Stability measurements on cored cables in normal and superfluid helium

The relative stability of LHC type cables has been measured by the direct heating of one of the individual strands with a short duration current pulse. The minimum energy required to initiate a quench has been determined for a number of cables which have a central core to increase the effective inter-strand cross-over resistance. Experiments were performed in both normal helium at 4.4 K and superfluid at 1.9 K. Conductors in general are less stable at the lower temperature when measured at the same fraction of critical current. Results show that the cored-cables, even when partially filled with solder or with a ‘porous-metal' filler exhibit a relatively low stability at currents close to the critical current. It is speculated that the high inter-strand electrical and thermal resistance inherent in these cables may affect the stability at high currents.     

beta-Acyloxysulfonyl tethers for intramolecular Diels-Alder cycloaddition reactions

[reaction: see text]. beta-Hydroxy sulfone-based tethers were employed for the first time to achieve thermally mediated intramolecular Diels-Alder cycloaddition. The reactions proceeded with complete regioselectivity and high (10/1) to complete endo/exo-selectivity and resulted in the preferential formation of one of the two possible endo-cycloadducts. The yields and stereoselectivities were proportional to the bulk of the R(1) substituent on the beta-acyloxysulfonyl tether.     

Reversal of enantioselectivity in the hydroformylation of styrene with [2S,4S-BDPP]Pt(SnCl3)Cl at high temperature arises from a change in the enantioselective-determining step

Deuterioformylation of styrene catalyzed by [(2S,4S)-BDPP]Pt(SnCl(3))Cl at 39 degrees C gave 3-phenylpropanal (3) and 2-phenylpropanal (2) (n:i = 1.8, 71% ee (S)-2) with deuterium only beta to the aldehyde carbonyl and in the formyl group. Small amounts of deuterium were also found in the internal (2.8%), cis terminal (1.4%), and trans terminal (1.3%) vinyl positions of the recovered styrene. Deuterioformylation of styrene at 98 degrees C gave 3- (3) and 2-phenylpropanal (2) (n:i = 2.3, 10% ee (R)-2) with deuterium both alpha and beta to the aldehyde carbonyl and in the formyl group. Deuterium was also found in the internal (20%), cis terminal (12%), and trans terminal (12%) vinyl positions of the recovered styrene. These deuterioformylation results establish that platinum hydride addition to styrene is largely irreversible at 39 degrees C but reversible at 98 degrees C. Hydroformylation of (E)- and (Z)-beta-deuteriostyrene at 40 degrees C, followed by oxidation of the aldehydes to acids, and subsequent derivitization to the (S)-mandelate esters confirmed that 84% of 2-phenylpropanal (2) arises from platinum hydride addition to the si-face of styrene, while 73% of 3-phenylpropanal (3) arises from platinum hydride addition to the re-face of styrene. At 100 degrees C, the effect of variable H(2) and CO pressure on n:i, % ee, and TOF of hydroformylation of styrene was investigated. The results are consistent with enantioselectivity not being fully determined until the final hydrogenolysis of a platinum acyl intermediate.     

Gender differences in vocal fold contact computed from electroglottographic signals: the influence of measurement criteria

EGGW is a phonatory parameter that can be derived from electroglottographic (EGG) signals and used to infer the relative degree of vocal fold contact. Vocal fold models predict that men will exhibit medial bulging of their vocal folds during phonation but women will not. These models lead us to expect gender differences in the magnitude of EGGW. Nevertheless, significant gender differences in EGGW for adults with normal voices have not been documented in previous studies when EGGW was computed from criterion lines placed at 25%-40% of the amplitude of the uninverted EGG wave form. We hypothesized that EGGW would better reflect gender differences in vocal fold adductory patterns if EGGW was computed from portions of the wave form that were associated with more vocal fold contact. EGGW was measured for seven men and seven women with normal voices. When EGGW was computed from segments of the wave form that were associated with relatively greater vocal fold contact (i.e., using criterion levels of > or = 55%), findings were consistent with the gender-specific adductory patterns that have been proposed from vocal fold models. Guidelines for appropriate placement of criterion lines when computing EGGW are discussed.     

Interplay of ionic and structural heterogeneity on functional action potential duration gradients: Implications for arrhythmogenesis

Action potential duration (APD) dispersion in the heart is governed by the underlying cellular architecture and the spatial distribution of the membrane properties. Understanding the contribution of each factor is important in designing more effective methods for the control of arrhythmias. Recent experimental studies have shown that the insertion of structural barriers in ionically heterogeneous tissue facilitates the formation of unidirectional block and discordant alternans. In this work, computational modeling is used to examine the effect of internal obstacles on the formation of functional APD gradients in ionically heterogeneous tissue. Intrinsic APD differences are introduced by assigning two discrete cell types to each half of a square domain. The combined effect of structural and ionic heterogeneities is shown to produce gradients in APD that are oblique to both the intrinsic gradients in APD and the physical boundary. Simulation results are presented that show that the magnitude and spatial extent of the subsequent APD gradients are modulated by the size and orientation of the obstacle, the degree of anisotropy, and the location of the pacing site. Long, thin internal obstacles are found to produce the greatest dispersion in APD. The combination of internal obstacles and ionic heterogeneities is shown to produce a substrate for re-entrant excitation following a pair of near threshold point stimuli. (c) 2002 American Institute of Physics.     

Room-Temperature Formation Pathway for CdTeSe Alloy Magic-Size Clusters

Little is known about the pathway of room-temperature formation of ternary CdTeSe magic-size clusters (MSCs) obtained by mixing binary CdTe and CdSe induction period samples containing binary precursor compounds (PCs) of MSCs, monomers (Ms), and fragments (Fs). Also, unestablished are dispersion effects that occur when as-mixed samples (without incubation) are placed in toluene (Tol) and octylamine (OTA) mixtures. The resulting ternary MSCs, exhibiting a sharp optical absorption peak at 399 nm, are labelled CdTeSe MSC-399, and their PCs are referred to as CdTeSe PC-399. When the amount of OTA is relatively small, single-ensemble MSC-399 evolved without either binary CdTe or CdSe MSCs. When the OTA amount is relatively large, CdTe MSC-371 appeared initially and then disappeared, while single-ensemble MSC-399 developed more deliberately. The larger the OTA amount, the more slowly these changes proceeded. The substitution reaction of CdTe PC + CdSe M/F↔CdTeSe PC-399 + CdTe M/F is proposed to be rate-determining for the MSC-399 formation in a Tol and OTA mixture. This study provides further understanding of the transformation pathway between MSCs.     

Identification and profiling of targeted oxidized linoleic acid metabolites in rat plasma by quadrupole time‐of‐flight mass spectrometry

Linoleic acid (LA) and LA‐esters are the precursors of LA hydroperoxides, which are readily converted to 9‐ and 13‐hydroxy‐?octadecadienoic acid (HODE) and 9‐ and 13‐oxo‐?octadecadienoic acid (oxo ODE) metabolites in vivo. These four oxidized LA metabolites (OXLAMs) have been implicated in a variety of pathological conditions. Therefore, their accurate measurement may provide mechanistic insights into disease pathogenesis. Here we present a novel quadrupole time‐of‐flight mass spectrometry (Q‐TOFMS) method for quantitation and identification of target OXLAMs in rat plasma. In this method, the esterified OXLAMs were base‐hydrolyzed and followed by liquid–liquid extraction. Quantitative analyses were based on one‐point standard addition with isotope dilution. The Q‐TOFMS data of target metabolites were acquired and multiple reaction monitoring extracted‐ion chromatograms were generated post‐acquisition with a 10 ppm extraction window. The limit of quantitation was 9.7–35.9 nmol/L depending on the metabolite. The method was reproducible with a coefficient of variation of <18.5%. Mean concentrations of target metabolites in rat plasma were 57.8, 123.2, 218.1 and 57.8 nmol/L for 9‐HODE, 13‐HODE, 9‐oxoODE and 13‐oxoODE, respectively. Plasma levels of total OXLAMs were 456.9 nmol/L, which correlated well with published concentrations obtained by gas chromatography/mass spectrometry (GC/MS). The concentrations were also obtained utilizing a standard addition curve approach. The calibration curves were linear with correlation coefficients of >0.991. Concentrations of 9‐HODE, 13‐HODE, 9‐oxoODE and 13‐oxoODE were 84.0, 138.6, 263.0 and 69.5 nmol/L, respectively, which were consistent with the results obtained from one‐point standard addition. Target metabolites were simultaneously characterized based on the accurate Q‐TOFMS data. This is the first study of secondary LA metabolites using Q‐TOFMS. Published 2012. This article is a U.S. Government work and is in the public domain in the USA.