Double-quantum Single-quantum Research Articles

Low-silica Cu-CHA Zeolite Enriched with Al Pairs Transcribed from Silicoaluminophosphate Seed: Synthesis and Ammonia Selective Catalytic Reduction Performance.

Cu-exchanged low-silica CHA zeolites (Si/Al ≤ 4) synthesized without organic templates are promising candidate catalysts for ammonia selective catalytic reduction of nitrogen oxides (NH3-SCR), but their practical application is restricted due to the low hydrothermal stability. Here, inspired by the transcription from duplex DNA to RNA, we synthesized Al pairs enriched low-silica CHA zeolite (CHA-SPAEI, Si/Al = 3.7) by using silicoaluminophosphate (SAPO) featured by strict alternation of -Al-O-P(Si)-O-Al-O- tetrahedra as seed. The proportion of Al pairs in CHA-SPAEI is 78%, which is much higher than that in the conventional low-silica CHA (CHA-LS, 52%). After hydrothermal ageing at 800 °C for 6 h, Cu-exchanged CHA-SPAEI shows NO conversion above 90% within 225-500 °C under a gas hourly space velocity of 200,000 h-1, which is much better than that of Cu-exchanged CHA-LS. The spatial close proximity of Al pairs in CHA-SPAEI is confirmed by the 27Al double-quantum single-quantum two-dimensional NMR analyses. The strict -P(Si)-O-Al-O-P(Si)-O- sequence in the fragments from the dissolution of SAPO seed promotes the Al pairs with the -Al-O-Si-O-Al-O- sequence via a transcription process. The utilization of aluminophosphate-based zeolites as seeds opens up a new avenue for the regulation of the Al distribution in zeolites.

Multiple acquisitions in a single scan: exhausting abundant 1H polarization at fast MAS

Proton-detected solid-state NMR spectroscopy is emerging as a unique tool for atomic characterization of organic solids due to the boost of resolution and sensitivity afforded by the combined use of high magnetic field and ultrafast magic angle spinning (MAS). Here, we proposed a new set of proton-detected solid-state NMR sequences that hybrid multi-dimensional 1H–1H homonuclear chemical shift correlation (HOMCOR) and two-dimensional 1H–13C heteronuclear chemical shift correlation (HETCOR) sequences into a single experiment, enabling the simultaneous acquisition of multidimensional HOMCOR and HETCOR spectra and thus significant time savings. Based on the core idea of exhausting 1H polarization in each transient scan, we firstly demonstrated that 3D 1H multiple-quantum (MQ) HOMCOR sequence can be combined with 2D HETCOR sequence into a single experiment, leading to the simultaneous acquisition of a 3D 1H MQ HOMCOR and a 2D 1H–13C HETCOR spectrum. Besides, we also showed that 2D 1H/1H double-quantum/single-quantum (DQ/SQ) and single-quantum/single-quantum (SQ/SQ) HOMCOR sequence can be simultaneously combined with HETCOR sequence either, and thus three spectra can be simultaneously obtained from one experiment, including 2D 1H DQ/SQ, 2D 1H SQ/SQ and 2D 1H–13C HETCOR spectra. Since there is only one recycle delay in each experiment, experimental time is substantially reduced compared to separate acquisition of each multi-dimensional solid-state NMR spectrum. Furthermore, those new sequences can be implemented on any standard solid-state spectrometer with only one receiver. Thus, we foresee that these approaches can be valuable for the study of a broad range of molecular systems, including polymers, pharmaceuticals, covalent-organic frameworks (COF) and so on.

Atomic-Level Structure of Mesoporous Hexagonal Boron Nitride Determined by High-Resolution Solid-State Multinuclear Magnetic Resonance Spectroscopy and Density Functional Theory Calculations

Mesoporous hexagonal boron nitride (p-BN) has received significant attention over the last decade as a promising candidate for water cleaning/pollutant removal and hydrogen storage applications. Here, high-resolution solid-state NMR spectroscopy and plane-wave density-functional theory (DFT) calculations are used to obtain an atomic-level description of p-BN. 1H–15N or 1H–14N heteronuclear (HETCOR) correlation experiments recorded with either conventional NMR at room temperature or dynamic nuclear polarization surface-enhanced spectroscopy (DNP-SENS) at ca. 100 K reveal NB2H, NBH2, NBH3+ species residing on the edges of BN sheets. Ultra-high field 35.2 T 11B NMR spectroscopy was used to resolve 11B NMR signals from BN3, BN2Ox(OH)1–x (x = 0–1), BNOx(OH)2–x (x = 0–2), BOx(OH)3–x (x = 0–3), and BOx(OH)4–x– (x = 0–4). Importantly, 2D 11B dipolar double-quantum–single-quantum homonuclear correlation spectra reveal that many pore/defect sites are composed of boron oxide/hydroxide clusters connected to the BN framework through BN2O units. 1D and 2D 11B{15N} HETCOR NMR experiments, in addition to plane-wave DFT calculations of nine different structural models, further confirm the assignment of all NMR signals. The detailed structure determination of the pore and edge/defect sites within p-BN should further enable the rational design and development of next-generation p-BN-based materials. In addition, the techniques outlined here should be applicable to determine structure within other porous and/or boron-based materials.

One-Dimensional Conjugated Carbon Nitrides: Synthesis and Structure Determination by HRTEM and Solid-State NMR.

Two-dimensional (2D) graphitic carbon nitrides (g-C3N4) have sparked much interest as photocatalysts. However, they suffer from high activation energy and a low separation rate of photoexcited charge carriers. Here we report a viable strategy to craft one-dimensional carbon nitrides denoted as polymelem (PM). Our PM possesses NH-bridged and the N-bridged tautomers, both of which are π-conjugated polymers based on aromatic tri-s-triazine units, as revealed by solid-state nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR), and Raman techniques. A 2D 1H double-quantum-single-quantum (DQ-SQ) NMR spectrum illustrates that the 2D architecture of PM is constructed by the formation of interchain N-H···N hydrogen bonds between different 1D PM chains. PM exhibits largely improved photocatalytic efficiency compared to g-C3N4. This can be attributed to the conjugated structures of PM, which are conducive to the decrease in activation energy and separation rate of photogenerated charge carriers.

Cooperative Self-Assembly Driven by Multiple Noncovalent Interactions: Investigating Molecular Origin and Reassessing Characterization.

Cooperative interactions play a pivotal role in programmable supramolecular assembly. Emerging from a complex interplay of multiple noncovalent interactions, achieving cooperativity has largely relied on empirical knowledge. Its development as a rational design tool in molecular self-assembly requires a detailed characterization of the underlying interactions, which has hitherto been a challenge for assemblies that lack long-range order. We employ extensive one- and two-dimensional magic-angle-spinning (MAS) solid-state NMR spectroscopy to elucidate key structure-directing interactions in cooperatively bound aggregates of a perylene bisimide (PBI) chromophore. Analysis of 1H–13C cross-polarization heteronuclear correlation (CP-HETCOR) and 1H–1H double-quantum single-quantum (DQ-SQ) correlation spectra allow the identification of through-space 1H···13C and 1H···1H proximities in the assembled state and reveals the nature of molecular organization in the solid aggregates. Emergence of cooperativity from the synergistic interaction between a stronger π-stacking and a weaker interstack hydrogen-bonding is elucidated. Finally, using a combination of optical absorption, circular dichroism, and high-resolution MAS NMR spectroscopy based titration experiments, we investigate the anomalous solvent-induced disassembly of aggregates. Our results highlight the disparity between two well-established approaches of characterizing cooperativity, using thermal and good solvent-induced disassembly. The anomaly is explained by elucidating the difference between two disassembly pathways.

Direct observation of the active sites in methane dehydroaromatization by NMR

Direct observation of the active sites in methane dehydroaromatization by NMR

Efficient symmetry-based γ-encoded DQ recoupling sequences for suppression of t1-noise in solid-state NMR spectroscopy at fast MAS

Solid-state NMR spectroscopy has played a significant role in elucidating the structure and dynamics of materials and biological solids at a molecular level for decades. In particular, the 1H double-quantum/single-quantum (DQ/SQ) chemical shift correlation experiment is widely used for probing the proximity of protons, rendering it a powerful tool for elucidating the hydrogen-bonding interactions and molecular packing of various complex molecular systems. Two factors, namely, the DQ filtering efficiency and t1-noise, dictate the quality of the 2D 1H DQ/SQ spectra. Experimentally different recoupling sequences show varied DQ filtering efficiencies and t1-noise. Herein, after a systematic search of symmetry-based DQ recoupling sequences, we report that the symmetry-based γ-encoded RNnν sequences show superior performance to other DQ recoupling sequences, which not only have a higher DQ recoupling efficiency but can also significantly reduce t1-noise. The origin of t1-noise is further discussed in detail via extensive numerical simulations. We envisage that such γ-encoded RNnν sequences are superior candidates for DQ recoupling in proton-based solid-state NMR spectroscopy due to its capability of efficiently exciting DQ coherences and suppressing t1-noise.

Control the position of framework defects in zeolites by changing the symmetry of organic structure directing agents

Double quantum-single quantum (DQ/SQ) 1 H NMR spectroscopy has been used to localize the siloxy/silanol defects in two pure silica MFI zeolite samples synthesized by the symmetric tetrapropylammonium hydroxide (TPAOH) and non-symmetric methyltributylammonium hydroxide (MeTrBA) templates. Using the 1 H DQ/SQ NMR, we provide important information on the positions of the structural defects in the MFI zeolite framework that have been tuned during the hydrothermal synthesis by changing the symmetry of the templates. The preferential location of the defects is found to be near the terminal methyl groups of the longer alkyl chains and far from the nitrogen atoms: in the case of the non-symmetric MeTrBA template, the defects are located in the sinusoidal channels, while for the symmetric TPA template they are randomly distributed among the two types of channels. It is foreseen that control the position of framework defects in zeolites might be the way to control the position of the active sites in acid zeolite catalysts. • Synthesis of MFI zeolite with symmetric and asymmetric templates. • The position of silanols defects in MFI zeolites is tuned. • Organic structure directing agents control the localization of defects. • Proton NMR is a method of choice to localize defects. • Active sites in zeolites catalysts may be tailored.

Structure Determination of Boron-Based Oxidative Dehydrogenation Heterogeneous Catalysts with Ultra-High Field 35.2 T 11B Solid-State NMR Spectroscopy.

Boron-based heterogenous catalysts, such as hexagonal boron nitride (h-BN) as well as supported boron oxides, are highly selective catalysts for the oxidative dehydrogenation (ODH) of light alkanes to olefins. Previous catalytic measurements and molecular characterization of boron-based catalysts by 11B solid-state NMR spectroscopy and other techniques suggests that oxidized/hydrolyzed boron clusters are the catalytically active sites for ODH. However, 11B solid-state NMR spectroscopy often suffers from limited resolution because boron-11 is an I = 3/2 half-integer quadrupolar nucleus. Here, ultra-high magnetic field (B 0 = 35.2 T) is used to enhance the resolution of 11B solid-state NMR spectra and unambiguously determine the local structure and connectivity of boron species in h-BN nanotubes used as a ODH catalyst (spent h-BNNT), boron substituted MCM-22 zeolite [B-MWW] and silica supported boron oxide [B/SiO2] before and after use as an ODH catalyst. One-dimensional direct excitation 11B NMR spectra recorded at B 0 = 35.2 T are near isotropic in nature, allowing for the easy identification of all boron species. Two-dimensional 1H-11B heteronuclear correlation NMR spectra aid in the identification of boron species with B-OH functionality. Most importantly, 2D 11B dipolar double-quantum single-quantum homonuclear correlation NMR experiments were used to unambiguously probe boron-boron connectivity within all heterogeneous catalysts. These experiments are practically infeasible at lower, more conventional magnetic fields due to a lack of resolution and reduced NMR sensitivity. The detailed molecular structures determined for the amorphous oxidized/hydrolyzed boron layers on these heterogenous catalysts will aid in the future development of next generation ODH catalysts.

A Practical Review of NMR Lineshapes for Spin-1/2 and Quadrupolar Nuclei in Disordered Materials.

NMR is a powerful spectroscopic method that can provide information on the structural disorder in solids, complementing scattering and diffraction techniques. The structural disorder in solids can generate a dispersion of local magnetic and electric fields, resulting in a distribution of isotropic chemical shift δiso and quadrupolar coupling CQ. For spin-1/2 nuclei, the NMR linewidth and shape under high-resolution magic-angle spinning (MAS) reflects the distributions of isotropic chemical shift, providing a rich source of disorder information. For quadrupolar nuclei, the second-order quadrupolar broadening remains present even under MAS. In addition to isotropic chemical shift, structural disorder can impact the electric field gradient (EFG) and consequently the quadrupolar NMR parameters. The distributions of quadrupolar coupling and isotropic chemical shift are superimposed with the second-order quadrupolar broadening, but can be potentially characterized by MQMAS (multiple-quantum magic-angle spinning) spectroscopy. We review analyses of NMR lineshapes in 2D DQ–SQ (double-quantum single-quantum) and MQMAS spectroscopies, to provide a guide for more general lineshape analysis. In addition, methods to enhance the spectral resolution and sensitivity for quadrupolar nuclei are discussed, including NMR pulse techniques and the application of high magnetic fields. The role of magnetic field strength and its impact on the strategy of determining optimum NMR methods for disorder characterization are also discussed.

Mapping the oxygen structure of \u03b3-Al2O3 by high-field solid-state NMR spectroscopy

γ-Al2O3 is one of the most widely used catalysts or catalyst supports in numerous industrial catalytic processes. Understanding the structure of γ-Al2O3 is essential to tuning its physicochemical property, which still remains a great challenge. We report a strategy for the observation and determination of oxygen structure of γ-Al2O3 by using two-dimensional (2D) solid-state NMR spectroscopy at high field. 2D 17O double-quantum single-quantum homonuclear correlation NMR experiment is conducted at an ultra-high magnetic field of 35.2 T to reveal the spatial proximities between different oxygen species from the bulk to surface. Furthermore, 2D proton-detected 1H-17O heteronuclear correlation NMR experiments allow for a rapid identification and differentiation of surface hydroxyl groups and (sub-)surface oxygen species. Our experimental results demonstrate a non-random distribution of oxygen species in γ-Al2O3.

High-resolution proton-detected MAS experiments on self-assembled diphenylalanine nanotubes enabled by fast MAS and high magnetic field

The advent of ultrahigh magnetic field and fast magic-angle-spinning (MAS) probe technology has led to dramatically enhanced spectral resolution and sensitivity in solid-state NMR spectroscopy. In particular, proton-based multidimensional solid-state NMR techniques have become feasible to investigate the structure and dynamics at atomic resolution, due to the increased chemical shift span and spectral resolution. Herein, the benefits of faster MAS and higher magnetic field are demonstrated on a self-assembled diphenylalanine (Phe-Phe) nanomaterial. Proton-detected 2D 1H/1H single-quantum/single-quantum (SQ/SQ) correlation, double-quantum/single-quantum (DQ/SQ) correlation, and 1H chemical shift anisotropy/chemical shift (CSA/CS) correlation spectra obtained at two different spinning speeds (60 and 100 kHz) and two different magnetic fields (600 and 900 MHz) are reported. The dramatic enhancement of proton spectral resolution achieved with the use of a 900 MHz magnetic field and 100 kHz MAS is remarkable and enabled the measurement of proton CSA tensors, which will be useful to better understand the self-assembled structures of Phe-Phe nanotubes. We also show through numerical simulations that the unaveraged proton-proton dipolar couplings can result in broadening of CSA lines, leading to inaccurate determination of CSA tensors of protons. Thus, our results clearly show the insufficiency of a 600 MHz magnetic field to resolve 1H spectra lines and the inability of a moderate spinning speed of 60 kHz to completely suppress 1H–1H dipolar couplings, which further justify the pursuit of ultrahigh magnetic field beyond 1 GHz and ultrafast MAS beyond 100 kHz.

Solid-state nuclear magnetic resonance investigation of synthetic phlogopite and lepidolite samples.

In the present work, our aim is to decipher the cationic ordering in the octahedral and tetrahedral sheets of two Al-rich synthetic materials, namely, phlogopites of nominal composition K(Mg3-x Alx )[Al1+x Si3-x O10 ](OH)y F2-y and lepidolites in the system trilithionite-polylithionite with composition K (Lix Al3-x )[Al4-2x Si2x O10 ](OH)y F2-y , by directly probing the aluminium distribution through 27 Al and 17 O magic-angle spinning, multiple-quantum magic-angle spinning, and 27 Al-27 Al double-quantum single-quantum nuclear magnetic resonance (NMR) experiments. Notably, 27 Al-27 Al double-quantum single-quantum magic-angle spinning NMR spectra, recorded at 9.34 and/or 20.00 T, show the spatial proximity or avoidance of the Al species inside or between the sheets. In both studied minerals, the ensemble of NMR data suggests a preference for [4] Al in the tetrahedral sheet to occupy position close to the [6] Al of the octahedral sheets.

Selective detection of active pharmaceutical ingredients in tablet formulations using solid-state NMR spectroscopy

Atomic-level characterization of active pharmaceutical ingredients (API) is crucial in pharmaceutical industry because APIs play an important role in physicochemical properties of drug formulations. However, the analysis of targeted APIs in intact tablet formulations is less straightforward due to the coexistence of excipients as major components and different APIs at dilute concentrations (often below 10 ​wt% loading). Although solid-state (ss) NMR spectroscopy is widely used to investigate short-range order, polymorphism, and pseudo-polymorphism in neat pharmaceutical compounds, the analysis of complex drug formulations is often limited by overlapped signals that originate from structurally different APIs and excipients. In particular, such examples are frequently encountered in the analysis of 1H ssNMR spectra of pharmaceutical formulations. While the high-resolution in 1H ssNMR spectra can be attained by, for example, high magnetic fields accompanied by fast magic-angle spinning (MAS) approaches, the spectral complexity associated with the mixtures of compounds hinders the accurate determination of chemical shifts and through-space proximities. Here we propose a fast MAS (70 ​kHz) NMR experiment for the selective detection of 1H signals associated with an API from a severely overlapped NMR spectrum of a tablet formulation. Spectral simplification is achieved by combining (i) symmetry-based dipolar recoupling (SR412) rotational-echo saturation-pulse double-resonance (RESPDOR) with phase-modulate (PM) saturation pulses, (ii) radio frequency-driven recoupling (RFDR), and (iii) double-quantum excitation using Back-to-Back (BaBa) pulse sequence elements. First, 1H sites in close proximities to 14N nuclei of an API are excited using a PM-S-RESPDOR sequence, and simultaneously, the other unwanted 1H signals of excipients are suppressed. Then, 1H magnetization transfer to adjacent 1H sites in the API is achieved by spin diffusion process using a RFDR sequence, which polarizes to 1H sites within the crystalline API regions of the drug formulation. Next, a PM-S-RESPDOR-RFDR sequence is combined with a Back-to-Back (BaBa) sequence to elucidate local-structures and 1H–1H proximities of the API in a dosage form. The PM-S-RESPDOR-RFDR-BaBa experiment is employed in one- (1D) and two-dimensional (2D) versions to selectively detect the 1H ssNMR spectrum of l-cysteine (10.6 ​wt% or 0.11 ​mg) in a commercial formulation, and compared with the spectra of neat l-cysteine recorded using a standard BaBa experiment. The 2D 1H double-quantum−single-quantum (DQ-SQ) spectrum of the API (l-cysteine)-detected pharmaceutical tablet is in good agreement with the 2D 1H DQ-SQ spectrum obtained from the pure API molecule. Furthermore, the sensitivity and robustness of the experiment is examined by selectively detecting 1H{14N} signals in an amino acid salt, l-histidine.H2O.HCl.

Investigating the Microstructure of Poly(cyclosilane) by 29Si Solid-State NMR Spectroscopy and DFT Calculations

Using high-resolution magic angle spinning (MAS) solid-state NMR spectroscopy and density-functional theory (DFT) calculations, we determine the microstructure of the silicon-based functional polymer poly(1,4Si6) arising from the dehydrocoupling polymerization of cyclosilane 1,4Si6. 1H–29Si refocused-INEPT solid-state NMR experiments allow the unambiguous determination of the number of attached protons to a silicon atom for each 29Si NMR signal in 1,4Si6 and poly(1,4Si6). One-dimensional 1H → 29Si cross-polarization MAS (CPMAS) NMR spectra of poly(1,4Si6) show the development of SiH resonances upon polymerization, and peak integration indicates an average degree of polymerization of 20. The 1H → 29Si CPMAS spectrum of poly(1,4Si6) also shows two sets of isotropic signals, suggesting the presence of at least two distinct species. Two-dimensional 29Si dipolar double-quantum–single-quantum and single-quantum–single-quantum homonuclear correlation NMR spectra reveal similar connectivity in the two species, po...

Solid-state NMR tools for the structural characterization of POSiSils: 29 Si sensitivity improvement with MC-CP and 2D 29 Si-29 Si DQ-SQ at natural abundance.

The 1 H-29 Si multiple-contact cross polarization (MC-CP) MAS NMR experiment is evaluated for the class of silicate-siloxane copolymers called POSiSils, that is, polyoligosiloxysilicones. It proves a reasonably good solution to tackle the challenge of recording quantitative 29 Si NMR data in experimental time much reduced compared with single pulse acquisition. In a second time, we report 29 Si-29 Si MC-CP double-quantum single-quantum (MC-CP-DQ-SQ) NMR experiment, which provides information about the through-space proximities between all silicon species despite the high degree of heterogeneity of this material. This work furthers the NMR tools for NMR crystallography for inorganic polymers, as it covers flexible polymers with different dimensionalities and long or heterogeneous relaxation characteristics at low 29 Si natural abundance.

Crude Oil Adsorbates on Calcite and Quartz Surfaces Investigated by NMR Spectroscopy

The complexity of crude oils may contribute to alteration of petroleum reservoir wetting states in ways that cannot be mimicked by model oils. Subsequent to a wet aging procedure, the molecular arrangements of crude oil adsorbates and water on calcite and quartz surfaces were investigated by various 1H NMR techniques. Solid state magic angle spinning (MAS) magnitude mode, 1H–1H double-quantum single-quantum (DQSQ), and 1H single pulse NMR spectra were used to directly observe molecules on both surfaces. T1 and T2 relaxation time measurements were used to determine molecular surface arrangement. Liquid state 1H NMR was used to investigate possible differences in the crude oil caused by the aging procedure. 1H DQSQ spectra were found most valuable in assignment of the quartz surface where the resonances from the entire adsorbate were relatively well resolved. In addition to adsorbate molecular positioning, this study also provides quantitative measurements of water present at both surfaces subsequent to wet...

Proton Environments in Biomimetic Calcium Phosphates Formed from Mesoporous Bioactive CaO-SiO2-P2O5 Glasses in Vitro: Insights from Solid-State NMR.

When exposed to body fluids, mesoporous bioactive glasses (MBGs) of the CaO–SiO2–P2O5 system develop a bone-bonding surface layer that initially consists of amorphous calcium phosphate (ACP), which transforms into hydroxy-carbonate apatite (HCA) with a very similar composition as bone/dentin mineral. Information from various 1H-based solid-state nuclear magnetic resonance (NMR) experiments was combined to elucidate the evolution of the proton speciations both at the MBG surface and within each ACP/HCA constituent of the biomimetic phosphate layer formed when each of three MBGs with distinct Ca, Si, and P contents was immersed in a simulated body fluid (SBF) for variable periods between 15 min and 30 days. Directly excited magic-angle-spinning (MAS) 1H NMR spectra mainly reflect the MBG component, whose surface is rich in water and silanol (SiOH) moieties. Double-quantum–single-quantum correlation 1H NMR experimentation at fast MAS revealed their interatomic proximities. The comparatively minor H species of each ACP and HCA component were probed selectively by heteronuclear 1H–31P NMR experimentation. The initially prevailing ACP phase comprises H2O and “nonapatitic” HPO42–/PO43– groups, whereas for prolonged MBG soaking over days, a well-progressed ACP → HCA transformation was evidenced by a dominating O1H resonance from HCA. We show that 1H-detected 1H → 31P cross-polarization NMR is markedly more sensitive than utilizing powder X-ray diffraction or 31P NMR for detecting the onset of HCA formation, notably so for P-bearing (M)BGs. In relation to the long-standing controversy as to whether bone mineral comprises ACP and/or forms via an ACP precursor, we discuss a recently accepted structural core–shell picture of both synthetic and biological HCA, highlighting the close relationship between the disordered surface layer and ACP.

Low-power broadband solid-state MAS NMR of 14N.

We propose two broadband pulse schemes for 14N solid-state magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) that achieves (i) complete population inversion and (ii) efficient excitation of the double-quantum spectrum using low-power single-sideband-selective pulses. We give a comprehensive theoretical description of both schemes using a common framework that is based on the jolting-frame formalism of Caravatti et al. [J. Magn. Reson. 55, 88 (1983)]. This formalism is used to determine for the first time that we can obtain complete population inversion of 14N under low-power conditions, which we do here using single-sideband-selective adiabatic pulses. It is then used to predict that double-quantum coherences can be excited using low-power single-sideband-selective pulses. We then proceed to design a new experimental scheme for double-quantum excitation. The final double-quantum excitation pulse scheme is easily incorporated into other NMR experiments, as demonstrated here for double quantum-single quantum 14N correlation spectroscopy, and 1H-14N dipolar heteronuclear multiple-quantum correlation experiments. These pulses and irradiation schemes are evaluated numerically using simulations on single crystals and full powders, as well as experimentally on ammonium oxalate ((NH4)2C2O4) at moderate MAS and glycine at ultra-fast MAS. The performance of these new NMR methods is found to be very high, with population inversion efficiencies of 100% and double-quantum excitation efficiencies of 30%-50%, which are hitherto unprecedented for the low radiofrequency field amplitudes, up to the spinning frequency, that are used here.

Direct Spectroscopic Evidence for Isolated Silanols in SiOx/Al2O3 and Their Formation Mechanism

The preparation and unambiguous characterization of isolated Bronsted-acidic silanol species on silica–alumina catalysts presents a key challenge in the rational design of solid acid catalysts. In this report, atomic layer deposition (ALD) and liquid-phase preparation (chemical liquid deposition, CLD) are used to install the SiOx sites on Al2O3 catalysts using the same Si source (tetraethylorthosilicate, TEOS). The ALD-derived and CLD-derived SiOx sites are probed with dynamic nuclear polarization (DNP)-enhanced 29Si–29Si double-quantum/single-quantum (DQ/SQ) correlation NMR spectroscopy. The investigation reveals conclusively that the SiOx/Al2O3 material prepared by ALD and CLD, followed by calcination under an O2 stream, contains fully spatially isolated Si species, in contrast with those resulting from the calcination under static air, which is widely accepted as a postgrafting treatment for CLD. Insight into the formation mechanism of these sites is obtained via in situ monitoring of the TEOS + γ-Al2O...