Applied Magnetic Resonance

The role of membrane cholesterol in cellular function and dysfunction has been the subject of much inquiry. A few studies have suggested that cholesterol may slow oxygen diffusive transport, altering membrane physical properties and reducing oxygen permeability. The primary experimental technique used in recent years to study membrane oxygen transport is saturation-recovery electron paramagnetic resonance (EPR) oximetry, using spin-label probes targeted to specific regions of a lipid bilayer. The technique has been used, in particular, to assess the influence of cholesterol on oxygen transport and membrane permeability...

This review is motivated by the exciting new area of radiation therapy using a phenomenon termed FLASH in which oxygen is thought to have a central role. Well-established principles of radiation biology and physics suggest that if oxygen has a strong role, it should be the level at the DNA. The key aspect discussed is the rate of oxygen diffusion. If oxygen freely diffuses into cells and rapidly equilibrates, then measurements in the extracellular compartment would enable FLASH to be investigated using existing methodologies that can readily measure oxygen in the extracellular compartment...

EPR can uniquely measure paramagnetic species. Although commercial EPR was introduced in 1950s, the early studies were mostly restricted to chemicals in solution or cellular experiments using X-band EPR equipment. Due to its limited penetration (<1 mm), experiments with living animals were almost impossible. To overcome these difficulties, Swartz group, along with several other leaders in field, pioneered the technology of low frequency EPR (e.g., L-band, 1-2 GHz). The development of low frequency EPR and the associated probes have dramatically expanded the application of EPR technology into the biomedical research field, providing answers to important scientific questions by measuring specific parameters that are impossible or very difficult to obtain by other approaches...

Objectives: (1) Summarize revisions made to the implantable resonator (IR) design and results of testing to characterize biocompatibility;(2) Demonstrate safety of implantation and feasibility of deep tissue oxygenation measurement using electron paramagnetic resonance (EPR) oximetry. Study Design: In vitro testing of the revised IR and in vivo implantation in rabbit brain and leg tissues. Methods: Revised IRs were fabricated with 1-4 OxyChips with a thin wire encapsulated with two biocompatible coatings...

In this work, we investigated the redox transients of a number of water-soluble spin labels upon their interactions with Photosystem II (PS II) core complexes isolated from spinach leaves. We have found that the reactivity of nitroxide radicals, determined by the rate of their reduction upon illumination of PS II, depends on the chemical structure of radicals and the capability of their coming close to low-potential redox centers of photoactive PS II complexes. An enhanced capability of nitroxide radicals to accept electrons from PS II correlates with their chemical structure...

Proton Hyperfine Sublevel Correlation (1 H-HYSCORE) experiments have been used to probe the ligation structure of the Fe(II) active site of taurine:2-oxoglutarate dioxygenase (TauD), a non-heme Fe(II) hydroxylase. To facilitate Electron Paramagnetic Resonance (EPR) experiments, Fe(II) derivatives of the enzyme were studied using nitric oxide as a substitute for molecular oxygen. The addition of NO to the enzyme yields an S = 3/2 {FeNO}7 paramagnetic center characterized by nearly axial EPR spectra with g⊥ = 4 and g|| = 2...

No abstract text is available yet for this article.

No abstract text is available yet for this article.

Photo-CIDNP (photo-chemically induced dynamic nuclear polarization) refers to nuclear polarization created by the spin-chemical evolution of spin-correlated radical pairs (SCRPs). This phenomenon occurs in gases, liquids and solids. Based on the solid-state photo-CIDNP effect observed under magic-angle spinning (MAS), photo-CIDNP MAS NMR has been developed as analytical method. Here we report the origin, the theory and the state of the art of this method.

Carotenoids are indispensable molecules for life. They are present everywhere in plants, algae, bacteria whom they protect against free radicals and oxidative stress. Through the consumption of fruits and vegetables and some carotenoid-containing fish, they are introduced into the human body and, similarly, protect it. There are numerous health benefits associated with the consumption of carotenoids. Carotenoids are antioxidants but at the same time they are prone to oxidation themselves. Electron loss from the carotenoid forms a radical cation...

This review is inspired by the contributions from the University of Denver group to low-field EPR, in honor of Professor Gareth Eaton's 80th birthday. The goal is to capture the spirit of innovation behind the body of work, especially as it pertains to development of new EPR techniques. The spirit of the DU EPR laboratory is one that never sought to limit what an EPR experiment could be, or how it could be applied. The most well-known example of this is the development and recent commercialization of rapid-scan EPR...

Structural investigations of proteins and their biological complexes are now frequently complemented by distance constraints between spin labeled cysteines generated using double electron-electron resonance (DEER) spectroscopy, via site directed spin labeling (SDSL). Methanethiosulfonate spin label (MTSSL), has become ubiquitous in the SDSL of proteins, however, has limitations owing to its high number of rotamers, and reducibility. In this article we introduce the use of bromoacrylaldehyde spin label (BASL) as a cysteine spin label, demonstrating an advantage over MTSSL due to its increased selectivity for surface cysteines, eliminating the need to 'knock out' superfluous cysteine residues...

In the study of biological structures, pulse dipolar spectroscopy (PDS) is used to elucidate spin-spin distances at nanometre-scale by measuring dipole-dipole interactions between paramagnetic centres. The PDS methods of Double Electron Electron Resonance (DEER) and Relaxation Induced Dipolar Modulation Enhancement (RIDME) are employed, and their results compared, for the measurement of the dipolar coupling between nitroxide spin labels and copper-II (Cu(II)) paramagnetic centres within the copper amine oxidase from Arthrobacter globiformis (AGAO)...

The presented data clearly demonstrate that multinuclear MRI has a great potential in research and clinical fields. The biomedical value of many heavy nuclei that are part of drugs, contrast agents, and molecular complexes in live tissues emphasizes the need for creating and using MRI scanners tuned to the Larmor frequencies of such nuclei. This article discusses a number of specific problems solved with the use of multinuclear MRI. Since the sensitivity of the MRI on heavy nuclei, as a rule, is insufficient for obtaining images of satisfactory quality, it is proposed to use hyperpolarization techniques for preparing objects for the MRI diagnostics...

A probability distribution of rate constants contained within an exponential-like saturation recovery (SR) electron paramagnetic resonance signal can be constructed using stretched exponential function fitting parameters. Previously (Stein et al. Appl. Magn. Reson. 2019.), application of this method was limited to the case where only one relaxation process, namely spin-lattice relaxations due to the rotational diffusion of the spin labels in the intact eye-lens membranes, contributed to an exponential-like SR signal...

No abstract text is available yet for this article.

The present work provides theoretical and experimental foundations for the ability of dinitrosyl iron complexes (DNICs) with thiol - containing ligands to be not only the donors of neutral NO molecules, but also the donors of nitrosonium cations (NO+ ) in living organisms ensuring S-nitrosation of various proteins and low-molecular-weight compounds. It is proposed that the emergence of those cations in DNICs is related to disproportionation reaction of NO molecules, initiated by their binding with Fe2+ ions (two NO molecules per one ion)...

No abstract text is available yet for this article.

No abstract text is available yet for this article.

EPR spectroscopy is an important spectroscopic method for identification and characterization of radical species involved in many biological reactions. The tyrosyl radical is one of the most studied amino acid radical intermediates in biology. Often in conjunction with histidine residues, it is involved in many fundamental biological electron and proton transfer processes, such as in the water oxidation in photosystem II. As biological processes are typically extremely complicated and hard to control, molecular bio-mimetic model complexes are often used to clarify the mechanisms of the biological reactions...