Solid-state nuclear magnetic resonance technique

Characterization of the chemical structure of highly cross-linked polymers, and of the chemical changes that accompany degradation processes, relies on spectroscopic methods. Solid-state nuclear magnetic resonance techniques have the potential to allow a more detailed characterization than before possible of the chemical environment and structure of chemical crosslinks in elastomers and thermoset epoxies. Degradation processes in cross-linked systems have been studied by using infrared spectroscopy, solid-state NMR, and electron spin resonance. 

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. 

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. 

Several techniques have been used to characterise fluoridated apatites, especially XRD, fourier transform infrared (FTIR) spectroscopy and solid-state nuclear magnetic resonance (NMR). 

These ideas have been extended using new analytical techniques, in particular molecular modeling and solid-state nuclear magnetic resonance (nmr)... 

It is useful to emphasise from the outset that alternative techniques for investigating solid samples, other than NMR spectroscopy of the quadrupolar halogen nuclei, tend to be considered first this is likely due to the (perceived) difficulty of the technique and may be related to the issues of sensitivity and line broadening mentioned above. However, the information gained is often complementary, and hence solid state nuclear magnetic resonance (SS NMR) spectroscopy is primarily used when it can provide unique insight unavailable with other techniques. 

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]. 

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]. 

Wilson M. A. (1989) Solid-state nuclear magnetic resonance spectroscopy of humic substances basic concepts and techniques. In Humic Substances II in Search of Structure (eds. M. H. B. Hayes, P. MacCarthy, R. L. Malcolm, and M. J. Swift). Wiley, pp. 309-338. 

One technique that is becoming increasingly important for the characterization of materials is that of solid-state nuclear magnetic resonance (NMR) spectroscopy, and the application of this methodology to topics of pharmaceutical interest has been amply demonstrated.The NMR spectra of polymorphs or solvatomorphs often contains non-equivalent resonance peaks for analogous nuclei since the intimate details of the molecular environments associated with differing crystal structures can lead to perturbations in nuclear resonance energies. 

Solid-state nuclear magnetic resonance (SSNMR) spectroscopy is a powerful technique used in the analysis of solids, and is currently finding more and more applications, particularly in the analysis of pharmaceutical formulations. It is a non-destructive, non-invasive technique that can be employed to simultaneously examine the physical and chemical states of both the active pharmaceutical ingredient (API) and the excipients present as they exist within the formulation. It is also highly selective, as nuclei of the API often have different chemical shifts than do common excipients. 

Solid-state nuclear magnetic resonance (NMR), a canonical technique of chemistry and physics, possesses many versatile features such as, for example, elemental specificity and local structural, electronic, and motional sensitivity. In particular, NMR can characterize samples in most types of condensed matter, be it liquid or solid, single crystal or amorphous. Given adequate sensitivity it has, therefore, the unique ability of providing metal surface and adsorbate electronic and structural information on a molecular level and allows one to access motional information of adsorbate over a time range unattainable by any other single spectroscopic technique. In addition, solid-state NMR is nondestructive, technically versatile. 

There are many other characterization methods (e.g., small-angle X-ray scattering, solid-state nuclear magnetic resonance, and Fourier-transformed infrared analysis) for investigating nanocomposite structure. These techniques are extensively reviewed in Ray and Okamoto. ... 

Detection and characterization of polymorphs and/or solvates rely on various experimental techniques. X-ray powder diffraction (XRPD), solid state nuclear magnetic resonance (NMR), solid state infrared (IR) and solid state Raman are useful in demonstrating differences in the solid state. Thermal analytical techniques, including differential thermal analysis (DTA), differential scanning calorimetry (DSC), and thermogravimetry (TG), are also... 

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