Oliver Neudert

A comparative study of 1H and 19F Overhauser DNP in fluorinated benzenes

Hyperpolarization techniques, such as Overhauser dynamic nuclear polarization (DNP), can provide a dramatic increase in the signal obtained from nuclear magnetic resonance experiments and may therefore enable new applications where sensitivity is a limiting factor. In this contribution, studies of the (1)H and (19)F Overhauser dynamic nuclear polarization enhancements at 345 mT are presented for three different aromatic solvents with the TEMPO radical for a range of radical concentrations. Furthermore, nuclear magnetic relaxation dispersion measurements of the same solutions are analyzed, showing contributions from dipolar and scalar coupling modulated by translational diffusion and different coupling efficiency for different solvents and nuclei. Measurements of the electron paramagnetic resonance linewidth are included to support the analysis of the DNP saturation factor for varying radical concentration. The results of our study give an insight into the characteristics of nitroxide radicals as polarizing agents for (19)F Overhauser DNP of aromatic fluorinated solvents. Furthermore, we compare our results with the findings of the extensive research on Overhauser DNP that was conducted in the past for a large variety of other radicals.

Design and Control of Nanoconfinement to Achieve Magnetic Resonance Contrast Agents with High Relaxivity.

The enhanced relaxation of hydrogen atoms of surrounding water from suitable contrast agent promotes magnetic resonance imaging as one of the most important medical diagnosis technique. The key challenge for the preparation of performant contrast agents for magnetic resonance imaging with high relaxivity is to ensure a high local concentration of contrast agent while allowing a contact between water and the contrast agent. Both requirements are answered by tailoring a semipermeable confinement for a gadolinium complex used as contrast agent. A locally high concentration is achieved by successfully encapsulating the complex in polymer nanocontainers that serves to protect and retain the complex inside a limited space. The access of water to the complex is achieved by carefully controlling the chemistry of the shell and the core of the nanocontainers. The confinement of the nanocontainers enables an increased relaxivity compared to an aqueous solution of the contrast agent. The nanocontainers are successfully applied in vivo to yield enhanced contrast in magnetic resonance imaging.

An Alderman-Grant resonator for S-Band Dynamic Nuclear Polarization

An Alderman-Grant resonator with resonance at 2GHz (S-Band) was simulated, developed and constructed for Dynamic Nuclear Polarization (DNP) experiments at 73mT. The resonator fits into magnet bores with a minimum diameter of 20mm and is compatible with standard 3mm NMR tubes. The compact resonator design achieves good separation of electric and magnetic fields and therefore can be used with comparatively large sample volumes with only small sample heating effects comparable to those obtained with optimized X- and W-Band DNP setups. The saturation efficiency and sample heating effects were investigated for Overhauser DNP experiments of aqueous solutions of TEMPOL radical, showing relative saturation better than 0.9 and sample heating not exceeding a few Kelvin even at high microwave power and long irradiation time. An application is demonstrated, combining the DNP setup with a commercial fast field cycling NMR relaxometer. Using this resonator design at low microwave frequencies can provide DNP polarization for a class of low-field and time-domain NMR experiments and therefore may enable new applications that benefit from increased sensitivity.

X‐Band DNP Hyperpolarization of Viscous Liquids and Polymer Melts

NMR studies of synthetic polymers and biomacromolecules, which provide insight into the conformation and dynamics of these materials, can benefit strongly from the increased sensitivity offered by dynamic nuclear polarization (DNP) and other hyperpolarizing methods. In this study (1) H DNP nuclear spin hyperpolarization of two polybutadiene samples, representing a supercooled liquid and an entangled polymer melt, is demonstrated at 0.35 T magnetic field strength and at temperatures between -80 and +50 °C. Electron spin polarization transfer from the α,γ-bisdiphenylene-β-phenylallyl radical to the sample nuclei is achieved by the Overhauser and solid effect. DNP signal enhancements are studied, varying the electron spin resonance offset, microwave power, and sample temperature. The influence of spin relaxation times, line widths, and molecular dynamics are discussed. The results show promising, up to 15-fold NMR signal enhancements using noncryogenic temperatures and an inexpensive setup that is less technically demanding than current high-field DNP setups.

A compact X-Band resonator for DNP-enhanced Fast-Field-Cycling NMR

A new probehead was developed enabling Dynamic Nuclear Polarization (DNP)-enhanced Fast-Field-Cycling relaxometry at 340mT polarization field strength. It is based on a dielectric cavity resonator operating in the TM110 mode at 9.5GHz, which is suitable for both transverse and axial magnet geometries with a bore access of at least 20mm. The probehead includes a planar radio frequency coil for NMR detection and is compatible with standard 3mm NMR tubes. The resonator was assessed in terms of the microwave conversion factor and microwave-induced sample heating effects. Due to the compact size of the cavity, appreciable microwave magnetic field strengths were observed even with only moderate quality factors. Exemplary DNP experiments at 9.5GHz and 2.0GHz microwave frequency are compared for three different viscous samples, demonstrating the advantage of DNP at 9.5GHz for such systems. This new probehead enables new applications of DNP-enhanced Fast-Field-Cycling relaxometry of viscous and solid systems.

H-1 NMR Spectroscopy and MR Imaging with Hyperpolarised Substances

Abstract Despite their wide applicability in natural sciences, NMR and MRI still suffer from their inherently low sensitivity. This can be overcome by hyperpolarisation techniques, such as parahydrogen-induced polarisation and dynamic nuclear polarisation. Here, we focus on the generation of 1 H-hyperpolarised substances with both methods. We especially address the severe lifetime issue of the accomplished 1 H hyperpolarisation by demonstrating the production of hyperpolarised liquids in a continuous flow fashion and the storage of hyperpolarisation in slowly relaxing singlet states. Another problem of hyperpolarised proton NMR and MRI is the generation of contrast between a small amount of hyperpolarised molecules and a vast thermal background signal. In this contribution, we show the possibility to use the special signal pattern that is inherent to the hyperpolarisation method to generate excellent MRI contrast which may open up unprecedented opportunities to use the standard MRI nucleus 1 H, for example, biomedical applications in future.

Molecular dynamics-based selectivity for Fast-Field-Cycling relaxometry by Overhauser and solid effect dynamic nuclear polarization

In the last decade nuclear spin hyperpolarization methods, especially Dynamic Nuclear Polarization (DNP), have provided unprecedented possibilities for various NMR techniques by increasing the sensitivity by several orders of magnitude. Recently, in-situ DNP-enhanced Fast Field Cycling (FFC) relaxometry was shown to provide appreciable NMR signal enhancements in liquids and viscous systems. In this work, a measurement protocol for DNP-enhanced NMR studies is introduced which enables the selective detection of nuclear spin hyperpolarized by either Overhauser effect or solid effect DNP. Based on field-cycled DNP and relaxation studies it is shown that these methods allow for the independent measurement of polymer and solvent nuclear spins in a concentrated solution of high molecular weight polybutadiene in benzene doped with α,γ-bisdiphenylene-β-phenylallyl radical. Appreciable NMR signal enhancements of about 10-fold were obtained for both constituents. Moreover, qualitative information about the dynamics of the radical and solvent was obtained. Selective DNP-enhanced FFC relaxometry is applied for the measurement of the 1H nuclear magnetic relaxation dispersion of both constituents with improved precision. The introduced method is expected to greatly facilitate NMR studies of complex systems with multiple overlapping signal contributions that cannot be distinguished by standard methods.

Dynamic nuclear polarization fast field cycling method for selective study of molecular dynamics in block copolymers

Dynamic nuclear polarization (DNP) is one of the most useful methods to increase sensitivity in NMR spectroscopy. It is based on the transfer of magnetization from an electron to the nuclear spin system. Based on previous work that demonstrated the feasibility of integrating DNP with fast field cycling (FFC) relaxometry and the possibility to distinguish between different mechanisms, such as the Overhauser effect (OE) and the solid effect (SE), the first FFC study of the differential relaxation properties of a copolymer is presented. For this purpose, concentrated solutions of the polystyrene-block-polybutadiene-block-polystyrene (SBS) triblock copolymer and the corresponding homopolymers were investigated. T1 -T2 relaxation data are discussed in terms of molecular mobility and the presence of radicals. The DNP selective data indicate a dominant SE contribution to the enhancement of the NMR signal for both blocks of the triblock copolymer and for the homopolymer solutions. The enhancement factors are different for both polymer types and in the copolymer, which is explained by the individual 1 H T1 relaxation times and different electron-nucleus coupling strength. The T1 relaxation dispersion measurements of the SE enhanced signal were performed, which led to improved signal-to-noise ratios that allowed the site-specific separation of relaxation times and their dependence on the Larmor frequency with a higher accuracy.