Rotating-Frame Carbon Spin-Lattice Relaxation

Rotating-Frame Carbon Spin-Lattice Relaxation... 

In principal, resolution of Individual carbon resonances in bulk polymers, allows relaxation experiments to be performed which can be Interpreted in terms of main chain and side chain motions in the solid. In addition to the spin-lattice relaxation time in the Zeeman field, the spin-spin relaxation time and nuclear Overhauser enhancement, other parameters providing data on polymer dynamics include the proton and carbon spin-lattice relaxation times in the rotating-frame, T p, the cross-relaxation time Tqr, and proton relaxation in the dipolar field. Schaefer and Stejskal have carried out pioneering work in exploring polymer dynamics using solid-state NMR techniques. Measurement of T values in glassy PMMA at ambient temperature reveals that the a-CH3 carbon relaxes in <0.1s, the ester methyJL and methylene carbons in ca. Is and the two non-protonated (carbonyl and quaternary) carbons in ca. 10s. These results are consistent with the onset of internal reorientation of a-CH3 at this temperature relatively... 

Tipc Carbon spin-lattice relaxation time in the rotating frame... 

Spin-lattice relaxation of C nuclei is, in principle, very attractive for it is determined by local fluctuations at to c or cuof (rotating or lab frame respectively) spin diffusion among nuclei does not average relaxation rates among chemically distinct carbons. In solids one must append a cautionary note. 

In organic solids the determination of rotating frame relaxation is severely complicated by the presence of the strongly interacting proton spin system. Spin-spin fluctuations compete with spin-lattice fluctuations to produce an effective relaxation time large rf field amplitudes are mandated to discriminate against the spin-spin event. The burden of proof lies with the experimenter to establish that a rotating frame relaxation rate actually reflects a motional effect seen by the carbon nuclei. 

Polymer Dynamics. 13C spin-lattice relaxation times (Ti) were determined with either an inversion-recovery sequence (16) (for carbons observed by direct polarization) or with a modified cross-polarization experiment (17). 13C rotating-frame relaxation times (Tip(C)) were derived from measurements of the carbon signal that remained after a Tjp(C) hold time of... 

The precipitates of PVPh/PDMA from methanol and acetone solutions were examined by CPMAS NMR [51], and evidence for specific interaction was obtained with a 3 ppm shift in the phenolic carbon resonance peak. The proton spin-lattice relaxation times Tj were shorter than those predicted by a linear model, though the rotating frame spin-lattice relaxation times Tjp of the com-... 

Complementary NMR measurements, such as rises of carbon polarisation in a spin-lock experiment and determination of 13C spin-lattice relaxation times in the rotating frame, Tip(13C), support these conclusions about the correlation times of the side-ring CH and CH2 motions in the various poly(cycloalkyl methacrylates). 

The temperature dependencies of the ( 172)0/ 1/2 ratio, where ( 1/2)0 is the 1/2 value measured at room temperature, determined for the CHOH - CH2 - O and CH2 - N units of the hydroxylpropyl ether (HPE) sequence (Fig. 92) in the HMDA network [63] are shown in Fig. 97. It is worth noticing that the 1/2 values of these two types of carbons have the same temperature dependence. Up to 60 °C, the 1/2 values are constant and equal to the rigid-lattice values, indicating that the HPE sequence does not undergo any local motion at a frequency equal to or higher than 105 Hz in this temperature range. Above 60 °C, mobility develops, which leads at 100 °C to motions in the tens of kilohertz for the whole HPE sequence. These results are qualitatively confirmed by data on 13C spin-lattice relaxation time in the rotating frame, Tip(13C). 

The interpretation of carbon T p data is complicated by the fact that spin-spin (cross-relaxation) processes as well as rotating frame spin-lattice processes may contribute to the relaxation (40). Only the latter process provides direct information on molecular motion. For the CH and CH2 carbons of PP, the Tip s do not change greatly over the temperature interval -110°C to ambient and, as opposed to the T behavior, the CH2 carbon has a shorter T p than the CH carbon. These results suggest that spin-spin processes dominate the Tip (46). However, below ca. -115°C, the Tip s for both carbons shorten and tend toward equality. McBrierty et al. (45) report a proton Ti minimum (which reflects methyl group reorientation at KHz frequencies) at -180°C. No clear minimum is observed in the data, perhaps due to an interplay of spin-spin and spin-lattice processes. Nonetheless, it is apparent that the methyl protons are responsible for the spin-lattice portion of the Tip relaxation for CH and CH2 carbons. 

If the cross-relaxation to the dipolar reservoir is longer than the proton spin-lattice relaxation, T p, then the T p for the CH carbon will be ca. 1.7-2.Ox that of the CH2 carbon for spin-spin domination of the rotating-frame relaxation. This is roughly the result observed in the data displayed in Figure 13. The explanation is based on the approximate two-fold difference in the CH second moments for the two types of carbons (for full details see Reference 40). 

The miscibility of poly(methyl acrylate) (PMAA, Mw= 150,000)/PVAc (Mw= 167,000) blends at various mixing ratios was investigated by both Ti and Tip measurements. C CP/MAS NMR spectra of PMAA, PVAc and the PMAA/PVAc blends are shown in Fig. 2. Figure 3 shows the plots of the spin-lattice relaxation times in the laboratory (Ti , A) and in the rotating (Ti, B) frames against the molar ratio of PMAA (xpmaa)-The ll relaxation times from the CI 12 (O) and OCH (A) carbons for PMAA and PVAc, respectively, can be observed because these two carbons are observed separately even in the blends (Fig. 2), so that it is possible to obtain each relaxation time for PMAA or PVAc in the blends independently. 

Crystalline a-D-galacturonic acid monohydrate has been studied by C CPMAS NMR and X-ray crystallography. The molecular dynamics have been investigated by evaluating C spin-lattice relaxation in the rotating frame (Tip) and CSA properties of each carbon. It has been found that only limited molecular motions can be detected in the low frequency (<10 Hz) range by Tip( C) measurements and changes of CSA properties as a function of temperature. 

The dynamics of intact lime cuticle and its two major component polyesters, cutin and wax, have been studied by the MAS NMR experiment [134]. By the measurements of spin-lattice relaxation times and spin-lattice relaxation times in the rotating frame which characterize respectively the megahertz- and kilohertz-regime motions, it is indicated that motional restrictions are present at the crosslinks of the cutin polymer and along the alkyl chains of the wax. The values of relaxation times, which differ for analogous carbon sites of cutin and wax individually, approach common values for the two materials in the intact lime cuticle. These results are considered to provide evidence for hydrophobic association within the plant cuticle of the long aliphatic chains of cutin and wax. 

Relaxation parameters of interest for the study of polymers include 1) 13C and H spin-lattice relaxation times (T1C and T1H), 2) the spin-spin relaxation time T2, 3) the nuclear Overhauser enhancement (NOE), 4) the proton and carbon rotating-frame relaxation times (T p and T p), 5) the C-H cross-relaxation time TCH, and 6) the proton relaxation time in the dipolar state, T1D (2). Not all of these parameters provide information in a direct manner nonetheless, the inferred information is important in characterizing motional frequencies and amplitudes in solids. The measurement of data over a range of temperatures is fundamental to this characterization. 

Carbon spin-spin relaxation times, T2C, under CP-MAS conditions can provide motional information about the individual carbon site of interest, in contrast to the case of proton spin-lattice relaxation times in the rotating frame, TlpH, in which information on individual sites would be masked by the presence of a rapid spin-spin process. In general, the T2C values strongly depend on the... 

Garroway et al.(l ) have recently pointed out that the relative intensities of resonance lines of CP/MAS C NMR spectra are proportional to the number of carbons, when the time constant T y for H-13c cross polarization is much shorter than the spin-lattice relaxation times and tJp in the rotation frames of 1h and 13c nuclei, respectively. Since this condition has been found to be fulfilled under our experimental condition(15), such a quantitative analysis as shown in the text can be reasonably carried out for cellulose samples. 

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