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.
Geometrical confinement of gadolinium-based contrast agents in nanoporous particles enhances T1 contrast
Magnetic resonance imaging contrast agents are currently designed by modifying their structural and physiochemical properties in order to improve relaxivity and to enhance image contrast. Here we show a general method for increasing relaxivity by confining contrast agents inside the nanoporous structure of silicon particles. Magnevist, gadofullerenes and gadonanotubes were loaded inside the pores of quasi-hemispherical and discoidal particles. For all combinations of nanoconstructs, a boost in longitudinal proton relaxivity r1 was observed: for Magnevist, r1~14 mM-1s-1/Gd3+ion (~8.15×10+7 mM-1s-1/construct); for gadofullerenes, r1~200 mM-1s-1/Gd3+ion (~7×10+9 mM-1s-1/construct); for gadonanotubes, r1~150 mM-1s-1/Gd3+ion (~2×10+9 mM-1s-1/construct). These relaxivity values are about 4 to 50 times larger than that of clinically-available gadolinium-based agents (~4 mM-1s-1 /Gd3+ion). The enhancement in contrast is attributed to the geometrical confinement of the agents, which influences the paramagnetic behavior of the Gd3+ions. Thus, nanoscale confinement offers a new and general strategy for enhancing the contrast of gadolinium-based contrast agents.
Natural Radioactivity of Intrusive-Metamorphic and Sedimentary Rocks of the Balkan Mountain Range (Serbia, Stara Planina)
Stara Planina (also known as the Balkan mountain range) is known for numerous occurrences and deposits of uranium and associated radionuclides. It is also famous for its geodiversity. The geologic framework is highly complex. The mountain is situated between the latitudes of 43° and 44° N and the longitudes from 22°16′ to 23°00′ E. Uranium exploration and radioactivity testing on Stara Planina began back in 1948. Uranium has also been mined in the zone of Kalna, within the Janja granite intrusive. The naturally radioactive geologic units of Stara Planina are presented in detail in this paper. The main sources of radioactivity on Stara Planina can be classified as: 1. Granitic endogenous—syngenetic–epigenetic deposits and occurrences; 2. Metamorphogenic—syngenetic; and 3. Sedimentary, including occurrences of uranium deposition and fluctuation caused by water in different types of sedimentary rocks formed in a continental setting, which could be classified under epigenetic types. The area of Stara Planina with increased radioactivity (higher than 200 cps), measured by airborne gamma spectrometry, is about 380 square kilometers. The highest values of measured radioactivity and uranium grade were obtained from a sample taken from the Mezdreja uranium mine tailing dump, where 226Ra measures 2600 ± 100 Bq/kg and the uranium grade is from 76.54 to 77.65 ppm U. The highest uranium (and lead) concentration, among all samples, is measured in graphitic schist with high concentrations of organic (graphitic) material from the Inovska Series—99.47 ppm U and 107.69 ppm Pb. Thorium related radioactivity is the highest in granite samples from the Janja granite in the vicinity of the Mezdreja granite mine and the Gabrovnica granite mine tailing dump, and it is the same—250 ± 10 Bq/kg for 232Th, while the thorium grade varies from 30.82 to 60.27 ppm Th. In gray siltstones with a small amount of organic material, the highest radioactivity is related to potassium—2080 ± 90 Bq/kg for 40K.