Tumbling, electron spin resonance

We have studied demulsifier association by the electron spin resonance (ESR) technique. The spin label is covalently attached (Figure 5a) to the demulsifier. Normally, the ESR spectrum of a freely tumbling nitroxyl radical consists of three sharp peaks (Figure 5b). However, the spectrum for a tagged ethoxylated nonyl phenol resin (Figure 6a or 6b) shows only a single broad peak. 

As already mentioned, we chose three different physicochemical properties for studying the influence of the surface area and fractal dimension in the ability of dendritic macromolecules to interact with neighboring solvent molecules. These properties are (a) the differential chromatographic retention of the diastereoisom-ers of 5 (G = 1) and 6 (G = 1), (b) the dependence on the nature of solvents of the equilibrium constant between the two diastereoisomers of 5 (G = 1), and (c) the tumbling process occurring in solution of the two isomers of 5 (G = 1), as observed by electron spin resonance (ESR) spectroscopy. The most relevant results and conclusions obtained with these three different studies are summarized as follows. 

AcAc, acetylacetonate EPR, electron paramagnetic resonance DPM, dipivaloylmethane Tc, Correlation time for molecular tumbling A/x, concentration of spins X (per unit volume) D, mutual translational self-diffusion coefficient of the molecules containing A and X a, distance of closest approach of A and X ye, magnetogyric ratio for the electron C, spin-rotation interaction constant (assumed to be isotropic) Ashielding anisotropy <7 <7j ) coo, Debye frequency 0d, the corresponding Debye temperature Fa, spin-phonon coupling constant. 

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