Spin-lattice relaxation poly

Recently, Lipton et al. [25] have used zinc-67 NMR to investigate [Zn(HB(3,5-(CH3)2pz)3)2] complexes which have been doped with traces of paramagnetic [Fe(HB(3,4,5-(CH3)3pz)3)2]. The low-temperature Boltzmann enhanced cross polarization between XH and 67Zn has shown that the paramagnetic iron(II) dopant reduces the proton spin-lattice relaxation time, Tj, of the zinc complexes without changing the proton spin-lattice relaxation time in the Tip rotating time frame. This approach and the resulting structural information has proven very useful in the study of various four-coordinate and six-coordinate zinc(II) poly(pyrazolyl)borate complexes that are useful as enzymatic models. 

C Spin-Lattice Relaxation-Times and n.O.e. Values of Resonance of Poly(n-butyl methacrylate) as 50% (w/w) Solution in Toluene-2H8... 

Dynamics of Poly(oxyethylene) Melts Comparison of 13C Nuclear Magnetic Resonance Spin-Lattice Relaxation and Dielectric Relaxation as Determined from Simulations and Experiments. 

Poly(benzyl ether) dendrimers synthesized by Frechet el al. have been studied with many techniques in order to reveal their conformational properties. Size exclusion measurements performed by Mourey et al. [154], rotational-echo double resonance (REDOR) NMR studies by Wooley et al. [155] and spin lattice relaxation measurements by Gorman et al. [156] reveal that back-folding takes place and the end-groups can be found throughout the molecule. The observed trends are in qualitative agreement with the model of Lescanec and Muthukumar [54],... 

A similar continuity in the Tj s through the melting temperature was previously reported for linear polyethylene. (17) We have now investigated the temperature dependence of this quantity, for this polymer, in more detail and have also studied a low density (branched) polyethylene. The results for the poly-ethylenes are summarized in Fig. 8. The new data reported here substantiate the conclusion previously reached for linear polyethylene. A similar conclusion can now be reached for the baclc-bone carbons of low density (branched) polyethylene. The melting temperature for this particular sample, under the crystallization conditions studied, is less than 110°C. (33) Thus, the spin-lattice relaxation parameters for the bac)cbone carbons are the same for both the linear and branched polymers over the temperature range studied here. Changes that occur in Tq as the temperature is reduced below 0°C involve other considerations and will be discussed in detail elsewhere. (22)... 

Sphingomyehn, IR spectrophotometry, 683-4 Spin delocahzation, polar effects in decomposition, 903 Spin labels, free radicals, 665 Spin-lattice relaxation oxidized functional groups, 695 poly (methylstyrene peroxide), 709 Spin trapping artemisinin ESR, 1291 free radicals, 665... 

Indeed, 13C spin-lattice relaxation times can also reflect conformational changes of a protein, i.e. helix to random coil transitions. This was demonstrated with models of polyamino acids [178-180], in which definite conformations can be generated, e.g. by addition of chemicals or by changes in temperature. Thus effective molecular correlation times tc determined from spin-lattice relaxation times and the NOE factors were 24-32 ns/rad for the a carbons of poly-(/f-benzyl L-glutamate) in the more rigid helical form and about 0.8 ms/rad for the more flexible random coil form [180],... 

Spin-lattice relaxation times and 13C chemical shifts were used to study conformational changes of poly-L-lysine, which undergoes a coil-helix transition in a pH range from 9 to 11. In order to adopt a stable helical structure, a minimum number of residues for the formation of hydrogen bonds between the C = 0 and NH backbone groups is necessary therefore for the polypeptide dodecalysine no helix formation was observed. Comparison of the pH-dependences of the 13C chemical shifts of the carbons of poly-L-lysine and (L-Lys)12 shows very similar values for both compounds therefore downfield shifts of the a, / and peptide carbonyl carbons can only be correlated with caution with helix formation and are mainly due to deprotonation effects. On the other hand, a sharp decrease of the 7] values of the carbonyl and some of the side chain carbons is indicative for helix formation [854]. 

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). 

Table I. 13C Spin Lattice Relaxation Times of Poly(w-butyl...

The decay time constants for the polymeric radicals clearly vary from solvent to solvent, ranging over an order of magnitude from about 2 ps in tetrahydrofuran (THF) to 200 ns in methylene chloride. A similar solvent dependence of NMR Ti values has been reported by Spyros et al. They studied poly(naphthyl methacrylate) using the inversion recovery technique and found that the spin-lattice relaxation time of... 

Metal acetylacetonates can be used as NMR shift reagents. Thus, Cr(acac)3 and Fe-(acac)3 can be used as paramagnetic relaxation agents to decrease the spin-lattice relaxation times of all C signals in poly(Me methacrylate), poly(Bu methacrylate) and poly(hydroxyethyl methacrylate) . ... 

Chang et al. reported the miscibility of poly(vinylphenol) (PVPh) with poly(methyl methacrylate) (I MMA) Figure 1 shows the C CP/MAS spectra of pure PVPh, PMMA, PVPh-co-PMMA, PEG, and PVPh-co-PMMA/ poly(ethylene oxide) (PEO) blends of various compositions with peak assignments. VPh contents of PVPh-co-PMMA is 51 mol% and Mn of PEO is 20,000. The spin lattice relaxation time in the rotating frame (Tip ) was measured to examine the homogeneity of PVPh-co-PMMA/PEO blends on the molecular scale. 

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. 

The rotating-frame spin-lattice relaxation time for protons, Tip,( H), was measured indirectly from CPMAS/DD NMR to probe possible molecular scales of heterogeneity in the miscible poly(benzyl methacrylate)/poly(ethylene oxide) blend over the whole composition range. ... 

Carbon-13 spin-lattice relaxation times are measured for poly(octadecyl acrylate) above and below the melting point of the crystalline side chains. The behaviours of lithium ions in a polyether poly(urethane urea) (PEUU) were investigated by C MAS solid-state NMR. ... 

Figure 2. The 13C spin-lattice relaxation times at 15 MHz for isotactic poly (propylene) methylene ( ), methine (O), and methyl (A) carbons.

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