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21.
A combinatorial process has been developed for the high throughput production and evaluation of surface coatings. The workflow designed for the production of arrays of liquid coatings involves the robotic transfer of aliquots of solutions of raw materials to an array of glass vials and mixing of the coatings using an unconventional magnetic stirring process. An investigation of the capability of the workflow to accurately and repeatedly prepare coating arrays was conducted as a function of solution viscosity and aliquot size. In addition, mixing capability was evaluated as a function of solution viscosity, total solution volume, and mechanism of stirring. Overall, the results of the study indicated that adequate accuracy and repeatability of the coating preparation process can be achieved as long as raw material solutions are designed such that viscosity is below about 250 cP and aliquot sizes are above about 75 μl. With regard to mixing capability, total solution volume was found to have a profound affect as did the stirring mechanism. 相似文献
22.
An experimental study to determine the effect of copper (I) iodide (Cul) on the rate and product distribution of degradation of a model of an aliphatic–aromatic polyamide was carried out. N,N′-Dihexylisophthalamide (DHI) was reacted in both an inert argon atmosphere and a pure oxygen environment at 350°C with CuI added in amounts ranging from 0 to 20% by weight. The rate of disappearance of DHI was enhanced by an order of magnitude when 0.5% by weight of CuI was added and was an increasing function of increasing CuI loading. Reaction in pure O2 increased the rate of DHI degradation by two orders of magnitude over that for neat DHI pyrolysis. The rate of disappearance of DHI in O2 was relatively unchanged when 5% CuI by weight was added. The transformations of DHI and its products are organized in terms of a set of reaction rules. This “reaction operator” formalism allowed computer generation of the reaction network and facilitated estimation of kinetic parameters. © 1995 John Wiley & Sons, Inc. 相似文献
23.
Characterization of the adipose tissue atrophy induced by peroxisome proliferators in mice 总被引:4,自引:0,他引:4
In the present study, we characterized the effects of peroxisome proliferators (PP) on adipose tissue in mice. Treatment with
potent PP, such as perfluorooctanoic acid (PFOA), 2-methyl-2-(p(1,2,3,4-tetrahydroxy-naphthyl)-phenoxy)propionic acid, (4-chloro-6-(2,3-xylidino)2-pyrimidinylthio) acetic acid, and di(2-ethylhexyl)phthalate,
caused dramatic decreases in adipose tissue weight, whereas the moderately potent PP, acetylsalicylic acid, had a relatively
weak effect. This decrease in weight reflects a loss of fat from adipocytes rather than a loss of cells, as demonstrated by
constant DNA content. The dose-dependency and time-course experiments indicate that peroxisome proliferation occurs simultaneously
with or prior to adipose tissue atrophy. Thus, hepatic peroxisome proliferation might result in the increased mobilization
of lipids and lipid utilization in liver. The enhanced adipose tissue hormonesensitive lipase (HSL) activity and down-regulated
lipoprotein lipase (LPL) activity observed upon PP treatment might, at least in part, explain the loss of fat via increase FA release from adipocytes and/or decreased FA uptake from the circulation, respectively. In addition, the possible
involvement of the increased tumor necrosis factor α expression found upon PFOA treatment in reducing the insulin sensitivity
of adipose tissue and thereby altering LPL and HSL activities is discussed. 相似文献
24.
Morris Aaron J.; Davenport Robert C.; Tolan Dean R. 《Protein engineering, design & selection : PEDS》1996,9(1):61-67
Lys146 of rabbit aldolase A [D-fructose-1,6-bis(phosphate):D-glyceraldehyde-3-phosphate lyase, EC 4.1.2.13
[EC]
] was changedto arginine by site-directed mutagenesis. The kcat of the resultingmutant protein, K146R, was 500 times slower than wild-type insteady-state kinetic assays for both cleavage and condensationof fructose-1,6-bis(phosphate), while the Km for this substratewas unchanged. Analysis of the rate of formation of catalyticintermediates showed K146R was significantly different fromthe wild-type enzyme and other enzymes mutated at this site.Single-turnover experiments using acid precipitation to trapthe Schiff base intermediate on the wild-type enzyme failedto show a build-up of this intermediate on K146R. However, K146Rretained the ability to form the Schiff base intermediate asshown by the significant amounts of Schiff base intermediatetrapped with NaBH4. In the single-turnover experiments it appearedthat the Schiff base intermediate was converted to productsmore rapidly than it was produced. This suggested a maximalrate of Schiff base formation of 0.022 s1, which wasclose to the value of kcat for this enzyme. This observationis strikingly different from the wild-type enzyme in which Schiffbase formation is >100 times faster than kcat. For K146Rit appears that steps up to and including Schiff base formationare rate limiting for the catalytic reaction. The carbanionintermediate derived from either substrate or product, and theequilibrium concentrations of covalent enzyme-substrate intermediates,were much lower on K146R than on the wild-type enzyme. The greaterbulk of the guanidino moiety may destabilize the covalent enzyme-substrateintermediates, thereby slowing the rate of Schiff base formationsuch that it becomes rate limiting. The K146R mutant enzymeis significantly more active than other enzymes mutated at thissite, perhaps because it maintains a positively charged groupat an essential position in the active site or perhaps the Argfunctionally substitutes as a general acid/base catalyst inboth Schiff base formation and in subsequent abstraction ofthe C4-hydroxyl proton. 相似文献
25.
A number of urethane acrylate nano- and micro-composites have been developed using both ion exchange and silane grafting chemistry. The organically modified clays which were used contained either methacrylate or acrylate functionalities which were capable of reacting with the acrylate groups in the urethane acrylate matrix. [2-(Acryloyloxy)ethyl]trimethyl-ammonium ion (AOETMA) or [2-(methacryloyloxy)ethyl]trimethylammonium ion (MAOTMA) were exchanged onto montmorillonite (MMT) as shown by an increase in the inter-gallery spacing of the MMT. Silane grafting was undertaken using [3-(acryloxy)propyl]dimethylmethoxysilane (APDMMS) or [3-(methacryloxy)propyl]dimethylmethoxysilane (MAPDMMS) and also showed an increase in inter-gallery spacing. The structures of the resulting urethane acrylate composites were characterized using X-ray diffraction (XRD) and transmission electron microscopy (TEM) and showed predominantly intercalated structures with some exfoliation (more evident in the silane-grafted systems). Dynamical mechanical thermal analysis (DMTA) showed a more significant increase in effective crosslink density (as measured from the plateau of the rubbery modulus) in the composites containing the reactive clays as compared to the unmodified clay, supporting the concept that the acrylate and methacrylate functionalities of the modified clays had reacted with the matrix. Other thermal and mechanical properties were also evaluated. 相似文献
26.
27.
Electrochemical characterization of 8-hydroxyquinoline-5-sulphonate/aluminium(III) aqueous solutions
Denis Badocco Annalisa Dean Valerio Di Marco Paolo Pastore 《Electrochimica acta》2007,52(28):7920-7926
8-Hydroxyquinoline-5-sulphonate/Al(III) aqueous solutions were studied both by potentiometric titrations and voltammetric measurements, in order to obtain the number, the stoichiometry and the stability constants of the complexes formed at equilibrium, and to evaluate the redox and (electro)kinetic properties of the free ligand and of the metal/ligand complexes. The complexes formed in 0.2 m (Na)Cl aqueous solution (stability log beta values ± standard deviation) are AlL+ (8.95 ± 0.05), AlL2− (17.43 ± 0.03) and AlL33− (24.58 ± 0.05), where “L” denotes the free ligand in the completely deprotonated form (L2−, pKa1 = 3.910 ± 0.008, pKa2 = 8.319 ± 0.004). AlL33− is the predominant Al(III) species in a very wide range of pH, metal and ligand concentrations and metal-to-ligand ratios. The free ligand shows an oxidation wave at 0.62 V versus SCE. The proposed oxidation mechanism includes a first reversible one-electron oxidation of the ligand, followed by a coupling reaction and by a second reversible one-electron oxidation, and finally by a decomposition reaction. The addition of Al(III) lowers the intensity of the oxidation wave due to the formation of the redox-inactive complex AlL33−. A residual low signal was attributed to the free ligand produced by the complex dissociation, AlL33− = AlL2− + L2−. All the kinetic parameters involved in the ligand oxidation and in the complex disruption were calculated on the basis of the agreement between experimental and simulated linear sweep and cyclic voltammetries. Correctness of the mechanisms proposed was further confirmed “a posteriori” by the agreement between potentiometric and linear sweep voltammetric results. The low residual signal observed in the presence of fully formed complex was attributed to the free ligand produced by the complex dissociation, having a kinetic constant estimated 0.2 s−1. 相似文献
28.
Dan I. Enache Dean Barker Jennifer K. Edwards Stuart H. Taylor David W. Knight Albert F. Carley Graham J. Hutchings 《Catalysis Today》2007,122(3-4):407-411
The oxidation of benzyl alcohol with molecular oxygen under solvent-free conditions has been investigated using a range of titania-supported Au–Pd alloy catalysts to examine the effect of the Au–Pd ratio on the conversion and selectivity. The catalysts have been compared at high reaction temperature (160 °C) as well as at 100 °C, to determine the effect on selectivity since at lower reaction temperature the range of by-products that are formed are limited. Under these conditions the 2.5 wt.% Au–2.5 wt.% Pd/TiO2 was found to be the most active catalyst, whereas the Au/TiO2 catalyst demonstrated the highest selectivity to benzaldehyde. Toluene, formed via either a hydrogen transfer process or an oxygen transfer process, was observed as a major by-product under these forcing conditions. 相似文献
29.
Peter A. Edwards Grant Striemer Dean C. Webster 《Journal of Coatings Technology and Research》2005,2(7):517-527
Glycidyl carbamate chemistry combines the excellent properties of polyurethanes with the crosslinking chemistry of epoxy resins.
Glycidyl carbamate functional oligomers were synthesized by the reaction of polyfunctional isocyanate oligomers and glycidol.
The oligomers were formulated into coatings with several amine functional crosslinkers at varying stoichiometric ratios and
cured at different temperatures. Properties such as solvent resistance, hardness, and impact resistance were dependent on
the composition and cure conditions. Most coatings had an excellent combination of properties. Studies were carried out to
determine the kinetics of the curing reaction of the glycidyl carbamate functional oligomers with multifunctional and model
amines. Detailed kinetic analysis of the curing reactions was also undertaken. The results indicated that the glycidyl carbamate
functional group is more reactive than a glycidyl ether group.
Presented at the 82nd Annual Meeting of the Federation of Societies for Coatings Technology, on October 27–29, 2004, in Chicago,
IL. 相似文献
30.
Straight‐Line Tracking Control of an Agricultural Vehicle with Finite‐Time Control Technique 下载免费PDF全文
For the agricultural vehicle straight‐line tracking system, three control algorithms based upon the finite‐time control technique have been proposed to force the vehicle to track a straight line. Without considering the lumped disturbance, a backstepping‐like finite‐time state‐feedback controller is first developed. On this basis, an adaptive state‐feedback controller in conjunction with integral sliding mode is further developed in the presence of the lumped disturbance. Finally, a sliding mode disturbance observer is given to estimate the lumped disturbance, and the composite control scheme is presented. Under the composite controller, the lumped disturbance can be compensated and thus the disturbance rejection property has been significantly improved. Simulation results verify the proposed control algorithms. 相似文献