A tetrahedral lattice model for a polymer chain with three-unit kinetic elements was used to find the correlation functions which describe the local dynamics of unit vectors oriented in the longitudinal or transverse directions with respect to the chain. These unit vectors can represent the dynamics of the emitting oscillator of the marker. It is shown that the spectra for longitudinal and transverse components of the emitting oscillator differ greatly. It is also shown that at short relaxation times the anisotropy of local relaxation properties of a kinetic chain fragment may be described by an equivalent ellipsoid with an axes ratio of ca. 10.
The expressions for the functions of spectral density at different orientations of the components of the internuclear vector with respect to the chain backbone, the frequency dependences of the spin-lattice relaxation time of 13C nuclei (TIC) and the values of the nuclear Overhauser effect (NOE) were obtained for the tetrahedral lattice model of a polymer chain with three-unit kinetic elements. It was shown that peculiar features of the behavior of T , , and NOE reflect the characteristic properties of the spectra of relaxation (correlation) times for "longitudinal" and "transverse" components of the internuclear vector. It was established that in the range of relatively short times of the relaxation spectrum the dynamics of an anisotropic kinetic segment of the chain may be described with the aid of a simple model of an elongated ellipsoid of rotation with an axial ratio of about 10. It is shown that the equivalent-ellipsoid model leads to significant differences from a more specific model of chain dynamics when a broad frequency range is considered.
In the framework of the tetrahedral lattice model with a three-unit kinetic element, the time correlation functions were found. These functions describe the dynamics of "longitudinal" and "transverse" components of the emitting oscillator vector of the luminescent marker included in the side group or the dynamics of the internuclear vector of "C-IH. The expressions were obtained for the factor of luminescence depolarization ( y), the spin-latice relaxation time (TIC) and for the nuclear Overhauser effect (NOE) of the I3C nuclei.The specific features of the behaviour of TIC and NOE reflect the spectral characteristics of "longitudinal" and "transverse" relaxation processes.
Das dynamische Verhalten der longitudinalen rind transversalen Komponenten des emittierenden Oszillators und des internuklearen Vektors bei cler polarisierten Lumineszenz und dem Kern-Overhauser-EffektIm Rahmen des tetrahedralen Gittermodells mit einem kinetischen Element aus drei Einheiten wurden die Zeit-Korrelations-Funktionen ermittelt. Diese Funktionen beschreiben die Dynamik der,,Iongitudinalen"und ,,transversalen"Komponenten des emittierenden Oszillatorvektors einer in die Seitengruppe eingebauten lumineszierenden Markierung sowie die Dynamik des Zwischenkernvektors I3C-lH. Es wurden Beziehungen abgeleitet fur den Faktor der Lumineszenzdepolarisation ( v), fur die Spin-Gitter-Relaxationszeit (TIC) und fur den Kern-Overhauser-Effekt (NOE) der "C-Kerne. DieBesonderheiten des Verhaltens der GroBen r: TIC und NOE spiegeln die charakteristischen Eigenschaften der ,,longitudinalen" und der ,,transversalen" Relaxationsprozesse wider.
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