Anion optical

The anion optical sensor can also be fabricated with metalloporphyr-ins. For example, polymeric membranes doped with indium porphyrins and a lipophilic dichlorofluorescein derivative were shown to be very selective to chloride and acetate anions. The response mechanism is based on extraction of anions into the bulk organic film by indium porphyrins and a simultaneous coextraction of hydrogen ions. This results in protonation of the pH chromophore, and hence a change in the optical absorbance of the polymeric film. 

In aqueous solution, the equilibrium between the cis- and franj-diaqua complexes lies almost completely toward the cis isomer881 (K 0.17, pH 3-4). The sparingly soluble potassium salt of the tram isomer may, however, be prepared by the slow evaporation of a saturated solution at room temperature,878,880 and the cis isomer by cooling a hot solution or by allowing potassium dichromate and oxalic acid to react in the presence of a minimal quantity of water.878,879,882 The tris complex was resolved by Werner in 1912,883 providing the first example of an anionic optically active coordination complex. 

Neta P, Simic MG, and Hoffman MZ, Pulse radiolysis and electron spin resonance studies of nitroaromatic radical anions. Optical absorption spectra, kinetics, and one-electron redox potentials, J. Phys. Chem., 80, 2018, 1976. 

X = optically-active anion optical isomers not resolved... 

Each act of proton abstraction from the a carbon converts a chiral molecule to an achi ral enol or enolate ion The sp hybridized carbon that is the chirality center m the start mg ketone becomes sp hybridized m the enol or enolate Careful kinetic studies have established that the rate of loss of optical activity of sec butyl phenyl ketone is equal to Its rate of hydrogen-deuterium exchange its rate of brommation and its rate of lodma tion In each case the rate determining step is conversion of the starting ketone to the enol or enolate anion... 

PPQs possess a stepladder stmcture that combines good thermal stabiUty, electrical insulation, and chemical resistance with good processing characteristics (81). These properties allow unique appHcations in the aerospace and electronics industries (82,83). PPQ can be made conductive by the use of an electrochemical oxidation method (84). The conductivities of these films vary from 10 to 10 S/cm depending on the dopant anions, thus finding appHcations in electronics industry. Similarly, some thermally stable PQs with low dielectric constants have been produced for microelectronic appHcations (85). Thin films of PQs have been used in nonlinear optical appHcations (86,87). 

Addition to cis- and /n t-2-butene theiefoie yields different optical isomers (10,11). The failure of chlorine to attack isobutylene is attributed to the high degree of steric hindrance to approach by the anion. The reaction intermediate stabilizes itself by the loss of a proton, resulting in a very rapid reaction even at ambient temperature (12). 

The most important reaction with Lewis acids such as boron trifluoride etherate is polymerization (Scheme 30) (72MI50601). Other Lewis acids have been used SnCL, Bu 2A1C1, Bu sAl, Et2Zn, SO3, PFs, TiCU, AICI3, Pd(II) and Pt(II) salts. Trialkylaluminum, dialkylzinc and other alkyl metal initiators may partially hydrolyze to catalyze the polymerization by an anionic mechanism rather than the cationic one illustrated in Scheme 30. Cyclic dimers and trimers are often products of cationic polymerization reactions, and desulfurization of the monomer may occur. Polymerization of optically active thiiranes yields optically active polymers (75MI50600). 

The worked out soi ption-photometric method of NIS determination calls preliminary sorption concentration of NIS microamounts from aqueous solutions on silica L5/40. The concentrate obtained is put in a solution with precise concentration of bromthymol-blue (BTB) anionic dye and BaCl, excess. As a result the ionic associate 1 1 is formed and is kept comparatively strongly on a surface. The BTB excess remains in an aqueous phase and it is easy to determinate it photometrically. The linear dependence of optical density of BTB solutions after soi ption on NIS concentration in an interval ITO - 2,5T0 M is observed. The indirect way of the given method is caused by the fact the calibration plot does not come from a zero point of coordinates, and NIS zero concentration corresponds to initial BTB concentration in a solution. 

Similarly a suitable optically transparent anhydrous (strong) base, e.g. piperidine, could be used to obtain the spectra of anhydrous anions. 

In systems such as the 2- and 6-hydroxypteridines, sudden addition of an alkaline solution to a neutral buffer, or of a neutral solution to an alkaline buffer, displaces the equilibrium between hydrated and anhydrous species (because the anions are less hydrated than the neutral molecules). By measuring the time-dependent change of optical density at a selected wavelength, a first-order rate constant, obs5 can be obtained. This constant is a composite one, and to see its relationship to other quantities some discussion is necessary. 

Transition metal complexes with 2,2 -bipyridine ligands in anion-selective recognition and optical/electrochemical sensing 96CC689. 

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