High-pressure Raman, infrared, x-ray, and neutron studies show that H2 and H2O mixtures crystallize into the sII clathrate structure with an approximate H2/H2O molar ratio of 1:2. The clathrate cages are multiply occupied, with a cluster of two H2 molecules in the small cage and four in the large cage. Substantial softening and splitting of hydrogen vibrons indicate increased intermolecular interactions. The quenched clathrate is stable up to 145 kelvin at ambient pressure. Retention of hydrogen at such high temperatures could help its condensation in planetary nebulae and may play a key role in the evolution of icy bodies.
Synchrotron-based high-pressure x-ray diffraction measurements indicate that compressibility, a fundamental materials property, can have a size-specific minimum value. The bulk modulus of nanocrystalline titania has a maximum at particle size of 15 nm. This can be explained by dislocation behavior because very high dislocation contents can be achieved when shear stress induced within nanoparticles counters the repulsion between dislocations. As particle size decreases, compression increasingly generates dislocation networks ͑hardened by overlap of strain fields͒ that shield intervening regions from external pressure. However, when particles become too small to sustain high dislocation concentrations, elastic stiffening declines. The compressibility has a minimum at intermediate sizes.
We report hyperpolarized Xe signal advancement by metal-organic framework (MOF) entrapment (Hyper-SAME) in aqueous solution. The 129Xe NMR signal is drastically promoted by entrapping the Xe into the pores of MOFs. The chemical shift of entrapped 129Xe is clearly distinguishable from that of free 129Xe in water, due to the surface and pore environment of MOFs. The influences from the crystal size of MOFs and their concentration in water are studied. A zinc imidazole MOF, zeolitic imidazole framework-8 (ZIF-8), with particle size of 110 nm at a concentration of 100 mg/mL, was used to give an NMR signal with intensity four times that of free 129Xe in water. Additionally, Hyper-SAME is compatible with hyperpolarized 129Xe chemical exchange saturation transfer. The 129Xe NMR signal can be amplified further by combining the two techniques. More importantly, Hyper-SAME provides a way to make detection of hyperpolarized 129Xe in aqueous solution convenient and broadens the application area of MOFs.
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