Homogeneous broadenings in 2D solid-state NMR of half-integer quadrupolar nuclei

The question of the homogeneous broadening that occurs in 2D solid-state NMR experiments is examined. This homogeneous broadening is mathematically introduced in a simple way, versus the irreversible decay rates related to the coherences that are involved during t1 and t2. We give the pulse sequences and coherence transfer pathways that are used to measure these decay rates. On AlPO4 berlinite, we have measured the 27Al echo-type relaxation times of the central and satellite transitions on 1Q levels, so that of coherences that are situated on 2Q, 3Q, and 5Q levels. We compare the broadenings that can be deduced from these relaxation times to those directly observed on the isotropic projection of berlinite with multiple-quantum magic-angle spinning (MAS), or satellite-transition MAS. We show that the choice of the high-resolution method, should be done according to the spin value and the corresponding homogeneous broadening.     

Spectral editing in solid-state MAS NMR of quadrupolar nuclei using selective satellite inversion

A sensitivity enhancement method based on selective adiabatic inversion of a satellite transition has been employed in a (pi/2)CT-(pi)ST1-(pi/2)CT spectral editing sequence to both enhance and resolve multisite NMR spectra of quadrupolar nuclei. In addition to a total enhancement of 2.5 times for spin 3/2 nuclei, enhancements up to 2.0 times is reported for the edited sites in a mixture of rubidium salts.     

I-STMAS,a new high-resolution solid-state NMR method for half-integer quadrupolar nuclei

In complement to the previously proposed multiple-quantum magic-angle-spinning (MQMAS) and satellite transition MAS (STMAS) sequences, we describe a new two-dimensional high-resolution method, inverse-STMAS (I-STMAS) that allows second-order quadrupolar averaging. Like STMAS, I-STMAS correlates second-order quadrupole dephasing occurring on coherences related to the central transition (CT) and satellite transitions (STs), but does it in a reverse manner: CT evolves during the t₁ period while STs are detected during t₂. Although STMAS and I-STMAS are symmetric, there are some interesting and useful differences between the two methods. For example, we show that during the acquisition time t₂, it is possible to over-sample the data and then to process them to suppress the CT–CT correlation resonance.     

Comparison of high-resolution solid-state NMR MQMAS and STMAS methods for half-integer quadrupolar nuclei

Several different amplitude-modulated two-dimensional high-resolution methods, based on MQMAS and STMAS, are compared. They include 3QMAS, 5QMAS, DQ-STMAS, and DQF-STMAS experiments. A new method, called t1-split-STMAS, is also proposed for spin-3/2 nuclei. The comparison is performed in terms of isotropic resolution and spectral-width, efficiency, and sensitivity to magic-angle offset and spinning speed fluctuations.     

Enhancing sensitivity of quadrupolar nuclei in solid-state NMR with multiple rotor assisted population transfers

Rotor-assisted population transfer (RAPT) was developed as a method for enhancing MAS NMR sensitivity of quadrupolar nuclei by transferring polarization associated with satellite transitions to the central m=12-->-12 transition. After a single RAPT transfer, there still remains polarization in the satellite transitions that can be transferred to the central transition. This polarization is available without having to wait for the spin system to return to thermal equilibrium. We describe a new RAPT scheme that uses the remaining polarization of the satellites to obtain a further enhancement of the central transition by performing RAPT-enhanced experiments multiple times before waiting for re-equilibration of the spin system. For 27Al (I=5/2) in albite we obtain a multiple RAPT enhancement of 3.02, a 48% increase over single RAPT. For 93Nb (I=9/2) in NaNbO(3) we obtain a multiple RAPT enhancement of 5.76, an 89% increase over single RAPT. We also describe a data processing procedure for obtaining the maximum possible signal-to-noise ratio.     

Signal enhancement in 5QMAS spectra of spin-5/2 quadrupolar nuclei

5QMAS experiments on spin-5/2 systems display a low sensitivity compared with their 3QMAS counterparts. Nevertheless, the superior resolution of 5QMAS over 3QMAS makes these experiments a favorable choice for many materials. We report an enhancement scheme for the 5QMAS experiment, using an improved five-quantum excitation pulse scheme combined with a FAM-II conversion pulse. The results are verified experimentally on a polycrystalline sample of gamma-(27)Al(2)O(3), showing an enhancement factor of 2.4 over the simple two-pulse (CW) 5QMAS scheme. Numerical computations of the efficiency parameter epsilon support these results.     

Multiplex MQMAS NMR of quadrupolar nuclei

A multiplex phase cycling method (N. Ivchenko et al., J. Magn. Reson. 160 (2003) 52-58) has been used to record two-dimensional MQMAS spectra with a very short phase cycling. A straightforward procedure has been developed to easily process the data. Combining this Multiplex approach and the new Soft-Pulse-Adding-Mixing (SPAM) method considerably increases the signal-to-noise ratio of the conventional MQMAS experiment. The Multiplex acquisition procedure is much simpler than the echo/anti-echo method recently proposed, and has been applied with success to record (87)Rb spectra of RbNO(3) and (27)Al 3Q and 5Q MQMAS NMR of microporous aluminophosphate AlPO(4)-14.     

Sensitivity enhancement of the central-transition signal of half-integer spin quadrupolar nuclei in solid-state NMR: features of multiple fast amplitude-modulated pulse transfer

Sensitivity enhancement of solid-state NMR spectrum of half-integer spin quadrupolar nuclei under both magic-angle spinning (MAS) and static cases has been demonstrated by transferring polarisation associated with satellite transitions to the central m=-1/2-->1/2 transition with suitably modulated radio-frequency pulse schemes. It has been shown that after the application of such enhancement schemes, there still remains polarisation in the satellite transitions that can be transferred to the central transition. This polarisation is available without having to wait for the spin system to return to thermal equilibrium. We demonstrate here the additional sensitivity enhancement obtained by making use of this remaining polarisation with fast amplitude-modulated (FAM) pulse schemes under both MAS and static conditions on a spin-3/2 and a spin-5/2 system. Considerable signal enhancement is obtained with the application of the multiple FAM sequence, denoted as m-FAM. We also report here some of the salient features of these multiple FAM sequences with respect to the nutation frequency of the pulses and the spinning frequency.     

Correlation NMR spectroscopy involving quadrupolar nuclei

We review the recent developments proposed for integer or half-integer quadrupolar nuclei, focussing on the methods to observe them under high-resolution and to analyze their through-space and through-bond connectivities.     

Through-space MP-CPMAS experiments between spin-1/2 and half-integer quadrupolar nuclei in solid-state NMR

We present a new CPMAS method that allows the acquisition of through-space 2D HETCOR spectra between spin-1/2 nuclei and half-integer quadrupolar nuclei in the solid state. It uses rotor-synchronized selective pulses on the quadrupolar nucleus and continuous-wave RF irradiation on the spin-1/2 nucleus to create hetero-nuclear dipolar coherences. The method is more robust, more efficient, and easier to set up than the standard CPMAS transfer.     

19F-decoupling of half-integer spin quadrupolar nuclei in solid-state NMR: application of frequency-swept decoupling methods

In solid-state NMR studies of minerals and ion conductors, quadrupolar nuclei like ⁷Li, ²³Na or ¹³³Cs are frequently situated in close proximity to fluorine, so that application of ¹⁹F decoupling is beneficial for spectral resolution. Here, we compare the decoupling efficiency of various multi-pulse decoupling sequences by acquiring ¹⁹F-decoupled ²³Na-NMR spectra of cryolite (Na₃AlF₆). Whereas the MAS spectrum is only marginally affected by application of ¹⁹F decoupling, the 3Q-filtered ²³Na signal is very sensitive to it, as the de-phasing caused by the dipolar interaction between sodium and fluorine is three-fold magnified. Experimentally, we find that at moderate MAS speeds, the decoupling efficiencies of the frequency-swept decoupling schemes SW_f-TPPM and SW_f-SPINAL are significantly better than the conventional TPPM and SPINAL sequences. The frequency-swept sequences are therefore the methods of choice for efficient decoupling of quadrupolar nuclei with half-integer spin from fluorine.     

Sensitivity enhancement in quadrupolar nuclei double resonance detection

NMR imaging of quadrupolar nuclei in liquid system has received less attention than the imaging ofS=1/2 nuclei due to difficulties associated with the quadrupolar interaction. The¹⁰B spatial distribution in Na₂ ¹⁰B₁₂H₁₁SH in phantom has been obtained using an indirect J-coupling Double Resonance method. This procedure allows one to localize the quadrupolar nuclei by observing the protons J-coupled with them. The sensitivity gain in the indirect spatial localization of the¹⁰B nuclei with respect to to the direct one, is here computed and verified on the Na₂ ¹⁰B₁₂H₁₁SH images.     

Sensitivity enhancement of NMR spectra of half-integer spin quadrupolar nuclei in solids using hyperbolic secant pulses

The experimental factors influencing the enhancements achievable for the central NMR transition, m(I)=1/2-->m(I)=-1/2, of spin-3/2 and spin-5/2 nuclei in the solid state using hyperbolic secant, HS, pulses for population transfer are investigated. In the case of powder samples spinning at the magic angle, it is found that the spinning frequency, the bandwidth and the frequency offset of the HS pulse play a crucial role in determining the maximum enhancements. Specifically, the bandwidth must be set to the spinning frequency for maximum signal enhancements. The (87)Rb NMR enhancement obtained for RbClO(4) using HS pulses was relatively insensitive to the magic angle spinning frequency; however, in the case of Al(acac)(3), the (27)Al enhancement increased with MAS frequency. In order to obtain an adiabatic HS sweep, one should optimize the rf field for a given pulse duration or optimize the pulse duration for a given rf field.     

Through-space R3-HETCOR experiments between spin-1/2 and half-integer quadrupolar nuclei in solid-state NMR

We present several new methods that allow to obtain through-space 2D HETCOR spectra between spin-1/2 and half-integer quadrupolar nuclei in the solid state. These methods use the rotary-resonance concept to create hetero-nuclear coherences through the dipolar interaction instead of scalar coupling into the HMQC and refocused INEPT experiments for spin n/2 (n>1). In opposite to those based on the cross-polarization transfer to quadrupolar nuclei, the methods are very robust and easy to set-up.     

High-resolution NMR of quadrupolar nuclei using mixed multiple-quantum coherences

A multiple-quantum magic angle spinning (MQMAS) NMR experiment of quadrupolar nuclei is demonstrated, which uses two different multiple quantum coherences in t(1) to refocus the quadrupolar broadening. This experiment has the potential of achieving improved resolution over current techniques.     

Multiple-quantum cross-polarization and two-dimensional MQMAS NMR of quadrupolar nuclei

Cross-polarization from (1)H to the multiple-quantum coherences of a quadrupolar nucleus is used in combination with the two-dimensional multiple-quantum magic angle spinning (MQMAS) NMR experiment in order to extract high-resolution CPMAS NMR spectra. The technique is demonstrated on (23)Na (S = 3/2), (17)O, (27)Al (both S = 5/2), and (45)Sc (S = 7/2) nuclei, showing the applicability of multiple-quantum cross-polarization to systems with differing spin quantum number, gyromagnetic ratio, and relative nuclide abundance. The utility of this two-dimensional MAS NMR experiment for spectral editing and site-specific measurement of cross-polarization intensities is demonstrated. The possibility of direct cross-polarization to higher order multiple-quantum coherences is also considered and three-, five-, and seven-quantum cross-polarized (45)Sc MAS NMR spectra are presented.