RAPID MEASUREMENT OF 1H 90 PULSE IN THE SOLID STATE NMR VIA CROSS POLARIZATION P. Conte, R. Spaccini, A.

Piccolo
Dip. di Scienze del Suolo della Pianta e dellAmbiente, via Universit 100, 80055 Portici (Na) Italy E-Mail: pellegrino.conte@unina.it

Cross polarization magic angle spinning (CPMAS) 13C NMR spectroscopy is based on the excitation of carbons via proton nuclei. Namely, a 90 pulse applied on the protons is followed by a spin lock sequence on both 1H and 13C in order to excite the carbons. A proton decoupling sequence is then applied while the 13C signals are acquired. The CPMAS 13C sequence is the basis of more complicated and powerful experiments such as those based on the Lee-Goldburg decoupling. Key factors of the CPMAS 13C NMR spectroscopy are: 1. the matching of the Hartmann-Hahn condition, and, 2. the precision of the proton 90 pulse. If one of the two factors are not matched, NMR artefacts may arise. The present work deals with the precise calibration of the proton 90 pulse via cross polarization on standard molecules and natural organic matter. The normal method used to calibrate the proton 90 pulse via cross polarization is the use of an optimization method on a standard system such as the simple glycine. Namely, the proton pulse length is varied until 13C NMR signals are undetected. The undetectability of the carbon signals is due to the application of a proton pulse corresponding to a 180 1H magnetization inversion. The application of a 180 1H pulse prevents the 1H-13C crosspolarization. The main disadvantages of the standard 90 pulse measurements are related to: 1. the NMR pulse trapezoidal shapes that shorten the real pulse length to be applied in CPMAS 13C-NMR experiments, 2. the use of a recycle delay that can be inadequate as the proton pulse length is increased during the 90 proton pulse measurements, 3. the use of a simple organic standard that can have a NMR behaviour different from that of the natural organic matter. In order to account for all these problems, a new method for proton 90 pulse calibration was developed. The classical CPMAS 13C NMR pulse sequence was modified in order to apply a pulse train made by four 90 pulses on protons. The use of such a modified sequence minimizes the errors due to the trapezoidal pulse shapes, and allows the application of a very short recycle delay, thereby shortening the 90 pulse measuring time. In fact, the 4x90 pulse train corresponds to a rotation of 360 of the 1H magnetization. Being close to the equilibrium state, an unusually short recycle delay can be applied. Moreover, the absence of 13C NMR signals is a confirmation that the correct 90 1H pulse was measured. The modified 4x90 pulse sequence can be also used to rapidly measure the correct 90 1H pulse on natural organic matter (NOM), thereby preventing the use of standard organic systems that differ from NOM and can provide imprecise NOM 90 1H pulses.