Pulsed Electron-Nuclear Double Resonance in the Fourier Regime.

Nuclear magnetic resonance (NMR) spectroscopy provides atomic-level molecular structural information. However, in molecules containing unpaired electron spins, NMR signals are difficult to measure directly. In such cases, data is obtained using the electron-nuclear double resonance (ENDOR) method, where nuclei are detected through their interaction with nearby unpaired electron spins. Unfortunately, electron spins spread the ENDOR signals, which challenges current acquisition techniques, often resulting in low spectral resolution that provides limited structural details. Here, we show that by using miniature microwave resonators to detect a small number of electron spins, integrated with miniature NMR coils, one can excite and detect a wide bandwidth of ENDOR data in a single pulse. This facilitates the measurement of ENDOR spectra with narrow lines spread over a large frequency range at much better spectral resolution than conventional approaches, which helps reveal details of the paramagnetic molecules' chemical structure that were not accessible before.

Not only manganese, but fruit component effects dictate the efficiency of fruit juice as an oral magnetic resonance imaging contrast agent.

Several fruit juices are used as oral contrast agents to improve the quality of images in magnetic resonance cholangiopancreatography. They are often preferred to conventional synthetic contrast agents because of their very low cost, natural origin, intrinsic safety, and comparable image qualities. Pineapple and blueberry juices are the most employed in clinical practice due to their higher content of manganese(II) ions. The interest of pharmaceutical companies in these products is testified by the appearance in the market of fruit juice derivatives with improved contrast efficacy. Here, we investigate the origin of the contrast of blueberry juice, analyze the parameters that can effect it, and elucidate the differences with pineapple juice and manganese(II) solutions. It appears that, although manganese(II) is the paramagnetic ion responsible for the contrast, it is the interaction of manganese(II) with other juice components that modulates the efficiency of the juice as a magnetic resonance contrast agent. On these grounds, we conclude that blueberry juice concentrated to the same manganese concentration of pineapple juice would prove a more efficient contrast agent than pineapple juice.

Quantum-State Control and Manipulation of Paramagnetic Molecules with Magnetic Fields.

Since external magnetic fields were first employed to deflect paramagnetic atoms in 1921, a range of magnetic field-based methods have been introduced to state-selectively manipulate paramagnetic species. These methods include magnetic guides, which selectively filter paramagnetic species from all other components of a beam, and magnetic traps, where paramagnetic species can be spatially confined for extended periods of time. However, many of these techniques were developed for atomic-rather than molecular-paramagnetic species. It has proven challenging to apply some of these experimental methods developed for atoms to paramagnetic molecules. Thanks to the emergence of new experimental approaches and new combinations of existing techniques, the past decade has seen significant progress toward the manipulation and control of paramagnetic molecules. This review identifies the key methods that have been implemented for the state-selective manipulation of paramagnetic molecules-discussing the motivation, state of the art, and future prospects of the field. Key applications include the ability to control chemical interactions, undertake precise spectroscopic measurements, and challenge our understanding of chemical reactivity at a fundamental level.

Basic facts and perspectives of Overhauser DNP NMR.

After the first surprisingly large (1)H DNP enhancements of the water signal in aqueous solutions of nitroxide radicals observed at high magnetic fields, Overhauser DNP is gaining increasing attention for a number of applications now flourishing, showing the potentialities of this mechanism in solution and solid state NMR as well as in MRI. Unexpected Overhauser DNP enhancements in insulating solids were recently measured at 100K, with a magnitude which increases with the applied magnetic field. We recapitulate here the theoretical premises of Overhauser DNP in solution and analyze the effects of the various parameters on the efficacy of the mechanism, underlining the link between the DNP enhancements and the field dependent relaxation properties. Promisingly, more effective DNP enhancements are expected by exploiting the potentialities offered by (13)C detection and the use of supercritical fluids.

Spin-state-selective methods in solution- and solid-state biomolecular 13C NMR.

Spin-state-selective methods to achieve homonuclear decoupling in the direct acquisition dimension of (13)C detected NMR experiments have been one of the key contributors to converting (13)C detected NMR experiments into really useful tools for studying biomolecules. We discuss here in detail the various methods that have been proposed, summarize the large array of new experiments that have been developed and present applications to different kinds of proteins in different aggregation states.