0.1 Basics of solid-state nmr  (Page 2/2)

[link] can have E substituted for hν, leading to [link] , which can solve for the NMR resonance frequency (v).

Using the frequency (v), the δ, or expected chemical shift may be computed using [link] .

Delta (δ) is observed in ppm and gives the distance from a set reference. Delta is directly related to the chemical environment of the particular atom. For a low field, or high delta, an atom is in an environment which produces induces less shielding than in a high field, or low delta.

Nmr instrument

An NMR can be divided into three main components: the workstation computer where one operates the NMR instrument, the NMR spectrometer console, and the NMR magnet. A standard sample is inserted through the bore tube and pneumatically lowered into the magnet and NMR probe ( [link] ).

The first layer inside the NMR ( [link] ) is the liquid nitrogen jacket. Normally, this space is filled with liquid nitrogen at 77 K. The liquid nitrogen reservoir space is mostly above the magnet so that it can act as a less expensive refrigerant to block infrared radiation from reaching the liquid helium jacket.

The layer following the liquid nitrogen jacket is a 20 K radiation shield made of aluminum wrapped with alternating layers of aluminum foil and open weave gauze. Its purpose is to block infrared radiation which the 77 K liquid nitrogen vessel was unable to eliminate, which increases the ability for liquid helium to remain in the liquid phase due to its very low boiling point. The liquid helium vessel itself, the next layer, is made of stainless steel wrapped in a single layer of aluminum foil, acting once again as an infrared radiation shield. It is about 1.6 mm thick and kept at 4.2 K.

Inside the vessel and around the magnet is the aluminum baffle, which acts as another degree of infrared radiation protection as well as a layer of protection for the superconducting magnet from liquid helium reservoir fluctuations, especially during liquid helium refills. The significance is that superconducting magnets at low fields are not fully submerged in liquid helium, but higher field superconducting magnets must maintain the superconducting solenoid fully immersed in liquid helium The vapor above the liquid itself is actually enough to maintain superconductivity of most magnets, but if it reaches a temperature above 10 K, the magnet quenches. During a quench, the solenoid exceeds its critical temperature for superconductivity and becomes resistive, generating heat. This heat, in turn, boils off the liquid helium. Therefore, a small opening at the very base of the baffle exists as a path for the liquid helium to reach the magnet surface so that during refills the magnet is protected from accidental quenching.

Problems with solid state nmr

The most notable difference between solid samples and solution/gas in terms of NMR spectroscopy is that molecules in solution rotate rapidly while those in a solid are fixed in a lattice. Different peak readings will be produced depending on how the molecules are oriented in the magnetic field because chemical shielding depends upon the orientation of a molecule, causing chemical shift anisotropy. Therefore, the effect of chemical shielding also depends upon the orientation of the molecule with respect to the spectrometer. These counteracting forces are balanced out in gases and solutions because of their randomized molecular movement, but become a serious issue with fixed molecules observed in solid samples. If the chemical shielding isn’t determined accurately, neither will the chemical shifts (δ).

Another issue with solid samples are dipolar interactions which can be very large in solid samples causing linewidths of tens to hundreds of kilohertz to be generated. Dipolar interactions are tensor quantities, which demonstrate values dependent on the orientation and placement of a molecule in reference to its surroundings. Once again the issue goes back to the lattice structure of solids, which are in a fixed location. Even though the molecules are fixed, this does not mean that nuclei are evenly spread apart. Closer nuclei display greater dipolar interactions and vice versa, creating the noise seen in spectra of NMR not adapted for solid samples. Dipolar interactions are averaged out in solution states because of randomized movement. Spin state repulsions are averaged out by molecular motion of solutions and gases. However, in solid state, these interactions are not averaged and become a third source of line broadening.

Magic angle spinning

In order to counteract chemical shift anisotropy and dipolar interactions, magic angle spinning was developed. As discussed above, describing dipolar splitting and chemical shift aniostoropy interactions respectively, it becomes evident that both depend on the geometric factor (3cos ² θ-1).

If this factor is decreased to 0, then line broadening due to chemical shift anisotropy and dipolar interactions will disappear. Therefore, solid samples are rotated at an angle of 54.74˚, effectively allowing solid samples to behave similarly to solutions/gases in NMR spectroscopy. Standard spinning rates range from 12 kHz to an upper limit of 35 kHz, where higher spin rates are necessary to remove higher intermolecular interactions.

Application of solid state nmr

The development of solid state NMR is a technique necessary to understand and classify compounds that would not work well in solutions, such as powders and complex proteins, or study crystals too small for a different characterization method.

Solid state NMR gives information about local environment of silicon, aluminum, phosphorus, etc. in the structures, and is therefore an important tool in determining structure of molecular sieves. The main issue frequently encountered is that crystals large enough for X-Ray crystallography cannot be grown, so NMR is used since it determines the local environments of these elements. Additionally, by using ¹³ C and ¹⁵ N, solid state NMR helps study amyloid fibrils, filamentous insoluble protein aggregates related to neurodegenerative diseases such as Alzheimer’s disease, type II diabetes, Huntington’s disease, and prion diseases.

Bibliography

• J. W. Akitt, NMR and Chemistry , 3 ^rd Edn., Chapman&Hall, London (1992).
• A. R. Grimmer and B. Blümich, Introduction to Solid-State NMR , Springer-Verlag, Berlin(1994).
• J. A. Iggo, NMR Spectroscopy in Inorganic Chemistry , Oxford University Press, New York (1999).
• J. C. C. Chan, Top. Curr. Chem. , 2011, 306 , 47.
• R. Freeman, Chem Heterocyc Compd , 1995, 31 , 1004-1005.
• Jeol USA, JEOL Delta-GSX 270 NMR Magnet Destruction ,<http://www.jeolusa.com>
• University of Pittsburgh, Magnet Safety ,<http://www.ehs.pitt.edu/assets/docs/magnet-safety.pdf>, 2008, (accessed 15 February 2012).