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31.
Gottfried Lichti Brian S. Hawkett Robert G. Gilbert Donald H. Napper David F. Sangster 《Journal of polymer science. Part A, Polymer chemistry》1981,19(4):925-938
Data are presented on the time evolution of particle-size distributions (PSDs) in seeded and ab initio styrene emulsion polymerization systems. Initiation was by chemical reagent (potassium persulfate) or γ-radiation. The unswollen PSDs at various times during interval II of the polymerization were obtained by direct measurement of calibrated electron micrographs. Experimental results were fitted with the equations that describe the time evolution of an initial PSD. Analytic solutions to these equations that allow for entry, exit, and propagation of free radicals were obtained. The values of the rate coefficients for these processes used to fit the experimental data were in excellent agreement with those obtained from dilatometric kinetics experiments. 相似文献
32.
We have constructed molecular models of octameric micelles formed by a recently developed lipopeptide detergent consisting of a single amphipathic alpha-helix coupled to two acyl chains at either end of the helix. The models explain the experimentally observed aggregation behavior of peptides with different acyl chain lengths. The octameric micelles form a unique coiled-coil structure, with the acyl chains in a nearly frozen conformation inside the cylindrical assemblies. Two extreme models with helices either all parallel or in an alternating orientation suggest that the alternating orientation is energetically more favorable. The models suggest several new directions for further diversifying this new class of detergents for the structural studies of membrane proteins. 相似文献
33.
The optically and thermally induced electron transfer pathways of highly symmetrical (D(3)) hexaarylbenzene systems with six triarylamine redox sites have been investigated. Owing to slightly different local redox potentials, the radical trication could be selectively generated by electrochemical methods. This trication shows a strong intervalence charge-transfer band in the near infrared (NIR) that was measured by spectroelectrochemistry and analysed using multi-dimensional Mulliken-Hush theory. Quantum chemical AM1 CI calculations indicate that there is no optically induced concerted three-electron transfer that transforms the ground state into a state in which all three positively charged triarylamine moieties change place with their neutral neighbours. The potential energy surface of the ground state was constructed by using quadratic potentials. From this potential surface it is apparent that there is also no thermally allowed concerted three-electron transfer pathway. Instead, three consecutive one-electron transfer steps are necessary for this process. 相似文献
34.
Beech CL Coope JF Fairley G Gilbert PS Main BG Plé K 《The Journal of organic chemistry》2001,66(7):2240-2245
A new "safety catch" linker for esters has been synthesized on polystyrene resin. This 2-tert-butoxyphenol resin 10 may be acylated to give a relatively stable ester that will allow nucleophilic chemistry without reaction at the linking ester group. Removal of the tert-butyl group with acid unmasks a highly reactive 2-hydroxyphenyl ester that reacts readily with nucleophiles to cause release of the product from the resin. This sequence has been exemplified by acylating the resin with various bromo acids, carrying out nucleophilic displacements with thiols, phenols, or amines, activating the ester with trifluoroacetic acid and cleaving from the resin with amines to give the (nucleophile) substituted carboxamides in high yield and purity. Kinetic studies with a model ester revealed half-lives for reaction with morpholine of 119 h for the tert-butoxyphenyl ester and 1 min for the corresponding phenol. 相似文献
35.
Amperometric method for determining the degree of complexation of polyelectrolytes with cationic surfactants 总被引:1,自引:0,他引:1
Hakkarainen S Gilbert SL Kontturi AK Kontturi K 《Journal of colloid and interface science》2004,272(2):404-410
The complexation of sodium polystyrene sulfonate with monovalent cationic surfactants at a microsized liquid/liquid interface has been studied using electrochemistry. The method is based on measurement of surfactant ion transfer across the interface between two immiscible electrolyte solutions (ITIES). The complexation of various cationic surfactants (alkylpyridinium- and trimethylammonium-) with oligosized polystyrene sulfonate was measured. Binding isotherms were used to determine the degree of binding as a function of the surfactant chain length and type of head group. It was found that the hydrophobicity of the surfactant was the predominant factor. The effect of the polyelectrolyte chain length on the binding mechanism was studied using cetylpyridinium chloride as a complexing agent. It was found that binding affinity, as well as cooperativity of the binding process, decreases with decreasing polyelectrolyte chain length. Thermodynamics of surfactant binding was measured using titration microcalorimetry. The thermodynamic data obtained show that the enthalpy of surfactant binding is not dependent on polymer chain length, but an increase in chain length makes the binding process entropically more favorable. 相似文献
36.
A new procedure for simultaneous preconcentration, separation, and determination of permanganate, chromate and vanadate was developed for aqueous solutions containing p.p.b. levels of these anions (and molybdate). The presence of other (non-complexing) ions in p.p.m. concentrations did not interfere. The procedure consisted of reactive adsorption of all three anions as their reduced cations, on iron(II)-treated resin, followed by elution of vanadium(IV) with 0.01 M HNO3/H2O2, manganese(II) with 0.35 M HCl, and chromium(III) with 4M HCl. Concentration factors of 40 were obtained with 1-l “samples” 10 p.p.b. concentrations were determined with standard deviations of 4–5 % by a.a.s. and conventional spectrophotometry. 相似文献
37.
ETUDE EN SPECTROMETRIE DE MASSE DE PHOSPHONATES ENYNIQUES ET DE β-CETOPHOSPHONATES-γ, δ-ETHYLENIQUES
The mass spectrometric study of acetylenic dialkylphosphonates (I) and of γ, δ-éthylenic-β-ketophosphonates (II) is characterised by rearrangement processes of the phosphorylated group and cleavage of the phosphorus-carbon bond. The fragmentation patterns of compounds II were identical to those found for I by loss of water. 相似文献
38.
In the majority of the literature describing green coloured materials used on ancient painting layers (15th or 16th century), two copper greens are mainly cited: malachite [CuCOr3 x Cu(OH)2] and verdigris [Cu(CH3COO)2 x [Cu(OH)2]3 x 2H2O]. It is shown, by micro-Raman spectroscopy, that the artists were actually employing more than these two copper greens, in particular various copper sulfates, among which the most common pigment found is posnjakite [CuSO4 x 3Cu(OH)2 x H2O]. In contrast to the PIXE (particle induced X-ray emission) technique, Raman spectroscopy is a technique of choice, able to distinguish not only a copper sulfate from a carbonate or acetate but also the different sulfates themselves; in this respect, we found that the high wavenumber region (2800-4000 cm(-1)), characteristic of H2O vibrations, is of particular interest. It is also shown that numerous green areas were created with mixtures of a copper sulfate mixed with other pigments, for instance to enhance the colour depth. Finally, in some cases, no green pigment is actually employed but the colour is obtained by intimately mixing yellow and blue pigments. All these results led to a new look at the pigments which were in use on the palettes of the ancient artists. 相似文献
39.
Entwisle AC Williams AC Mann PJ Russell J Slack PT Gilbert J 《Journal of AOAC International》2001,84(2):444-450
A collaborative study was conducted to evaluate a liquid chromatography (LC) method for ochratoxin A using sequential phenyl silane and immunoaffinity column cleanup. The method was tested at 3 different levels of ochratoxin A in roasted coffee, which spanned the range of possible future European regulatory limits. The test portion was extracted with methanol and sodium bicarbonate by shaking for 30 min. The extract was filtered, centrifuged, and then cleaned up on a phenyl silane column before being eluted from the washed column with methanol-water. The eluate was diluted with phosphate-buffered saline (PBS) and applied to an ochratoxin A immunoaffinity column, which was washed with water. The ochratoxin A was eluted with methanol, the solvent was evaporated, and the residue was redissolved in injection solvent. After injection of this solution onto a reversed-phase LC apparatus, ochratoxin A was measured by fluorescence detection. Eight laboratory samples of low-level naturally contaminated roasted coffee and 2 laboratory samples of blank coffee (< 0.2 ng/g ochratoxin A at the signal-to-noise ratio of 3:1), along with ampules of ochratoxin A calibrant and spiking solutions, were sent to 15 laboratories in 13 different European countries. Test portions of the laboratory samples were spiked at levels of 4 ng/g ochratoxin A, and recoveries ranged from 65 to 97%. Based on results for spiked blank material (blind duplicates) and naturally contaminated material (blind duplicates at 3 levels), the relative standard deviation for repeatability (RSDr) ranged from 2 to 22% and the relative standard deviation for reproducibility (RSDR) ranged from 14 to 26%. The method showed acceptable within- and between-laboratory precision, as evidenced by HORRAT values, at the low level of determination for ochratoxin A in roasted coffee. 相似文献
40.
Ketene silylacetals derived from prenyl and (Z)- and (E)-crotyl 2-methylcyclopentanecarboxylates (9) were subjected to the Ireland-Claisen rearrangement. All three substrates rearranged with complete facial selectivity, but the (Z)- and (E)-crotyl systems gave a mixture comprised of the same diastereomers of 1-(1-methyl-2-propenyl)-2-methylcyclopentanecarboxylic acid (14) in ratios of 2:1 and 1:2, respectively. In contrast, the ketene silylacetals prepared from allyl and prenyl 2-methoxycyclopentanecarboxylates (22) underwent rearrangements with both facial stereochemistries. 相似文献