Gradient-echo and spin-echo blood oxygenation level-dependent functional MRI at ultrahigh fields of 9.4 and 15.2 Tesla.

PURPOSE: Sensitivity and specificity of blood oxygenation level-dependent (BOLD) functional MRI (fMRI) is sensitive to magnetic field strength and acquisition methods. We have investigated gradient-echo (GE)- and spin-echo (SE)-BOLD fMRI at ultrahigh fields of 9.4 and 15.2  Tesla. METHODS: BOLD fMRI experiments responding to forepaw stimulation were performed with 3 echo times (TE) at each echo type and B0 in α-chloralose-anesthetized rats. The contralateral forelimb somatosensory region was selected for quantitative analyses. RESULTS: At 9.4 T and 15.2 T, average baseline T2* (n = 9) was 26.6 and 17.1 msec, whereas baseline T2 value (n = 9) was 35.7 and 24.5 msec, respectively. Averaged stimulation-induced ΔR2* was -1.72 s-1 at 9.4 T and -3.09 s-1 at 15.2 T, whereas ΔR2 was -1.19 s-1 at 9.4 T and -1.97 s-1 at 15.2 T. At the optimal TE of tissue T2* or T2 , BOLD percent changes were slightly higher at 15.2 T than at 9.4 T (GE: 7.4% versus 6.4% and SE: 5.7% versus 5.4%). The ΔR2* and ΔR2 ratio of 15.2 T to 9.4 T was 1.8 and 1.66, respectively. The ratio of the macrovessel-containing superficial to microvessel-dominant parenchymal BOLD signal was 1.73 to 1.76 for GE-BOLD versus 1.13 to 1.19 for SE-BOLD, indicating that the SE-BOLD contrast is less sensitive to macrovessels than GE-BOLD. CONCLUSION: SE-BOLD fMRI improves spatial specificity to microvessels compared to GE-BOLD at both fields. BOLD sensitivity is similar at the both fields and can be improved at ultrahigh fields only for thermal-noise-dominant ultrahigh-resolution fMRI.

Synthesis of novel Schiff base ligands from gluco- and galactochloraloses for the Cu(II) catalyzed asymmetric Henry reaction.

A series of chiral Schiff base ligands has been prepared using aminochloralose derivatives of glucose and galactose. These ligands were used as catalysts in the asymmetric Henry reaction in the presence of Cu(II) ions giving yields of up to 95%. An interesting solvent dependency on enantiomeric control was observed with the best enantiomeric excesses (up to 91%) being obtained in the presence of water.

Acute monitoring of genitourinary function using intrafascicular electrodes: selective pudendal nerve activity corresponding to bladder filling, bladder fullness, and genital stimulation.

OBJECTIVE: To investigate the use of a microelectrode array with a high spatial density of penetrating intrafascicular electrodes for selective recording of pudendal nerve activity evoked by a variety of genitourinary stimuli. MATERIALS AND METHODS: Felines were anesthetized with alpha-chloralose and high-density Utah slanted electrode arrays (48 microelectrodes; 200-µm spacing) were implanted into the pudendal nerve for acute experimentation. Neural activity was recorded during bladder filling, spontaneous reflexive distention-evoked bladder contractions, and tactile somatosensory stimulation. RESULTS: The intrafascicularly implanted pudendal nerve electrodes were able to selectively record neural activity that corresponded to various genitourinary stimuli. Across all seven experimental animals, a total of 10 microelectrodes recorded neural units that were selectively driven by bladder filling or distention-evoked bladder contractions. Twenty-two electrodes were selectively driven by tactile stimulation. CONCLUSION: Microelectrode arrays implanted intrafascicularly into the pudendal nerve can be used to selectively record the neural responses that reflect bladder status and urogenital tactile stimulation. This work sets the stage for developing future implantable closed-loop neuroprosthetic devices for restoration of bladder function.

The Knoevenagel-Doebner reaction on 1,2-O-(2,2,2-trichloroethylidene) derivatives of D-gluco- and D-manno-furanose.

The synthesis of new α,ß-unsaturated furanuronic acid derivatives of α-gluco-, ß-gluco- and ß-manno-chloraloses via a convenient one pot procedure using the Knoevenagel-Doebner reaction approach are described. The dialdofuranose derivatives were reacted with malonic acid under Knoevenagel-Doebner reaction conditions and (E)-α,ß-unsaturated furanuronic acid derivatives were obtained.

Biologically relevant phosphoranes: structural characterization of glucofuranose- and xylofuranose-based phosphoranes.

Carbohydrate-based phosphoranes were synthesized by reacting 2,2'-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite with 1,2-O-isopropylidene-alpha-D-glucofuranose, beta-chloralose, and 1,2-isopropylidene-alpha-D-xylofuranose to form the monocyclic biophosphoranes 1-3, respectively, in the presence of N-chlorodiisopropylamine. Synthesis of the monocyclic biophosphorane 4 was achieved by reacting tris(2,6-di-isopropylphenyl)phosphite with 1,2-O-isopropylidene-alpha-D-glucofuranose in the presence of N-chlorodiisopropylamine. X-ray analysis of 1-4 revealed trigonal bipyramidal structures with the carbohydrate components occupying axial-equatorial sites. An eight-membered ring in 1-3 occupied diequatorial sites of the trigonal bipyramid. Solution and solid state 31P and solution 19F, 1H, and 13C NMR measurements including variable temperature and correlation spectroscopy studies established retention of the solid state structure in solution. A dynamic equilibrium exists among two isomeric forms. These biophosphoranes serve as models for active sites of phosphoryl transfer enzymes. The rapid exchange process reorients the carbohydrate component of the trigonal bipyramidal phosphorane. At an active site, this type of pseudorotational behavior provides a mechanism that could bring another active site residue into play and account for a means by which some phosphoryl transfer enzymes express promiscuous behavior.

Testing for alpha-chloralose by headspace-GC/MS. A case report.

A case is presented involving an acute fatality resulting from self-administered alpha-chloralose, a rodenticide. A 18-year-old man was found dead at home, with several stains of vomit on the carpet. An empty box of three bags of 5 g 100% alpha-chloralose (Corbeaux nuisibles, Rhône Poulenc) was found near the body. The compound was identified and quantified by headspace gas chromatography coupled to mass spectrometry. Alpha-chloralose was converted by concentrated sulphuric acid into chloral, a volatile compound, that was, after chromatography on a HP5-MS capillary column, identified by the following ions, m/z 82, 111 and 148. Peripheral blood concentration was 175.7 mg/l. Alpha-chloralose was quantified in several tissues, indicating kidney sequestration. No other drugs, including ethanol, were detected.