Development of a method to measure plasma and whole blood choline by liquid chromatography tandem mass spectrometry.

BACKGROUND: Current gold standard markers for myocardial damage are troponins I and T, which are both sensitive and specific for the detection of myocardial infarction, but require up to 6 h to become reliably elevated in serum. Investigation into markers with potential to identify patients with early ischaemic changes is therefore intense. Choline is reported to be prognostic in patients presenting with acute coronary syndromes via its release from ischaemic cell membranes. METHODS: Liquid chromatography tandem mass spectrometry was used to develop a method to quantitate choline in plasma and blood. The method involves addition of a deuterated internal standard to an aliquot of plasma or blood followed by organic solvent addition, which precipitates the proteins in the sample. Preparation was carried out directly into a 96-deep-well plate. Chromatography of choline used a strong cation exchange column and separation used a Waters Atlantis dC18 analytical column positioned directly before the mass spectrometer source, allowing on-line preanalytical clean up of the sample. RESULTS: The lower limit of quantitation was 0.38 micromol/L, linearity was observed up to 754 micromol/L, with a working concentration range of 0.38-224 micromol/L, inter- and intra-assay coefficients of variation were <6% and <4%, respectively. Samples were stable throughout five freeze-thaw cycles and recovery was between 94% and 114%. CONCLUSIONS: The assay was successfully validated in accordance with FDA guidelines and is suitable for quantitation of choline in research and clinical settings.

Evidence for a polar ethane cloud on Titan.

Spectra from Cassini's Visual and Infrared Mapping Spectrometer reveal the presence of a vast tropospheric cloud on Titan at latitudes 51 degrees to 68 degrees north and all longitudes observed (10 degrees to 190 degrees west). The derived characteristics indicate that this cloud is composed of ethane and forms as a result of stratospheric subsidence and the particularly cool conditions near the moon's north pole. Preferential condensation of ethane, perhaps as ice, at Titan's poles during the winters may partially explain the lack of liquid ethane oceans on Titan's surface at middle and lower latitudes.

The evolution of Titan's mid-latitude clouds.

Spectra from Cassini's Visual and Infrared Mapping Spectrometer reveal that the horizontal structure, height, and optical depth of Titan's clouds are highly dynamic. Vigorous cloud centers are seen to rise from the middle to the upper troposphere within 30 minutes and dissipate within the next hour. Their development indicates that Titan's clouds evolve convectively; dissipate through rain; and, over the next several hours, waft downwind to achieve their great longitude extents. These and other characteristics suggest that temperate clouds originate from circulation-induced convergence, in addition to a forcing at the surface associated with Saturn's tides, geology, and/or surface composition.

Effects of a synthetic facial pheromone on behavior of cats.

OBJECTIVE: TO evaluate the effects of a synthetic feline facial pheromone (FFP) on behavior and food intake of healthy versus clinically ill cats. DESIGN: Original study. ANIMALS: 20 cats were used in each of 2 studies. In each study, 7 cats were considered healthy, and 13 cats were determined to be clinically ill. PROCEDURE: In study 1, cats were assigned either to exposure to FFP (treated group; 4 healthy, 6 ill cats) or to exposure to the vehicle (70% ethanol solution; control group; 3 healthy, 7 ill cats). Cats were placed in a cage containing a small cotton towel that had been sprayed with FFP or vehicle 30 minutes previously. Cats were then videotaped for 125 minutes, and food intake was measured during this period. Videotapes were scored at 5-minute intervals for various behaviors. In study 2, cats were categorized in 1 of 2 groups; group 1 (2 healthy, 8 ill cats) had a cat carrier placed in their cages, and group 2 (5 healthy, 5 ill cats) did not. All cats were exposed to FFP, and 24-hour food intake was measured. RESULTS: Differences between behaviors of healthy versus clinically ill cats were not identified. In the first study, significant increases in grooming and interest in food were found in cats exposed to FFP compared with vehicle. For all cats, significant positive correlations were detected between grooming and facial rubbing, walking and facial rubbing, interest in food and facial rubbing, eating and facial rubbing, grooming and interest in food, and grooming and eating. In the second study, 24-hour food intake was significantly greater in cats exposed to FFP and the cat carrier, compared with cats exposed to FFP alone. CONCLUSIONS AND CLINICAL RELEVANCE: Results suggest that exposure to FFP may be useful to increase food intake of hospitalized cats.

Detection of daily clouds on Titan.

We have discovered frequent variations in the near-infrared spectrum of Titan, Saturn's largest moon, which are indicative of the daily presence of sparse clouds covering less than 1% of the area of the satellite. The thermodynamics of Titan's atmosphere and the clouds' altitudes suggest that convection governs their evolutions. Their short lives point to the presence of rain. We propose that Titan's atmosphere resembles Earth's, with clouds, rain, and an active weather cycle, driven by latent heat release from the primary condensible species.

The dusty atmosphere of the brown dwarf Gliese 229B.

The brown dwarf Gliese 229B has an observable atmosphere too warm to contain ice clouds like those on Jupiter and too cool to contain silicate clouds like those on low-mass stars. These unique conditions permit visibility to higher pressures than possible in cool stars or planets. Gliese 229B's 0.85- to 1.0-micrometer spectrum indicates particulates deep in the atmosphere (10 to 50 bars) having optical properties of neither ice nor silicates. Their reddish color suggests an organic composition characteristic of aerosols in planetary stratospheres. The particles' mass fraction (10(-7)) agrees with a photochemical origin caused by incident radiation from the primary star and suggests the occurrence of processes native to planetary stratospheres.

Transient clouds in Titan's lower atmosphere.

The 1980 encounter by the Voyager 1 spacecraft with Titan, Saturn's largest moon, revealed the presence of a thick atmosphere containing nitrogen and methane (1.4 and approximately 0.05 bar, respectively). Methane was found to be nearly saturated at Titan's tropopause, which, with other considerations, led to the hypothesis that Titan might experience a methane analogue of Earth's vigorous hydrological cycle, with clouds, rain and seas. Yet recent analyses of Voyager data indicate large areas of super-saturated methane, more indicative of dry and stagnant conditions. A resolution to this apparent contradiction requires observations of Titan's lower atmosphere, which was hidden from the Voyager cameras by the photochemical haze (or smog) in Titan's stratosphere. Here we report near-infrared spectroscopic observations of Titan within four narrow spectral windows where the moon's atmosphere is ostensibly transparent. We detect pronounced flux enhancements that indicate the presence of reflective methane condensation clouds in the troposphere. These clouds occur at a relatively low altitude (15+/-10 km), at low latitudes, and appear to cover approximately 9 per cent of Titan's disk.

Temperature lapse rate and methane in Titan's troposphere.

We have reanalyzed the Voyager radio occultation data for Titan, examining two alternative approaches to methane condensation. In one approach, methane condensation is facilitated by the presence of nitrogen because nitrogen lowers the condensation level of a methane/nitrogen mixture. The resulting enhancement in methane condensation lowers the upper limit on surface relative humidity of methane obtained from the Voyager occultation data from 0.7 to 0.6. We conclude that in this case the surface relative humidity of methane lies between 0.08 and 0.6, with values close to 0.6 indicated. In the other approach, methane is allowed to become supersaturated and reaches 1.4 times saturation in the troposphere. In this case, surface humidities up to 100% are allowed by the Voyager occultation data, and thus the upper limit must be set by other considerations. We conclude that if supersaturation is included, then the surface relative humidity of methane can be any value greater than 0.08--unless a deep ocean is present, in which case the surface relative humidity is limited to less than 0.85. Again, values close to 0.6 are indicated. Overall, the tropospheric lapse rate on Titan appears to be determined by radiative equilibrium. The lapse rate is everywhere stable against dry convection, but is unstable to moist convection. This finding is consistent with a supersaturated atmosphere in which condensation-and hence moist convection-is inhibited.

Influx of cometary volatiles to planetary moons: the atmospheres of 1000 possible Titans.

We use a Monte Carlo model to simulate impact histories of possible Titans, Callistos, and Ganymedes. Comets create or erode satellite atmospheres, depending on their mass and velocity distributions: faster and bigger comets remove atmophiles; slower or smaller comets supply them. Mass distributions and the minimum total mass of comets passing through the Saturn system were derived from the crater records of Rhea and Iapetus. These were then scaled to give a minimum impact history for Titan. From this cometary population, of 1000 initially airless Titans, 16% acquired atmospheres larger than Titan's present atmosphere (9 x 10(21) g), and more than half accumulated atmospheres larger than 10(21) g. In contrasts to the work of Zahnle et al. (1992), we find that, in most trials, Callisto acquires comet-based atmospheres. Atmospheres acquired by Callisto and, especially, Ganymede are sensitive to assumptions regarding energy partitioning into the ejecta plume. If we assume that only the normal velocity component heats the plume, the majority of Ganymedes and half of the Callistos accreted atmospheres smaller than 10(20) g. If all the impactor's velocity heats the plume, Callisto's most likely atmosphere is 10(17) g and Ganymede's is negligible. The true cometary flux was most likely larger than that derived from crater records, which raises the probability that Titan, Ganymede, and Callisto acquired substantial atmospheres. However, other loss processes (e.g., sputtering by ions swept up by the planetary magnetic field, solar UV photolysis of hydrocarbons) are potentially capable of eliminating small atmospheres over the age of the solar system. The dark material on Callisto's surface may be a remnant of an earlier, now vanished atmosphere.

A physical model of Titan's aerosols.

Microphysical simulations of Titan's stratospheric haze show that aerosol microphysics is linked to organized dynamical processes. The detached haze layer may be a manifestation of 1 cm sec-1 vertical velocities at altitudes above 300 km. The hemispherical asymmetry in the visible albedo may be caused by 0.05 cm sec-1 vertical velocities at altitudes of 150 to 200 km, we predict contrast reversal beyond 0.6 micrometer. Tomasko and Smith's (1982, Icarus 51, 65-95) model, in which a layer of large particles above 220 km altitude is responsible for the high forward scattering observed by Rages and Pollack (1983, Icarus 55, 50-62), is a natural outcome of the detached haze layer being produced by rising motions if aerosol mass production occurs primarily below the detached haze layer. The aerosol's electrical charge is critical for the particle size and optical depth of the haze. The geometric albedo, particularly in the ultraviolet and near infrared, requires that the particle size be near 0.15 micrometer down to altitudes below 100 km, which is consistent with polarization observations (Tomasko and Smith 1982, West and Smith 1991, Icarus 90, 330-333). Above about 400 km and below about 150 km Yung et al.'s (1984, Astrophys. J. Suppl. Ser. 55, 465-506) diffusion coefficients are too small. Dynamical processes control the haze particles below about 150 km. The relatively large eddy diffusion coefficients in the lower stratosphere result in a vertically extensive region with nonuniform mixing ratios of condensable gases, so that most hydrocarbons may condense very near the tropopause rather than tens of kilometers above it. The optical depths of hydrocarbon clouds are probably less than one, requiring that abundant gases such as ethane condense on a subset of the haze particles to create relatively large, rapidly removed particles. The wavelength dependence of the optical radius is calculated for use in analyzing observations of the geometric albedo. The lower atmosphere and surface should be visible outside of regions of methane absorption in the near infrared. Limb scans at 2.0 micrometers wavelength should be possible down to about 75 km altitude.

The tropospheric abundances of NH3 and PH3 in Jupiter's Great Red Spot, from Voyager IRIS observations.

To investigate the chemistry and dynamics of Jupiter's Great Red Spot (GRS), the tropospheric abundances of NH3 and PH3 in the GRS are determined and compared to those of the surrounding region, the South Tropical Zone (STZ). These gases well up from deep in the atmosphere, and, in the upper troposphere, are depleted by condensation (in the case of NH3), chemical reactions, and UV photolysis. At Jupiter's tropopause, the chemical lifetimes of NH3 and PH3 are comparable to the time constant for vertical transport over the atmospheric scale height. The distributions of these gases are therefore diagnostic of the rate of vertical transport in the upper troposphere and lower stratosphere. Three groups of Voyager IRIS spectra are analyzed, two of the STZ and one of the GRS. The two groups of STZ spectra are defined on the basis of their radiances at 602 and 226 cm-1, which reflect, respectively, the temperature near 150 mbar and the cloud opacity in the 300-600 mbar region. One selection of STZ spectra is chosen to have the same radiance as does the GRS at 226 cm-1. The other STZ selection has a significantly greater radiance, indicative of reduced cloudiness. Variations in the abundances of NH3 and PH3 are determined within the STZ, as a background for our studies of the GRS. Within the uncertainty of our measurements (-55% and +75%), the PH3 mixing ratio at 600 mbar is 3 x 10(-7), the same for all three selections. The NH3 mixing ratio profile in the pressure region between 300 and 600 mbar is the same within error (-25% and +50% at 300 mbar) for both STZ selections. In the GRS, however, NH3 is significantly depleted at 300 mbar, with an abundance of 25% that derived for the STZ selections. Since the GRS is believed to be a region of strong vertical transport, our finding of a depletion of NH3 below the tropopause within the GRS is particularly unexpected. One of the STZ selections has a temperature-pressure profile similar to that of the GRS below the 300-mbar level; therefore, condensation at this level does not easily explain the low NH3 abundance in the GRS. All samples are taken at essentially the same latitude; photolysis and/or charged particle precipitation is probably not directly responsible either. The observed NH3 depletion may have a dynamical origin or result from some unidentified chemical processes at work in the GRS.

Titan's surface and troposphere, investigated with ground-based, near-infrared observations.

New observations of Titan's near-infrared spectrum (4000-5000 cm-1) combined with points taken from Fink and Larson's (1979) spectrum (4000-12500 cm-1) provide information on Titan's haze, possible clouds, surface albedo, and atmospheric abundance of H2. In the near-infrared, the main features in Titan's spectrum result from absorption of solar radiation by CH4. The strength of this absorption varies considerably with wavelength, allowing us to probe various atmospheric levels down to the surface itself by choosing specific wavelengths for analysis. At 4715 cm-1, the pressure-induced S(1) fundamental band of H2 lies in the wings of CH4 bands. Based on current values for the CH4 line parameters, Titan's spectrum can be best interpreted with a volume mixing ratio of H2 between 0.5 and 1.0%. Our observations suggest the existence of an optically thin CH4 cloud layer. The optical depths that we derive for Titan's haze and clouds are small enough to allow us to sense the surface of Titan at 4900, 6250, and 7700 cm-1. The most plausible interpretation of the albedos determined at these wavenumbers suggests a surface dominated by "dirty" water ice. A global ethane ocean is not compatible with these albedos.

The Marcy repair revisited.

Failure to close the internal ring in transversalis fascia is the primary cause of recurrent indirect inguinal hernia. Removal of the cremaster muscle provides optimal exposure for accurate identification and fascial closure of the ring.

Diagnosis of papillary stenosis by calibration: follow-up 15 to 25 years after sphincteroplasty.

In 178 patients undergoing elective cholecystectomy for biliary colic, the papilla was calibrated with a no. 10 French catheter through the cystic duct. The catheter passed through the papilla into the duodenum in 94 patients. Six (6 percent) had common duct stones. No postcholecystectomy colic occurred. In 37 patients the catheter was obstructed by papillary stenosis and sphincteroplasty was done. Common duct stones occurred in 17 patients (46 percent), jaundice in 7 and dilatation of the common duct in 6. Cholangiograms failed to detect small stones in seven patients and were of minimal value in positively identifying stenosis. In 49 control patients the papilla was not calibrated. Cholangiograms were normal. Postcholecystectomy colic occurred in seven patients, two of whom underwent subsequent sphincteroplasty. It is concluded that calibration is a worthwhile adjunct to cholangiography. Sphincteroplasty permits passage of small stones that may not be apparent on cholangiograms and are retained by papillary stenosis, and prevents colic (dyskinesia) of stenosis that also may not be apparent on cholangiograms.

Gallstones after vagotomy.

A control group of 53 patients with selective vagotomy plus pyloroplasty was studied with pre- and postoperative cholecystography. At the fourth to seventh years the size and motility of the gallbladders were the same. Gallstones developed in two patients. A series of 91 patients with total vagotomy plus pyloroplasty was studied by similar methods. In 46 patients the gallbladders were grossly dilated and in 30 of the 46 the gallbladders were noncontractile. Gallstones developed in nine of the 46 patients. In the other 45 patients hypotonic dysfunction of the gallbladder was insignificant, and stones developed in only 1 of them. Explanation of these variable results is thwarted by unknown variations in the degree of both hypotonic dysfunction of the gallbladder and lithogenic change in the bile of patients with complete hepatic and complete celiac vagotomy after total vagotomy, and also by the unknown occurrence of incomplete hepatic and incomplete celiac vagotomy in series of allegedly complete total vagotomy. It is concluded that total vagotomy increases the incidence of gallstones, and that this increase occurs primarily in patients with significant hypotonia of the gallbladder. Selective vagotomy prevents these sequelae.

Long-term results of selective vagotomy plus pyloroplasty. 12 to 17 year follow-up.

Among an initial series of 103 patients with selective vagotomy plus pyloroplasty for duodenal ulcer, 9 patients died of causes unrelated to ulcer and 7 were lost to follow-up without signs or symptoms of ulcer 8 to 15 years after operation; the remaining 87 patients were followed up for 12 to 17 years. Insulin testing revealed only one inadequate vagotomy in a patient who had a recurrence in the short term. Insulin tests were negative in 61 and negative or adequate in 6 other patients. Complete vagotomy reduced basal secretion effectively in the great majority of patients but not in a small minority. Three patients had antral hyperfunction with persistent hypersecretion despite complete vagotomy as indicated by two negative insulin tests in each patient. Inexplicably, only one of these patients had a stomal ulcer recurrence. Long-term follow-up revealed the development of gastric ulcer in one patient wit stasis from a pyloroplasty stenosed by angulation from adhesions. Three other patients, one with ulcer and two with hemorrhagic gastritis, developed gastric ulceration in the long term despite low acid output and negative insulin tests. Biliary reflux was demonstrated in two of these three patients and was probably the cause of gastric ulcer in the third. Pre- and postoperative cholecystograms in 66 patients showed the formation of gallstones in 4 patients after vagotomy. Another patient who did not undergo cholecystography developed acute cholecystitis from stone. This rate of gallstone formation was the normal expected rate and was not increased as in some series of total vagotomy. Dumping with and without associated diarrhea was the most frequent and troublesome sequela. Postvagotomy diarrhea did not occur. To prevent dumping, and also to decrease acid secretion more effectively, pyloroplasty was abandoned in favor of Maki's pyloruspreserving antrectomy to complement selective vagotomy in 1968.