Temperature and pH are two of the most important physiological parameters and are believed to be tightly regulated because they are intricately related to energy metabolism in living organisms. Temperature and/or pH data in mammalian brain are scarce, however, mainly due to lack of precise and non-invasive methods. At 11.7T, we demonstrate that a thulium-based macrocyclic complex infused through the blood stream can be used to obtain temperature and pH maps of rat brain in vivo by 1 H chemical shift imaging (CSI) of the sensor itself in conjunction with a multi-parametric model that depends on several proton resonances of the sensor. Accuracies of temperature and pH determination with the thulium sensor -which has a predominantly extracellular presence -depend on stable signals during the course of the CSI experiment as well as redundancy for temperature and pH sensitivities contained within the observed signals. The thulium-based method compared well with other methods for temperature ( 1 H magnetic resonance spectroscopy (MRS) of N-acetyl aspartate and water; copper-constantan thermocouple wire) and pH ( 31 P MRS of inorganic phosphate and phosphocreatine) assessment, as established by in vitro and in vivo studies. In vitro studies in phantoms with two compartments of differing pH values observed under different ambient temperature conditions generated precise temperature and pH distribution maps. In vivo studies in α-chloralose anesthetized and renal-ligated rats revealed temperature (33-34 °C) and pH (7.3-7.4) distributions in the cerebral cortex which are in agreement with observations by other methods. These results demonstrate that the thulium sensor can be used to measure temperature and pH distributions in rat brain in vivo simultaneously and accurately with 1 H CSI.
Improvements on a localized, automatic shimming method described by Gruetter and Boesch (J. Magn. Reson. 96, 323-334 (1992)) and Gruetter (Magn. Reson. Med. 29, 804-811 (1993)) are presented. A spin-echo sequence employing a double sech refocusing scheme is used to acquire a field map along linear projections that improves the signal-to-noise ratio by at least a factor of two over the stimulated echo sequence previously used. To further improve the reliability of shim adjustments, a variance-weighted polynomial regression analysis is performed. This also extends the scope of application of this technique to global shimming. Localized 1H spectra of human brain shimmed by this method are presented.
Irradiation of dTpdT with 300 kJ/m2 of 254 nm produces numerous photo-products, one of which labeled dT6pd4T[1] was purified by HPLC. dT6pd4T has a UV spectrum (H20, pH 7) with lambda max = 326 nm and lambda min = 265 nm, and a P-31 NMR resonance at -3.46 ppm (normal dTpdT occurs at -4.01 ppm; TMP, 30 degrees C). 2-D COSY NMR spectra facilitated proton resonance assignments and 2-D NOESY spectra aided analysis of spatial orientation. Carbon-13 and proton-coupled P-31 NMR spectra of dT6pd4T were also obtained. These analyses indicate: C5=C6 of dT6p- is saturated and the -pd4T base is more aromatic; the dT6p- base possesses a configuration of 5R, 6S; dT6p- and -pd4T have anti-type glycosidic conformations; furanose conformation of dT6p- is mainly C3'-endo and that of -pd4T exists in a C3'-endo in equilibrium C3'-exo; exocyclic bonds gamma (C5'-C4'), beta (05'-C5') and epsilon (C3'-03') are non-classical rotamers; dihedral angle about epsilon (C3'-03') is smaller relative to dTpdT.
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