We are grateful to Matthew Conley and Christophe Coperet from ETH Zurich for providing the mesoporous silica materials. We are grateful to Prof. P. Tordo, Dr. O. Ouari, and Dr. G. Casano (Aix-Marseille Universite, France) for providing the biradicals used in the DNP NMR experiments.International audienceWe show how dynamic nuclear polarization (DNP) NMR can be used in combination with models for polarization dynamics to determine the domain sizes in complex materials. By selectively doping a source component with radicals and leaving the target undoped, we Can measure experimental polarization buildup curves which can be compared with simulations based on heterogeneous distributions of polarization-within the sample. The variation of the integrated DNP enhancement as a function of the polarization time is found to be characteristic of the geometry. We demonstrate the method experimentally on four different systems where we successfully determine domain sizes between 200 and 20 000 nm, specifically in powdered histidine hydrochloride monohydrate) pore lengths of mesoporous silica materials, and two domain sizes in two component polymer film coatings. Additionally, we find that even in the apparently homogeneous frozen solutions used as polarization sources in most DNP experiments, polarization is relayed from protons near the radicals to the bulk of the solution by spin diffusion, which explains the experimentally observed buildup times in these samples

Dynamic Nuclear Polarization (DNP) solid-state NMR has developed into an invaluable tool for the investigation of a wide range of materials. However, the sensitivity gain achieved with many polarizing agents suffers from an unfavorable field and Magic Angle Spinning (MAS) frequency dependence. We present a series of new hybrid biradicals, soluble in organic solvents, that consist of an isotropic narrow EPR line radical, BDPA, tethered to a broad line nitroxide. By tuning the distance between the two electrons and the substituents at the nitroxide moiety, correlations between the electron-electron interactions and the electronic spin relaxation times on one hand, and the DNP enhancement factors on the other hand are established. The best radical in this series has a short methylene linker and bears bulky phenyl spirocyclohexyl ligands. In a 1.3 mm prototype DNP probe, it yields enhancements of up to 185 at 18.8 T (800 MHz 1H resonance frequency) and 40 kHz MAS. We show that this radical gives enhancement factors of over 60 in 3.2 mm sapphire rotors at both 18.8 and 21.1 T (900 MHz 1H resonance frequency), the highest magnetic field available today for DNP. The effect of the rotor size and of the microwave irradiation inside the MAS rotor is discussed. Finally, we demonstrate the potential of this new series of polarizing agents by recording high field 27Al and 29Si DNP Surface Enhanced NMR spectra (DNP SENS) of amorphous aluminosilicates and 17O NMR on silica nanoparticles.

Here, we show how dynamic nuclear polarization (DNP) NMR spectroscopy experiments permit the atomic level structural characterization of loaded and empty lipid nanoparticles (LNPs). The LNPs used here were synthesized by the microfluidic mixing technique and are composed of ionizable cationic lipid (DLin-MC3-DMA), a phospholipid (distearoylphosphatidylcholine, DSPC), cholesterol, and poly(ethylene glycol) (PEG) (dimyristoyl phosphatidyl ethanolamine (DMPE)-PEG 2000), as well as encapsulated cargoes that are either phosphorothioated siRNA (50 or 100%) or mRNA. We show that LNPs form physically stable complexes with bioactive drug siRNA for a period of 94 days. Relayed DNP experiments are performed to study H-H spin diffusion and to determine the spatial location of the various components of the LNP by studying the average enhancement factors as a function of polarization time. We observe a striking feature of LNPs in the presence and in the absence of encapsulating siRNA or mRNA by comparing our experimental results to numerical spin-diffusion modeling. We observe that LNPs form a layered structure, and we detect that DSPC and DMPE-PEG 2000 lipids form a surface rich layer in the presence (or absence) of the cargoes and that the cholesterol and ionizable cationic lipid are embedded in the core. Furthermore, relayed DNP P solid-state NMR experiments allow the location of the cargo encapsulated in the LNPs to be determined. On the basis of the results, we propose a new structural model for the LNPs that features a homogeneous core with a tendency for layering of DSPC and DMPE-PEG at the surface.

NMR is a method of choice to determine structural and electronic features in inorganic materials, and has been widely used in the past, but its application is severely limited by its low relative sensitivity. We show how the bulk of proton-free inorganic solids can be hyperpolarized with a general strategy using impregnation dynamic nuclear polarization through homonuclear spin diffusion between low-γ nuclei. This is achieved either through direct hyperpolarization or with a pulse cooling cross-polarization method, transferring hyperpolarization from protons to heteronuclei at particle surfaces. We demonstrate a factor of 50 gain in overall sensitivity for the Sn spectrum of powdered SnO, corresponding to an acceleration of a factor >2500 in acquisition times. The method is also shown for P spectra of GaP,Cd spectra of CdTe, and Si spectra of α-quartz.

Dynamic nuclear polarization (DNP) has recently emerged as a tool to enhance the sensitivity of solid-state NMR experiments. However, so far high enhancements (>100) are limited to relatively low magnetic fields, and DNP at fields higher than 9.4 T significantly drops in efficiency. Here we report solid-state Overhauser effect DNP enhancements of over 100 at 18.8 T. This is achieved through the unexpected discovery that enhancements increase rapidly with increasing magic angle spinning (MAS) rates. The measurements are made using 1,3-bisdiphenylene-2-phenylallyl dissolved in o-terphenyl at 40 kHz MAS. We introduce a source–sink diffusion model for polarization transfer which is capable of explaining the experimental observations. The advantage of this approach is demonstrated on mesoporous alumina with the acquisition of well-resolved DNP surface-enhanced 27Al cross-polarization spectra.