of test (700 °C), due to a progressive reduction of the PdOx active phase into the less active Pd° phase, whereas excellent stabilities in reaction were obtained on the pure and palladium-doped hexaaluminate and supported θ-Al2O3 samples. This clearly showed the beneficial effect of the support for the stabilization of the PdOx active phase at high reaction temperature. These properties are discussed in term of oxygen transfer from the support to the palladium particle. Oxygen transfer is directly related to the Mn3+/Mn2+ redox properties (in the case of the hexaaluminate and stabilized θ-Al2O3 samples), that allows a fast reoxidation of the metal palladium sites since palladium sites reoxidation cannot occur directly by gaseous dioxygen adsorption and dissociation on the surface. 相似文献
The impact of oxygen permeability using an ionic oxygen conducting membrane reactor with surface catalyst was investigated for the oxidative coupling of methane to higher hydrocarbons. Dense Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCFO), Ba0.5Sr0.5Mn0.8Fe0.2O3−δ (BSMFO) and BaBi0.4Fe0.6O3 (BBFO) membrane disks with Pt/MgO catalysts were prepared by sol–gel deposition or wash-coating. It is demonstrated that the oxygen supply by permeation needs to fit to the consumption during the coupling reaction. In case of insufficient oxygen supply comparably poor conversions are observed while higher oxygen fluxes lead to increased methane conversions, especially in the presence of an efficient catalyst. Generally, increasing catalytic activity leads to lower C2 selectivity, especially for low oxygen permeation fluxes. The concept of a reactor employing dense catalytic membranes is viable, but the present study identifies further potential when the activity of the catalyst for the oxidative coupling is improved, leading to an overall enhanced performance of the membrane reactor. 相似文献
In Leucophaea maderae, male calling behavior involves the release of a sex pheromone from the abdominal sternal glands. An extract of sternal glands
attracted conspecific females over a distance. The compounds present were identified as hydroxy-3-butan-2-one, (2R, 3R)-butanediol, senecioic acid, and (E)-2-octenoic acid. The same components are also present in male tergal glands. The identified compounds were tested on their
own and in mixtures. Their biological function is discussed. 相似文献
The use of pesticides is widespread in citrus fruits production for pre- and post-harvest protection and many chemical substances may be applied in order to control undesirable moulds or insects. A survey was carried out to evaluate levels of pesticide residues in citrus fruits. Two multiresidue analytical methods were used to screen samples for more than 200 different fungicides, insecticides and acaricides. A total of 240 samples of citrus fruits including lemon, orange, mandarin, grapefruit, lime, pomelo and kumquat were taken in various markets in the Geneva area during the year 2003. Ninety-five percent of the 164 samples issued from classical agriculture contained pesticides and 38 different compounds have been identified. This high percentage of positive samples was mainly due to the presence of two post-harvest fungicides, imazalil and thiabendazole, detected in 70% and 36% of samples respectively. Only three samples exceeded the Swiss maximum residue limits (MRLs). Fifty-three samples sold with the written indication “without post-harvest treatment” were also controlled. Among theses samples, three exceeded the Swiss MRLs for penconazole or chlorpyrifos and 18 (34%) did not respect the written indication since we found large amounts of post-harvest fungicides. Finally, 23 samples coming from certified organic production were analysed. Among theses samples, three contained small amounts of pesticides and the others were pesticides free. 相似文献
Two tunicates, Eudistoma sp. and Leptoclinides uniorbis, collected from the tropical waters off Djibouti were investigated for lipids and phospholipid (PL) fatty acids. PL accounted
for 38.2% of the total lipids in Eudistoma sp. and for 30.2% in L. uniorbis. PL classes were quantified by normal-phase high-performance liquid chromatography using an evaporative light-scattering detector
and revealed essential differences. Eudistoma sp. contained mainly phosphatidylcholine (PC, 70.3% of total PL) and lysophosphatidylcholine (LPC, 11.9%) and was devoid
of phosphatidylserine (PS), whereas the major PL of L. uniorbis was PS (59.1%) followed by PC (22.5%) and LPC (8.8%). Gas chromatography–mass spectrometry analyses of fatty acid (FA) derivatives
revealed 38 FA in Eudistoma sp., and 35 FA in L. uniorbis, ranged from C12 to C24 chain lengths. Polyunsaturated FA accounted for 25.9% in Eudistoma sp. and for 32.3% in L. uniorbis. Interestingly, L. uniorbis contained a high percentage (16.7%) of the 20:5n-3 acid (8.9% in Eudistoma sp.) and the 18:4n-3 acid (4.1%). Significant levels of the 20:4n-6 acid were observed in both organisms (7.8 and 6.0% respectively).
Eudistoma sp. contained the rare 20:3n-7 acid (2.3%) only recorded to date in hydrothermal vent animals. The cyclopropane dihydrosterculic
acid was identified in both tunicates (0.7 and 0.5% respectively). These latter FA, together with some unusual branched saturated
and monounsaturated FA, revealed the occurrence of associated bacteria in the tunicates. Another noticeable feature was a
series of eight C16 to C18 aldehyde dimethylacetals revealing the presence of plasmalogens at 5.0% in Eudistoma sp. and 14.2% in L. uniorbis. The results of this study were compared with those previously published for other tunicates regarding mainly PL content
and FA composition. 相似文献
Symmetric porous membranes were prepared from concentrated poly(ether-imide) (PEI) solutions using vapor-induced phase separation (VIPS) coupled with a drying pretreatment. Moderately concentrated solutions of PEI in N-methylpyrrolidinone (NMP) (14–16 wt%) were first cast on glass plates and the solvent was then allowed to evaporate under a dry air flow up to the desired concentration (16–38 wt%) before forming the membrane structure by VIPS. The polymer concentration profiles (confocal Raman microscopy) and model predictions were in good agreement to show that the evaporation stage did not induce a polymer gradient concentration with PEI/NMP systems. These results were confirmed by examination of the final membrane morphology (SEM). 相似文献