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An in-depth theoretical analysis of key chemical equilibria in Signal Amplification by Reversible Exchange (SABRE) is provided, employing density functional theory calculations to characterize the likely reaction network. For all reactions in the network, the potential energy surface is probed to identify minimum energy pathways. Energy barriers and transition states are calculated, and harmonic transition state theory is applied to calculate exchange rates that approximate experimental values. The reaction network energy surface can be modulated by chemical potentials that account for the dependence on concentration, temperature, and partial pressure of molecular constituents (hydrogen, methanol, pyridine) supplied to the experiment under equilibrium conditions. We show that, under typical experimental conditions, the Gibbs free energies of the two key states involved in pyridine-hydrogen exchange at the common Ir-IMes catalyst system in methanol are essentially the same, i. e., nearly optimal for SABRE. We also show that a methanol-containing intermediate is plausible as a transient species in the process.

Signal Amplification By Reversible Exchange (SABRE) is a particularly simple hyperpolarisation approach. However, compared to other hyperpolarisation methods, SABRE is more limited in substrate scope. Therefore, it is critical to understand and overcome the factors limiting generalization. Past developments in SABRE catalyst optimization have emphasized large enhancements in the canonical SABRE substrate: pyridine and structurally closely related motifs. However, the pyridine-optimized catalysts are not efficient at hyperpolarising more sterically demanding substrates, including 2-substituted pyridine derivatives. Here we report that modifications of the catalyst ligand sphere, using a chelating ligand in particular, can increase the volume fraction available for substrate coordination to the iridium catalyst, thus permitting significant signal enhancements on otherwise sterically hindered substrates. The system yields (1)H enhancements on the order of 100-fold over 8.5 T thermal measurements for 2-substituted pyridine derivatives, and smaller, yet significant (1)H enhancement for provitamin B(6) and caffeine. For the 2-substituted pyridine derivatives we further show (15)N enhancements on the order of 1000-fold and (19)F enhancements of 30-fold over 8.5 T thermal polarisations.

Parahydrogen is an inexpensive and readily available source of hyperpolarization used to enhance magnetic resonance signals by up to four orders of magnitude above thermal signals obtained at ∼10 T. A significant challenge for applications is fast signal decay after hyperpolarization. Here we use parahydrogen-based polarization transfer catalysis at microtesla fields (first introduced as SABRE-SHEATH) to hyperpolarize 13C2 spin pairs and find decay time constants of 12 s for magnetization at 0.3 mT, which are extended to 2 min at that same field, when long-lived singlet states are hyperpolarized instead. Enhancements over thermal at 8.5 T are between 30 and 170 fold (0.02 to 0.12% polarization). We control the spin dynamics of polarization transfer by choice of microtesla field, allowing for deliberate hyperpolarization of either magnetization or long-lived singlet states. Density functional theory calculations and experimental evidence identify two energetically close mechanisms for polarization transfer...

The decay kinetics of the excitonic emission of CdWO4 scintillators was studied under excitation by powerful 100 fs laser pulses in the band tail (Urbach) absorption region. A special imaging technique possessing both spatial and temporal resolution provided a unique insight into the Förster dipole-dipole interaction of self-trapped excitons, which is the main cause of the nonlinear quenching of luminescence in this material. In addition, the saturation of phonon-assisted excitonic absorption due to extremely short excitation pulses was discovered. A model describing the evolution of electronic excitations in the conditions of absorption saturation was developed and an earlier model of decay kinetics based on the Förster interaction was extended to include the saturation effect. Compared to the previous studies, a more accurate calculation yields 3.7 nm as the Förster interaction radius. It was shown that exciton-exciton interaction is the main source of scintillation nonproportionality in CdWO4. A quantitative description using a new model of nonproportionality was presented, making use of the corrected value of the Förster radius.