Solid-state 15N Nuclear Magnetic Resonance Research Articles

Compatibilization of Polymer Blends by Complexation. 1. Spectroscopic Characterization of Ion−Amide Interactions in Ionomer/Polyamide Blends

Electron paramagnetic resonance (EPR), Fourier transform infrared (FTIR), and solid-state 15N nuclear magnetic resonance (15N-NMR) spectroscopies were used to characterize the structure and relative strength of the interactions between metal sulfonate and amide groups in blends of lightly sulfonated polystyrene ionomers and an N-methylated polyamide, poly(N,N‘-dimethylethylene sebacamide), and low molecular weight model complexes. The metal sulfonate groups, which aggregate in the neat ionomer, were dispersed by the polyamide in the blend as a consequence of a complexation that involved the sulfonate cation and both the carbonyl oxygen and the amide nitrogen of the polyamide. The FTIR and 15N-NMR spectra were consistent with a 2pz electron redistribution model for the complex, in which electrons migrate from the nitrogen to the metal ion through the carbonyl group. The sulfonate anion did not appear to particpate in the complex, but it remained in the vicinity of the metal cation. The strength of the ion−...

Titanium carbide, nitride and carbonitrides: a 13C, 14N, 15N and 47,49Ti solid-state nuclear magnetic resonance study

The first 47,49Ti, 13C, 14N and 15N solid-state nuclear magnetic resonance (NMR) spectra of titanium carbide, nitride and a series of cubic carbonitrides have been obtained under both static and magic-angle spinning (MAS) conditions. The 15N samples were isotopically enriched by gas-solid exchange at 1000 ° C in a closed system. The Ti spectra of the carbide and nitride are sharp, reflecting the well defined cubic symmetry of these compounds, but become considerably broadened in the carbonitride series, with the spectra being approximately the sum of TiC and TiN together with some small electric field gradient (EFG) effects. The resonance positions and widths of all the NMR spectra change as carbon is progressively replaced by nitrogen. A relationship is observed between the 13C chemical shift and the nitrogen content of the carbonitrides, suggesting a possible NMR method for estimating the composition of these compounds. Although electron paramagnetic resonance (EPR) spectra of all these compounds show typically metallic behaviour, the NMR spectra show few effects attributable to conduction electrons, probably due to the lack of s-orbital contributions to the conduction band.

Structural analysis of highly oriented poly( p-phenylene-terephthalamide) by 15N solid-state nuclear magnetic resonance

The structure of an aromatic polyamide, poly( p-phenylene-terephthalamide) (PPTA), was studied in the solid state using 15N nuclear magnetic resonance (NMR) spectroscopy. Spectra of uniaxially aligned molecules placed with the axis of alignment both parallel with and perpendicular to the applied magnetic field were analyzed to yield the orientations of specific molecular bonds with respect to the fiber axis. The 15N chemical shift tensor was characterized by simulating powder pattern spectra of both PPTA and a model compound, benzanilide. Chemical shift and dipolar coupled chemical shift line shapes were calculated through Euler angle transformations from the principal axis system (PAS) reference frame to the fiber axis system (FAS) frame. The orientations of NH and NC' bonds in PPTA are determined as well as the orientational distribution of the PPTA fiber axis. The structural parameters determined for PPTA are compared with those obtained by X-ray diffraction.

Solid-phase peptide synthesis and solid-state NMR spectroscopy of [Ala3-15N][Val1]gramicidin A.

[Ala3-15N][Val1]Gramicidin A has been prepared by solid-phase peptide synthesis and studied by solid-state 15N nuclear magnetic resonance spectroscopy. The synthesis of desformyl[Ala3-15N][Val1]gramicidin A employed N-hydroxysuccinimide esters of 9-fluorenylmethoxycarbonyl-N alpha-amino acids and completely avoided the use of acid. Since deblocking was done with piperidine and the peptide was removed from the resin by treatment with ethanolamine, this synthetic protocol prevented oxidation of the indole rings of this tryptophan-rich peptide and reduced truncations produced by acid hydrolysis. After formylation and purification by anion-exchange and high-pressure liquid chromatography, the peptide was obtained in an overall yield of 30%. Solid-state 15N nuclear magnetic resonance spectra of this peptide and uniformly labeled [15N]gramicidin A' oriented in hydrated lipid bilayers have been obtained, allowing unambiguous assignment of the [15N]Ala3 resonance in the latter. The solid-state 15N nuclear magnetic resonance experiments provide evidence that [Val1]gramicidin A is rotating about an axis that is perpendicular to the plane of the lipid bilayer and that the N--H axis is nearly parallel with the rotational axis. This study demonstrates that site-specifically labeled [15N]gramicidin A analogs prepared by solid-phase peptide synthesis are valuable tools in the study of the solid-state nuclear magnetic resonance spectra of samples in oriented lipid bilayers.