The solid effect of dynamic nuclear polarization in liquids - accounting for g-tensor anisotropy at high magnetic fields.

In spite of its name, the solid effect of dynamic nuclear polarization (DNP) is also operative in viscous liquids, where the dipolar interaction between the polarized nuclear spins and the polarizing electrons is not completely averaged out by molecular diffusion on the timescale of the electronic spin-spin relaxation time. Under such slow-motional conditions, it is likely that the tumbling of the polarizing agent is similarly too slow to efficiently average the anisotropies of its magnetic tensors on the timescale of the electronic T2. Here we extend our previous analysis of the solid effect in liquids to account for the effect of g-tensor anisotropy at high magnetic fields. Building directly on the mathematical treatment of slow tumbling in electron spin resonance , we calculate solid-effect DNP enhancements in the presence of both translational diffusion of the liquid molecules and rotational diffusion of the polarizing agent. To illustrate the formalism, we analyze high-field (9.4 T) DNP enhancement profiles from nitroxide-labeled lipids in fluid lipid bilayers. By properly accounting for power broadening and motional broadening, we successfully decompose the measured DNP enhancements into their separate contributions from the solid and Overhauser effects.

13C Hyperpolarization of Viscous Liquids by Transfer of Solid-Effect 1H Dynamic Nuclear Polarization at High Magnetic Field.

Dynamic nuclear polarization (DNP) is routinely used as a method for increasing the sensitivity to nuclear magnetic resonance (NMR). Recently, high-field solid-effect DNP in viscous liquids on 1H nuclei was demonstrated using narrow-line polarizing agents. Here we expand the applicability of DNP in viscous media to 13C nuclei. To hyperpolarize 13C nuclei, we combined solid-effect 1H DNP with a subsequent transfer of the 1H polarization to 13C via insensitive nuclei enhanced by polarization transfer (INEPT). We demonstrate this approach using a triarylmethyl radical as a polarizing agent and glycerol-13C3 as an analyte. We achieved 13C enhancement factors of up to 45 at a magnetic field of 9.4 T and room temperature.

Rhodium(III)-catalyzed oxidative cross-coupling of benzoxazinones with styrenes via C-H activation.

Vinylarenes represent an important class of core skeleton embedded in natural products, organic materials, and pharmaceutical molecules. Therefore, numerous efforts have been devoted to developing efficient methods for their preparation. Among them, transition-metal-catalyzed oxidative coupling of arenes and alkenes has proved to be a powerful method due to its high atom and step economy. Although a wide range of oxidative alkenylations of arenes have been developed, the alkenes employed in most cases are still limited to electron-deficient alkenes. Reported herein is a Rh(III)-catalyzed C-H cross-coupling of benzoxazinones and simple unactivated styrenes to furnish a variety of vinylarene scaffolds. This established protocol is characterized by wide functional group compatibility, high yields, and excellent regio- and chemo-selectivity. Mechanistic studies and gram-scale experiments on this high-value conversion are disclosed. Moreover, the potential utility of this method was highlighted by a series of further transformations.

A triple resonance (e, 1H, 13C) probehead for liquid-state DNP experiments at 9.4 Tesla.

In DNP experiments, NMR signal intensity is increased by transferring the much larger electron spin polarization to nuclear spins via microwave irradiation. Here we describe the design and performance of a probehead that makes it possible to perform Overhauser DNP experiments at 1H and 13C in liquid samples with a volume of up to 100 nl. We demonstrate on a 13C-labeled sodium pyruvate sample in water that proton decoupling under DNP conditions is possible with this new triple-resonance DNP probehead. In addition, the heat dissipation from the sample has been greatly improved with our new probe design. This makes it possible to keep liquid samples at a constant temperature under irradiation with a high-frequency 263 GHz microwave gyrotron with a few watts of output power. This improved performance opens up the possibility to disentangle the role of sample temperature and applied microwave power for DNP efficiency in liquids and to obtain a quantitative determination of EPR saturation by observing the suppression of paramagnetic shift as a function of microwave power.

Solid-like Dynamic Nuclear Polarization Observed in the Fluid Phase of Lipid Bilayers at 9.4 T.

Dynamic nuclear polarization (DNP) is a powerful method to enhance NMR sensitivity. Much progress has been achieved recently to optimize DNP performance at high magnetic fields in solid-state samples, mostly by utilizing the solid or the cross effect. In liquids, only the Overhauser mechanism is active, which exhibits a DNP field profile matching the EPR line shape of the radical, distinguishable from other DNP mechanisms. Here, we observe DNP enhancements with a field profile indicative of the solid effect and thermal mixing at ∼320 K and a magnetic field of 9.4 T in the fluid phase of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) lipid bilayers doped with the radical BDPA (1,3-bis(diphenylene)-2-phenylallyl). This interesting observation might open up new perspectives for DNP applications in macromolecular systems at ambient temperatures.

Room-temperature dynamic nuclear polarization enhanced NMR spectroscopy of small biological molecules in water.

Nuclear magnetic resonance (NMR) spectroscopy is a powerful and popular technique for probing the molecular structures, dynamics and chemical properties. However the conventional NMR spectroscopy is bottlenecked by its low sensitivity. Dynamic nuclear polarization (DNP) boosts NMR sensitivity by orders of magnitude and resolves this limitation. In liquid-state this revolutionizing technique has been restricted to a few specific non-biological model molecules in organic solvents. Here we show that the carbon polarization in small biological molecules, including carbohydrates and amino acids, can be enhanced sizably by in situ Overhauser DNP (ODNP) in water at room temperature and at high magnetic field. An observed connection between ODNP 13C enhancement factor and paramagnetic 13C NMR shift has led to the exploration of biologically relevant heterocyclic compound indole. The QM/MM MD simulation underscores the dynamics of intermolecular hydrogen bonds as the driving force for the scalar ODNP in a long-living radical-substrate complex. Our work reconciles results obtained by DNP spectroscopy, paramagnetic NMR and computational chemistry and provides new mechanistic insights into the high-field scalar ODNP.