Solid-state NMR studies of polymers

The intense interest in solid-state polymers has driven development of new methods for materials characterisation by solid-state NMR. Although solid-state NMR spectra are more difficult to acquire than solution spectra, solid-state NMR has become a routine technique in many laboratories. These spectra can be acquired in the high-resolution or wide-line mode, methods that yield different but complementary information. 

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In the past 4-5 years, quite a number of relevant review articles and books have appeared. These included general reviews on NMR of polymers (1 10), reviews on solid state NMR (11-15), solid state multidimensional techniques (16-19), spatially resolved techniques (20), solid state NMR studies of polymer dynamics and structure (21), hydrated polymers (22), vulcanized elastomers (23), crosslinked polymers (24), and polymer networks (25), Reviews have also been written on polymer gels (26-28), polymer colloids (29), polymer-surfactant systems (30), and polymers on surfaces (31). 

High resolution solid-state NMR studies of polymer chemical and physical structures... 

Simmons A, Natansohn A. (1991) Solid-state NMR study of charge-transfer interactions in polymer blends. Macromolecules 24 3651-3661. 

Volume 52 of Annual Reports on NMR is devoted to Advances in Solid-State NMR Studies of Materials and Polymers and is dedicated to my longstanding co-worker, Professor Isao Ando of Tokyo Institute of Technology who is planning to retire early in 2005. 

R549 H. W. Spiess, Multidimensional Solid State NMR Studies of Complex Dynamics in Polymers , AIP Conf. Proc., 2000, 519, 33 R550 O. Spring, Chemotaxonomy Based on Metabolites from Glandular Trichomes , Adv. Bot. Res., 2000, 31, 153 R551 M. Springborg, Density-Functional Theory , Chem. Model ., 2000, 1, 306... 

Many solid-state NMR studies of oriented polymer fibers or film other than silk have been described. Orientation-dependent chemical shielding tensors especially serve as probes with which the relative orientations of specific bond vectors can be determined [10]. This analytical method can be applied to obtain structural information from oriented polyamide fibers such as poly (p-phenylene terephthalamide) (PPTA) [11], poly(m-phenylene isophthalamide) (PMIA) and poly(4-methyl-m-phenylene terephthalamide) (P4M-MPTA) fibers without isotope labeling of the samples [12] (Chapter 12). Oriented carbonyl carbon labeled poly (ethylene terephthalate) (PET) films have also been analyzed with this method [13] (Chapter 14). Especially, more quantitative structural information will be obtained for a locally ordered domain which has been recognized as an amorphous domain in X-ray diffraction analysis in heterogeneous polymer samples. 

To extract information on molecular orientation distribution from experimental data, the most widely known technique, the Legendre moment expansion approach can be taken. In this section, this approach will be discussed first, followed by methods to elucidate atomic resolution details of the structures of ordered polymers with orientation-dependent NMR interactions, such as those from chemical shielding, dipole-dipole and quadrupolar coupling. Then, solid-state NMR studies of the torsion angles of the peptide backbone of highly ordered silk fibroin fiber, a protein that has been studied extensively as a model for fibrous proteins, will be described. 

Solid state NMR studies of pharmaceutical solids in polymer matrices have been presented by Lubach et Two systems were chosen. The first system... 

Brus, J. Dybal, J., Solid-State NMR Study of Structure, Size and Dynamics of Domains in Hybrid Siloxane Networks. Polymer 2000,41, 5269-5282. 

M. M. Guo. Variable temperature solid-state NMR studies of conformation change and order-disorder transition of poly(3-alkylthiophene). Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 43(2), 487-488 (2002). 

G. Ye, N. Janzen, G.R. Goward, Solid-state NMR study of two classic proton conducting polymers NAFION and sulfonated poly(ether ether ketone)s. Macromolecules 39 (2006) 3283—3290. 

Fu W, Sun P (2011) Solid state NMR study of hydrogen bonding, miscibility, and dyntimics in multiphase polymer systems. Front Chem China 6173-189 Gaisford S (2005) Stability assessment of pharmaceuticals and biopharmaceuticals by isothermtd calorimetry. Curr Pharm Biotechnol 6 181-191... 

Horii E, Hirai A., and Kitamaru R. 1983. Solid-state -NMR study of conformations of oligosaccharides and cellulose conformation of CHpH group about the exo-cyclic C-C bond. Polym Bull 10 357-361. 

Xie X Q, Ranade S V and DiBenedetto A T (1999) A solid state NMR study of polycarbonate oligomer grafted onto the surface of amorphous silica. Polymer 40 6297-6306. 

In this study we have presented the first simulations of solid state NMR spectra of polymers that are based on ab initio quantum chemistry. By combining statistical conformational models, empirical force-field optimization of geometries, and the Individual Gauges for Localized Molecular Orbitals (IGLO) method for the calculation of the chemical shift, it is possible to reproduce the shape and the width of the experimental solid state NMR spectra. 

Page KA, Jarrett W, Moore RB (2007) Variable temperature F-19 solid-state NMR study of the effect of electrostatic interactions on thermally-stimulated molecular motions in perfiuor-osulfonate Ionomers. J Polym Sci B Polym Phys 45(16) 2177-2186... 

Recent Solid-State NMR Studies of Quadrupo-lar Nuclei in Metal-Organic Frameworks Single-Crystal to Single-Crystal Transformations in Metal-Organic Frameworks Interpenetration and Entanglement in Coordination Polymers. 

Lee, Y.J., Bingol, B., Murakhtina, T., Sebastian , D., Meyer, W.H., Wegner, G., Spiess, H.W. (2007) High-resolution solid-state NMR studies of poly(vinyl phosphonic acid) proton-conducting polymer molecular structure and proton dynamics. The Journal of Physical Chemistry B, 111, 9711-9721. 

Journal of Polymer Science Polymer Physics Edition 38, No.ll, 1st June 2000, p.1417-23 SOLID-STATE NMR STUDIES OF CIS-1,4-POLYISOPRENE CROSSLESKED WITH DICUMYL PEROXIDE IN THE PRESENCE OF TRIALLYL CYANURATE Sung Joon Oh Koenig J L Case Western Reserve University... 

Through a combination of X-ray crystallography and solid-state NMR studies, they were able to correlate chromic transitions with motion, and an increase in disorder within the backbone of the polymer [1]. As the temperature increased, so did disorder within the polymer, resulting in a blue-shift of the UV-vis spectra (Fig. 4). 

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