Oleg G. Salnikov

Propane-d6 Heterogeneously Hyperpolarized by Parahydrogen.

Long-lived spin states of hyperpolarized propane-d6 gas were demonstrated following pairwise addition of parahydrogen gas to propene-d6 using heterogeneous parahydrogen-induced polarization (HET-PHIP). Hyperpolarized molecules were synthesized using Rh/TiO2 solid catalyst with 1.6 nm Rh nanoparticles. Hyperpolarized (PH ∼ 1%) propane-d6 was detected at high magnetic field (9.4 T) spectroscopically and by high-resolution 3D gradient-echo MRI (4.7 T) as the gas flowed through the radiofrequency coil with a spatial and temporal resolution of 0.5 × 0.5 × 0.5 mm3 and 17.7 s, respectively. Stopped-flow hyperpolarized propane-d6 gas was also detected at 0.0475 T with an observed nuclear spin polarization of PH ∼ 0.1% and a relatively long lifetime with T1,eff = 6.0 ± 0.3 s. Importantly, it was shown that the hyperpolarized protons of the deuterated product obtained via pairwise parahydrogen addition could be detected directly at low magnetic field. Importantly, the relatively long low-field T1,eff of HP propane-d6 gas is not susceptible to paramagnetic impurities as tested by exposure to ∼0.2 atm oxygen. This long lifetime and nontoxic nature of propane gas could be useful for bioimaging applications including potentially pulmonary low-field MRI. The feasibility of high-resolution low-field 2D gradient-echo MRI was demonstrated with 0.88 × 0.88 mm2 spatial and ∼0.7 s temporal resolution, respectively, at 0.0475 T.

High‐Resolution 3D Proton MRI of Hyperpolarized Gas Enabled by Parahydrogen and Rh/TiO2 Heterogeneous Catalyst

Several supported metal catalysts were synthesized, characterized, and tested in heterogeneous hydrogenation of propene with parahydrogen to maximize nuclear spin hyperpolarization of propane gas using parahydrogen induced polarization (PHIP). The Rh/TiO2 catalyst with a metal particle size of 1.6 nm was found to be the most active and effective in the pairwise hydrogen addition and robust, demonstrating reproducible results with multiple hydrogenation experiments and stability for ≥1.5 years. 3D (1) H magnetic resonance imaging (MRI) of 1 % hyperpolarized flowing gas with microscale spatial resolution (625×625×625 μm(3) ) and large imaging matrix (128×128×32) was demonstrated by using a preclinical 4.7 T scanner and 17.4 s imaging scan time.

NMR Hyperpolarization Techniques of Gases

Nuclear spin polarization can be significantly increased through the process of hyperpolarization, leading to an increase in the sensitivity of nuclear magnetic resonance (NMR) experiments by 4-8 orders of magnitude. Hyperpolarized gases, unlike liquids and solids, can often be readily separated and purified from the compounds used to mediate the hyperpolarization processes. These pure hyperpolarized gases enabled many novel MRI applications including the visualization of void spaces, imaging of lung function, and remote detection. Additionally, hyperpolarized gases can be dissolved in liquids and can be used as sensitive molecular probes and reporters. This Minireview covers the fundamentals of the preparation of hyperpolarized gases and focuses on selected applications of interest to biomedicine and materials science.

NMR Signal Enhancement for Hyperpolarized Fluids Continuously Generated in Hydrogenation Reactions with Parahydrogen

In the present study we analyze the factors which can lower hyperpolarization of fluids produced in a continuous flow regime by the parahydrogen-induced polarization technique. We use the findings of this analysis to examine the flow rate dependence of propane hyperpolarization produced in the heterogeneous propylene hydrogenation by parahydrogen over Rh/TiO2 catalyst. We have estimated the maximum attainable propane (1)H hyperpolarization yield and the corrected percentage of pairwise hydrogen addition in heterogeneous hydrogenation, which was found to be ∼7%. The approach developed for polarization analysis is useful for the optimization of experimental setup and reaction conditions to obtain maximum hyperpolarization for parahydrogen-based catalyst-free continuously generated fluids applicable in biomedical magnetic resonance imaging.

Single-atom gold catalysis in the context of developments in parahydrogen-induced polarization.

A highly isolated monoatomic gold catalyst, with single gold atoms dispersed on multiwalled carbon nanotubes (MWCNTs), has been synthesized, characterized, and tested in heterogeneous hydrogenation of 1,3-butadiene and 1-butyne with parahydrogen to maximize the polarization level and the contribution of the pairwise hydrogen addition route. The Au/MWCNTs catalyst was found to be active and efficient in pairwise hydrogen addition and the estimated contributions from the pairwise hydrogen addition route are at least an order of magnitude higher than those for supported metal nanoparticle catalysts. Therefore, the use of the highly isolated monoatomic catalysts is very promising for production of hyperpolarized fluids that can be used for the significant enhancement of NMR signals. A mechanism of 1,3-butadiene hydrogenation with parahydrogen over the highly isolated monoatomic Au/MWCNTs catalyst is also proposed.

Strong Metal–Support Interactions for Palladium Supported on TiO2 Catalysts in the Heterogeneous Hydrogenation with Parahydrogen

Parahydrogen‐induced polarization (PHIP) was successfully utilized to demonstrate the strong metal–support interaction (SMSI) effect for palladium supported on titania catalysts. Heterogeneous hydrogenation of 1,3‐butadiene over Pd/TiO2 catalysts led to the formation of 1‐ and 2‐butenes and butane, and hyperpolarized products were obtained if parahydrogen was used in the reaction. However, if the catalysts were reduced in H2 flow at 500 °C before the hydrogenation reaction, the observed polarization levels were significantly lower or even zero, which was indicative of the suppression of the pairwise addition of hydrogen route. This observation indicated the possibility to detect the SMSI effect by the PHIP technique. Moreover, by using X‐ray photoelectron spectroscopy it was shown that Pd is partially present as Pdδ+ after reduction under a hydrogen atmosphere at 500 °C. These results were confirmed by transmission electron microscopy, which revealed the formation of Pdδ+ and the dissolution of Pd in the titania lattice.

A Mechanistic Study of Thiophene Hydrodesulfurization by the Parahydrogen-Induced Polarization Technique

Thiophenic compounds are the least reactive organosulfur compounds in fossil fuels, and thiophene is widely used as a model substrate in studies of industrially important hydrodesulfurization (HDS) processes. It is generally presumed that the HDS process can proceed by two possible pathways, namely hydrogenation or direct desulfurization. In this work, the parahydrogen‐induced polarization technique was successfully utilized in a mechanistic study of a hydrodesulfurization reaction by example of a heterogeneous hydrodesulfurization of thiophene over supported catalysts in the presence of parahydrogen. It was demonstrated that the HDS of thiophene on a MoS2/γ‐Al2O3 catalyst proceeds preferentially by the hydrogenation pathway to form tetrahydrothiophene, followed by desulfurization. In contrast, if a Pt/TiO2 catalyst was used, direct desulfurization to 1,3‐butadiene and the hydrogenation pathway both contributed to the overall reaction mechanism.

Production of Catalyst-Free Hyperpolarised Ethanol Aqueous Solution via Heterogeneous Hydrogenation with Parahydrogen

An experimental approach for the production of catalyst-free hyperpolarised ethanol solution in water via heterogeneous hydrogenation of vinyl acetate with parahydrogen and the subsequent hydrolysis of ethyl acetate was demonstrated. For an efficient hydrogenation, liquid vinyl acetate was transferred to the gas phase by parahydrogen bubbling and almost completely converted to ethyl acetate with Rh/TiO2 catalyst. Subsequent dissolution of ethyl acetate gas in water containing OH− ions led to the formation of catalyst- and organic solvent-free hyperpolarised ethanol and sodium acetate. These results represent the first demonstration of catalyst- and organic solvent-free hyperpolarised ethanol production achieved by heterogeneous hydrogenation of vinyl acetate vapour with parahydrogen and the subsequent ethyl acetate hydrolysis.

NMR Spin-Lock Induced Crossing (SLIC) dispersion and long-lived spin states of gaseous propane at low magnetic field (0.05 T)

When parahydrogen reacts with propylene in low magnetic fields (e.g., 0.05T), the reaction product propane develops an overpopulation of pseudo-singlet nuclear spin states. We studied how the Spin-Lock Induced Crossing (SLIC) technique can be used to convert these pseudo-singlet spin states of hyperpolarized gaseous propane into observable magnetization and to detect 1H NMR signal directly at 0.05T. The theoretical simulation and experimental study of the NMR signal dependence on B1 power (SLIC amplitude) exhibits a well-resolved dispersion, which is induced by the spin-spin couplings in the eight-proton spin system of propane. We also measured the exponential decay time constants (TLLSS or TS) of these pseudo-singlet long-lived spin states (LLSS) by varying the time between hyperpolarized propane production and SLIC detection. We have found that, on average, TS is approximately 3 times longer than the corresponding T1 value under the same conditions in the range of pressures studied (up to 7.6atm). Moreover, TS may exceed 13s at pressures above 7atm in the gas phase. These results are in agreement with the previous reports, and they corroborate a great potential of long-lived hyperpolarized propane as an inhalable gaseous contrast agent for lung imaging and as a molecular tracer to study porous media using low-field NMR and MRI.

Toward production of pure 13C hyperpolarized metabolites using heterogeneous parahydrogen-induced polarization of ethyl[1-13C]acetate

Here, we report the production of 13C-hyperpolarized ethyl acetate via heterogeneously catalyzed pairwise addition of parahydrogen to vinyl acetate over TiO2-supported rhodium nanoparticles, followed by magnetic field cycling. Importantly, the hyperpolarization is demonstrated even at the natural abundance of 13C isotope (ca. 1.1%) along with the easiest separation of the catalyst from the hyperpolarized liquid.