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11.
Dr. David Lindsay Professor Egon Matijević Professor Josip P. Kratohvil 《Colloid and polymer science》1976,254(4):421-428
Summary The effects of dextran sulfates of different molecular weights and charge densities on the stability of positively and negatively charged silver bromide solsin statu nascendi have been studied by means of light scattering.The plots of scattering intensities of a positively charged sol against the concentration of the added dextran sulfates show one pronounced maximum, the position which is independent on the molecular weight of the polyelectrolyte used. The maximum shifts to lower polyion concentrations with dilution of the sol.The effect of polyanions on the stability of silver bromide sols of the same sign of charge were investigated as a function of molecular weight of the polymers, the sol concentration, the charge and the concentration of counterions, and the addition of methanol. Destabilization only occurred if sufficient amount of indifferent electrolyte was present in the system. However, the concentration of counterions necessary to produce a flocculation maximum was lower in the presence of the polyelectrolytes than in their absence. The results obtained were compared with the data on sols containing nonionic dextrans reported earlier.
5 figures and 1 table
Supported by the NSF Grant GP 42331 X.
A part of the Ph.D. Thesis by David Lindsay. 相似文献
Zusammenfassung Der Einfluß der Dextransulfate von verschiedenen Molekulargewichten und Ladungsdichten auf die Stabilität der positiv und negativ geladenen Silberbromid-Solein statu nascendi wurden durch Lichtstreuung untersucht. Wenn die Intensitäten der Lichtstreuung eines positiv geladenen Silberbromid-Sols gegen die Konzentration der zugesetzten DextranSulfate aufgetragen werden, tritt ein ausgeprägtes Maximum auf, dessen Lage von dem Molekulargewicht des angewandten Polyelektrolyten unabhängig ist. Bei Verdünnung des Sols wird das Maximum zur niedrigeren Konzentration des Polyanions verschoben.Der Einfluß der Polyanionen auf die Stabilität der Silberbromid-Sole mit gleichem Ladungsvorzeichen wurde in Abhängigkeit von dem Molekulargewicht des zugesetzten Dextransulfats, der Solkonzentration, der Ladung und Konzentration der Gegenionen und dem Zusatz von Methylalkohol untersucht. Destabilisierung wird nur in Anwesenheit einer genügenden Menge von Neutralelektrolyten in den untersuchten Systemen beobachtet. Die Konzentration der Gegenionen, die ein Flockungsmaximum verursachen, ist immer niedriger als die kritische Koagulationsmenge derselben Ionen für das gleiche Sol in Abwesenheit von Makroionen. Die Resultate wurden mit den Wechselwirkungen der Silberbromid-Sole mit nichtionogenen Dextranen verglichen, und der Mechanismus der Flockung durch Polyelektrolyte wurde diskutiert.
5 figures and 1 table
Supported by the NSF Grant GP 42331 X.
A part of the Ph.D. Thesis by David Lindsay. 相似文献
12.
J. H. Augustson J. W. Haynes T. W. Sanders 《Journal of Radioanalytical and Nuclear Chemistry》1980,60(2):373-383
A method for the determination of uranium based on235U thermal neutron fission, has been developed and employed on samples of ashed fish tissue and seaweed. The method involves
a post-irradiation ion exchange separation of iodine isotopes. The 884 keV photopeak of134I is used for measurement. Uranium detection limits in the samples concerned have been estimated to be 1·10−8g in terms of natural uranium. The precision achieved in analysing several series of 3–5 samples was 4–10 per cent. The accuracy
of the method was tested by employing an independent neutron activation procedure based on239U measurement. The accuracy of both methods was checked by analysing NBS SRM 1571 ‘Orchard Leaves’. 相似文献
13.
Dyer JA Trivedi P Sanders SJ Scrivner NC Sparks DL 《Journal of colloid and interface science》2004,270(1):66-76
Previous studies demonstrated the environmental and economic benefits of treating lead(II)-contaminated water streams with ferrihydrite in multiple equilibrium sorption stages. In this work, multistage ferrihydrite sorption systems were evaluated for their effectiveness in reducing single-solute zinc(II) (Zn(II)) concentrations in contaminated water streams to very low levels. As for lead(II) (Pb(II)), experimental data and modeling results indicate that a multistage sorption system can significantly reduce Zn(II) effluent concentrations for the same total amount of sorbent or, alternatively, dramatically lower total sorbent consumption for the same effluent Zn(II) concentration. Compared to Pb(II), however, Zn(II) removal requires on the order of 10 times more sorbent to achieve the same target effluent concentration for the same pH and number of stages. Model predictions were made using a steady-state, multistage, equilibrium adsorber model that was previously developed for and integrated into OLI Systems' Environmental Simulation Program (ESP). The modified triple-layer model was used to simulate Zn(II) surface-liquid equilibria within the adsorber model. Engineering screening evaluations again indicate that a 2- to 3-stage sorption process can provide significant economic savings when compared to a 1-stage process operating with the same target effluent Zn(II) concentration. Additional equilibrium stages beyond 2 or 3 provide diminishing economic returns. The major economic driver for multiple contacting stages is reduced capital investment and operating costs for sludge handling, dewatering, and disposal. 相似文献
14.
A kinetic study of the fluoride ion catalyzed isomerization of a series of 2-aryl1-butenes shows the reactions to be pseudo first order in olefin at constant fluoride ion concentration. The resultant Hammett plot is non-linear witb a concave downward break near =0. A two step mechanism involving formation of a carbanionic intermediate is proposed. A change in the rate limiting step causes the break in the Hammett plot. Carbanion trapping experiments are also reported. 相似文献
15.
Gillespie KM Sanders CJ O'Shaughnessy P Westmoreland I Thickitt CP Scott P 《The Journal of organic chemistry》2002,67(10):3450-3458
Racemic 2,2'-diamino-6,6'-dimethylbiphenyl is resolved using simulated moving bed chromatography, and the absolute configuration of the enantiomers is confirmed via the X-ray crystal structure of a derivative. The diamine is condensed with a range of aldehydes to give bidentate aldimine proligands L. Molecular structures of the complexes formed between L and Cu(I) fall into two classes; bimetallic double helices ([Cu(2)L(2)](2+)) and monometallic ([CuL](+)). The latter are strikingly more efficient in the aziridination of alkenes than are the former in terms of rate, turnover, and enantioselection. In particular, the imine ligand formed from the diamine and 2,6-dichlorobenzaldehyde gives, in combination with Cu(I) or Cu(II), up to 99% ee in the aziridination of 6-acyl-2,2-dimethylchromene and 88-98% ee for a range of cinnamate esters. Styrenic and other alkenes are converted with lower selectivities (5-54%). The catalytic system shows a linear response in product ee to catalyst ee, and the product ee does not vary significantly during the reaction. UV spectrophotometric investigations indicate that conversion of Cu(I) to Cu(II) is not essential for catalysis but that Cu(II) is probably also a competent system. 相似文献
16.
17.
The distribution of the likelihood ratio for mixtures of densities from the one-parameter exponential family 总被引:2,自引:0,他引:2
Dankmar Böhning Ekkehart Dietz Rainer Schaub Peter Schlattmann Bruce G. Lindsay 《Annals of the Institute of Statistical Mathematics》1994,46(2):373-388
We here consider testing the hypothesis ofhomogeneity against the alternative of a two-component mixture of densities. The paper focuses on the asymptotic null distribution of 2 log
n
, where
n
is the likelihood ratio statistic. The main result, obtained by simulation, is that its limiting distribution appears pivotal (in the sense of constant percentiles over the unknown parameter), but model specific (differs if the model is changed from Poisson to normal, say), and is not at all well approximated by the conventional
(2)
2
-distribution obtained by counting parameters. In Section 3, the binomial with sample size parameter 2 is considered. Via a simple geometric characterization the case for which the likelihood ratio is 1 can easily be identified and the corresponding probability is found. Closed form expressions for the likelihood ratio
n
are possible and the asymptotic distribution of 2 log
n
is shown to be the mixture giving equal weights to the one point distribution with all its mass equal to zero and the 2-distribution with 1 degree of freedom. A similar result is reached in Section 4 for the Poisson with a small parameter value (0.1), although the geometric characterization is different. In Section 5 we consider the Poisson case in full generality. There is still a positive asymptotic probability that the likelihood ratio is 1. The upper precentiles of the null distribution of 2 log
n
are found by simulation for various populations and shown to be nearly independent of the population parameter, and approximately equal to the (1–2)100 percentiles of
(1)
2
. In Sections 6 and 7, we close with a study of two continuous densities, theexponential and thenormal with known variance. In these models the asymptotic distribution of 2 log
n
is pivotal. Selected (1–) 100 percentiles are presented and shown to differ between the two models. 相似文献
18.
Arisaka K Auerbach LB Axelrod S Belz J Biery KA Buchholz P Chapman MD Cousins RD Diwan MV Eckhause M Ginkel JF Guss C Hancock AD Heinson AP Highland VL Hoffmann GW Horvath J Irwin GM Joyce D Kaarsberg T Kane JR Kenney CJ Kettell SH Kinnison WW Knibbe P Konigsberg J Kuang Y Lang K Lee DM Margulies J Mathiazhagan C McFarlane WK McKee RJ Melese P Milner EC Molzon WR Ouimette DA Riley PJ Ritchie JL Rubin P Sanders GH Schwartz AJ Sivertz M Slater WE Urheim J Vulcan WF Wagner DL Welsh RE Whyley RJ 《Physical review letters》1993,71(24):3910-3913
19.
20.
Charles M. Lindsay Keith Smith Charles Allan Brown Kathleen Betterton-Cruz 《Tetrahedron letters》1984,25(9):995-998
Unsymmetrical hexathioorthooxalates of types () and () undergo elimination of dialkyl disulfide on heating in an organic solvent; the reaction, which is catalyzed by acid, proceeds without fission of the central C:C bond and provides the first general, high yield synthesis of unsymmetrical benzotetrathiafulvalenes of types () and (). 相似文献