Solid State NMR

The nuclear magnetic resonance (NMR) spectroscopy is a very powerful tool in the chemical characterization, both in solution and in solid state. With the development of NMR spectrometers more potent field, employing radio frequency pulse, provided the development of studies on materials, especially amorphous materials. Thus, there was a need to develop techniques to obtain spectra in solid state with high resolution in comparison to those obtained in solution. Therefore, the study of polymers and polymeric materials could be developed quickly as a result a lot of information about the structure-property could be obtained with more details. The use of NMR in the solid state has become particularly important in the study of amorphous materials, as well as in the study of crystal structures, and permits us to detect different constituents present in material. This chapter covers the basic solid-state NMR techniques that provide important information on sample molecular behavior because they are powerful and versatile tools to evaluate polymer and complex materials like nanomaterials

Solid-state NMR spectroscopy

M.H. acknowledges support by National Institutes of Health (NIH) grant GM066976.Solid-state nuclear magnetic resonance (NMR) spectroscopy is an atomic-level method used to determine the chemical structure, three-dimensional structure, and dynamics of solids and semi-solids. This Primer summarizes the basic principles of NMR as applied to the wide range of solid systems. The fundamental nuclear spin interactions and the effects of magnetic fields and radiofrequency pulses on nuclear spins are the same as in liquid-state NMR. However, because of the anisotropy of the interactions in the solid state, the majority of high-resolution solid-state NMR spectra is measured under magic-angle spinning (MAS), which has profound effects on the types of radiofrequency pulse sequences required to extract structural and dynamical information. We describe the most common MAS NMR experiments and data analysis approaches for investigating biological macromolecules, organic materials, and inorganic solids. Continuing development of sensitivity-enhancement approaches, including 1H-detected fast MAS experiments, dynamic nuclear polarization, and experiments tailored to ultrahigh magnetic fields, is described. We highlight recent applications of solid-state NMR to biological and materials chemistry. The Primer ends with a discussion of current limitations of NMR to study solids, and points to future avenues of development to further enhance the capabilities of this sophisticated spectroscopy for new applications.PostprintPeer reviewe

Blind spheres of paramagnetic dopants in solid state NMR

Solid-state NMR on paramagnetically doped crystal structures gives information about the spatial distribution of dopants in the host. Paramagnetic dopants may render NMR active nuclei virtually invisible by relaxation, paramagnetic broadening or shielding. In this contribution blind sphere radii r(0) have been reported, which could be extracted through fitting the NMR signal visibility function f (x) = exp(-ar(0)(3)x) to experimental data obtained on several model compound series: La(1-x)Ln(x)PO(4) (Ln = Nd, Sm, Gd, Dy, Ho, Er, Tm, Yb), Sr1-xEuxGa2S4 and (Zn1-xMnx)(3)(PO4)(2)center dot 4H(2)O. Radii were extracted for H-1, P-31 and Ga-71, and dopants like Nd3+, Gd3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+ and Mn2+. The observed radii determined differed in all cases and covered a range from 5.5 to 13.5 angstrom. While these radii were obtained from the amount of invisible NMR signal, we also show how to link the visibility function to lineshape parameters. We show under which conditions empirical correlations of linewidth and doping concentration can be used to extract blind sphere radii from second moment or linewidth parameter data. From the second moment analysis of La1-xSmxPO4 P-31 MAS NMR spectra for example, a blind sphere size of Sm3+ can be determined, even though the visibility function remains close to 100% over the entire doping range. Dependence of the blind sphere radius r(0) on the NMR isotope and on the paramagnetic dopant could be suggested and verified: for different nuclei, r(0) shows a 3 root gamma-dependence, gamma being the gyromagnetic ratio. The blind sphere radii r(0) for different paramagnetic dopants in a lanthanide series could be predicted from the pseudo-contact term

Molecular architecture of softwood revealed by solid-state NMR

Economically important softwood from conifers is mainly composed of the polysaccharides cellulose, galactoglucomannan and xylan, and the phenolic polymer, lignin. The interactions between these polymers lead to wood mechanical strength and must be overcome in biorefining. Here, we use 13C multidimensional solid-state NMR to analyse the polymer interactions in never-dried cell walls of the softwood, spruce. In contrast to some earlier softwood cell wall models, most of the xylan binds to cellulose in the two-fold screw conformation. Moreover, galactoglucomannan alters its conformation by intimately binding to the surface of cellulose microfibrils in a semi-crystalline fashion. Some galactoglucomannan and xylan bind to the same cellulose microfibrils, and lignin is associated with both of these cellulose-bound polysaccharides. We propose a model of softwood molecular architecture which explains the origin of the different cellulose environments observed in the NMR experiments. Our model will assist strategies for improving wood usage in a sustainable bioeconomy

Fluoro-substituted prolines as structural labels for solid state ¹⁹F-NMR of polypeptides

Proline substitution useful for the solid state NMR structure analysis was explored on two peptides: gramicidin S and SAP. Corresponding microbiologial and conformational effects were correlated with the solid state NMR response