The electron nuclear dipolar interactions responsible for some dynamic nuclear polarization (DNP) mechanisms also are responsible for the presence formally in CW EPR spectra of forbidden satellite lines in which both the electron spin and a nuclear spin flip. Such lines arising from 1H nuclei are easily resolved in CW EPR measurements of trityl radicals, a popular family of DNP reagents. The satellite lines overlap some of the hyperfine features from 13C in natural abundance in the trityl radical, but their intensity can be easily determined by simple simulations of the EPR spectra using the hyperfine parameters of the trityl radical. Isotopic substitution of 2H for 1H among the hydrogens of the trityl radical and/or the solvent allows the dipolar interactions from the 1H on the trityl radical and from the solvent to be determined. The intensity of the dipolar interactions, integrated over all the 1H in the system, is characterized by the traditional parameter called reff. For the so-called Finland trityl in methanol, the reff values indicate that collectively the 1H in the unlabeled solvent have a stronger integrated dipolar interaction with the unpaired electron spin of the Finland trityl than do the 1H in the radical and consequently will be a more important DNP route. Although reff has the dimensions of distance, it does not correspond to any simple physical dimension in the trityl radical because the details of the unpaired electron spin distribution and the hydrogen distribution are important in the case of trityls.
A comparison of the behavior of asphaltene molecules extracted from crude oil and dissolved in aromatic solvent as a model system with the behavior of vanadium-containing molecules in real crude oils via ESR in-situ technique showed that the changes of rotational mobility of asphaltene molecules can be related to the changes of the local viscosity and environment of the asphaltenes as well as the characteristic sizes of vanadyl-containing fragments due to aggregation/disaggregation processes in crude oils. The information about the mobility of asphaltene molecules in different local environments at different temperatures and pressures is 1
Crude oil phase behavior and asphaltene precipitation have been studied by two complementary chemical imaging methods for the first time. ATR-FTIR spectroscopic imaging approach has revealed the chemical composition of agglomerated and precipitated asphaltenes upon dilution with a flocculant. Asphaltenes, containing oxygen and nitrogen heteroatomic functional groups, have been detected to be least stable. Aromatic abundant asphaltenes have been observed to have relatively high solubility in crude oil/heptane blends. NMR imaging approach, capable of imaging in the bulk of crude oil samples, has demonstrated that n-heptane causes aggregation which can lead to the stable suspension or to the sedimentation followed by the formation of deposits, depending on flocculant concentration. These processes have been monitored for small and large amounts of heptane added to crude oil. The data obtained by ATR-FTIR spectroscopic imaging and NMR imaging have been correlated to propose a possible link between the chemical structure of asphaltenes and a mechanism of the formation of deposits.
The dynamic magnetic properties of two-dimensional periodic Co antidot arrays were studied by X-band ferromagnetic resonance. The experimental results on geometrically scaled antidot arrays reveal a strong attenuation of the uniform ferromagnetic resonance mode in comparison to a continuous film, but an excitation of nonuniform in-plane spin-wave modes. Micromagnetic finite-element simulations show that the static magnetic structure in an antidot array depends on the direction of the external field with respect to the symmetry axes of the antidot lattice, even if the external field is strong enough to enforce a technically saturated magnetization state. The analysis gives evidence that characteristic inhomogeneities in the magnetization distribution around the antidots give rise to the changes of the resonance modes with the in-plane direction of the magnetization.
The approach for
quantitative estimation of asphaltene sizes in
crude oils in situ via precise simulation of electron spin resonance
(ESR) spectra of the slowly rotating VO2+-containing fragments
was developed. The method is based on the correlation between the
size of the paramagnetic particles and their characteristic rotational
time that can be determined by ESR in situ while incomplete averaging
of anisotropic hyperfine interactions is observed. The precise simulation
of the ESR spectra of heavy molecules, labeled naturally with vanadyl
ions, allows one to find their size distribution in crude oils. In
particular, the method is demonstrated to be an effective tool for
the quantitative determination of the asphaltene sizes in different
oil fractions in situ.
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