Dynamic Nuclear Polarization Enhanced Multiple-Quantum Spin Counting of Molecular Assemblies in Vitrified Solutions.

Crystallization pathways are essential to various industrial, geological, and biological processes. In nonclassical nucleation theory, prenucleation clusters (PNCs) form, aggregate, and crystallize to produce higher order assemblies. Microscopy and X-ray techniques have limited utility for PNC analysis due to the small size (0.

NMR investigations unveil phase composition-property correlations in SrNaSiO fast ion conductor.

This paper reports results of Na and Si solid-state NMR investigations carried out on sodium strontium silicate ion conductor, SrNaSiO and presents the first experimental evidence to show that different synthesis conditions induce multiple devitrified phases. Along with 1-dimensional NMR, Na MQMAS spectra have been used to identify the phases corresponding to polymorphs of NaSiO, in addition to the crystalline SrSiO and the glass/amorphous NaSiO phases. The surprising observation of about an order of magnitude higher ionic conductivity achieved in devitrified samples is attributed to the growth of the crystalline δ-NaSiO phase within the amorphous NaSiO phase domains, identified using NMR.

Low-power broadband homonuclear dipolar recoupling in MAS NMR by two-fold symmetry pulse schemes for magnetization transfers and double-quantum excitation.

We provide an experimental, numerical, and high-order average Hamiltonian evaluation of an open-ended series of homonuclear dipolar recoupling sequences, SR [Formula: see text] with p=1,2,3,…. While operating at a very low radio-frequency (rf) power, corresponding to a nutation frequency of 1/2 of the magic-angle spinning (MAS) rate (ωnut=ωr/2), these recursively generated double-quantum (2Q) dipolar recoupling schemes offer a progressively improved compensation to resonance offsets and rf inhomogeneity for increasing pulse-sequence order p. The excellent recoupling robustness to these experimental obstacles, as well as to CSA, is demonstrated for 2Q filtering (2QF) experiments and for driving magnetization transfers in 2D NMR correlation spectroscopy, where the sequences may provide either double or zero quantum dipolar Hamiltonians during mixing.

Multiple-quantum spin counting in magic-angle-spinning NMR via low-power symmetry-based dipolar recoupling.

By using a symmetry-based R2(8)(1)R2(8)(-1) double-quantum (2Q) dipolar recoupling sequence, we demonstrate high-order multiple-quantum coherence (MQC) excitation at fast magic-angle spinning (MAS) frequencies up to 34 kHz. This scheme combines several attractive features, such as a relatively high dipolar scaling factor, good compensation to rf-errors, isotropic and anisotropic chemical shifts, as well as an ultra-low radio-frequency (rf) power requirement. The latter translates into nutation frequencies below 30 kHz for MAS rates up to 60 kHz, thereby permitting rf application for very long excitation periods without risk of damaging the NMR probehead or sample, while the compensation to chemical shifts improves as the MAS rate increases.

Local structures and Al/Si ordering in lanthanum aluminosilicate glasses explored by advanced 27Al NMR experiments and molecular dynamics simulations.

The structures of 15 La-Al-Si-O glasses, whose compositions span 11-28 mol% La(2)O(3), 11-30 mol% Al(2)O(3), and 45-78 mol% SiO(2), are explored over both short and intermediate length-scales by using a combination of solid-state (27)Al magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and molecular dynamics (MD) simulations. MAS NMR reveals Al speciations dominated by AlO(4) groups, with minor but significant fractions of AlO(5) (5-10%) and AlO(6) (≲3%) polyhedra present in all La(2)O(3)-Al(2)O(3)-SiO(2) glasses; the amounts of Al([5]) and Al([6]) coordinations increase for decreasing molar fraction of Si. The MD simulations reproduce this compositional trend, with the fractional populations of AlO(p) groups (p = 4, 5, 6) according well with the experimental results.

Analysis of the local structure of phosphorus-substituted LAMOX oxide ion conductors.

The effect of partial substitution of molybdenum by phosphorus on the global and local structural arrangement of the fast oxide-ion conductor La(2)Mo(2)O(9) (LAMOX) has been studied by X-ray powder diffraction as well as (139)La and (31)P solid state NMR. The diffraction patterns show that La(2)Mo(2-y)P(y)O(9-y/2) forms a solid solution at low phosphorus concentrations, and that there is a structural phase transition upon increasing phosphorus concentration. This phase transition is also reflected in (139)La and (31)P NMR spectra.

Phase diagram of NdFeAsO(1-x)F(x): essential role of chemical composition.

In this Article, we provided the complete phase diagram of NdFeAsO(1-x)F(x) solid solution as a function of electron doping thanks to the careful determination of F- and O-content and phase content. We gave direct evidence of the source of F-depletion in the superconducting main phase, that is, the formation of oxyfluoride spurious phase. The approach reported in this work clearly showed that to give reliable results on these complex new superconducting materials, a rigorous control of the chemical composition of the considered phases has to be carried out.