Solid state nuclear magnetic resonance dynamics

Crosslinked polymer networks formed from multifunctional acrylates are completely insoluble. Consequently, solid-state nuclear magnetic resonance (NMR) spectroscopy becomes an attractive method to determine the degree of crosslinking of such polymers (1-4). Solid-state NMR spectroscopy has been used to study the homopolymerization kinetics of various diacrylates and to distinguish between constrained and unconstrained, or unreacted double bonds in polymers (5,6). Solid-state NMR techniques can also be used to determine the domain sizes of different polymer phases and to determine the presence of microgels within a poly multiacrylate sample (7). The results of solid-state NMR experiments have also been correlated to dynamic mechanical analysis measurements of the glass transition (1,8,9) of various polydiacrylates. 

R. M. Kowalczyk, T. F. Kemp, D. Walker, K. J. Pike, P. A. Thomas, J. Kreisel, R. Dupree, M. E. Newton, J. V. Flanna and M. E. Smith, A variable temperature solid-state nuclear magnetic resonance, electron paramagnetic resonance and Raman scattering study of molecular dynamics in ferroelectric fluorides. /. Phys. Condens. Matter, 2011, 23, 315402. 

For the investigation of the molecular dynamics in polymers, deuteron solid-state nuclear magnetic resonance (2D-NMR) spectroscopy has been shown to be a powerful method [1]. In the field of viscoelastic polymers, segmental dynamics of poly(urethanes) has been studied intensively by 2D-NMR [78, 79]. In addition to ID NMR spectroscopy, 2D NMR exchange spectroscopy was used to extend the time scale of molecular dynamics up to the order of milliseconds or even seconds. In combination with line-shape simulation, this technique allows one to obtain correlation times and correlation-time distributions of the molecular mobility as well as detailed information about the geometry of the motional process [1]. 

All the powerful methods of magnetic resonance, from solid-state nuclear magnetic resonance (NMR) to medical magnetic resonance imaging, depend on measuring the time evolution of a spin system following the application of one or more radio frequency pulses. In the visible and ultraviolet, ultrafast optical pulse sequences have been used for many years to measure both population dynamics and coherence phenomena. At low... 

Solid-state nuclear magnetic resonance (NMR) has been extensively used to assess structural properties, electronic parameters and diffusion behavior of the hydride phases of numerous metals and alloys using mostly transient NMR techniques or low-resolution spectroscopy [3]. The NMR relaxation times are extremely useful to assess various diffusion processes over very wide ranges of hydrogen mobility in crystalline and amorphous phases [3]. In addition, several borohydrides [4-6] and alanates [7-11] have also been characterized by these conventional solid-state NMR methods over the years where most attention was on rotation dynamics of the BHT, A1H4, and AlHe anions detection of order-disorder phase transitions or thermal decomposition. There has been little indication of fast long-range diffusion behavior in any complex hydride studied by NMR to date [4-11]. 

Bechinger, B., Zasloff, M. and Opella, S. J. (1998) Structure and dynamics of the antibiotic peptide PGLa in membranes by solution and solid-state nuclear magnetic resonance spectroscopy. Biophysical Journal, 74, 981-987. 

G. Neue, Simplification of Dynamic NMR Spectroscopy by Wavelet Transform Solid State Nuclear Magnetic Resonance. 5 (1996), 305-314. 

Volume 83 of Annual Reports on NMR Spectroscopy commences with an interesting account of Dynamic Pictures of Proteins by NMR from H. Saito this is followed by a report on Recent Progress in the Solid-State NMR Studies of Short Peptides—Techniques, Structure and Dynamics by A. Jezioma, S. Kazmierski, P. Paluch, E. Skorupska and M. J. Potrzebowski an account of Solid-State NMR Studies of Biomolecules is presented by A. Wong and F. PoU G. A. Monti, A. K. Chattah and Y. G. Linck report on Solid-State Nuclear Magnetic Resonance in Pharmaceutical Compounds the final report by M. Jaeger andR. L. E. G. Aspers is on Covariance NMR and Small-Molecule Applications . 

Several interesting review articles have been recently published focusing on the use of NMR methods to study peptide-lipid and small molecular weight molecule interactions in model and natural membranes. Maler as well as Kang and Li highlighted the unique possibilities of solution-state NMR to investigate the structure, dynamics and location of proteins and peptides in artificial bilayers and peptide-lipid interactions. On the other hand, Renault et reviewed recent advances in cellular solid-state nuclear magnetic resonance spectroscopy (SSNMR) to follow the structure, function, and molecular interactions of protein-lipid complexes in their cellular context and at atomic resolution. 

Schaefer et al. (19) studied the interphase microstructure of ternary polymer composites consisting of polypropylene, ethylene-propylene-diene-terpolymer (EPDM), and different types of inorganic fillers (e.g., kaolin clay and barium sulfate). They used extraction and dynamic mechanical methods to relate the thickness of absorbed polymer coatings on filler particles to mechanical properties. The extraction of composite samples with xylene solvent for prolonged periods of time indicated that the bound polymer around filler particles increased from 3 to 12 nm thick between kaolin to barium sulfate filler types. Solid-state Nuclear Magnetic Resonance (NMR) analyses of the bound polymer layers indicated that EPDM was the main constituent adsorbed to the filler particles. Without doubt, the existence of an interphase microstructure was shown to exist and have a rather sizable thickness. They proceeded to use this interphase model to fit a modified van der Poel equation to compute the storage modulus G (T) and loss modulus G"(T) properties. 

Solid state nuclear magnetic resonance (SSNMR) spectroscopy, which in many respects complements the most powerful tool for structure determination. X-ray crystallography, has become an indispensable tool for the characterization of both structure and dynamics in molecular materials.This nondestructive technique has the unique ability to probe electronic environments and the dipolar connectivity of NMR-active nuclei (e.g.,... 

R 2 M.H. Levitt, Spin Dynamics Basics of Nuclear Magnetic Resonance , John Wiley Sons, Inc., Chichester, UK, 2001 R 3 K.J.D. MacKenzie and M.E. Smith, Multinuclear Solid-State Nuclear Magnetic Resonance of Inorganic Materials in Pergamon Materials Series, Vol. 6, Pergamon, New York, N.Y., 2002 R 4 I. Noda and Y. Ozaki, Two-Dimensional Correlation Spectroscopy , Wiley, Chichester, UK, 2001... 

E. D. Watt and C. M. Rienstra, Recent Advances in Solid-State Nuclear Magnetic Resonance Techniques to Quantify Biomolecular Dynamics, Anal Chem., 2014, 86, 58. 

Tycko, R. Molecular dynamics, phase diagrams and electronic properties of fuller-enes and alkali fullerides Insights from sohd-state nuclear magnetic resonance spectroscopy.. Solid State Nud. Masn. Reson. 1994 3 303-314. 

Nuclear magnetic resonance provides means to study molecular dynamics in every state of matter. When going from solid state over liquids to gases, besides mole- cular reorientations, translational diffusion occurs as well. CD4 molecule inserted into a zeolite supercage provides a new specific model system for studies of rotational and translational dynamics by deuteron NMR. 

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