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71.
Simone C. Godoy Marco Flôres Ferrão Annelise E. Gerbase 《Journal of the American Oil Chemists' Society》2007,84(6):503-508
A rapid method for the quantitative determination of the hydroxyl value (OHV) of hydroxylated soybean oils by HATR/FTIR spectroscopy
is described. Calibration standards were prepared by the formic acid/hydrogen peroxide method and OH values were determined
by the official method of AOCS Tx 1a-66, covering an analytical range of 3.5–125 mg of KOH/g of sample. A partial least squares
(PLS) calibration model for the prediction of the hydroxyl value (OHV) was developed based on eight different spectral subregions
between 3,150 and 990 cm−1 and combinations of them. On average, 36 samples were used for the modeling and 17 were used for external validation. The
resulting calibration was linear over the analytical range and had a standard deviation of 2.334. Validation of the method
was carried out by comparing the OHV of a series of hydroxylated soybean oils predicted by the PLS model to the values obtained
by the AOCS standard method. A correlation coefficient of R
2 = 0.9843 and RMSEC and RMSEP values of, respectively, 3.393 and 3.643 were obtained. After the calibration of the spectrometer,
the OHV could be obtained in 2–3 min per sample, a major improvement over conventional wet chemical methods. The advantages
of these methodologies are that they do not destroy the sample, have a lower cost, expedite the analysis and do not produce
residues. Therefore, they may yield excellent results when used to quantify OHV of soybean polyols obtained by hydroxylation
reaction. 相似文献
72.
José Iglesias Dolores Gonzalez-Pacanowska Carmen Marco Eduardo Garcia-Peregrin 《Lipids》1993,28(6):549-553
The purpose of the present study was to investigate the physiological control of the main regulatory enzymes of cholesterol
metabolism in isolated enterocytes obtained from chick duodenum, jejunum and ileum. Cholesterol feeding resulted in an inhibition
of 3-hydroxy-3-methylglutaryl-CoA reductase and mevalonate 5-pyrophosphate decarboxylase, while cholestyramine feeding increased
reductase activity in all the regions studied and decarboxylase activity only in duodenum. Cholesterol feeding markedly increased
acyl-CoA:cholesterol acyltransferase, but the effects of cholestyramine were less clear. The effects on transferase activity
cannot be due to differences in the availability of acyl-CoA as exogenous substrate as no significant differences were found
in acyl-CoA hydrolase activity after any of the dietary treatments. The effects of cholesterol feeding were related to changes
in the cholesterol content of epithelial cells, whereas in the case of cholestyramine this relationship was less apparent. 相似文献
73.
Funke SA Otte N Eggert T Bocola M Jaeger KE Thiel W 《Protein engineering, design & selection : PEDS》2005,18(11):509-514
Chiral compounds can be produced efficiently by using biocatalysts. However, wild-type enzymes often do not meet the requirements of a production process, making optimization by rational design or directed evolution necessary. Here, we studied the lipase-catalyzed hydrolysis of the model substrate 1-(2-naphthyl)ethyl acetate both theoretically and experimentally. We found that a computational equivalent of alanine scanning mutagenesis based on QM/MM methodology can be applied to identify amino acid positions important for the activity of the enzyme. The theoretical results are consistent with concomitant experimental work using complete saturation mutagenesis and high-throughput screening of the target biocatalyst, a lipase from Bacillus subtilis. Both QM/MM-based calculations and molecular biology experiments identify histidine 76 as a residue that strongly affects the catalytic activity. The experiments demonstrate its important influence on enantioselectivity. 相似文献
74.
Marco Lattuada 《Chemical engineering science》2004,59(21):4401-4413
The radial density distributions of fractal clusters generated in both DLCA and RLCA conditions by Monte-Carlo off-lattice cluster-cluster aggregation have been investigated. It has been computed by averaging a large number of clusters of same mass to form an average cluster, which is then considered as spherically symmetric. It is found that the radial density distribution, calculated using the mass center of the cluster as the center point, does not follow the fractal scaling, as sometimes assumed in the literature. An empirical model has been proposed to describe the dependence of the radial density distribution on the number of particles in the cluster. The obtained radial density distribution is used to compute permeability profile of the fractal cluster using several literature models, which is then applied to estimate the cluster hydrodynamic radius, Rh, by considering the cluster as a porous permeable object and using the solution of Brinkman equations for the fluid flow inside the cluster. The so obtained Rh values are compared to those in the literature, computed using the Kirkwood-Riseman (KR) theory. It has been found that, among the five permeability models examined, only the model proposed by Davis (Proceedings of the Institution of Mechanical Engineers Part B 1, 185) provides results in good agreement with those obtained using the KR model. Furthermore, it has been verified that the Rh values are insensitive to the model used for the density distribution. 相似文献
75.
Shampa Kandoi Jeff Greeley Marco A. Sanchez-Castillo Steven T. Evans Amit A. Gokhale James A. Dumesic Manos Mavrikakis 《Topics in Catalysis》2006,37(1):17-28
A microkinetic model for methanol decomposition on platinum is presented. The model incorporates competitive decomposition
pathways, beginning with both O–H and C–H bond scission in methanol, and uses results from density functional theory (DFT)
calculations [Greeley and Mavrikakis, J. Am. Chem. Soc. 124 (2002) 7193, Greeley and Mavrikakis, J. Am. Chem. Soc. 126 (2004)
3910]. Results from reaction kinetics experiments show that the rate of H2 production increases with increasing temperature and methanol concentration in the feed and is only nominally affected by
the presence of CO or H2 with methanol. The model, based on the values of binding energies, pre-exponential factors and activation energy barriers
derived from first principles calculations, accurately predicts experimental reaction rates and orders. The model also gives
insight into the most favorable reaction pathway, the rate-limiting step, the apparent activation energy, coverages, and the
effects of pressure. It is found that the pathway beginning with the C–H bond scission (CH3OH→H2COH→HCOH→CO) is dominant compared with the path beginning with O–H bond scission. The cleavage of the first C–H bond in methanol
is the rate-controlling step. The surface is highly poisoned by CO, whereas COH appears to be a spectator species. 相似文献
76.
Massimo Guglielmi Giovanna Brusatin Giacomo Facchin Mario Gleria Roger De Jaeger Marco Musiani 《Journal of Inorganic and Organometallic Polymers》1996,6(3):221-236
In this paper the sol-gel preparation of hybrid materials made of metal oxide and polytorganophosphazenel components is described. The main problem focused on during this research was to avoid phase separation in order to get homogeneous materials. This problem was pursued looking at the formation of genuine chemical bonds between the exploited polyphosphazenes and the inorganic composite networks. Investigations on the thermal, mechanical, and electroconductive properties of the synthesized, phosphazene-containing composite materials showed that these matrices presented improved mechanical and thermal features with respect to those of the original phosphazene macromolecule, while the ionic conductivities of the prepared molecular hybrids doped with lithium or silver trillate are of the same order of magnitude as those measured for the neat, original phosphazene substrate.Presented at the Ist Italian Workshop on Cyclo- and Polytphosphazenel Materials. February 15–16, 1996. at the CNR Research Area in Padova, Italy. 相似文献
77.
4D Video Textures (4DVT) introduce a novel representation for rendering video‐realistic interactive character animation from a database of 4D actor performance captured in a multiple camera studio. 4D performance capture reconstructs dynamic shape and appearance over time but is limited to free‐viewpoint video replay of the same motion. Interactive animation from 4D performance capture has so far been limited to surface shape only. 4DVT is the final piece in the puzzle enabling video‐realistic interactive animation through two contributions: a layered view‐dependent texture map representation which supports efficient storage, transmission and rendering from multiple view video capture; and a rendering approach that combines multiple 4DVT sequences in a parametric motion space, maintaining video quality rendering of dynamic surface appearance whilst allowing high‐level interactive control of character motion and viewpoint. 4DVT is demonstrated for multiple characters and evaluated both quantitatively and through a user‐study which confirms that the visual quality of captured video is maintained. The 4DVT representation achieves >90% reduction in size and halves the rendering cost. 相似文献
78.
79.
Sara Filippi Hristo Yordanov Liliya Minkova Giovanni Polacco Marco Talarico 《大分子材料与工程》2004,289(6):512-523
Summary: The effectiveness of some thermoplastic elastomers grafted with maleic anhydride (MA) or with glycidyl methacrylate (GMA) as compatibilizer precursors (CPs) for blends of low density polyethylene (LDPE) with polyamide‐6 (PA) has been studied. The CPs were produced by grafting different amounts of MA or GMA onto a styrene‐block‐(ethylene‐co‐1‐butene)‐block‐styrene copolymer (SEBS) (KRATON G 1652), either in the melt or in solution. A commercially available SEBS‐g‐MA copolymer with 1.7 wt.‐% MA (KRATON FG 1901X) was also used. The effect of the MA concentration and of other characteristics of the SEBS‐g‐MA CPs was also studied. The specific interactions between the CPs and the blends components were investigated through characterizations of the binary LDPE/CP and PA/CP blends, in the whole composition range. It was demonstrated that the SEBS‐g‐GMA copolymers display poor compatibilizing effectiveness due to cross‐linking resulting from reactions of the epoxy rings of these CPs with both the amine and the carboxyl end groups of PA. On the contrary, the compatibilizing efficiency of the MA‐grafted elastomers, as revealed by the thermal properties and the morphology of the compatibilized blends, was shown to be excellent. The results of this study confirm that the anhydride functional groups possess considerably higher efficiency, for the reactive compatibilization of LDPE/PA blends, than those of the ethylene‐acrylic acid and ethylene‐glycidyl methacrylate copolymers investigated in previous works.
80.
Chiara Damiani Dario Pescini Riccardo Colombo Sara Molinari Lilia Alberghina Marco Vanoni Giancarlo Mauri 《Natural computing》2014,13(3):321-331
Constraint-based modeling is largely used in computational studies of metabolism. We propose here a novel approach that aims to identify ensembles of flux distributions that comply with one or more target phenotype(s). The methodology has been tested on a small-scale model of yeast energy metabolism. The target phenotypes describe the differential pattern of ethanol production and O2 consumption observed in “Crabtree-positive” and “Crabtree-negative” yeasts in changing environment (i.e., when the upper limit of glucose uptake is varied). The ensembles were obtained either by selection among sampled flux distributions or by means of a search heuristic (genetic algorithm). The former approach provided indication about the probability to observe a given phenotype, but the resulting ensembles could not be unambiguously partitioned into “Crabtree-positive” and “Crabtree-negative” clusters. On the contrary well-separated clusters were obtained with the latter method. The cluster analysis further allowed identification of distinct groups within each target phenotype. The method may thus prove useful in characterizing the design principles underlying metabolic plasticity arising from evolving physio-pathological or developmental constraints. 相似文献