Adiabatic Passage through Level Anticrossings in Systems of Chemically Inequivalent Protons Incorporating...

Level anticrossings (LACs) are ubiquitous in quantum systems and have been exploited for spin-order transfer in hyperpolarized nuclear magnetic resonance spectroscopy. This paper examines the manifestations of adiabatic passage through a specific type of LAC found in homonuclear systems of chemically inequivalent coupled protons incorporating parahydrogen (pH₂). Adiabatic passage through such a LAC is shown to elicit translation of the pH₂ spin order. As an example, with prospective applications in biomedicine, proton spin polarizations of at least 19.8 ± 2.6% on the methylene protons and 68.7 ± 0.5% on the vinylic protons of selectively deuterated allyl pyruvate ester are demonstrated experimentally. After ultrasonic spray injection of a precursor solution containing propargyl pyruvate and a dissolved Rh catalyst into a chamber pressurized with 99% para-enriched H₂, the products are collected and transported to a high magnetic field for NMR detection. The LAC-mediated hyperpolarization of the methylene protons is significant because of the stronger spin coupling to the pyruvate carbonyl ¹³C, setting up an ideal initial condition for subsequent coherence transfer by selective INEPT. Furthermore, the selective deuteration of the propargyl side arm increases the efficiency and polarization level. LAC-mediated translation of parahydrogen spin order completes the first step toward a new and highly efficient route for the ¹³C NMR signal enhancement of pyruvate via side-arm hydrogenation with parahydrogen.