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The dynamic nuclear polarization (DNP) efficiency is critically dependent on the properties of the radical, solvent, and solute constituting the sample system. In this study, we focused on the three spin e-e-n cross effect (CE)'s influence on the nuclear longitudinal relaxation time constant T1n, the build-up time constants of nuclear magnetic resonance (NMR) signal, TDNP and DNP-enhancement of NMR signal. The dipolar interaction strength between the electron spins driving the e-e-n process was systematically modulated using mono-, di-, tri-, and dendritic-nitroxide radicals, while maintaining a constant global electron spin concentration of 10 mM. Experimental results showed that an increase in electron spin clustering led to an increased electron spin depolarization, as mapped by electron double resonance (ELDOR), and a dramatically shortened T1n and TDNP time constants under static and magic angle spinning (MAS) conditions. A theoretical analysis reveals that strong e-e interactions, caused by electron spin clustering, increase the CE rate. The three spin e-e-n CE is a hitherto little recognized mechanism for shortening T1n and TDNP in solid-state NMR experiments at cryogenic temperatures, and offers a design principle to enhance the effective CE DNP enhancement per unit time. Fast CE rates will benefit DNP at liquid helium temperatures, or at higher magnetic fields and pulsed DNP, where slow e-e-n polarization transfer rate is a key bottleneck to achieving maximal DNP performance.

The discovery of a truncated cross-effect (CE) in dynamic nuclear polarization (DNP) NMR that has the features of an Overhauser-effect DNP (OE-DNP) is reported here. The apparent OE-DNP, where minimal μw power achieved optimum enhancement, was observed when doping Trityl-OX063 with a pyrroline nitroxide radical that possesses electron-withdrawing tetracarboxylate substituents (tetracarboxylate-ester-pyrroline or TCP) in vitrified water/glycerol at 6.9 T and at 3.3 to 85 K, in apparent contradiction to expectations. While the observations are fully consistent with OE-DNP, we discover that a truncated cross-effect ( tCE) is the underlying mechanism, owing to TCPs shortened T1e. We take this observation as a guideline and demonstrate that a crossover from CE to tCE can be replicated by simulating the CE of a narrow-line (Trityl-OX063) and a broad-line (TCP) radical pair, with a significantly shortened T1e of the broad-line radical.

Solid-state dynamic nuclear polarization (DNP) at higher magnetic fields (>3T) and cryogenic temperatures (∼ 2-90K) has gained enormous interest and seen major technological advances as an NMR signal enhancing technique. Still, the current state of the art DNP operation is not at a state at which sample and freezing conditions can be rationally chosen and the DNP performance predicted a priori, but relies on purely empirical approaches. An important step towards rational optimization of DNP conditions is to have access to DNP instrumental capabilities to diagnose DNP performance and elucidate DNP mechanisms. The desired diagnoses include the measurement of the "DNP power curve", i.e. the microwave (MW) power dependence of DNP enhancement, the "DNP spectrum", i.e. the MW frequency dependence of DNP enhancement, the electron paramagnetic resonance (EPR) spectrum, and the saturation and spectral diffusion properties of the EPR spectrum upon prolonged MW irradiation typical of continuous wave (CW) DNP, as well as various electron and nuclear spin relaxation parameters. Even basic measurements of these DNP parameters require versatile instrumentation at high magnetic fields not commercially available to date. In this article, we describe the detailed design of such a DNP instrument, powered by a solid-state MW source that is tunable between 193 and 201 GHz and outputs up to 140 mW of MW power. The quality and pathway of the transmitted and reflected MWs is controlled by a quasi-optics (QO) bridge and a corrugated waveguide, where the latter couples the MW from an open-space QO bridge to the sample located inside the superconducting magnet and vice versa. Crucially, the versatility of the solid-state MW source enables the automated acquisition of frequency swept DNP spectra, DNP power curves, the diagnosis of MW power and transmission, and frequency swept continuous wave (CW) and pulsed EPR experiments. The flexibility of the DNP instrument centered around the QO MW bridge will provide an efficient means to collect DNP data that is crucial for understanding the relationship between experimental and sample conditions, and the DNP performance. The modularity of this instrumental platform is suitable for future upgrades and extensions to include new experimental capabilities to meet contemporary DNP needs, including the simultaneous operation of two or more MW sources, time domain DNP, electron double resonance measurements, pulsed EPR operation, or simply the implementation of higher power MW amplifiers.

The magneto-optical and dielectric behavior of M-type hexaferrites as permanent magnets in the THz band is essential for potential applications like microwave absorbers and antennas, while are rarely reported in recent years. In this work, single-phase SrFe 12- x Nb x O 19 hexaferrite ceramics were prepared by the conventional solid-state sintering method. Temperature dependence of dielectric parameters was investigated here to determine the relationship between dielectric response and magnetic phase transition. The saturated magnetization increases by nearly 12%, while the coercive field decreases by 30% in the x = 0.03 composition compared to that of the x = 0.00 sample. Besides, the Nb substitution improves the magneto-optical behavior in the THz band by comparing the Faraday rotation parameter from 0.75 ( x = 0.00) to 1.30 ( x = 0.03). The changes in the magnetic properties are explained by a composition-driven increase of the net magnetic moment and enhanced ferromagnetic exchange coupling. The substitution of the donor dopant Nb on the Fe site is a feasible way to obtain multifunctional M-type hexaferrites as preferred candidates for permanent magnets, sensors, and other electronic devices.