Sensitive molecules 322 INDEX

The refractive index is an important quantity for characterizing the structure of polymers. This is because it depends sensitively on the chemical composition, on the tacticity, and - for oligomeric samples - also on the molecular weight of a macromolecular substance. The refractive indices (determined using the sodium D line) of many polymers are collected in the literature. In order to characterize a molecule s constitution one requires knowledge of the mole refraction, Rg. For isotropic samples, it can be calculated in good approximation by the Lorentz-Lorenz equation ... 

Other detection modes employed in capillary electromigration techniques include chemiluminescence [69-71], Raman spectroscopy [72,73], refractive index [74,75], photothermal absorbance [76,77], and radioisotope detection [78]. Some of these detection modes have found limited use due to their high specificity, which restricts the area of application and the analytes that can be detected, such as radioisotope and Raman-based detection that are specific for radionuclides and polarizable molecules, respectively. On the other hand, the limited use of more universal detection modes, such as refractive index, is either due to the complexity of coupling them to capillary electromigration techniques or to the possibility of detecting the analytes of interest with comparable sensitivity by one of the less problematic detection modes described above. 

In addition to allowing comparison among experiments carried out in different solvents, the m—Y system serves as an important tool for study of mechanism. Sensitivity to ionizing power, measured by m, is an index of the degree of charge separation at the transition state. The ratio of rates in two solvents of equal Y but different nucleophilicity provides evidence about nucleophilic assistance by a solvent molecule during the ionization. 

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