Improved synthesis of 6,6,7,7-tetramethyl-1-azabicyclop[2.2.2]octan-2-one and its stability toward base-induced methanolysis

The published method for synthesis of the bridgehead lactam 6,6,7,7-tetramethyl-1-azabicyclo [2.2.2]octan-2-one yields polymers almost exclusively. Use of dilution techniques provides a 27% yield of this highly strained molecule. Base-induced methanolysis of this tetramethyl compound occurs exceedingly slowly compared to some other less crowded homologues. A buttressing effect is postulated to account for part of this effect.     

Quantitative determination of tolazoline in serum and urine

A high-performance liquid chromatographic procedure is described for the analysis of tolazoline in serum and urine. This assay procedure is suitable for the analysis of micro-samples (50 or 100 microliters serum and 100 microliters urine). Samples are extracted in a single step and injected into a reversed-phase high-performance liquid chromatography system for detection at 210 nm. The clinical applicability of this assay is demonstrated by the determination of tolazoline serum and urine concentrations in neonates. In addition, the presence of urine conjugates and the extent of serum protein binding were investigated. This assay procedure has the required sensitivity (0.1 microgram/ml), accuracy and precision for both routine monitoring and pharmacokinetic characterization of tolazoline in neonates and adults.     

Semi-empirical molecular orbital conformational study of benzannelated cyclooctatetraenes and related compounds, and x-ray crystal structure of benzocyclooctatetraene

Semi-empirical molecular orbital conformational analyses of benzocyclooctatetraene, 1, dibenzo [a, c] cyclooetatetraene, 2 dibenzo [a, e] cyclooctatetraene, 3 tribenzo[a, c, e]-cyclooctatetraene, 4 tetrabenzo[a, c, e, g] cyclooetatetraene, 5 octafluorocyclooetatetraene, 6A, and cyclooctatetraene, 6B, have been done at the MNDO and MINDO/3 (excluding 4 and 5) levels of approximation. Comparison of these results with the X-ray structural data for 1 (as determined in the present work and the other benzannelated cyclooctatetraenes showed that, while MNDO is vastly superior to MINDO/3 both fail to account for the subtle effects of benzannelation on the conformation of the cyclooetatetraene ring. The experimental data indicate that the tub conformation of cyclooetatetraene is only slightly perturbed by the successive fusion of one and two non-adjacent benzene rings, but steric repulsion between adjacent annelated benzene rings, when present, predominates and gives rise to more folded configurations. Compound 1 crystallizes in space group P2₁/n with a = 1 1.856(2 B = 6.327(1 c = 12.470(3 Å, β = 110.03(2)°, and Z = 4. The structure has been solved by direct methods and refined to R = 0.049 for 1435 observed Mo-K diffractometer data.     

Formation of porous carbon materials with in situ generated NaF nanotemplate

Porous carbon materials with pore sizes from 3 to 200 nm were synthesized by reacting hexafluorobenzene with Na liquid at 623 K. NaF crystals, a byproduct formed in the reaction, acted as nanotemplate to assist the pore formation. By employing hexafluorobenzene to react with Na incorporated within the channels (diameter 200 nm) of anodized aluminum oxide (AAO) membranes at 323-623 K, the carbon material can be fabricated into aligned porous nanotube arrays (ca. 250 nm in diameter, ca. 20 nm in wall thickness, ca. 0.06 mm in length, and ca. 3-90 nm in pore diameter). These materials were characterized by X-ray diffraction, scanning and transmission electron microscopy, X-ray energy dispersive spectroscopy, electron diffraction, thermal gravimetric analysis, and nitrogen physical adsorption experiments.     

Isotropy of optical excitations in few-layer graphenes

The geometric and the most band structures of monolayer and AB-stacked bilayer graphenes exhibit strong anisotropy. Nevertheless, the absorption spectra are isotropic for the polarization vector on graphene plane. The velocity matrix elements dominate this property. These results suggest that AA- and AB-stacked few-layer graphenes and graphites manifest this feature.     

Concurrent sympathetic activation and vagal withdrawal in hyperthyroidism: Evidence from detrended fluctuation analysis of heart rate variability

Despite many previous studies on the association between hyperthyroidism and the hyperadrenergic state, controversies still exist. Detrended fluctuation analysis (DFA) is a well recognized method in the nonlinear analysis of heart rate variability (HRV), and it has physiological significance related to the autonomic nervous system. In particular, an increased short-term scaling exponent α1 calculated from DFA is associated with both increased sympathetic activity and decreased vagal activity. No study has investigated the DFA of HRV in hyperthyroidism. This study was designed to assess the sympathovagal balance in hyperthyroidism. We performed the DFA along with the linear analysis of HRV in 36 hyperthyroid Graves’ disease patients (32 females and 4 males; age 30 ± 1 years, means ± SE) and 36 normal controls matched by sex, age and body mass index. Compared with the normal controls, the hyperthyroid patients revealed a significant increase (P<0.001) in α1 (hyperthyroid 1.28±0.04 versus control 0.91±0.02), long-term scaling exponent , overall scaling exponent , low frequency power in normalized units (LF%) and the ratio of low frequency power to high frequency power (LF/HF); and a significant decrease (P<0.001) in the standard deviation of the R-R intervals (SDNN) and high frequency power (HF). In conclusion, hyperthyroidism is characterized by concurrent sympathetic activation and vagal withdrawal. This sympathovagal imbalance state in hyperthyroidism helps to explain the higher prevalence of atrial fibrillation and exercise intolerance among hyperthyroid patients.     

Growth of b-axis oriented VO2 thin films on glass substrates using ZnO buffer layer

VO₂ thin films are grown on glass substrates by pulsed laser deposition using vanadium metal as a target. In this study, a ZnO thin film was used as a buffer layer for the growth of VO₂ thin films on glass substrates. X-ray diffraction studies showed that the VO₂ thin film had b-axis preferential orientation on a c-axis oriented ZnO buffer layer. The thickness of the ZnO buffer layer and the oxygen pressure during VO₂ deposition were optimized to grow highly b-axis oriented VO₂ thin films. The metal-insulator transition properties of the VO₂ film samples were investigated in terms of infrared reflectance and electrical resistance with varying temperatures.