Very fast MAS and MQMAS NMR studies of the spectroscopically challenging minerals kyanite and andalusite on 400, 500, and 800 MHz spectrometers.
The well-characterized minerals kyanite and andalusite have long presented great challenges in using solid state 27Al NMR to determine the isotropic chemical shift deltaCS, quadrupole coupling constant e2qQ/h, and asymmetry parameter eta for each of the inequivalent aluminum sites in these minerals. Indeed, these minerals have frequently been used to test advances in instrumentation. Recent advances in magnet technology (up to 18.8 T = 800 MHz 1H) and in MAS probe technology (spinning up to 35 kHz and considerably stronger rf) and refinements of the two-dimensional, multiple quantum magic angle spinning (MQMAS) technique suggested that these developments could be profitably used to study kyanite and andalusite by solid state 27Al NMR. The benefit of being able to study kyanite both by MAS and MQMAS techniques on 400, 500, and 800 MHz spectrometers is demonstrated. The two octahedral aluminum sites with the largest (and nearly equal) e2qQ/h values give overlapping 1D MAS or 2D 3QMAS signals at all three field strengths. Nevertheless, quantitatively accurate 3Q signal intensities at 9.4 T for all four octahedral aluminum sites (with e2qQ/h values up to 10 MHz) allow more detailed analysis. Even if the 3Q signal intensities are not quantitative, their isotropic shifts provide an approach (if accurate e2qQ/h and eta values are available) other than deconvolution of the MAS spectrum for calculating deltaCS values. For andalusite, 34 kHz MAS on the 800 MHz spectrometer significantly narrows the extremely broad signal for the octahedral aluminum, and only slight difficulties are encountered in quantitating the relative amounts of AlO5 and AlO6 present. Even with e2qQ/h = 15.3 MHz, the octahedral aluminum in andalusite gives a signal in a MQMAS experiment, albeit of reduced intensity. As appropriate, we discuss some of the benefits and limitations of these advances in instrumentation and of different experimental approaches for studying non-integral spin quadrupolar nuclei in solids.
Rice University, Department of Chemistry, Houston, TX 77005-1892, USA.
L B
LB
Alemany
S
S
Steuernagel
J P
JP
Amoureux
R L
RL
Callender
A R
AR
Barron
D000538:Aluminum Silicates / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy / Q000295:instrumentation / Q000379:methods*; D008903:Minerals / Q000737:chemistry
D000538:Aluminum Silicates; D008903:Minerals; C121090:andalusite; C121089:kyanite