Cardiac function and lipid distribution in rats fed a high-fat diet: in vivo magnetic resonance imaging and spectroscopy.

Obesity is a major risk factor in the development of cardiovascular disease, type 2 diabetes, and its pathophysiological precondition insulin resistance. Very little is known about the metabolic changes that occur in the myocardium and consequent changes in cardiac function that are associated with high-fat accumulation. Therefore, cardiac function and metabolism were evaluated in control rats and those fed a high-fat diet, using magnetic resonance imaging, magnetic resonance spectroscopy, mRNA analysis, histology, and plasma biochemistry. Analysis of blood plasma from rats fed the high-fat diet showed that they were insulin resistant (P < 0.001). Our high-fat diet model had higher heart weight (P = 0.005) and also increasing trend in septal wall thickness (P = 0.07) compared with control diet rats. Our results from biochemistry, magnetic resonance imaging, and mRNA analysis confirmed that rats on the high-fat diet had moderate diabetes along with mild cardiac hypertrophy. The magnetic resonance spectroscopy results showed the extramyocellular lipid signal only in the spectra from high-fat diet rats, which was absent in the control diet rats. The intramyocellular lipids in high-fat diet rats was higher (8.7%) compared with rats on the control diet (6.1%). This was confirmed by electron microscope and light microscopy studies. Our results indicate that lipid accumulation in the myocardium might be an early indication of the cardiovascular pathophysiology associated with type 2 diabetes.

EPR detected polarization transfer between Gd3+ and protons at low temperature and 3.3 T: the first step of dynamic nuclear polarization.

Electron-electron double resonance pulsed electron paramagnetic resonance (EPR) at 95 GHz (3.3 T) is used to follow the dynamics of the electron spin polarization during the first stages of dynamic nuclear polarization in solids. The experiments were performed on a frozen solution of Gd(+3) (S=7/2) in water/glycerol. Focusing on the central vector -1/2 --> vector +1/2 transition we measured the polarization transfer from the Gd(3+) electron spin to the adjacent (1)H protons. The dependence of the echo detected EPR signal on the length of the microwave irradiation at the EPR "forbidden" transition corresponding to an electron and a proton spin flip is measured for different powers, showing dynamics on the microsecond to millisecond time scales. A theoretical model based on the spin density matrix formalism is suggested to account for this dynamics. The central transition of the Gd(3+) ion is considered as an effective S = 1/2 system and is coupled to (1)H (I = 1/2) nuclei. Simulations based on a single electron-single nucleus four level system are shown to deviate from the experimental results and an alternative approach taking into account the more realistic multinuclei picture is shown to agree qualitatively with the experiments.

Determination of the 14N quadrupole coupling constant of nitroxide spin probes by W-band ELDOR-detected NMR.

Nitroxide spin probe electron paramagnetic resonance (EPR) has proven to be a very successful method to probe local polarity and solvent hydrogen bonding properties at the molecular level. The g(xx) and the (14)N hyperfine A(zz) principal values are the EPR parameters of the nitroxide spin probe that are sensitive to these properties and are therefore monitored experimentally. Recently, the (14)N quadrupole interaction of nitroxides has been shown to be also highly sensitive to polarity and H-bonding (A. Savitsky et al., J. Phys. Chem. B 112 (2008) 9079). High-field electron spin echo envelope modulation (ESEEM) was used successfully to determine the P(xx) and P(yy) principal components of the (14)N quadrupole tensor. The P(zz) value was calculated from the traceless character of the quadrupole tensor. We introduce here high-field (W-band, 95 GHz, 3.5 T) electron-electron double resonance (ELDOR)-detected NMR as a method to obtain the (14)N P(zz) value directly, together with A(zz). This is complemented by W-band hyperfine sublevel correlation (HYSCORE) measurements carried out along the g(xx) direction to determine the principal P(xx) and P(yy) components. Through measurements of TEMPOL dissolved in solvents of different polarities, we show that A(zz) increases, while |P(zz)| decreases with polarity, as predicted by Savitsky et al.

Structure and bonding of [V(IV)O(acac)(2)] on the surface of AlF(3) as studied by pulsed electron nuclear double resonance and hyperfine sublevel correlation spectroscopy.

Well defined isolated [V(IV)O(acac)(2)] surface complexes have been prepared on aluminium trifluoride, alpha-AlF(3), as solid support by equilibrium adsorption from liquid solution. The paramagnetic vanadium(iv) surface complexes were studied by pulsed electron spin resonance spectroscopy in combination with quantum chemical calculations using density functional theory. (19)F and (27)Al ligand hyperfine interactions with the nuclei of the AlF(3) support observed by pulsed electron nuclear double resonance and hyperfine sublevel correlation spectroscopy experiments verify the direct chemical bonding between the vanadium and a surface fluorine atom. Detailed analysis of the ligand hyperfine couplings supported by quantum chemical calculations indicates that the axial position of [V(IV)O(acac)(2)]trans to the oxo ligand is bound directly to a terminal fluorine atom of the support. Analysis of the (1)H ligand hyperfine interaction revealed that an acidic H(+) of the AlF(3) surface protonated a donor oxygen of the acetylacetone ligand in the surface complex.