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Quenching experiment

For critical quench experiments there is a synnnetry < )q = 0 and from equation (A3,3,50) S( ) = ( ), leading to a syimnetric local free energy ( figure A3,3,6) and a scaled order parameter whose average is zero, 8v / = i /. For off-critical quenches this synnnetry is lost. One has 8( ) = ( ) -t ( ) which scales to 5 j/ = with... [Pg.739]

The economics of the arc-coal process is sensitive to the electric power consumed to produce a kilogram of acetylene. Early plant economic assessments indicated that the arc power consumption (SER = kwh/kgC2H2) must be below 13.2. The coal feedcoal quench experiments yielded a 9.0 SER with data that indicated a further reduction to below 6.0 with certain process improvements. In the propane quench experiment, ethylene as well as acetylene is produced. The combined process SER was 6.2 with a C2H2/C2H4 production ratio of 3 to 2. Economic analysis was completed uti1i2ing the achieved acetylene yields, and an acetylene price approximately 35% lower than the price of ethylene was projected. [Pg.393]

A radical pathway has been proposed to account for the isolation of (381)-(383) from the irradiation of the 3//-indazole (380) (73T1833). Results of sensitization and quenching experiments suggest that the reaction proceeds from the excited singlet state. [Pg.252]

It was predicted, a priori, that isocomene could be formed simply by treating 4 with methyllithium, followed by exposure of the resultant tertiary carbinol to acid.2b However, many attempts to effect the addition of a variety of nucleophilic methyl derivatives to ketone 4 were unsuccessful. It was revealed by deuterium quenching experiments that ketone 4 undergoes ready enolization in the presence of nucleophilic methyl derivatives. Despite its hindered nature, however, the ketone carbonyl in 4 reacts with methylenetri-... [Pg.223]

Suzuki, N., etal. (1991). Reaction rates for the chemiluminescence of Cypridina luciferin analogs with superoxide a quenching experiment with superoxide dismutase. Agric. Biol. Chem. 55 157-160. [Pg.441]

However, with the advent of the superacid solvents, a multitude of long-lived stable carbonium ions have been made available for extended study. Clearly, then, the door is open to quantum 5ueld determinations, kinetic treatment, studies on the effects of various solvents and sensitizers and quenching experiments (compare the very recent study by Bethell and Clare, 1972). In short, the photochemistry of carbonium ions is still in its infancy and there is a wealth of information yet to be gained. [Pg.151]

In a comparison of fluorescence spectra between the ester and thioester derivative crystals of PDA, the ester crystal shows a strong emission whereas the thioester crystal fluoresces much more weakly. For example, the intensity of a PDA methyl thioester crystal is about one-thousandth of that of a PDA methyl ester crystal. Furthermore, the fluorescence lifetime of mixed crystals which consist of a large amount of PDA methyl ester and a small amount of the corresponding thioester moiety is much shortened, compared to the lifetime of pure PDA methyl ester crystals. In quenching experiments in solutions of PDA ester, the fluorescence of the PDA ester is dramatically quenched by thioacetate. Similar behaviour has been obtained with several types of diolefin derivatives having a thioester moiety, where crystal structures are isomorphous with the corresponding ester derivatives. [Pg.133]

This method is applicable when the fluorescence of a ligand is quenched in presence of DNA or RNA and provides base-dependent specificity [135]. In fluorescence quenching experiments the titration data is plotted according to the Stern-Volmer equation ... [Pg.170]

In order to investigate the competition between magnetic interaction and spin transition in (bpym, S), quenching experiments have been performed at 0.63 GPa. Fig. 7 displays the magnetic behaviour of the quenched sample at increasing temperatures. It can be inferred from the thermal dependence of XmT that [HS-HS] entities can be frozen-in as a metastable state at low temperatures. Heating the sample above ca. 60 K leads to re-formation of... [Pg.191]

The values for ka and kq are determined from quenching experiments in the homogeneous solvent, while the value of is determined from the triplet state decay in the presence of host but absence of quencher. These values are fixed when fitting the quenching plot in the presence of host to Equation (6). [Pg.178]

The mechanistic basis of 3 and 4 is a double application of the argument used for the YES operation with 1. Each receptor in 3 is capable of launching a PET process if the lumophore is powered up by ultraviolet excitation. In other words, the fluorescence of the 9-cyanoanthracene unit is efficiently quenched by either the amine or the 1,2-dioxybenzene group within the benzo-15-crown-5 ether unit. These quenching processes are predictable from thermodynamic calculations or from related bimolecular quenching experiments in the literature. The small separation of the amine from the lumophore ensures rapid PET kinetics. On the other hand, the presence of four bonds between the benzo-15-crown-5 ether and the lumophore is probably responsible for the incomplete quenching seen between this pair. No information is yet available regarding possible folded conformations of 3. [Pg.311]

T. N. Wassermann, D. Luckhaus, S. Coussan, and M. A. Suhm, Proton tunneling estimates for malonaldehyde vibrations from supersonic jet and matrix quenching experiments. Phys. Chem. Chem. Phys. 8, 2344 2348 (2006). [Pg.50]

Quenching experiments show that the phosphorescence emission is strongly quenched by oxygen, whereas the presence of oxygen has no... [Pg.181]

Photoinduced electron transfer (PET) is often responsible for fluorescence quenching. This process is involved in many organic photochemical reactions. It plays a major role in photosynthesis and in artificial systems for the conversion of solar energy based on photoinduced charge separation. Fluorescence quenching experiments provide a useful insight into the electron transfer processes occurring in these systems. [Pg.90]

Short-wavelength spectral shifts may also be observed for proteins under conditions of dynamic quenching by oxygen and acrylamide. However, the existing data do not yield reliable estimates of rRJf, under the initial conditions, xR xF, then the quenching experiments do not allow v. to be determined and Eq. (2.9) cannot be applied. [Pg.96]

The measurement of fluorescence lifetimes is an integral part of the anisotropy, energy transfer, and quenching experiment. Also, the fluorescence lifetime provides potentially useful information on the fluorophore environment and therefore provides useful information on membrane properties. An example is the investigation of lateral phase separations. Recently, interest in the fluorescence lifetime itself has increased due to the introduction of the lifetime distribution model as an alternative to the discrete multiexponential approach which has been prevalent in the past. [Pg.232]

In addition to the partition coefficient, the bimolecular quenching constant (km) is obtained from quenching experiments. 1"1 "7-IIX i and, in principle, this can be used to obtain the lateral diffusion constant of the quencher by using the Smoluchowski equation ... [Pg.256]

Figure 4. DSC Quenching Experiment. E normal DSC F DSC of a sample previously quenched at the start of the exotherm G DSC of a sample previously quenched at the height of the exotherm. Figure 4. DSC Quenching Experiment. E normal DSC F DSC of a sample previously quenched at the start of the exotherm G DSC of a sample previously quenched at the height of the exotherm.
The fluorescence quenching experiments (Fig. 7) revealed a binding constant d i2) = 8.3 x Due to its saddle-shaped con-... [Pg.37]

Another very complicated problem where the approach to equilibrium with time after a quenching experiment is described by an asymptotic law is the owth of wetting layers, in a situation where thermal equilibrium would require the surface to be coated with a macroscopically thick film, but is initially nonwet. For a short-range surface potoitial as discussed in section 3.5, analytical theories predict for a non-conserved density a growth of the thicknm of the layer according to a law f(t) oc In t, and this has in fact been observed by simulations . In the case where the surface potential decays with stance z from the surface as z, the prediction for the thickness l(t) is for the nonconserved case and... [Pg.144]

Fig. 3.14 Simulated ALIS-based dissociation rate measurements. See text for details. (A) Quench experiments modeled at varying inhibitor association rates. Even with a very slow-binding inhibitor, the decay curve resembles pure first-order dissociation kinetics. (B) Data in (A), shown on a log axis. (C) Simulated ALIS quench experiment with varying protein-ligand dissociation rates,... Fig. 3.14 Simulated ALIS-based dissociation rate measurements. See text for details. (A) Quench experiments modeled at varying inhibitor association rates. Even with a very slow-binding inhibitor, the decay curve resembles pure first-order dissociation kinetics. (B) Data in (A), shown on a log axis. (C) Simulated ALIS quench experiment with varying protein-ligand dissociation rates,...

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See also in sourсe #XX -- [ Pg.356 , Pg.357 , Pg.395 , Pg.408 , Pg.409 ]




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