Induced shift

FKI073 Relation between different measures of Exposure-Induced Shifts in Ductile-Srittle Transition temDeratures-Validalion of surveillance oractice mitiaation methods Dr E. G. Taylor Magnox Electric Pic... 

The isotropic shift and the quadnipole-induced shift (QIS) can easily be obtained from the data. The QIS is different m both dimensions, however, and is given by... 

The equilibrium constants obtained using the metal-ion induced shift in the UV-vis absorption spectrum are in excellent agreement with the results of the Lineweaver-Burke analysis of the rate constants at different catalyst concentrations. For the copper(II)ion catalysed reaction of 2.4a with 2.5 the latter method gives a value for of 432 versus 425 using the spectroscopic method. 

In retrospect, this study has demonstrated the limitations of two commonly accepted methods of analysing solubilisation and micellar catalysis, respectively. It has become clear that solubilisate ririg-current induced shifts need to be interpreted with due caution. These data indicate a proximity of solubilisate and parts of the surfactant and, strictly, do not specify the location within the micelle where the encounter takes place. Also the use of the pseudophase model for bimolecular reactions requires precaution. When distribution of the reactants over the micelle is not comparable, erroneous results are likely to be obtained... 

Fmctose is sweeter than sucrose at low temperatures (- S C) at higher temperatures, the reverse is tme. At 40°C, they have equal sweetness, the result of a temperature-induced shift in the percentages of a- and P-fmctose anomers. The taste of sucrose is synergistic with high intensity sweeteners (eg, sucralose and aspartame) and can be enhanced or prolonged by substances like glycerol monostearate, lecithin, and maltol (19). 

The H NMR spectrum of thiirane 1-oxide is complex (AA BB ) at 60 MHz 24 lines are cfbserved consisting of two sets of 12 centered about a midpoint. The H NMR chemical shift in thiirane 1,1-dioxide is fairly sensitive to solvent variations partly because of the high dipole moment (4.4 D) of the sulfone. The benzene-induced shift, A5 (CeDe-CCLt), is large (-1.04 p.p.m.), as expected from the presence of a sulfone group. Oxygen-17 chemical shifts for thiirane 1-oxide and thiirane 1,1-oxide are -71 and +111 p.p.m. respectively, relative to H2O. 

Surmountable antagonism, an antagonist-induced shift to the right of an agonist dose-response curve with no diminution of the maximal response to the agonist (observed with simple competitive antagonists and some types of allosteric modulators). 

A study195 based on the NMR lanthanide-induced shifts (LIS) for a series of cis- and trans-3-substituted, and 3,3-disubstituted thietane oxides concluded that all cis-substituted oxides (5c R = CH3, t-Bu and aryl) exist exclusively in the diequatorial conformation. The trans-3-substituted isomers (185) prefer the equatorial oxygen conformation (R = CH3,86% t-Bu, 65-75% aryl, 75%), which means an axial preference for the substituents (e.g. 185d), at least when they are bound to a shift reagent (equation 75). 

In some cases it is possible to differentiate between the various alkyl substituents. Primary, secondary and tertiary nitrates and nitrites all show clearly different infrared absorptions. The spectra of acid fluorides can be used to differentiate chain-end groups from pendant acid groups. Furthermore, the loss of all -OH species upon sulfur tetrafluoride exposure allows the reliable estimation of ketones, esters and lactones without the complication of hydrogen-bonding induced shifts in the spectra. Preliminary results from the use of these reactions to characterize y-ray oxidized polyethylene and polypropylene are used to illustrate the scope of the methods. 

Duarte, S., Pascoal, C., Alves, A., Correia, A., and Cassio, F., Copper and zinc mixtures induce shifts in microbial communities and reduce leaf litter decomposition in streams, Freshwater Biol, 53 (1), 91-101, 2008. 

Numerous studies of carotenoid aggregates have focused on the molecular organization of the aggregates (Simonyi et al. 2003), but little is known about aggregation-induced effects on carotenoid excited states. Classical exciton theory can qualitatively explain the aggregation-induced shifts of absorption bands (Section 8.3.1), but a detailed understanding of the parameters governing the... 

Mechanisms of voltage sensitivity in the styryl-type dyes depend on their unusual trends in solvent and lipid-induced shifts of absorption and fluorescence... 

An additional example of cycloamylose-induced catalysis which can probably be attributed to a microsolvent effect is the oxidation of a-hy-droxyketones to a-diketones (Scheme VIII). The rate of this oxidation is accelerated by factors ranging from 2.1 to 8.3 as the structure of the substrate is varied. As noted by Cramer (1953), these accelerations may be attributed to a cycloamylose-induced shift of the keto-enol equilibrium to the more reactive enol form. 

Computer simulation of lanthanide-induced shifts in the 2-formyl and 2-acetyl derivatives of furan, thiophene, selenophene, and tellurophene108 indicate a nearly equipopulated mixture of trans and cis conformers of the furan, and a preponderance of the cis for the thiophene, selenophene, and tellurophene derivatives. This difference is due to an interaction between the ring heteroatom and the carbonyl oxygen lone pair electrons. 

Isotropic Chemical Shift and Second-Order Quadrupolar Induced Shift... 

The rank 0 term, referred to as the quadrupolar-induced shift (QIS) operator, is independent of the molecular and rotor orientation (Bp0 = Bq0). Using (11), (13), and (18), this term can be written... 

Table I) is due to the so1ute-s01vent interactions that result in solvent induced shifts of the singlet-singlet excitation energies readily observable in solution absorption s p ec t r a (J 2). As expressed in... 

Fig. 17. Stress-induced shifts and polarization characteristics of the Si B—H stretching mode measured near 15 K. [Reprinted with permission from The American Physical Society, Bergman, K., Stavola, M., Pearton, S.J., Hayes, T. (1988). Phys. Rev. B 38, 9643.]...

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