New line-narrowing effect in triple-quantum resonance in a two-level NMR system

We report a new line-narrowing effect associated with triple-quantum resonance in a two-level NMR system. The experiment was carried out in the rotating frame on (19)F nuclei in Teflon; namely, the magnetization is spin-locked along the RF field and the triple-quantum resonance is induced by the oscillating field perpendicular to the RF field. We observed that the decay time of the triple-quantum nutation becomes extraordinarily long at a particular intensity and frequency of the oscillating field. The decay time is about seven times as long as that of the single-quantum nutation and also much longer than that of the magic angle nutation. The mechanism is not interpreted by straightforward analogy to the theory of the current magic angle narrowing.     

The generation of intense radiofrequency fields in microcoils

Large amplitude radiofrequency (rf) fields hold great promise in wide line NMR where it becomes possible to excite the full breadth of the line in a quantitative fashion. Applications in quadrupole NMR and in NMR of paramagnetic systems benefit greatly from intense fields. Spin manipulations in multiple quantum NMR experiments, specifically, the generation of multiple quantum coherence in MQ NMR, are more efficiently produced using intense rf fields. In this work we describe a microcoil probe that produces an rf field of 25 MHz, more than five times larger than the greatest rf field reported in the literature. We accomplish this in a robust, 127 microm diameter solenoid coil using 1 kW of rf power.     

Determination of NMR cogwheel phase cycle with XML

The selection of correct coherence transfer pathways is an essential component of an NMR pulse sequence. This article describes a new method based on the use of web tools (eXtensible Markup Language and eXtensible Stylesheet Language Transformation) to generate a cogwheel phase cycle for selecting coherence transfer pathways. We illustrate this method with the three-pulse phase-modulated shifted-echo or split-t₁ MQMAS sequences for triple-quantum spin-3/2 systems. After generalization to the different half-integer quadrupole spins, we use the SIMPSON program to confirm our results. Finally, we apply our method to the case of the z-filter 3QMAS sequence for I=3/2 systems.     

Use of composite refocusing pulses to form spin echoes

The radiofrequency pulses used in NMR are subject to a number of imperfections such as those caused by inhomogeneity of the radiofrequency (B(1)) field and an offset of the transmitter frequency from precise resonance. The effect of these pulse imperfections upon a refocusing pulse in a spin-echo experiment can be severe. Many of the worst effects, those that distort the phase of the spin echo, can be removed completely by selecting the echo coherence pathway using either the "Exorcycle" phase cycle or magnetic field gradients. It is then tempting to go further and try to improve the amplitude of the spin-echo signal by replacing the simple refocusing pulse with a broadband composite 180° pulse that compensates for the relevant pulse imperfection. We show here that all composite pulses with a symmetric or asymmetric phase shift scheme will reintroduce phase distortions into the spin echo, despite the selection of the echo coherence pathway. In contrast, all antisymmetric composite pulses yield no phase distortion whatsoever, both on and off resonance, and are therefore the correct symmetry of composite refocusing pulse to use. These conclusions are verified using simulations and (31)P MAS NMR spin-echo experiments performed on a microporous aluminophosphate.     

Application of amplitude-modulated radiofrequency fields to the magic-angle spinning NMR of spin-7/2 nuclei

We report pulse sequences for the sensitivity enhancement of magic-angle spinning and multiple-quantum magic-angle spinning spectra of spin-72 systems. Sensitivity enhancement is obtained with the use of fast amplitude-modulated (FAM) radiofrequency pulses. In one-dimensional magic-angle spinning experiments, signal enhancement of 3 is obtained by a FAM pulse followed by a soft 90 degrees pulse. In two-dimensional multiple-quantum magic-angle spinning experiments, FAM pulses are used for both the excitation of multiple-quantum coherences and for their conversion into observable single-quantum coherences. The observed signal enhancements are 2.2 in 3Q experiments, 3.1 in 5Q experiments, and 4.1 in 7Q experiments, compared to the conventional two-pulse scheme. The pulse schemes are demonstrated on the 45Sc NMR of Sc2(SO4)3 x 5H2O and the 139La NMR of LaAlO3. We also demonstrate the generation of FAM pulses by double-frequency irradiation.     

1H NMR imaging of residual dipolar couplings in cross-linked elastomers: dipolar-encoded longitudinal magnetization, double-quantum, and triple-quantum filters.

Contrastfilters for NMR imaging of residual 1H dipolar couplings of elastomers are introduced based on dipolar-encoded longitudinal magnetization, as well as double- and triple-quantum coherences. The spin response is discussed in the initial excitation time regime for methylene, methyl, and methine protons applicable to poly(isoprene) and other elastomers, taking into account the hierarchy of dipolar couplings and the associated editing features of multiple-quantum experiments. The efficiency of these filters is investigated for a series of cross-linked poly(isoprene) samples. Spatially resolved dipolar-encoded longitudinal magnetization decays and double-quantum and triple-quantum buildup curves are presented for a phantom made of poly(isoprene) with different cross-link densities. Two-dimensional images representing residual dipolar couplings are presented using dipolar-encoded longitudinal magnetization, double-quantum, and triple-quantum contrast filters. Images from dipolar-encoded longitudinal magnetization and triple-quantum coherences show the highest resolution and contrast, respectively.     

H NMR Imaging of Residual Dipolar Couplings in Cross-Linked Elastomers: Dipolar-Encoded Longitudinal Magnetization, Double-Quantum, and Triple-Quantum Filters

Contrastfilters for NMR imaging of residual ¹H dipolar couplings of elastomers are introduced based on dipolar-encoded longitudinal magnetization, as well as double- and triple-quantum coherences. The spin response is discussed in the initial excitation time regime for methylene, methyl, and methine protons applicable to poly(isoprene) and other elastomers, taking into account the hierarchy of dipolar couplings and the associated editing features of multiple-quantum experiments. The efficiency of these filters is investigated for a series of cross-linked poly(isoprene) samples. Spatially resolved dipolar-encoded longitudinal magnetization decays and double-quantum and triple-quantum buildup curves are presented for a phantom made of poly(isoprene) with different cross-link densities. Two-dimensional images representing residual dipolar couplings are presented using dipolar-encoded longitudinal magnetization, double-quantum, and triple-quantum contrast filters. Images from dipolar-encoded longitudinal magnetization and triple-quantum coherences show the highest resolution and contrast, respectively.     

Spin-locking and recoupling of homonuclear dipolar interaction between spin-3/2 nuclei under magic-angle sample spinning

Numerical simulations and experiments were used to examine the possibility of employing strong spin-lock fields for recoupling of homonuclear dipolar interactions between spin-3/2 quadrupolar nuclei and to compare it to the rotary-resonance recoupling at weak spin-lock fields. It was shown that strong spin-lock pulses under MAS conditions can lead to recoupling, provided that the electric-field gradient principal axes systems of the coupled nuclei are aligned and that their quadrupolar coupling constants are approximately the same. The phenomenon is based on the fact that strong spin-lock pulses induce adiabatic transfer of magnetization between the central-transition coherence and the triple-quantum coherence with equal periodicity as is the periodicity of the time-dependent dipolar coupling. Because of the synchronous variation of the state of the spin system and of the dipolar interaction, the effect of the latter on the central-transition coherence and on the triple-quantum coherence is not averaged out by sample rotation. The approach is, however, very sensitive to the relative orientation of the electric-field gradient principal axes systems and therefore less robust than the approach based on weak spin-lock pulses that satisfy rotary-resonance condition.     

Small 51V chemical shift anisotropy for LaVO4 from MQMAS and MAS NMR spectroscopy

51V MQMAS NMR of the triple-quantum transitions is shown to be particularly useful in the determination of the sign and magnitude of the chemical shift anisotropy (CSA) parameter delta(sigma)(= delta(iso)-delta(zz)) along with the asymmetry parameter (eta(sigma)) for a vanadium environment with a small CSA and a rather strong quadrupole coupling. This is demonstrated for the orthovanadate LaVO(4) for which 51V magic-angle spinning (MAS) NMR of the central and satellite transitions at 14.1T gives precise values for the quadrupole coupling parameters, however, an ambiguous sign for delta(sigma). The CSA parameters are reliably obtained from analysis of the spinning sidebands observed in a 51V triple-quantum MAS experiment. Combining these data with least-squares analysis of the manifold of spinning sidebands in the single-pulse MAS NMR spectrum results in a precise determination of the magnitudes and relative orientation of the 51V quadrupole coupling and CSA tensors for LaVO(4).     

Double-quantum excitation in the NMR of spinning solids by pulse-assisted rotational resonance

We describe a new technique for double-quantum excitation in magic-angle-spinning NMR of powdered solids. The technique is designed to efficiently excite double-quantum coherence in the vicinity of a rotational resonance condition. The offset from rotational resonance allows the double-quantum filtered signals to be observed with high resolution and sensitivity. The method uses rotational excitation of zero-quantum coherence, assisted by radiofrequency pulse cycles. The zero-quantum coherence is converted into double-quantum coherence by a frequency-selective inversion sequence. Experiments on [(13)C(2), (15)N]-glycine demonstrate a double-quantum filtering efficiency of approximately 41% at a sample rotation frequency of 8.300 kHz, which is 1.600 kHz away from the n = 1 rotational resonance. We achieve 32% double-quantum filtering efficiency at a spinning frequency of 9.250 kHz, which is 2.550 kHz away from rotational resonance.     

Multispin moments edited by multiple-quantum NMR: application to elastomers

The spin system response to the five-pulse sequence used for measurements of double-quantum and triple-quantum buildup curves is evaluated in the initial excitation/reconversion regime. The multispin dipolar network that is present also in many soft solids like elastomers was considered. It is proved rigorously that the relevant quantity for analysis of double-quantum build-up curves in the initial regime is the second van Vleck moment. The higher-order moments edited by double-quantum as well as higher-order coherences in the multiple-quantum build-up experiments are different from van Vleck moments. These results can be applied to compare (1)H residual moments edited by double-quantum and triple-quantum experiments with those measured by other NMR methods. The sensitivity of multiple-quantum coherences to the changes in the values of residual dipolar couplings for cross-linked natural rubber under uniaxial elongation is also discussed. Under such conditions (1)H second van Vleck moments were measured for different elongation ratios of a cross-linked natural rubber. Moreover, (1)H triple-quantum edited moments were also measured for the same sample under uniaxial compression. The dependence of the second van Vleck moment and the time of the maximum of the double-quantum buildup curve on the cross-link density of natural rubber measured at low magnetic field was also investigated.     

Fast amplitude-modulated pulse trains with frequency sweep (SW-FAM) in solid-state NMR of spin-7/2 nuclei

We here investigate the sensitivity enhancement of central-transition NMR spectra of quadrupolar nuclei with spin-7/2 in the solid state, generated by fast amplitude-modulated RF pulse trains with constant (FAM-I) and incremented pulse durations (SW-FAM). Considerable intensity is gained for the central-transition resonance of single-quantum spectra by means of spin population transfer from the satellite transitions, both under static and magic-angle-spinning (MAS) conditions. It is also shown that incorporation of a SW-FAM train into the excitation part of a 7QMAS sequence improves the efficiency of 7Q coherence generation, resulting in improved signal-to-noise ratio. The application of FAM-type pulse trains may thus facilitate faster spectra acquisition of spin-7/2 systems.     

Solid-state single and triple-quantum 93Nb MAS NMR studies of ferroelectric Pb(Mg1/3Nb2/3)O3 and a related pyrochlore

Pb(Mg1/3Nb2/3)O3 (PMN), a well-known relaxor ferroelectric material, and a related pyrochlore phase have been studied by single- and triple-quantum 93Nb MAS NMR spectroscopy. The assignment of the NMR resonances has been attempted.     

Efficient triple-quantum excitation in modified RIACT MQMAS NMR for I=3/2 nuclei

A new approach involving the creation of triple-quantum (TQ) coherences from both TQ and central transitions (CT) is investigated, in order to enhance the efficiency of triple-quantum excitation for I=3/2 nuclei. The RIACT excitation scheme, a soft pi/2 and hard spin-locking pulse, is shown to induce both adiabatic coherence transfer between CT and TQ coherences and TQ nutation. By combining the RIACT scheme with the presaturation of the satellite transitions, a significant improvement in the TQ excitation can be achieved mainly through enhanced CT polarization via the RIACT mechanism, in particular for nuclei with moderate to large quadrupole coupling constants (> or = 2.0 MHz). There also exists a nontrivial contribution from the TQ transition, which depends on the size of the quadrupole interaction.     

Solid-state NMR studies of 17O-enriched pyrophosphates

For the first time, 17O NMR studies were performed on 17O-enriched crystalline pyrophosphates (magnesium-, sodium- and barium-pyrophosphate) by means of triple-quantum magic-angle spinning (3QMAS) and double-rotation (DOR) in the high external field of 17.6 T. Oxygen atoms in bridging positions (P-OB-P) exhibit a significant higher quadrupole coupling constant compared to oxygen atoms in terminal positions (P-OT). With increasing cationic radius a higher value of the chemical shift of the terminal oxygen atoms is observed.     

单扫描快速采样方法及其在NMR中的应用

单扫描快速采样方法利用空间编码技术,只需单次扫描就能获得二维及多维核磁共振(NMR)谱数据,极大地缩短了二维和多维核磁共振谱的采样时间,有望在NMR领域得到广泛的应用. 该文以离散编码单扫描快速采样方法为例阐明了单扫描快速采样方法的原理,介绍了连续幅度调制、连续相位调制等各种单扫描快速采样新方法及其在NMR领域中的应用, 指出了单扫描快速采样方法的局限性,并对其未来发展进行了展望.     

Enhanced sensitivity in RIACT/MQ-MAS NMR experiments using rotor assisted population transfer

The rotor assisted population transfer (RAPT) sequence is used to enhance the sensitivity of the RIACT(II) experiment for spin-3/2 quadrupolar nuclei. A detailed theoretical analysis of the polarizations that contribute to different types of MQ-MAS experiments is provided. In particular, two polarization pathways are distinguished for the creation of triple-quantum coherence. The existence of these pathways is experimentally demonstrated by comparing the sensitivities of different sequences with and without RAPT preparation.     

The Signs of Frequencies and Phases in NMR

The signs of radiofrequency phases and frequencies used in NMR are examined carefully. Some fundamental problems with current usage are exposed by simple examples. The entire chain of events leading to the NMR spectrum is examined closely, including generation and phase-shifting of the radiofrequency carrier wave, nuclear-spin dynamics in the presence of the radiofrequency field, quadrature detection, signal digitization, post-digitization phase shifting, Fourier transformation, and spectral presentation. Recommendations are given for software modifications which should facilitate the correspondence between pulse programming, spectral presentation, and spin dynamical theory.     

Improved quantitation in 3QMAS of spin 5/2 nuclei by RF power modulation of FAM-II

High-resolution NMR of quadrupolar I = 5/2 nuclei using triple-quantum magic angle spinning (3QMAS) techniques can provide more accurate quantitative information on sites with small quadrupolar coupling constants by changing the pulse strength in addition to the pulse length in the FAM-II multiple-quantum conversion sequence. These effects are illustrated using (27)Al NMR of yttrium aluminium garnet and andalusite.     

Optimal control of coupled spin dynamics: design of NMR pulse sequences by gradient ascent algorithms

In this paper, we introduce optimal control algorithm for the design of pulse sequences in NMR spectroscopy. This methodology is used for designing pulse sequences that maximize the coherence transfer between coupled spins in a given specified time, minimize the relaxation effects in a given coherence transfer step or minimize the time required to produce a given unitary propagator, as desired. The application of these pulse engineering methods to design pulse sequences that are robust to experimentally important parameter variations, such as chemical shift dispersion or radiofrequency (rf) variations due to imperfections such as rf inhomogeneity is also explained.