ABSTRACT
Real-time imaging of free-radical formation is important in physical chemistry, biochemistry, and radiobiology, especially for the study of radiation dose-rate effects. Herein, we show for the first time that the formation of free radicals during the time course of a chemical reaction can be imaged through NMR relaxation measurements of water protons in the Earth's magnetic field, in an open-coil spectrometer. The relaxation rate constants of water magnetisation are enhanced as reactions leading to the formation of hydroxyl radicals and oxygen proceed on the timescale of tens of minutes. The reaction rate of iodide-catalysed H2O2 decay was followed by Earth-field 1H NMR relaxation in real time. The relaxivities of the reaction product and several other paramagnetic compounds were determined. Spin-trap molecules were then used to capture ËOH radical species, thus altering the reaction rate in proportion to the formation of new paramagnetic compounds. Thereby, a new experimental method for magnetic resonance imaging of the formation of intermediate and stable radical species in water is proposed.
ABSTRACT
Imaging the molecular kinetics of antioxidants by magnetic resonance can contribute to the mechanistic understanding of therapeutic approaches. Magnetic resonance detection of the response to flashes of oxidative stress requires sequential spectroscopy on the same time scale on which reactive oxygen species are generated. To this effect, we propose a single-polarization multiple-detection stroboscopic experiment. We demonstrate this experiment for the follow-up of glutathione oxidation kinetics. On-the-fly stroboscopic detection minimizes the durations necessary for single acquisitions yet necessitates sustaining of magnetization lifetimes. Long-lived proton spin states (LLS) in the cysteine and glycine residues of glutathione with TLLS up to 16 s are reached. Based on 1H LLS, we followed fast oxidation kinetics in the glutathione redox pair GSH/GSSG. This new detection method allows sampling of long-lived spin order multiple times via small flip-angle excitations. This establishes the ground for the follow-up of redox processes detecting GSH/GSSG kinetics as magnetic-resonance biomarker of FLASH oxidative processes on time scales of tens of seconds.
ABSTRACT
A lightweight Halbach magnet system for use in nuclear magnetic resonance (NMR) studies on drill cores was designed and built. It features an improved homogeneous magnetic field with a strength of 0.22 T and a maximum accessible sensitive volume. Additionally, it is furnished with a sliding table for automatic scans of cylindrical samples. This device is optimized for nondestructive online measurements of porosity and pore size distributions of water-saturated full cylindrical and split semicylindrical drill cores of different diameters. The porosity of core plugs with diameters from 20 to 80 mm can be measured routinely using exchangeable radiofrequency coils. Advanced NMR techniques that provide 2D T(1)-T(2) correlations with an average measurement time of 30 min and permeability estimates can be performed with a special insert suitable for small core plugs with diameter and length of 20 mm.
