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.

动态核极化 (DNP) 已成为核磁共振 (NMR) 光谱的强大灵敏度助推器，用于表征生物固体、催化剂和其他功能材料，但尚未充分发挥其潜力。DNP 使用微波辐射作为扰动将电子自旋的高极化转移到核自旋。DNP 研究的一个主要重点是提高其在与固态 NMR 密切相关的条件下、在高磁场和快速魔角旋转下的效率。在这篇综述中，我们强调了设计 DNP 实验的三个关键策略：时域“智能”微波操作以优化和/或调节电子自旋极化，在 DNP 操作条件下进行 EPR 检测以破译潜在的电子自旋动力学，和耦合电子自旋的量子力学模拟，以获得对 DNP 机制的微观见解。这些策略旨在理解和模拟电子自旋动力学和耦合网络的特性。这些策略的结果有望成为开发下一代极化剂和 DNP 方法的关键。