The morphology of zeolite W (MER topology) synthesized from Hydrated Silicate Ionic Liquids (HSILs) shows a distinct temperature dependence, reflected in a fundamental difference in the underlying crystal growth mechanism as revealed by Atomic Force Microscopy (AFM). Zeolite W crystals obtained at 90 °C develop in a highly supersaturated solution through birth and spread growth, whereas synthesis at 175 °C results in elongated, spiral grown zeolite W particles. Supersaturation was measured through the concentration of dissolved aluminate, being the limiting species. The evolution of the aluminum concentration during crystallization at different temperatures was monitored with 27 Al Nuclear Magnetic Resonance (NMR) spectroscopy. Supersaturation conditions determine the nucleation rate, the prevailing crystal growth mechanism, and resulting crystal morphology.

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Efficient, room temperature hyperpolarization of exchangeable solvent protons combining parahydrogen (p-H 2 ), aminopropyldiethoxymethylsilane (APDMS), and IrCl(COD)-(IMes) to generate an active aminosilane−iridium complex broadens the capabilities of signal amplification by reversible exchange (SABRE)-type hyperpolarization of protons. A primary pool of hyperpolarized exchangeable protons transfers its hyperpolarization to cosolutes with labile protons, partly overcoming the catalytic specificity of SABRE-type spin-transfer catalysis. The silane functionality of APDMS appears to be crucial to its improvement. Its role is unprecedented in p-H 2 -based hyperpolarization of nuclear spins and promises to broaden its applicability of ultrasensitive solution-state NMR spectroscopy for the detection and elucidation of molecular behavior, at concentrations undetectable by conventional NMR spectroscopy.

Symmetry breaking of parahydrogen using iridium catalysts converts singlet spin order into observable hyperpolarization. In this contribution, iridium catalysts are designed to exhibit asymmetry in their hydrides, regulated by in situ generation of deuterated ammonia governed by ammonium buffers. The concentrations of ammonia (N) and pyridine (P) provide a handle to generate a variety of stereo‐chemically asymmetric N‐heterocyclic carbene iridium complexes, ligating either [3xP], [2xP;N], [P;2xN] or [3xN] in an octahedral SABRE type configuration. The non‐equivalent hydride positions, in correspondence with the ammonium buffer solutions, enables to extend singlet‐triplet or S⟩→|T0⟩ mixing at high magnetic field and experimentally induce prolonged generation of non‐equilibrium longitudinal two‐spin order. This long‐lasting magnetization can be exploited in hyperpolarized 2D‐OPSY‐COSY experiments providing direct structural information on the catalyst using a single contact with parahydrogen. Separately, field cycling revealed hyperpolarization properties in low‐field conditions. Controlling catalyst stereochemistry by introducing small and deuterated ligands, such as deuterated ammonia, simplifies the spin‐system. This is shown to unify experimental and theoretically derived field‐sweep experiments for four‐spin systems.

Arabinoxylan oligosaccharides (AXOS) are a complex mixture of cereal derived, water soluble prebiotics, obtained by enzymatic hydrolysis of arabinoxylan, a group of dietary fibers exerting numerous nutritional and health-beneficial effects. Such complex biomolecular mixtures are notoriously difficult to characterize without initial physical fractionation. Here we present the in situ analysis of AXOS using a variety of state-of-the-art sensitivity-enhanced 13 C-DOSY methods, enabling virtual separation and identification of the components. Three dimensional correlation plots displaying 13 C diffusivity (DOSY), relaxation parameters (TOSY) and chemical shift offer a unique way to elucidate the composition of mixtures. We have demonstrated this multifaceted 13 C probed correlation strategy in standard mixtures of aliphatic and aromatic compounds, before implementing it on AXOS. These 3D-DOSY-TOSY plots in combination with 2D-NMR correlation experiments offer unprecedented clarity for assigning chemical functions, molecular size distribution and dynamics of oligosaccharide mixtures.