INEPT Experiments Involving Quadrupolar Nuclei in Solids

Coherence transfer from quadrupolar²⁷Al (I= ) nuclei to³¹P (I= ) via INEPT experiments is investigated.²⁷Al →³¹P INEPT experiments on a (CH₃)₃P–AlCl₃complex in zeolite NaX are performed, and the results demonstrate that the³¹P INEPT signals strongly depend on whether or not the²⁷Al pulses are applied synchronously with the rotor period, and on the length of the²⁷Al pulses. A density-matrix calculation involving the use of the spin operators for spin and nuclei has been performed to help understand the evolution behavior of the density matrix under the influence of the quadrupolar interaction, the dipolar andJ-couplings, and the pulse lengths applied to the quadrupolar nuclei. The theoretical predictions obtained from these calculations are consistent with the INEPT experimental observations.     

Determination of J coupling constants between spin-1/2 and quadrupolar nuclei in inorganic solids from spin echo and refocused INEPT experiments: a case study on AlPO₄ berlinite

A systematic study utilizing rotor-synchronized homonuclear ((31)P, (27)Al) and heteronuclear ({(31)P}(27)Al and {(27)Al}(31)P) spin echo, and {(27)Al}(31)P refocused INEPT experiments (employing soft pulses for selective excitation of the central transition for the quadrupolar (27)Al (I=5/2)) have been performed on AlPO(4) berlinite at 30 kHz MAS to better understand the J modulation behavior involving half-integer quadrupolar nuclei in solid materials with framework structure. Analyses of the J modulation on either the (27)Al or (31)P coherence in both the {(31)P}(27)Al and {(27)Al}(31)P spin echo experiments, and both periods of the refocused INEPT experiment yield consistent results for the (2)J(AlP) (Al-O-P) coupling constant (ca. 25 Hz). It is noted that the coupling of each (27)Al to four (31)P spins during the first ((27)Al) evolution period of the refocused INEPT, and the populations of (31)P coupled to different numbers (0-4) of (27)Al in the ± 1/2 Zeeman states during (31)P coherence evolution, which have been neglected in previous studies, must be taken into account for proper treatment. Analysis of J modulation on the spin ((27)Al) coupled to spin-1/2 nuclei in general gives more accurate results. Weak long-range homonuclear (4)J(PP) (P-O-Al-O-P) coupling was also observed from the (31)P spin echo and INADEQUATE experiments.     

1D and 2D solid state NMR investigations of the framework structure of As-synthesized AlPO4-14

The framework structure of As-synthesized A1PO₄-14 has been investigated with a combination of different one-dimensional ²⁷Al and ³¹P solid state NMR techniques and ²⁷Al/³¹P double resonance methods. The results are found to be fully consistent with the assumed structural model. ²⁷Al MAS and DOR experiments at three different magnetic field strengths together with simulations show the presence of two tetrahedral sites, one pentacoordinated and one octahedral aluminum site. The ²⁷Al quadrupolar coupling constants and the ³¹P isotropic chemical shifts of the tetrahedral sites correlate well with tetrahedral shear-strain parameters and mean P-O-A1 bond angles, respectively. These correlations allow one to assign all of the NMR resonances to specific T-sites in the proposed framework structure. The assignments are then further confirmed by the application of three different two-dimensional heteronuclear correlation methods (i.e., ²⁷Al → ³¹P TEDOR, CP, and INEPT) which reveal the connectivities between AlO_x and PO₄ polyhedra. The two-dimensional INEPT experiment is applied here for the first time in the solid state.     

Three-dimensional through-bond homonuclear-heteronuclear correlation experiments for quadrupolar nuclei in solid-state NMR applied to (27)Al-O-(31)P-O-(27)Al networks

We present here the first 3D homonuclear/heteronuclear correlation experiment applied to quadrupolar nuclei and making use of the sole scalar J-coupling. This experiment, based on the 2D-Homonuclear-Heteronuclear Single Quantum Correlation (H-HSQC) experiment, uses a relayed transfer from the (27)Al central transition to neighbouring (31)P spins and to the central transition of a second (27)Al. It confirms the correlation map characterizing the two (27)Al and the (31)P NMR signatures of (27)Al-O-(31)P-O-(27)Al chemically bonded molecular motifs.     

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 heteronuclear correlation spectra between 31P and 27Al in microporous aluminophosphates

A solid-state nuclear magnetic resonance (NMR) experiment, which provides high-resolution two-dimensional heteronuclear correlation (HETCOR) spectra between 27Al and 31P, is described. The first part of the experiment uses triple-quantum or quintuple-quantum magic-angle spinning (MQMAS) NMR of spin-5/2 nuclei (27Al) to produce an isotropic echo that is unaffected by the second-order quadrupolar broadening. The magnetization is then transferred to the spin-1/2 (31P) nuclei via cross-polarization (CP), resulting in isotropic resolution in both spectral dimensions. To illustrate its usefulness, this method (referred to as MQHETCOR) is applied to two important microporous framework aluminophosphates, hydrated VPI-5 and AIPO4-40.     

Resolution enhancement using a new multiple-pulse decoupling sequence for quadrupolar nuclei

A new decoupling composite pulse sequence is proposed to remove the broadening on spin S=1/2 magic-angle spinning (MAS) spectra arising from the scalar coupling with a quadrupolar nucleus I. It is illustrated on the (31)P spectrum of an aluminophosphate, AlPO(4)-14, which is broadened by the presence of (27)Al/(31)P scalar couplings. The multiple-pulse (MP) sequence has the advantage over the continuous wave (CW) irradiation to efficiently annul the scalar dephasing without reintroducing the dipolar interaction. The MP decoupling sequence is first described in a rotor-synchronised version (RS-MP) where one parameter only needs to be adjusted. It clearly avoids the dipolar recoupling in order to achieve a better resolution than using the CW sequence. In a second improved version, the MP sequence is experimentally studied in the vicinity of the perfect rotor-synchronised conditions. The linewidth at half maximum (FWHM) of 65 Hz using (27)Al CW decoupling decreases to 48 Hz with RS-MP decoupling and to 30 Hz with rotor-asynchronised MP (RA-MP) decoupling. The main phenomena are explained using both experimental results and numerical simulations.     

High resolution 2D 1H-13C correlation of cholesterol in model membrane

High resolution 2D NMR MAS spectra of liposomes, in particular 1H-13C chemical shifts correlations have been obtained on fluid lipid bilayers made of pure phospholipids for several years. We have investigated herein the possibility to obtain high resolution 2D MAS spectra of cholesterol embedded in membranes, i.e. on a rigid molecule whose dynamics is characterized mainly by axial diffusion without internal segmental mobility. The efficiency of various pulse sequences for heteronuclear HETCOR has been compared in terms of resolution, sensitivity and selectivity, using either cross polarization or INEPT for coherence transfer, and with or without MREV-8 homonuclear decoupling during t1. At moderately high spinning speed (9 kHz), a similar resolution is obtained in all cases (0.2 ppm for 1H(3,4), 0.15 ppm for 13C(3,4) cholesterol resonances), while sensitivity increases in the order: INEPT < CP(x4) < CP + MREV. At reduced spinning speed (5 kHz), the homonuclear dipolar coupling between the two geminal protons attached to C(4) gives rise to spinning sidebands from which one can estimate a H-H dipolar coupling of 10 kHz which is in good agreement with the known dynamics of cholesterol in membranes.     

Sensitivity enhancement, assignment, and distance measurement in 13C solid-state NMR spectroscopy for paramagnetic systems under fast magic angle spinning

Despite success of previous studies, high-resolution solid-state NMR (SSNMR) of paramagnetic systems has been still largely unexplored because of limited sensitivity/resolution and difficulty in assignment due to large paramagnetic shifts. Recently, we demonstrated that an approach using very-fast magic angle spinning (VFMAS; spinning speed 20kHz) enhances resolution/sensitivity in (13)C SSNMR for paramagnetic complexes [Y. Ishii, S. Chimon, N.P. Wickramasinghe, A new approach in 1D and 2D (13)C high resolution solid-state NMR spectroscopy of paramagnetic organometallic complexes by very fast magic-angle spinning, J. Am. Chem. Soc. 125 (2003) 3438-3439]. In this study, we present a new strategy for sensitivity enhancement, signal assignment, and distance measurement in (13)C SSNMR under VFMAS for unlabeled paramagnetic complexes using recoupling-based polarization transfer. As a robust alternative of cross-polarization (CP), rapid application of recoupling-based polarization transfer under VFMAS is proposed. In the present approach, a dipolar-based analog of INEPT (dipolar INEPT) methods is used for polarization transfer and a (13)C signal is observed under VFMAS without (1)H decoupling. The resulting low duty factor permits rapid signal accumulation without probe arcing at recycle times ( approximately 3 ms/scan) matched to short (1)H T(1) values of small paramagnetic systems ( approximately 1 ms). Experiments on Cu(dl-Ala)(2) showed that the fast repetition approach under VFMAS provided sensitivity enhancement by a factor of 8-66 for a given sample, compared with the (13)C MAS spectrum under moderate MAS at 5kHz. The applicability of this approach was also demonstrated for a more challenging system, Mn(acac)(3), for which (13)C and (1)H paramagnetic shift dispersions reach 1500 and 700 ppm, respectively. It was shown that effective-evolution-time dependence of transferred signals in dipolar INEPT permitted one to distinguish (13)CH, (13)CH(2), (13)CH(3), (13)CO2- groups in 1D experiments for Cu(DL-Ala)(2) and Cu(Gly)(2). Applications of this technique to 2D (13)C/(1)H correlation NMR under VFMAS yielded reliable assignments of (1)H resonances as well as (13)C resonances for Cu(DL-Ala)(2) and Mn(acac)(3). Quantitative analysis of cross-peak intensities in 2D (13)C/(1)H correlation NMR spectra of Cu(DL-Ala)(2) provided distance information between non-bonded (13)C-(1)H pairs in the paramagnetic system.     

Determination and assignment of heteronuclear long-range coupling constants. Methods based on semiselective INEPT

One-dimensional methods for the determination and assignment of heteronuclear ¹H-X (X = rare spin-z) coupling constants based on the semiselective polarization transfer via INEPT pulse sequence are proposed. Here the selectivity of the polarization transfer plays a positive role with respect to the sensitivity of the measurement and purity of the observed multiplets. In nonrefocused experiments the acquired antiphase multiplets enable an unambiguous assignment of long-range couplings of a preselected proton. The analysis of such multiplets is also discussed. In the refocused version the purging pulse (INEPT+) was used to provide pure in-phase multiplets. The spectral editing technique DISCO was applied to simplify the spectra and to extract the couplings from complex multiplets. Finally, the modified INEPT experiments which combine semiselective polarization transfer with selective proton decoupling are proposed.     

Effect of pressure on structure of oxide glasses at high pressure: Insights from solid-state NMR of quadrupolar nuclides

Revealing the structure of oxide glasses at high pressure remains a fundamental yet difficult problem in modern physical and chemical sciences. The recent advances in solid-state NMR techniques used for quadrupolar nuclides offer a considerably improved resolution of atomic sites, unveiling previously unknown structural details of oxides glasses at high pressure. Here, we present an overview of the recent progress and insights by high-resolution multi-nuclear triple quantum magic angle spinning (3QMAS) NMR into pressure-induced changes in coordination number, connectivity, and topological disorder in oxide glasses quenched from melts at high pressure. (11)B and (27)Al 3QMAS NMR studies of oxide glasses show that the formation of highly coordinated Al (([5,6])Al) and four coordinated ([4])B are prevalent at high pressure up to 8 GPa. The formation of oxygen clusters linking these highly coordinated framework units and Si (e.g., ([5,6])Al-O-([4])Si, ([5,6])Si-O-([4])Si, and Na-O-([5,6])Si) is observed in the (17)O NMR spectra at higher pressure, leading to an overall increase in the degree of polymerization with pressure. (23)Na MAS NMR spectra of diverse oxide glasses at high pressure and high magnetic field also indicate that the Na-O bond distance may decrease with pressure. Pressure-induced changes in structurally relevant NMR parameters such as the (17)O quadrupolar coupling product (P(q)) for the Si-O-Si cluster and (27)Al P(q) for Al sites in oxide glasses indicate the occurrence of pressure-induced reductions in the Si-O-Si angle and an increase in the Al-O bond length distribution with pressure, indicating an increase in the overall topological disorder in oxide glasses with pressure. All the pressure-induced changes in structure and topology are characterized by strong composition dependence. These experimental results highlight a new opportunity to investigate the molecular structures of silicate melts at high pressure and reveal connections between the microscopic signatures of anomalous and non-linear changes in the macroscopic properties of the corresponding liquids. While many challenges still remain in the synthesis of oxide glasses with wider range of melt composition at higher pressure above 12 GPa, recent progress in enhancement of sensitivity and resolution in the solid state NMR hold strong promise for study exploring additional details of connectivity among quadrupolar nuclides and medium-range order of the more complex, multi-components glasses at high pressure.     

SCAM-STMAS: satellite-transition MAS NMR of quadrupolar nuclei with self-compensation for magic-angle misset

Several methods are available for the acquisition of high-resolution solid-state NMR spectra of quadrupolar nuclei with half-integer spin quantum number. Satellite-transition MAS (STMAS) offers an approach that employs only conventional MAS hardware and can yield substantial signal enhancements over the widely used multiple-quantum MAS (MQMAS) experiment. However, the presence of the first-order quadrupolar interaction in the satellite transitions imposes the requirement of a high degree of accuracy in the setting of the magic angle on the NMR probehead. The first-order quadrupolar interaction is only fully removed if the sample spinning angle, chi, equals cos(-1)(1/3) exactly and rotor synchronization is performed. The required level of accuracy is difficult to achieve experimentally, particularly when the quadrupolar interaction is large. If the magic angle is not set correctly, the first-order splitting is reintroduced and the spectral resolution is severely compromised. Recently, we have demonstrated a novel STMAS method (SCAM-STMAS) that is self-compensated for angle missets of up to +/-1 degrees via coherence transfer between the two different satellite transitions ST(+)(m(I)=+3/2<-->+1/2) and ST(-)(m(I)=-1/2<-->-3/2) midway through the t(1) period. In this work we describe in more detail the implementation of SCAM-STMAS and demonstrate its wider utility through 23Na (I=3/2), 87 Rb (I=3/2), 27 Al (I=5/2), and 59 Co (I=7/2) NMR. We discuss linewidths in SCAM-STMAS and the limits over which angle-misset compensation is achieved and we demonstrate that SCAM-STMAS is more tolerant of temporary spinning rate fluctuations than STMAS, resulting in less "t(1) noise" in the two-dimensional spectrum. In addition, alternative correlation experiments, for example involving the use of double-quantum coherences, that similarly display self-compensation for angle misset are investigated. The use of SCAM-STMAS is also considered in systems where other high-order interactions, such as third-order quadrupolar effects or second-order quadrupole-CSA cross-terms, are present. Finally, we show that the sensitivity of the experiment can be improved through the use of amplitude-modulated pulses.     

Double-resonance decoupling for resolution enhancement of 31P solid-state MAS and 27Al --> 31P MQHETCOR NMR

27Al decoupling has been used to remove residual J-coupling interactions between 31P and 27Al in microporous aluminophosphates AlPO4-14 and AlPO4-40. In combination with 1H high-power decoupling, 27Al adapted decoupling yields 31P spectra with optimal sensitivity and resolution. The importance of double-resonance decoupling is further demonstrated by incorporating this technique in the MQHETCOR sequence. Unambiguous assignment of all the AlPO4-14 nuclear magnetic resonances is achieved by combining multiple-quantum evolution in the 27Al dimension and double-resonance decoupling in the 31P acquisition domain.     

Characterization of microporous aluminophosphate IST-1 using (1)H Lee-Goldburg techniques

The presence of two independent methylamine species in microporous aluminophosphate IST-1 (|(CH(3)NH(2))(4)(CH(3)NH(+)(3))(4)(OH(-))(4)|[Al(12)P(12)O(48)]) has been shown previously by synchrotron powder X-ray diffraction. One of these species, [N(1)-C(1)], links to a six-coordinated framework Al-atom [Al(1)], while the other methylamine [N(2)-C(2)] is protonated and hydrogen-bonded to three O-atoms [O(1), O(2) and O(12)]. We revisit the structure of IST-1 and report the complete assignment of the (1)H NMR spectra by combining X-ray data and high-resolution heteronuclear/homonuclear solid-state NMR techniques based on frequency-switched Lee-Goldburg homonuclear decoupling and (31)P-(31)P homonuclear recoupling. Careful analysis of the 2D (1)H-X homonuclear correlation (X=(1)H) and 2D heteronuclear correlation (X=(13)C, (31)P and (27)Al) spectra allowed the distinction of both methylamine species and the assignment of all (31)P and (13)C resonances. For the first time at a relatively high (9.4 T) magnetic field, symmetric doublet patterns have been observed in the (13)C spectra, caused by the influence of the (14)N second-order quadrupolar interaction.     

增强灵敏度和识别不同类型原子的几种技术和应用

本文介绍了利用自旋回波和J调制的办法识别化合物中不同类型碳原子的APT技术。比较了极化转移增强核灵敏度的INEPT和DEPT技木,并给出利用INEPT改善¹⁵N核磁共振谱信噪比的实例。讨论了这几种方法的优缺点。     

(1)H-(13)C INEPT MAS NMR correlation experiments with (1)H-(1)H mediated magnetization exchange to probe organization in lipid biomembranes

Two-dimensional (1)H-(13)C INEPT MAS NMR experiments utilizing a (1)H-(1)H magnetization exchange mixing period are presented for characterization of lipid systems. The introduction of the exchange period allows for structural information to be obtained via (1)H-(1)H dipolar couplings but with (13)C chemical shift resolution. It is shown that utilizing a RFDR recoupling sequence with short mixing times in place of the more standard NOE cross-relaxation for magnetization exchange during the mixing period allowed for the identification and separation of close (1)H-(1)H dipolar contacts versus longer-range inter-molecular (1)H-(1)H dipolar cross-relaxation. These 2D INEPT experiments were used to address both intra- and inter-molecular contacts in lipid and lipid/cholesterol mixtures.     

Implementing solenoid microcoils for wide-line solid-state NMR

Solid-state nuclear magnetic resonance (NMR) probeheads using solenoid microcoils with an inner diameter of 300-400 microm are developed for the study of mass-limited solid samples. Some attention is paid to the mechanical ruggedness of the probes allowing sample changing. The performance, in terms of sensitivity and RF-characteristics, of these probeheads is studied for (1)H, (31)P, and (27)Al in different model compounds in view of the feasibility of specific applications. The results show that the sensitivity is high enough to detect approximately 10(14) spins/sqrt Hz with a signal-to-noise ratio of 1 in a single scan. A specific advantage of microcoils for solid-state NMR applications is that they can generate extremely high RF-fields if implemented in appropriate circuits. Using RF-powers in the hundreds of Watts range, RF-fields well in excess of 1MHz can be made. This allows the excitation of spectra of nuclei whose resonance lines are dispersed of several megahertz. This is particularly useful for quadrupolar nuclei experiencing large quadrupolar interactions as is demonstrated for (27)Al in single crystal and powdered minerals.     

Off-angle correlation spectroscopy applied to spin-1/2 and quadrupolar nuclei

A two-dimensional correlation experiment is described, in which homonuclear dipolar couplings are used to realize through-space magnetization exchange on spin-1/2 (³¹P) and on quadrupolar nuclei (²³Na and ¹¹B). In the detection period, Magic Angle Spinning is applied to enhance resolution, and the dipole couplings are re-introduced in the mixing period by spinning off the Magic Angle. The dependency of the exchange rates on the mixing time and the spinning angle is investigated. The influence of strong spin-locking during mixing is discussed, and shown in the spin-1/2 case to remove the dependence on chemical shift offset effects. For quadrupolar spins, the experiment yields information on the relative tensor orientations of the coupled quadrupoles. Applications to crystalline sodium aluminum diphosphate, sodium sulphite, and potassium borate glasses are shown.