980 resultados para Order of Convergence


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Fundamental studies of magnetic alignment of highly anisotropic mesostructures can enable the clean-room-free fabrication of flexible, array-based solar and electronic devices, in which preferential orientation of nano- or microwire-type objects is desired. In this study, ensembles of 100 micron long Si microwires with ferromagnetic Ni and Co coatings are oriented vertically in the presence of magnetic fields. The degree of vertical alignment and threshold field strength depend on geometric factors, such as microwire length and ferromagnetic coating thickness, as well as interfacial interactions, which are modulated by varying solvent and substrate surface chemistry. Microwire ensembles with vertical alignment over 97% within 10 degrees of normal, as measured by X-ray diffraction, are achieved over square cm scale areas and set into flexible polymer films. A force balance model has been developed as a predictive tool for magnetic alignment, incorporating magnetic torque and empirically derived surface adhesion parameters. As supported by these calculations, microwires are shown to detach from the surface and align vertically in the presence of magnetic fields on the order of 100 gauss. Microwires aligned in this manner are set into a polydimethylsiloxane film where they retain their vertical alignment after the field has been removed and can subsequently be used as a flexible solar absorber layer. Finally, these microwires arrays can be protected for use in electrochemical cells by the conformal deposition of a graphene layer.

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In order to develop better catalysts for the cleavage of aryl-X bonds fundamental studies of the mechanism and individual steps of the mechanism have been investigated in detail. As the described studies are difficult at best in catalytic systems, model systems are frequently used. To study aryl-oxygen bond activation, a terphenyl diphosphine scaffold containing an ether moiety in the central arene was designed. The first three chapters of this dissertation focus on the studies of the nickel complexes supported by this diphosphine backbone and the research efforts in regards to aryl-oxygen bond activation.

Chapter 2 outlines the synthesis of a variety of diphosphine terphenyl ether ligand scaffolds. The metallation of these scaffolds with nickel is described. The reactivity of these nickel(0) systems is also outlined. The systems were found to typically undergo a reductive cleavage of the aryl oxygen bond. The mechanism was found to be a subsequent oxidative addition, β-H elimination, reductive elimination and (or) decarbonylation.

Chapter 3 presents kinetic studies of the aryl oxygen bond in the systems outlined in Chapter 2. Using a series of nickel(0) diphosphine terphenyl ether complexes the kinetics of aryl oxygen bond activation was studied. The activation parameters of oxidative addition for the model systems were determined. Little variation was observed in the rate and activation parameters of oxidative addition with varying electronics in the model system. The cause of the lack of variation is due to the ground state and oxidative addition transition state being affected similarly. Attempts were made to extend this study to catalytic systems.

Chapter 4 investigates aryl oxygen bond activation in the presence of additives. It was found that the addition of certain metal alkyls to the nickel(0) model system lead to an increase in the rate of aryl oxygen bond activation. The addition of excess Grignard reagent led to an order of magnitude increase in the rate of aryl oxygen bond activation. Similarly the addition of AlMe3 led to a three order of magnitude rate increase. Addition of AlMe3 at -80 °C led to the formation of an intermediate which was identified by NOESY correlations as a system in which the AlMe3 is coordinated to the ether moiety of the backbone. The rates and activation parameters of aryl oxygen bond activation in the presence of AlMe3 were investigated.

The last two chapters involve the study of metalla-macrocycles as ligands. Chapter 5 details the synthesis of a variety of glyoxime backbones and diphenol precursors and their metallation with aluminum. The coordination chemistry of iron on the aluminum scaffolds was investigated. Varying the electronics of the aluminum macrocycle was found to affect the observed electrochemistry of the iron center.

Chapter 6 extends the studies of chapter 5 to cobalt complexes. The synthesis of cobalt dialuminum glyoxime metal complexes is described. The electrochemistry of the cobalt complexes was investigated. The electrochemistry was compared to the observed electrochemistry of a zinc analog to identify the redox activity of the ligand. In the presence of acid the cobalt complexes were found to electrochemically reduce protons to dihydrogen. The electronics of the ancillary aluminum ligands were found to affect the potential of proton reduction in the cobalt complexes. These potentials were compared to other diglyoximate complexes.

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Part I.

In recent years, backscattering spectrometry has become an important tool for the analysis of thin films. An inherent limitation, though, is the loss of depth resolution due to energy straggling of the beam. To investigate this, energy straggling of 4He has been measured in thin films of Ni, Al, Au and Pt. Straggling is roughly proportional to square root of thickness, appears to have a slight energy dependence and generally decreases with decreasing atomic number of the adsorber. The results are compared with predictions of theory and with previous measurements. While Ni measurements are in fair agreement with Bohr's theory, Al measurements are 30% above and Au measurements are 40% below predicted values. The Au and Pt measurements give straggling values which are close to one another.

Part II.

MeV backscattering spectrometry and X-ray diffraction are used to investigate the behavior of sputter-deposited Ti-W mixed films on Si substrates. During vacuum anneals at temperatures near 700°C for several hours, the metallization layer reacts with the substrate. Backscattering analysis shows that the resulting compound layer is uniform in composition and contains Ti, Wand Si. The Ti:W ratio in the compound corresponds to that of the deposited metal film. X-ray analyses with Reed and Guinier cameras reveal the presence of the ternary TixW(1-x)Si2 compound. Its composition is unaffected by oxygen contamination during annealing, but the reaction rate is affected. The rate measured on samples with about 15% oxygen contamination after annealing is linear, of the order of 0.5 Å per second at 725°C, and depends on the crystallographic orientation of the substrate and the dc bias during sputter-deposition of the Ti-W film.

Au layers of about 1000 Å thickness were deposited onto unreacted Ti-W films on Si. When annealed at 400°C these samples underwent a color change,and SEM micrographs of the samples showed that an intricate pattern of fissures which were typically 3µm wide had evolved. Analysis by electron microprobe revealed that Au had segregated preferentially into the fissures. This result suggests that Ti-W is not a barrier to Au-Si intermixing at 400°C.

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This work contains 4 topics dealing with the properties of the luminescence from Ge.

The temperature, pump-power and time dependences of the photoluminescence spectra of Li-, As-, Ga-, and Sb-doped Ge crystals were studied. For impurity concentrations less than about 1015cm-3, emissions due to electron-hole droplets can clearly be identified. For impurity concentrations on the order of 1016cm-3, the broad lines in the spectra, which have previously been attributed to the emission from the electron-hole-droplet, were found to possess pump-power and time dependent line shape. These properties show that these broad lines cannot be due to emission of electron-hole-droplets alone. We interpret these lines to be due to a combination of emissions from (1) electron-hole- droplets, (2) broadened multiexciton complexes, (3) broadened bound-exciton, and (4) plasma of electrons and holes. The properties of the electron-hole-droplet in As-doped Ge were shown to agree with theoretical predictions.

The time dependences of the luminescence intensities of the electron-hole-droplet in pure and doped Ge were investigated at 2 and 4.2°K. The decay of the electron-hole-droplet in pure Ge at 4.2°K was found to be pump-power dependent and too slow to be explained by the widely accepted model due to Pokrovskii and Hensel et al. Detailed study of the decay of the electron-hole-droplets in doped Ge were carried out for the first time, and we find no evidence of evaporation of excitons by electron-hole-droplets at 4.2°K. This doped Ge result is unexplained by the model of Pokrovskii and Hensel et al. It is shown that a model based on a cloud of electron-hole-droplets generated in the crystal and incorporating (1) exciton flow among electron-hole-droplets in the cloud and (2) exciton diffusion away from the cloud is capable of explaining the observed results.

It is shown that impurities, introduced during device fabrication, can lead to the previously reported differences of the spectra of laser-excited high-purity Ge and electrically excited Ge double injection devices. By properly choosing the device geometry so as to minimize this Li contamination, it is shown that the Li concentration in double injection devices may be reduced to less than about 1015cm-3 and electrically excited luminescence spectra similar to the photoluminescence spectra of pure Ge may be produced. This proves conclusively that electron-hole-droplets may be created in double injection devices by electrical excitation.

The ratio of the LA- to TO-phonon-assisted luminescence intensities of the electron-hole-droplet is demonstrated to be equal to the high temperature limit of the same ratio of the exciton for Ge. This result gives one confidence to determine similar ratios for the electron-hole-droplet from the corresponding exciton ratio in semiconductors in which the ratio for the electron-hole-droplet cannot be determined (e.g., Si and GaP). Knowing the value of this ratio for the electron-hole-droplet, one can obtain accurate values of many parameters of the electron-hole-droplet in these semiconductors spectroscopically.

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Part I. Novel composite polyelectrolyte materials were developed that exhibit desirable charge propagation and ion-retention properties. The morphology of electrode coatings cast from these materials was shown to be more important for its electrochemical behavior than its chemical composition.

Part II. The Wilhelmy plate technique for measuring dynamic surface tension was extended to electrified liquid-liquid interphases. The dynamical response of the aqueous NaF-mercury electrified interphase was examined by concomitant measurement of surface tension, current, and applied electrostatic potential. Observations of the surface tension response to linear sweep voltammetry and to step function perturbations in the applied electrostatic potential (e.g., chronotensiometry) provided strong evidence that relaxation processes proceed for time-periods that are at least an order of magnitude longer than the time periods necessary to establish diffusion equilibrium. The dynamical response of the surface tension is analyzed within the context of non-equilibrium thermodynamics and a kinetic model that requires three simultaneous first order processes.

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The intensities and relative abundances of galactic cosmic ray protons and antiprotons have been measured with the Isotope Matter Antimatter Experiment (IMAX), a balloon-borne magnet spectrometer. The IMAX payload had a successful flight from Lynn Lake, Manitoba, Canada on July 16, 1992. Particles detected by IMAX were identified by mass and charge via the Cherenkov-Rigidity and TOP-Rigidity techniques, with measured rms mass resolution ≤0.2 amu for Z=1 particles.

Cosmic ray antiprotons are of interest because they can be produced by the interactions of high energy protons and heavier nuclei with the interstellar medium as well as by more exotic sources. Previous cosmic ray antiproton experiments have reported an excess of antiprotons over that expected solely from cosmic ray interactions.

Analysis of the flight data has yielded 124405 protons and 3 antiprotons in the energy range 0.19-0.97 GeV at the instrument, 140617 protons and 8 antiprotons in the energy range 0.97-2.58 GeV, and 22524 protons and 5 antiprotons in the energy range 2.58-3.08 GeV. These measurements are a statistical improvement over previous antiproton measurements, and they demonstrate improved separation of antiprotons from the more abundant fluxes of protons, electrons, and other cosmic ray species.

When these results are corrected for instrumental and atmospheric background and losses, the ratios at the top of the atmosphere are p/p=3.21(+3.49, -1.97)x10^(-5) in the energy range 0.25-1.00 GeV, p/p=5.38(+3.48, -2.45) x10^(-5) in the energy range 1.00-2.61 GeV, and p/p=2.05(+1.79, -1.15) x10^(-4) in the energy range 2.61-3.11 GeV. The corresponding antiproton intensities, also corrected to the top of the atmosphere, are 2.3(+2.5, -1.4) x10^(-2) (m^2 s sr GeV)^(-1), 2.1(+1.4, -1.0) x10^(-2) (m^2 s sr GeV)^(-1), and 4.3(+3.7, -2.4) x10^(-2) (m^2 s sr GeV)^(-1) for the same energy ranges.

The IMAX antiproton fluxes and antiproton/proton ratios are compared with recent Standard Leaky Box Model (SLBM) calculations of the cosmic ray antiproton abundance. According to this model, cosmic ray antiprotons are secondary cosmic rays arising solely from the interaction of high energy cosmic rays with the interstellar medium. The effects of solar modulation of protons and antiprotons are also calculated, showing that the antiproton/proton ratio can vary by as much as an order of magnitude over the solar cycle. When solar modulation is taken into account, the IMAX antiproton measurements are found to be consistent with the most recent calculations of the SLBM. No evidence is found in the IMAX data for excess antiprotons arising from the decay of galactic dark matter, which had been suggested as an interpretation of earlier measurements. Furthermore, the consistency of the current results with the SLBM calculations suggests that the mean antiproton lifetime is at least as large as the cosmic ray storage time in the galaxy (~10^7 yr, based on measurements of cosmic ray ^(10)Be). Recent measurements by two other experiments are consistent with this interpretation of the IMAX antiproton results.

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Flies are the largest order of wetland insects in Britain. Of 6668 known species, larvae of at least 1138 are considered to be aquatic while a large number, perhaps as many again, are associated with wetlands. Despite this abundance of species they have been neglected in nearly all studies of temporary ponds. The prerequisites that are usually quoted for surviving in temporary pools are an ability to reach maturity before the system dries out, physiological or behavioural mechanisms to survive the dry period, and an ability to recolonise. Larvae of many British wetland Diptera have these features, which should enable them to develop and survive in temporary ponds. Some examples are considered in this article, with brief comments on adaptations in insects from other geographical regions.

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Part I

The spectrum of dissolved mercury atoms in simple liquids has been shown to be capable of revealing information concerning local structures in these liquids.

Part II

Infrared intensity perturbations in simple solutions have been shown to involve more detailed interaction than just dielectric polarization. No correlation has been found between frequency shifts and intensity enhancements.

Part III

Evidence for perturbed rotation of HCl in rare gas matrices has been found. The magnitude of the barrier to rotation is concluded to be of order of 30 cm^(-1).

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The access of 1.2-40 MeV protons and 0.4-1.0 MeV electrons from interplanetary space to the polar cap regions has been investigated with an experiment on board a low altitude, polar orbiting satellite (OG0-4).

A total of 333 quiet time observations of the electron polar cap boundary give a mapping of the boundary between open and closed geomagnetic field lines which is an order of magnitude more comprehensive than previously available.

Persistent features (north/south asymmetries) in the polar cap proton flux, which are established as normal during solar proton events, are shown to be associated with different flux levels on open geomagnetic field lines than on closed field lines. The pole in which these persistent features are observed is strongly correlated to the sector structure of the interplanetary magnetic field and uncorrelated to the north/south component of this field. The features were observed in the north (south) pole during a negative (positive) sector 91% of the time, while the solar field had a southward component only 54% of the time. In addition, changes in the north/south component have no observable effect on the persistent features.

Observations of events associated with co-rotating regions of enhanced proton flux in interplanetary space are used to establish the characteristics of the 1.2 - 40 MeV proton access windows: the access window for low polar latitudes is near the earth, that for one high polar latitude region is ~250 R behind the earth, while that for the other high polar latitude region is ~1750 R behind the earth. All of the access windows are of approximately the same extent (~120 R). The following phenomena contribute to persistent polar cap features: limited interplanetary regions of enhanced flux propagating past the earth, radial gradients in the interplanetary flux, and anisotropies in the interplanetary flux.

These results are compared to the particle access predictions of the distant geomagnetic tail configurations proposed by Michel and Dessler, Dungey, and Frank. The data are consistent with neither the model of Michel and Dessler nor that of Dungey. The model of Frank can yield a consistent access window configuration provided the following constraints are satisfied: the merging rate for open field lines at one polar neutral point must be ~5 times that at the other polar neutral point, related to the solar magnetic field configuration in a consistent fashion, the migration time for open field lines to move across the polar cap region must be the same in both poles, and the open field line merging rate at one of the polar neutral points must be at least as large as that required for almost all the open field lines to have merged in 0 (one hour). The possibility of satisfying these constraints is investigated in some detail.

The role played by interplanetary anisotropies in the observation of persistent polar cap features is discussed. Special emphasis is given to the problem of non-adiabatic particle entry through regions where the magnetic field is changing direction. The degree to which such particle entry can be assumed to be nearly adiabatic is related to the particle rigidity, the angle through which the field turns, and the rate at which the field changes direction; this relationship is established for the case of polar cap observations.

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The differential energy spectra of cosmic-ray protons and He nuclei have been measured at energies up to 315 MeV/nucleon using balloon- and satellite-borne instruments. These spectra are presented for solar quiet times for the years 1966 through 1970. The data analysis is verified by extensive accelerator calibrations of the detector systems and by calculations and measurements of the production of secondary protons in the atmosphere.

The spectra of protons and He nuclei in this energy range are dominated by the solar modulation of the local interstellar spectra. The transport equation governing this process includes as parameters the solar-wind velocity, V, and a diffusion coefficient, K(r,R), which is assumed to be a scalar function of heliocentric radius, r, and magnetic rigidity, R. The interstellar spectra, jD, enter as boundary conditions on the solutions to the transport equation. Solutions to the transport equation have been calculated for a broad range of assumed values for K(r,R) and jD and have been compared with the measured spectra.

It is found that the solutions may be characterized in terms of a dimensionless parameter, ψ(r,R) = r V dr'/(K(r',R). The amount of modulation is roughly proportional to ψ. At high energies or far from the Sun, where the modulation is weak, the solution is determined primarily by the value of ψ (and the interstellar spectrum) and is not sensitive to the radial dependence of the diffusion coefficient. At low energies and for small r, where the effects of adiabatic deceleration are found to be large, the spectra are largely determined by the radial dependence of the diffusion coefficient and are not very sensitive to the magnitude of ψ or to the interstellar spectra. This lack of sensitivity to jD implies that the shape of the spectra at Earth cannot be used to determine the interstellar intensities at low energies.

Values of ψ determined from electron data were used to calculate the spectra of protons and He nuclei near Earth. Interstellar spectra of the form jD α (W - 0.25m)-2.65 for both protons and He nuclei were found to yield the best fits to the measured spectra for these values of ψ, where W is the total energy and m is the rest energy. A simple model for the diffusion coefficient was used in which the radial and rigidity dependence are separable and K is independent of radius inside a modulation region which has a boundary at a distance D. Good agreement was found between the measured and calculated spectra for the years 1965 through 1968, using typical boundary distances of 2.7 and 6.1 A.U. The proton spectra observed in 1969 and 1970 were flatter than in previous years. This flattening could be explained in part by an increase in D, but also seemed to require that a noticeable fraction of the observed protons at energies as high at 50 to 100 MeV be attributed to quiet-time solar emission. The turnup in the spectra at low energies observed in all years was also attributed to solar emission. The diffusion coefficient used to fit the 1965 spectra is in reasonable agreement with that determined from the power spectra of the interplanetary magnetic field (Jokipii and Coleman, 1968). We find a factor of roughly 3 increase in ψ from 1965 to 1970, corresponding to the roughly order of magnitude decrease in the proton intensity at 250 MeV. The change in ψ might be attributed to a decrease in the diffusion coefficient, or, if the diffusion coefficient is essentially unchanged over that period (Mathews et al., 1971), might be attributed to an increase in the boundary distance, D.

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The problem is to calculate the attenuation of plane sound waves passing through a viscous, heat-conducting fluid containing small spherical inhomogeneities. The attenuation is calculated by evaluating the rate of increase of entropy caused by two irreversible processes: (1) the mechanical work done by the viscous stresses in the presence of velocity gradients, and (2) the flow of heat down the thermal gradients. The method is first applied to a homogeneous fluid with no spheres and shown to give the classical Stokes-Kirchhoff expressions. The method is then used to calculate the additional viscous and thermal attenuation when small spheres are present. The viscous attenuation agrees with Epstein's result obtained in 1941 for a non-heat-conducting fluid. The thermal attenuation is found to be similar in form to the viscous attenuation and, for gases, of comparable magnitude. The general results are applied to the case of water drops in air and air bubbles in water.

For water drops in air the viscous and thermal attenuations are camparable; the thermal losses occur almost entirely in the air, the thermal dissipation in the water being negligible. The theoretical values are compared with Knudsen's experimental data for fogs and found to agree in order of magnitude and dependence on frequency. For air bubbles in water the viscous losses are negligible and the calculated attenuation is almost completely due to thermal losses occurring in the air inside the bubbles, the thermal dissipation in the water being relatively small. (These results apply only to non-resonant bubbles whose radius changes but slightly during the acoustic cycle.)

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The O18/O16 ratios of coexisting minerals from a number of regionally metamorphosed rocks have been measured, using a bromine pentafluoride extraction-technique. Listed in order of their increasing tendency to concentrate O18, the minerals analyzed are magnetite, ilmenite, chlorite, biotite, garnet, hornblende, kyanite, muscovite, feldspar, and quartz. The only anomalous sequence detected occurs in a xenolith of schist, in which quartz, muscovite, biotite, and ilmenite, but not garnet, have undergone isotopic exchange with surrounding trondjemite.

With few exceptions, quartz-magnetite and quartz-ilmenite fractionations decrease with increasing metamorphic grade determined by mineral paragenesis and spatial distribution. This consistency does not apply to quartz-magnetite and quartz-ilmenite fractionations obtained from rocks in which petrographic evidence of retrogradation is present.

Whereas measured isotopic fractionations among quartz, garnet, ilmenite, and magnetite are approximately related to metamorphic grade, fractionations between these minerals and biotite or muscovite show poor correlation with grade. Variations in muscovite-biotite fractionations are relatively small. These observations are interpreted to mean that muscovite and biotite are affected by retrograde re-equilibration to a greater extent than the anhydrous minerals analyzed.

Measured quartz-ilmenite fractionations range from 12 permil in the biotite zone of central Vermont to 6.5 permil in the sillimanite-orthoclase zone of southeastern Connecticut. Analyses of natural assemblages from the kyanite and sillimanite zones suggest that equilibrium quartz-ilmenite fractionations are approximately 8 percent smaller than corresponding quartz-magnetite fractionations. Employing the quartz-magnetite geothermometer calibrated by O'Neil and Clayton (1964), a temperature of 560°C was obtained for kyanite-bearing schists from Addison County, Vermont. Extending the calibration to quartz-ilmenite fractionations, a temperature of 600°C was obtained for kyanite-schists from Shoshone County, Idaho. At these temperatures kyanite is stable only at pressures exceeding 11 kbars (Bell, 1963), corresponding to lithostatic loads of over 40 km.

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1. The effect of 2,2’-bis-[α-(trimethylammonium)methyl]azobenzene (2BQ), a photoisomerizable competitive antagonist, was studied at the nicotinic acetycholine receptor of Electrophorus electroplaques using voltage-jump and light-flash techniques.

2. 2BQ, at concentrations below 3 μΜ, reduced the amplitude of voltage-jump relaxations but had little effect on the voltage-jump relaxation time constants under all experimental conditions. At higher concentrations and voltages more negative than -150 mV, 2BQ caused significant open channel blockade.

3. Dose-ratio studies showed that the cis and trans isomers of 2BQ have equilibrium binding constants (K) of .33 and 1.0 μΜ, respectively. The binding constants determined for both isomers are independent of temperature, voltage, agonist concentration, and the nature of the agonist.

4. In a solution of predominantly cis-2BQ, visible-light flashes led to a net cis→trans isomerization and caused an increase in the agonist-induced current. This increase had at least two exponential components; the larger amplitude component had the same time constant as a subsequent voltage-jump relaxation; the smaller amplitude component was investigated using ultraviolet light flashes.

5. In a solution of predominantly trans-2BQ, UV-light flashes led to a net trans→cis isomerization and caused a net decrease in the agonist-induced current. This effect had at least two exponential components. The smaller and faster component was an increase in agonist-induced current and had a similar time constant to the voltage-jump relaxation. The larger component was a slow decrease in the agonist-induced current with rate constant approximately an order of magnitude less than that of the voltage-jump relaxation. This slow component provided a measure of the rate constant for dissociation of cis-2BQ (k_ = 60/s at 20°C). Simple modelling of the slope of the dose-rate curves yields an association rate constant of 1.6 x 108/M/s. This agrees with the association rate constant of 1.8 x 108/M/s estimated from the binding constant (Ki). The Q10 of the dissociation rate constant of cis-2BQ was 3.3 between 6° and 20°C. The rate constants for association and dissociation of cis-28Q at receptors are independent of voltage, agonist concentration, and the nature of the agonist.

6. We have measured the molecular rate constants of a competitive antagonist which has roughly the same K as d-tubocurarine but interacts more slowly with the receptor. This leads to the conclusion that curare itself has an association rate constant of 4 x 109/M/s or roughly as fast as possible for an encounter-limited reaction.

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This translation presents identification keys to the subfamilies, genera, species and subspecies of Chydoridae of the USSR. Chydoridae are a family in the order of Cladocera.