Role of electron spin dynamics and coupling network in designing dynamic nuclear polarization.

Dynamic nuclear polarization (DNP) has emerged as a powerful sensitivity booster of nuclear magnetic resonance (NMR) spectroscopy for the characterization of biological solids, catalysts and other functional materials, but is yet to reach its full potential. DNP transfers the high polarization of electron spins to nuclear spins using microwave irradiation as a perturbation. A major focus in DNP research is to improve its efficiency at conditions germane to solid-state NMR, at high magnetic fields and fast magic-angle spinning. In this review, we highlight three key strategies towards designing DNP experiments: time-domain "smart" microwave manipulation to optimize and/or modulate electron spin polarization, EPR detection under operational DNP conditions to decipher the underlying electron spin dynamics, and quantum mechanical simulations of coupled electron spins to gain microscopic insights into the DNP mechanism. These strategies are aimed at understanding and modeling the properties of the electron spin dynamics and coupling network. The outcome of these strategies is expected to be key to developing next-generation polarizing agents and DNP methods.

Cross-Effect Dynamic Nuclear Polarization Explained: Polarization, Depolarization, and Oversaturation.

The scope of this Perspective is to analytically describe NMR hyperpolarization by the three-spin cross effect (CE) dynamic nuclear polarization (DNP) using an effective Hamiltonian concept. We apply, for the first time, the bimodal operator-based Floquet theory in the Zeeman-interaction frame for two and three coupled spins to derive the known interaction Hamiltonian for CE-DNP. With a unified understanding of CE-DNP, and supported by empirical observation of the state of electron spin polarization under the given experimental conditions, we explain diverse manifestations of CE from oversaturation, enhanced hyperpolarization by broad-band saturation, to nuclear spin depolarization under magic-angle spinning.

Design and experimental investigations on six-stroke SI engine using acetylene with water injection.

In the present study, a four-stroke cycle gasoline engine is redesigned and converted into a six-stroke cycle engine and experimental study has been conducted using gasoline and acetylene as fuel with water injection at the end of the recompression stroke. Acetylene has been used as an alternative fuel along with gasoline and performance of the six-stroke spark ignition (SI) engine with these two fuels has been studied separately and compared. Brake power and thermal efficiency are found to be 5.18 and 1.55% higher with acetylene as compared to gasoline in the six-stroke engine. However, thermal efficiency is found to be 45% higher with acetylene in the six-stroke engine as compared to four-stroke SI engine. The CO and HC emissions were found to be reduced by 13.33 and 0.67% respectively with acetylene as compared to gasoline due to better combustion of acetylene. The NOx emission was reduced by 5.65% with acetylene due to lower peak temperature by water injection. The experimental results showed better engine performance and emissions with acetylene as fuel in the six-stroke engine.

Efficient polarization transfer between spin-1/2 and ¹4N nuclei in solid-state MAS NMR spectroscopy.

Polarization transfer between spin-1/2 nuclei and quadrupolar spin-1 nuclei such as (14)N in solid-state NMR is severely challenged by the typical presence of large quadrupole coupling interactions. This has effectively prevented the use of the abundant (14)N spin as a probe to structural information and its use as an element in multi-dimensional solid-state NMR correlation experiments for assignment and structural characterization. In turn, this has been a contributing factor to the extensive use of isotope labeling in biological solid-state NMR, where (14)N is replaced with (15)N. The alternative strategy of using the abundant (14)N spins calls for methods enabling efficient polarization transfer between (14)N and its binding partners. This work demonstrates that the recently introduced (RESPIRATION)CP transfer method can be optimized to achieve efficient (1)H ↔(14)N polarization transfer under magic angle spinning conditions. The method is demonstrated numerically and experimentally on powder samples of NH4NO3 and L-alanine.