Ion clustering in aqueous salt solutions near the liquid/vapor interface

Molecular dynamics simulations of aqueous NaCl, KCl, NaI, and KI solutions are used to study the effects of salts on the properties of the liquid/vapor interface. The simulations use the models which include both charge transfer and polarization effects. Pairing and the formation of larger ion clusters occurs both in the bulk and surface region, with a decreased tendency to form larger clusters near the interface. An analysis of the roughness of the surface reveals that the chloride salts, which have less tendency to be near the surface, have a roughness that is less than pure water, while the iodide salts, which have a greater surface affinity, have a larger roughness. This suggests that ions away from the surface and ions near the surface affect the interface in opposite ways.Comment: 10 pages, 5 figure

X-ray vs. Optical Variations in the Seyfert 1 Nucleus NGC 3516: A Puzzling Disconnectedness

We present optical broadband (B and R) observations of the Seyfert 1 nucleus NGC 3516, obtained at Wise Observatory from March 1997 to March 2002, contemporaneously with X-ray 2-10 keV measurements with RXTE. With these data we increase the temporal baseline of this dataset to 5 years, more than triple to the coverage we have previously presented for this object. Analysis of the new data does not confirm the 100-day lag of X-ray behind optical variations, tentatively reported in our previous work. Indeed, excluding the first year's data, which drive the previous result, there is no significant correlation at any lag between the X-ray and optical bands. We also find no correlation at any lag between optical flux and various X-ray hardness ratios. We conclude that the close relation observed between the bands during the first year of our program was either a fluke, or perhaps the result of the exceptionally bright state of NGC 3516 in 1997, to which it has yet to return. Reviewing the results of published joint X-ray and UV/optical Seyfert monitoring programs, we speculate that there are at least two components or mechanisms contributing to the X-ray continuum emission up to 10 keV: a soft component that is correlated with UV/optical variations on timescales >1 day, and whose presence can be detected when the source is observed at low enough energies (about 1 keV), is unabsorbed, or is in a sufficiently bright phase; and a hard component whose variations are uncorrelated with the UV/optical.Comment: 9 pages, AJ, in pres

Operative versus nonoperative treatment of acute Achilles tendon ruptures: A pilot economic decision analysis

Background: The operative treatment of Achilles tendon ruptures has been associated with lower rerupture rates and better function but also a risk of surgery-related complications compared with nonoperative treatment, which may provide improved outcomes with accelerated rehabilitation protocols. However, economic decision analyses integrating the updated costs of both treatment options are limited in the literature. Purpose: To compare the cost-effectiveness of operative and nonoperative treatment of acute Achilles tendon tears. Study Design: Economic and decision analysis; Level of evidence, 2. Methods: An economic decision model was built to assess the cost-utility ratio (CUR) of open primary repair versus nonoperative treatment for acute Achilles tendon ruptures, based on direct costs from the practices of sports medicine and foot and ankle surgeons at a single tertiary academic center, with published outcome probabilities and patient utility data. Multiway sensitivity analyses were performed to reflect the range of data. Results: Nonoperative treatment was more cost-effective in the average scenario (nonoperative CUR, US$520; operative CUR, US$1995), but crossover occurred during the sensitivity analysis (nonoperative CUR range, US$224-US$2079; operative CUR range, US$789-US$8380). Operative treatment cost an extra average marginal CUR of US$1475 compared with nonoperative treatment, assuming uneventful healing in both treatment arms. The sensitivity analysis demonstrated a decreased marginal CUR of operative treatment when the outcome utility was maximized, and rerupture rates were minimized compared with nonoperative treatment. Conclusion: Nonoperative treatment was more cost-effective in average scenarios. Crossover indicated that open primary repair would be favorable for maximized outcome utility, such as that for young athletes or heavy laborers. The treatment decision for acute Achilles tendon ruptures should be individualized. These pilot results provide inferences for further longitudinal analyses incorporating future clinical evidence

Kinetic Characterization and X-ray Structure of a Mutant of Haloalkane Dehalogenase with Higher Catalytic Activity and Modified Substrate Range

Conversion of halogenated aliphatics by haloalkane dehalogenase proceeds via the formation of a covalent alkyl-enzyme intermediate which is subsequently hydrolyzed by water. In the wild type enzyme, the slowest step for both 1,2-dichloroethane and 1,2-dibromoethane conversion is a unimolecular enzyme isomerization preceding rapid halide dissociation. Phenylalanine 172 is located in a helix-loop-helix structure that covers the active site cavity of the enzyme, interacts with the Clβ of 1,2-dichloroethane during catalysis, and could be involved in stabilization of this helix-loop-helix region of the cap domain of the enzyme. To obtain more information about the role of this residue in dehalogenase function, we performed a mutational analysis of position 172 and studied the kinetics and X-ray structure of the Phe172Trp enzyme. The Phe172Trp mutant had a 10-fold higher kcat/Km for 1-chlorohexane and a 2-fold higher kcat for 1,2-dibromoethane than the wild-type enzyme. The X-ray structure of the Phe172Trp enzyme showed a local conformational change in the helix-loop-helix region that covers the active site. This could explain the elevated activity for 1-chlorohexane of the Phe172Trp enzyme, since it allows this large substrate to bind more easily in the active site cavity. Pre-steady-state kinetic analysis showed that the increase in kcat found for 1,2-dibromoethane conversion could be attributed to an increase in the rate of an enzyme isomerization step that preceeds halide release. The observed conformational difference between the helix-loop-helix structures of the wild-type enzyme and the faster mutant suggests that the isomerization required for halide release could be a conformational change that takes place in this region of the cap domain of the dehalogenase. It is proposed that Phe172 is involved in stabilization of the helix-loop-helix structure that covers the active site of the enzyme and creates a rigid hydrophobic cavity for small apolar halogenated alkanes.