Spin-lattice relaxation heteronuclear chemical shift

In this section 10.2, we review the various solid-state NMR methods used to investigate interpolymer interactions, molecular motion and the spatial structure of a polymer blend. An interaction between component polymers affects the chemical shifts and lineshapes (see Section 10.2.2.1) and the molecular motions of the component polymers (see Section 10.2.2.2). In Section 10.2.3.1, microheterogeneity from 2 to 50 nm is studied by measuring spin diffusion indirectly from its effects on H spin-lattice relaxation. The spin-diffusion processes can also be monitored by several methods based on the Goldman-Shen experiment [8] (see Section 10.2.3.2). Homonuclear and heteronuclear two-dimensional correlation experiments reveal how and to what extent component polymers interact with each other (see Section... 

Heteronuclear chemical shift correlation techniques can be used to infer spin-lattice relaxation times of the protons attached to the observe nucleus (39). This is accomplished by saturation of the protons and observe nucleus followed by a variable time t (saturation recovery) during which the observe nucleus is continued at saturation (by repeated pulsing) and the attached proton remagnetizes. This process is followed by the normal H/X 2D shift correlation experiment. The t-dependence of the 2D peak intensities is then used to extract H T s by exponential analysis. This approach can be used to extract proton Ti s in polymers via observation of their attached obtaining motional data nor-... 

D J-resolved NMR experiments are a conceptual amalgamation of two topics discussed above, the /-modulated spin echo and the two-dimensional characteristic of the spin—lattice relaxation experiments. As the name of these experiments implies, scalar coupling information, /, will be displayed in the one frequency domain chemical shift information will be presented in the second frequency domain. The simplest 2D/ experiments sort chemical shift information in the detected time domain, labeled by convention, while the heteronuclear scalar couplings of each carbon are sorted into the indirectly determined time domain, tj (do not be confuse lower case h with the spin—lattice relaxation time, Tj). 

Temperature Dependence of Spin-Lattice Relaxation. The spin-lattice relaxation rate T ) is comprised of various contributions to the relaxation process, including homo- and heteronuclear dipolar interactions, quadrupolar interactions, chemical shift anisotropy, spin-rotation, and others (10). When the relaxation mechanism is dominated by inter- and intramolecular dipole-dipole interactions, the will increase with temperature, pass through a maximum, and decrease with increasing temperature. Since the relaxation rate is the inverse of the relaxation time, the Ti will decrease, pass through a minimum (Timin), and then increase with increasing temperature (77). The T lmin values are proportional to the internuclear distances. 

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