General treatment of paramagnetic relaxation enhancement associated with translational diffusion.
A theory of nuclear spin relaxation in isotropic liquids for nuclear spins interacting with electron spins, residing in other molecules (the outer-sphere relaxation), is presented. The approach, valid outside of the Redfield limit for electron spin relaxation, is an extension of the Swedish slow motion theory [Benetis et al., Mol. Phys. 48, 329 (1983); Nilsson and Kowalewski, J. Magn. Reson. 146, 345 (2000)] for inner-sphere relaxation. It is demonstrated that the outer-sphere relaxation rate can be expressed as an integral of a product of a translational diffusion correlation function and a function analogous to the inner-sphere spectral density. A numerical implementation of the theory is described and applied to a large number of realistic parameter sets for S = 7/2 and S = 1, which may correspond to Gd(III) and Ni(II) systems. It is shown that the outer-sphere contribution is relevant and should be included into the analysis of nuclear magnetic relaxation dispersion relaxation profiles, especially for slow relative translational diffusion and fast molecular tumbling.
Diffusional mechanisms augment the fluorine MR relaxation in paramagnetic perfluorocarbon nanoparticles that provides a “relaxation switch” for detecting cellular endosomal activation
To develop a physical model for the 19F relaxation enhancement in paramagnetic perfluorocarbon nanoparticles (PFC NP) and demonstrate its application in monitoring cellular endosomal functionality through a “19F relaxation switch” phenomenon.
O2 constraints from Paleoproterozoic detrital pyrite and uraninite
Redox-sensitive detrital grains such as pyrite and uraninite in sedimentary successions provide one of the most conspicuous geological clues to a different composition of the Archean and early Paleoproterozoic atmosphere. Today, these minerals are rapidly chemically weathered within short transport distances. Prior to the rise of oxygen, low O2 concentrations allowed their survival in siliciclastic deposits with grain erosion tied only to physical transport processes. After the rise of oxygen, redox-sensitive detrital grains effectively vanish from the sedimentary record. To get a better understanding of the timing of this transition, we examined sandstones recorded in a scientifi c drill core from the South African 2.415 Ga Koegas Subgroup, a mixed siliciclastic and iron formation–bearing unit deposited on the western deltaic margin of the Kaapvaal craton in early Paleoproterozoic time. We observed detrital pyrite and uraninite grains throughout all investigated sandstone beds in the section, indicating the rise of oxygen is younger than 2.415 Ga. To better understand how observations of detrital pyrite and uraninite in sedimentary rocks can quantitatively constrain Earth surface redox conditions, we constructed a model of grain erosion from chemical weathering and physical abrasion to place an upper limit on ancient environmental O2 concentrations. Even conservative model calculations for deltaic depositional systems with suffi cient transport distances (approximately hundreds of kilometers) show that redox-sensitive detrital grains are remarkably sensitive to environmental O2 concentrations, and they constrain the Archean and early Paleoproterozoic atmosphere to have <3.2 × 10 –5 atm of molecular O2. These levels are lower than previously hypothesized for redox-sensitive detrital grains, but they are consistent with estimates made from other redox proxy data, including the anomalous fractionation of sulfur isotopes. The binary loss of detrital pyrite and uraninite from the sedimentary record coincident with the rise of oxygen indicates that atmospheric O2 concentrations rose substantially at this time and were never again suffi ciently low (<0.01 atm) to enable survival and preservation of these grains in short transport systems.