Probing the water adsorption and stability under steam flow of Zr-based metal-organic frameworks using Zr solid-state NMR spectroscopy.

The stability of metal-organic frameworks (MOFs) in the presence of water is crucial for a wide range of applications, including the production of freshwater, desiccation, humidity control, heat pumps/chillers and capture and separation of gases. In particular, their stability under steam flow is essential since most industrial streams contain water vapor. Nevertheless, to the best of our knowledge, the stability under steam flow of Zr-based MOFs, which are among the most widely studied MOFs, has not been investigated so far.

High-resolution indirect detection of spin-3/2 quadrupolar nuclei in solids using multiple-quantum-filtered through-space D-HMQC experiments.

Through-space heteronuclear correlation experiments under magic-angle spinning (MAS) conditions can provide unique insights into inter-atomic proximities. In particular, it has been shown that experiments based on two consecutive coherence transfers, H → I → H, like D-HMQC (dipolar-mediated heteronuclear multiple-quantum correlation), are usually more sensitive for the indirect detection via protons of spin-3/2 quadrupolar nuclei with low gyromagnetic ratio. Nevertheless, the resolution is often decreased by the second-order quadrupolar broadening along the indirect dimension.

Probing the Surface of Oxide Nanoparticles Using DNP-Enhanced High-Resolution NMR of Quadrupolar Nuclei.

The surfaces of nanomaterials with applications in optoelectronics and catalysis control their physicochemical properties. NMR spectroscopy, enhanced by dynamic nuclear polarization (DNP), is a powerful approach to probe the local environment of spin-1/2 nuclei near surfaces. However, this technique often lacks robustness and resolution for half-integer quadrupolar nuclei, which represent more than 66% of the NMR-active isotopes.

Identification of phosphorus sites in amorphous LiPON thin film by observing internuclear proximities.

Amorphous lithium phosphorus oxynitrides (LiPON), prepared by reactive magnetron sputtering, have become the electrolytes of choice for all-solid-state thin film microbatteries since its discovery in early 1990s. Nevertheless, there is still a lack of understanding of their atomic-level structure and its influence on ionic conductivity. Solid-state NMR spectroscopy represents a promising technique to determine the atomic-level structure of LiPON glasses but is challenging owing to its low sensitivity in the case of thin film materials.

On the applicability of cosine-modulated pulses for high-resolution solid-state NMR of quadrupolar nuclei with spin > 3/2.

In MQMAS-based high-resolution solid-state NMR experiments of half-integer spin quadrupolar nuclei, the high radiofrequency (RF) field requirement for the MQ excitation and conversion steps with two hard-pulses is often a sensitivity limiting factor in many practical applications. Recently, the use of two cosine-modulated (cos) low-power (lp) pulses, lasting one-rotor period each, was successfully introduced for efficient MQ excitation and conversion of spin-3/2 nuclei with a reduced RF amplitude. In this study, we extend our previous investigations of spin-3/2 nuclei to systems with higher spin values and discuss the applicability of coslp-MQ excitation and conversion in MQMAS and MQ-HETCOR experiments under slow and fast spinning conditions.

Comparison of through-space homonuclear correlations between quadrupolar nuclei in solids.

Various two-dimensional (2D) homonuclear correlation experiments have been proposed to observe proximities between identical half-integer spin quadrupolar nuclei in solids. These experiments select either the single- or double-quantum coherences during the indirect evolution period, t. We compare here the efficiency and the robustness of the 2D double-quantum to single-quantum (DQ-SQ) and SQ-SQ homonuclear correlations for two half-integer spin quadrupolar isotopes subject to small chemical shift anisotropy (CSA): B with a nuclear spin I = 3/2 and Al with I = 5/2.

C, Mg, and Ca Solid-State NMR for the Purpose of Dolomitic Marbles Provenance Elucidation.

The study of the provenance of dolomitic marble artefacts has become relevant since it was discovered that quarries of this marble other than that of Cape-Vathy located on the island of Thasos have been exploited since Antiquity. To improve our knowledge about the provenance of materials and the extent of their dispersion, multiple archaeometric studies were performed in the past including isotope analyses, petrography, cathodoluminescence, and elemental analyses. In the present work, solid-state nuclear magnetic resonance (NMR) spectroscopy has been added to this panel of techniques.

Practical considerations on the use of low RF-fields and cosine modulation in high-resolution NMR of I = 3/2 spin quadrupolar nuclei in solids.

Despite its ease in experimental set up, the low sensitivity of MQMAS experiments is often a limiting factor in many practical applications. This is mainly due to the large radiofrequency (RF) field requirement of the two short hard-pulses often used for the optimum MQ excitation and conversion steps. Very recently, two novel MQMAS experiments have been proposed for I = 3/2 nuclei, namely lp-MQMAS and coslp-MQMAS, enabling an efficient MQ excitation/conversion with a reduced RF requirement, by utilizing two long pulses lasting one rotor period each, with or without cosine modulation.

Mechanochemical Synthesis and Study of the Local Structure of NaGaS Glass and Glass-Ceramics.

NaGaS is a newly discovered compound that has already shown great promise for a variety of applications because of its layered structure and ion exchange properties. In this work, crystalline NaGaS has been synthesized by an alternative method to what has been previously published, namely, by mechanochemistry, either by a direct one-step process or by a two-step process. In the one-step process, crystalline NaGaS is directly formed by milling sodium sulfide NaS and gallium(III) sulfide GaS.

Improved resolution for spin-3/2 isotopes in solids via the indirect NMR detection of triple-quantum coherences using the T-HMQC sequence.

The indirect NMR detection of quadrupolar nuclei in solids under magic-angle spinning (MAS) is possible with the through-space HMQC (heteronuclear multiple-quantum coherence) scheme incorporating the TRAPDOR (transfer of population in double-resonance) dipolar recoupling. This sequence, called T-HMQC, exhibits limited t-noise. In this contribution, with the help of numerical simulations of spin dynamics, we show that most of the time, the fastest coherence transfer in the T-HMQC scheme is achieved when TRAPDOR recoupling employs the highest radiofrequency (rf) field compatible with the probe specifications.

Correction to "First Direct Insight into the Local Environment and Dynamics of Water Molecules in the Whewellite Mineral Phase: Mechanochemical Isotopic Enrichment and High-Resolution O and H NMR Analyses".

[This corrects the article DOI: 10.1021/acs.jpcc.

Chemical exchange of labile protons by deuterium enables selective detection of pharmaceuticals in solid formulations.

Chemically assisted swapping of labile protons by deuterons is presented for amino acids, polysaccharides, pharmaceutical compounds, and their solid formulations. Solid-state packing interactions in these compounds are elucidated by H-H isotope correlation NMR spectroscopy (iCOSY). A minuscule concentration of dopamine, 5 wt% or ∼100 μg, in a solid formulation can be detected by H NMR at 28.

O solid state NMR as a valuable tool for deciphering reaction mechanisms in mechanochemistry: the case study on the O-enrichment of hydrated Ca-pyrophosphate biominerals.

The possibility of enriching in O the water molecules within hydrated biominerals belonging to the Ca-pyrophosphate family was investigated, using liquid assisted grinding (LAG) in the presence of O-labelled water. Two phases with different hydration levels, namely triclinic calcium pyrophosphate dihydrate (CaPO·2HO, denoted -CPPD) and monoclinic calcium pyrophosphate tetrahydrate (CaPO·4HO, denoted -CPPT β) were enriched in O using a "post-enrichment" strategy, in which the non-labelled precursors were ground under gentle milling conditions in the presence of stoichiometric quantities of O-enriched water (introduced here in very small volumes ∼10 μL). Using high-resolution O solid-state NMR (ssNMR) analyses at multiple magnetic fields, and dynamic nuclear polarisation (DNP)-enhanced O NMR, it was possible to show that the labelled water molecules are mainly located at the core of the crystal structures, but that they can enter the lattice in different ways, namely by dissolution/recrystallisation or by diffusion.

Combining heteronuclear correlation NMR with spin-diffusion to detect relayed Cl-H-H and N-H-H proximities in molecular solids.

Analysis of short-to-intermediate range intermolecular interactions offers a great way of characterizing the solid-state organization of small molecules and materials. This can be achieved by two-dimensional (2D) homo- and heteronuclear correlation NMR spectroscopy, for example, by carrying out experiments at high magnetic fields in conjunction with fast magic-angle spinning (MAS) techniques. But, detecting 2D peaks for heteronuclear dipolar coupled spin pairs separated by greater than 3 Å is not always straightforward, particularly when low-gamma quadrupolar nuclei are involved.

Indirect NMR detection via proton of nuclei subject to large anisotropic interactions, such as N, Pt, and Cl, using the T-HMQC sequence.

Recently, the T-hetero-nuclear multiple quantum coherence (T-HMQC) sequence using the TRAPDOR (transfer of population in double resonance) recoupling has been introduced for the indirect detection via protons of quadrupolar nuclei with spin I = 1 (N) or 3/2 (Cl) in solids at fast magic-angle spinning (MAS). The sequence is simple as it only uses four rectangular pulses and exhibits low t-noise because the recoupling pulses are applied to the indirectly detected isotope, I. We demonstrate that this sequence is applicable for the detection via protons of spin-1/2 nuclei subject to large chemical shift anisotropy, such as Pt.

Revealing Brønsted Acidic Bridging SiOHAl Groups on Amorphous Silica-Alumina by Ultrahigh Field Solid-State NMR.

Amorphous silica-aluminas (ASAs) are important acidic catalysts and supports for many industrially essential and sustainable processes. The identification of surface acid sites with their local structures on ASAs is of critical importance for tuning their catalytic properties but still remains a great challenge and is under debate. Here, ultrahigh magnetic field (35.

Accelerating the acquisition of high-resolution quadrupolar MQ/ST-HETCOR 2D spectra under fast MAS via H detection and through-space population transfers.

Recently, we established an experimental setup protocol to perform the population transfer from half-integer quadrupolar spin to H nuclei under fast MAS in the context of MQ-HETCOR experiments. In this article, we further develop the high-resolution 2D HETCOR methods by ST-based approaches, making use of the sensitivity advantage of STMAS over its MQMAS counterpart. In a similar manner to the previous work, which utilized CP and RINEPT for the population transfer, we also demonstrate the experimental setup protocol for PRESTO.

Probing Si-O connectivities and proximities by solid-state NMR.

The measurement of dipolar and J- couplings between Si and O isotopes is challenging owing to (i) the low abundance of both isotopes and (ii) their close Larmor frequencies, which only differ by 19%. These issues are circumvented here by the use of isotopic enrichment and dedicated triple-resonance magic-angle spinning NMR probe. The surface of Si-enriched silica was labelled with O isotope and heated at 80 and 200 °C.

A comparison of through-space population transfers from half-integer spin quadrupolar nuclei to H using MQ-HETCOR and MQ-SPAM-HETCOR under fast MAS.

In this article, we compare the various schemes of magnetization transfer from half-integer quadrupolar spins to H nuclei and we establish an efficient protocol to perform these transfers under MQMAS high-resolution with the MQ-HETCOR and MQ-SPAM-HETCOR experiments under fast MAS. The MQMAS efficiencies are analyzed with SIMPSON simulations, and the CPMAS and RINEPT magnetization transfers are compared at 62.5 kHz MAS using {Na}-H and {Al}-H MQ-HETCOR and MQ-SPAM-HETCOR experiments performed on NaHPO4, NaHPO, Na citrate dihydrate and ipa-AlPO-14 powder samples.

Improved NMR transfer of magnetization from protons to half-integer spin quadrupolar nuclei at moderate and high magic-angle spinning frequencies.

Half-integer spin quadrupolar nuclei are the only magnetic isotopes for the majority of the chemical elements. Therefore, the transfer of polarization from protons to these isotopes under magic-angle spinning (MAS) can provide precious insights into the interatomic proximities in hydrogen-containing solids, including organic, hybrid, nanostructured and biological solids. This transfer has recently been combined with dynamic nuclear polarization (DNP) in order to enhance the NMR signal of half-integer quadrupolar isotopes.

Labeling and Probing the Silica Surface Using Mechanochemistry and O NMR Spectroscopy*.

In recent years, there has been increasing interest in developing cost-efficient, fast, and user-friendly O enrichment protocols to help to understand the structure and reactivity of materials by using O NMR spectroscopy. Here, we show for the first time how ball milling (BM) can be used to selectively and efficiently enrich the surface of fumed silica, which is widely used at industrial scale. Short milling times (up to 15 min) allowed modulation of the enrichment level (up to ca.

Through-space B- Al correlation: Influence of the recoupling channel.

Through-space heteronuclear correlation (D-HETCOR) experiments based on heteronuclear multiple-quantum correlation (D-HMQC) and refocused insensitive nuclei enhanced by polarization transfer (D-RINEPT) sequences have been proven to be useful approaches for the detection of the spatial proximity between half-integer quadrupolar nuclei in solids under magic-angle spinning (MAS) conditions. The corresponding pulse sequences employ coherence transfers mediated by heteronuclear dipolar interactions, which are reintroduced under MAS by radiofrequency irradiation of only one of the two correlated nuclei. We investigate herein using numerical simulations of spin dynamics and solid-state NMR experiments on magnesium aluminoborate glass how the choice of the channel to which the heteronuclear dipolar recoupling is applied affects the transfer efficiency of D-HMQC and D-RINEPT sequences between B and Al nuclei.

Efficient transfer of DNP-enhanced H magnetization to half-integer quadrupolar nuclei in solids at moderate spinning rate.

We show herein how the proton magnetization enhanced by dynamic nuclear polarization (DNP) can be efficiently transferred at moderate magic-angle spinning (MAS) frequencies to half-integer quadrupolar nuclei, S ≥ 3/2, using the Dipolar-mediated Refocused Insensitive Nuclei Enhanced by Polarization Transfer (D-RINEPT) technique, in which a symmetry-based recoupling scheme built from adiabatic inversion H pulses reintroduces the H-S dipolar couplings, while suppressing the H- H ones. The use of adiabatic pulses also improves the robustness to offsets and radiofrequency (rf)-field inhomogeneity. Furthermore, the efficiency of the polarization transfer is further improved by using H composite pulses and continuous-wave irradiations between the recoupling blocks, as well as by manipulating the S satellite transitions during the first recoupling block.