Chemistry of small organic molecules on snow grains: the applicability of artificial snow for environmental studies

The utilization of artificial snow for environmentally relevant (photo)chemical studies was systematically investigated. Contaminated snow samples were prepared by various methods: by shock freezing of the aqueous solutions sprayed into liquid nitrogen or inside a large walk-in cold chamber at -35 °C, or by adsorption of gaseous contaminants on the surface of artificially prepared pure or natural urban snow. The specific surface area of artificial snow grains produced in liquid nitrogen was determined using valerophenone photochemistry (400-440 cm(2) g(-1)) to estimate the surface coverage by small hydrophobic organic contaminants. The dynamics of recombination/dissociation (cage effect) of benzyl radical pairs, photochemically produced from 4-methyldibenzyl ketone on the snow surface, was investigated. The initial ketone loading, c = 10(-6)-10(-8) mol kg(-1), only about 1-2 orders of magnitude higher than the contaminant concentrations commonly found in nature, was already well below monolayer coverage. We found that the efficiency of out-of-cage reactions decreased at much higher temperatures than those previously determined for frozen solutions; however, the cage effect was essentially the same no matter what technique of snow production or ketone deposition/uptake was used, including the experiments with collected natural snow. The experimental observation that the contaminant molecules are initially self-associated even at the lowest concentrations was supported by DFT calculations. We conclude that, contrary to frozen aqueous solutions, in which the impurities reside in a 3D cage (micropocket), contaminant molecules located on the artificial snow grain surface at low concentrations can be visualized in terms of a 2D cage. Artificial snow thus represents a readily available study matrix that can be used to emulate the natural chemical processes of trace contaminants occurring in natural snow.     

Microfluidic transendothelial electrical resistance measurement device that enables blood flow and postgrowth experiments

Transendothelial electronic resistance (TEER) measurements are performed across a cell layer immobilized on a microfluidic device that also enables the cell layer to interact with a flowing stream of red blood cells (RBCs). A bipolar pulsed square wave potential is applied across a monolayer of bovine pulmonary artery endothelial cells, and the resulting current response is measured and integrated. The overall impedance of the cell layer provides an indicator of cell layer integrity. After cell seeding on the device, a decrease in TEER signal from 22.3 ± 1.6 μC to 3.5 ± 0.4 μC (corresponding to a resistance of 40.9 ± 2.9 Ω·cm(2) to 259.1 ± 27.4 Ω·cm(2)) was observed after 8 h of cell growth. Intracellular nitric oxide (NO) production by the immobilized endothelial cells that had reached confluence was 34% higher than those cells that had not reached confluence, as indicated by the integrated TEER system. Importantly, this NO production by the confluent endothelium was stimulated by ATP released from RBCs flowing under the endothelial cells. In this construct, the described microfluidic device enables both a TEER-based evaluation of cell layer integrity and molecularly communicated interactions of these cells with a flowing stream of blood components.     

Alkaline hydrothermal kinetics in titanate nanostructure formation

In this study, the mechanism of precursor dissolution and the influence of kinetics of dissolution on titanate nanotube formation were investigated. This comparative study explored the dissolution kinetics for the case of commercial titania powders, one composed of predominantly anatase (>95%) and the other rutile phase (>93%). These nanoparticle precursors were hydrothermally reacted in 9 mol L⁻¹ NaOH at 160 °C over a range of reaction times of between 2 and 32 h. The high surface area nanotube-form product was confirmed using X-ray diffraction, FT-Raman spectroscopy, and transmission electron microscopy. The concentration of nanotubes produced from the different precursors was established using Rietveld analysis with internal and external corundum standardization to calibrate the absolute concentrations of the samples. Interpretation of the dissolution process of the precursor materials indicated that the dissolution of anatase proceeds via a zero-order kinetic process, whereas rutile dissolution is through a second-order process. The TiO₂ nanostructure formation process and mechanism of TiO₂ precursor dissolution was confirmed by non-invasive dynamic light scattering measurements. Significant observations are that nanotube formation occurred over a broad range of hydrothermal treatment conditions and was strongly influenced by the order of precursor dissolution.     

Uniqueness logic

A uniqueness type system is used to distinguish values which are referenced at most once from values which may be referenced an arbitrary number of times in a program. Uniqueness type systems are used in the Clean and Mercury programming languages to provide efficiently updatable data-structures and I/O without compromising referential transparency.     

Creativity of undergraduates with and without family history of alcohol and other drug problems

BACKGROUND: Colonoscopic surveillance is a standard procedure in many patients with long standing, extensive ulcerative colitis (UC), in order to avoid death from colorectal cancer. No conclusive proof of its benefits has been presented however. AIMS: To evaluate the association between colonoscopic surveillance and colorectal cancer mortality in patients with UC. PATIENTS: A population based, nested case control study comprising 142 patients with a definite UC diagnosis, derived from a study population of 4664 patients with UC, was conducted. METHODS: Colonoscopic surveillance in all patients with UC who had died from colorectal cancer after 1975 was compared with that in controls matched for age, sex, extent, and duration of the disease. Information on colonoscopic surveillance was obtained from the medical records. RESULTS: Two of 40 patients with UC and 18 of 102 controls had undergone at least one surveillance colonoscopy (relative risk (RR) 0.29, 95% confidence interval 0.06 to 1.31). Twelve controls but only one patient with UC had undergone two or more surveillance colonoscopies (RR 0.22, 95% confidence interval 0.03 to 1.74), indicating a protective dose response relation. CONCLUSION: Colonoscopic surveillance may be associated with a decreased risk of death from colorectal cancer in patients with long standing UC.     

Clearance of technetium 99m N-NOET in normal, ischemic-reperfused, and membrane-disrupted myocardium

BACKGROUND: Technetium 99m-labeled bis(N-ethoxy, N-ethyl dithiocarbamato) nitrido technetium(v) (99mTcN-NOET) is a new neutral cardiac perfusion imaging agent that has been shown to have very high uptake and retention in vitro. The purpose of this study was to determine the clearance kinetics of 99mTcN-NOET in control, ischemic-reperfused, and membrane-disrupted myocardium. METHODS AND RESULTS: After a 100 microCi (3.7 x 10(6) Bq) bolus of 99mTcN-NOET was injected, myocardial clearance was monitored for 1 hour by the use of a sodium iodide detector in 30 isolated, Krebs-Henseleit (KH) perfused rat hearts. Seven hearts were used as controls (group 1). In seven ischemic-reperfused hearts, tracer administration and uptake was followed by 30 minutes of no flow and 1 hour of reflow (group 2). In six additional ischemic-reperfused hearts, tracer administration was followed by deprivation of flow for 1 hour followed by 1 hour of reflow (group 3). Six hearts were perfused with a 0.5% Triton X-100 KH perfusate for 1 hour (group 4). Four hearts were perfused with KH for 10 minutes, followed by cyanide for 10 minutes (group 5). This cycle was repeated three times. Activities remaining in each heart at the end of each experiment were quantitated, and activity at peak uptake was calculated. The 99mTcN-NOET myocardial clearance was near linear in the control (0.6 +/- 0.4) and both ischemic-reperfused groups with virtually no fractional clearance (1.2% +/- 0.6% and 2.1% +/- 0.6%, respectively; p = NS). In the Triton X-100 membrane-disrupted hearts, clearance was substantial (94.2% +/- 4.0%; p < 0.0001 compared with the control and ischemic-reperfused groups). Cyanide treatment produced rapid clearance, which was arrested by a return to the standard KH perfusate. Peak uptake as a percentage of injected dose was 74.9% +/- 1.4% for all groups combined. CONCLUSION: Thus 99mTcN-NOET has extremely high myocardial retention after 1 hour in normal myocardium and is not significantly affected by ongoing myocardial ischemia or reperfusion injury in this model. Clearance is increased markedly in extreme conditions of membrane disruption. These data are consistent with the concept that 99mTc-NOET is localized predominantly in or on cell membranes. 99mTcN-NOET is a promising, new myocardial perfusion imaging agent that exhibits a stable myocardial distribution in the setting of acute developing injury.     

Age differences in trust and reliance of a medication management system

The present study examined age differences in trust and reliance of an automated decision aid. In Experiment 1, older and younger participants performed a simple mathematical task concurrent with a simulated medication management task. The decision aid was designed to facilitate medication management, but with varying reliability. Trust, self-confidence and usage of the aid were measured. The results indicated that older adults had greater trust in the aid and were less confident in their performance, but they did not calibrate trust differently than younger adults. In Experiment 2, a variant of the same task was used to investigate whether older adults are subject to over-reliance on the automation. Differences in omission and commission errors were examined. The results indicated that older adults were more reliant on the decision aid and committed more automation-related errors. A signal detection analyses indicated that older adults were less sensitive to automation failures. Results are discussed with respect to the perceptual and cognitive factors that influence age differences in the use of fallible automation.