Characterizing the surface quality and droplet interface shape for microarray plates

The variation in the surface quality of microarray plates was examined by measuring the contact angles of 480 droplets on five microarray plates. It was found that the measured contact angle did not accurately predict the droplet shape for moderate Bond numbers (~0.5 ≤ N(B) ≤ 5). By defining an apparent contact angle using the ratio of the contact radius to the height, the variance in the predicted interface shape decreased by greater than a factor of 3 for both local and globally averaged characteristics. The error in the predicted droplet height was also reduced by 3 orders of magnitude.     

Surfactant presence in a multilayer polyelectrolyte–enzyme system improves its catalytic response

Self-assembling of poly(allylamine) containing an osmium polypyridil complex (PAOs) alternatively with sodium dodecyl sulfate (SDS) and glucose oxidase (GOx) generates a ternary multilayer system, (PAOs/SDS/PAOs/GOx)_n. The introduction of this anionic surfactant allows a sensitive increase of the polyelectrolyte and the enzyme uptake at pH 7.0, enhancing its catalytic behavior in presence of glucose more than 5 times, compared to the system (PAOs/GOx)_n constructed at the same pH. The balance between ionic and hydrophobic interactions in the construction of this system is discussed.     

Cooperative hydration of pyruvic acid in ice

About 3.5 +/- 0.3 water molecules are still involved in the exothermic hydration of 2-oxopropanoic acid (PA) into its monohydrate (2,2-dihydroxypropanoic acid, PAH) in ice at 230 K. This is borne out by thermodynamic analysis of the fact that QH(T) = [PAH]/[PA] becomes temperature independent below approximately 250 K (in chemically and thermally equilibrated frozen 0.1 < or = [PA]/M < or = 4.6 solutions in D2O), which requires that the enthalpy of PA hydration (DeltaHH approximately -22 kJ mol(-1)) be balanced by a multiple of the enthalpy of ice melting (DeltaHM = 6.3 kJ mol(-1)). Considering that: (1) thermograms of frozen PA solutions display a single endotherm, at the onset of ice melting, (2) the sum of the integral intensities of the 1deltaPAH and 1deltaPA methyl proton NMR resonances is nearly constant while, (3) line widths increase exponentially with decreasing temperature before diverging below approximately 230 K, we infer that PA in ice remains cooperatively hydrated within interstitial microfluids until they vitrify.     

Chemical composition of secondary organic aerosol formed from the photooxidation of isoprene

Recent work in our laboratory has shown that the photooxidation of isoprene (2-methyl-1,3-butadiene, C(5)H(8)) leads to the formation of secondary organic aerosol (SOA). In the current study, the chemical composition of SOA from the photooxidation of isoprene over the full range of NO(x) conditions is investigated through a series of controlled laboratory chamber experiments. SOA composition is studied using a wide range of experimental techniques: electrospray ionization-mass spectrometry, matrix-assisted laser desorption ionization-mass spectrometry, high-resolution mass spectrometry, online aerosol mass spectrometry, gas chromatography/mass spectrometry, and an iodometric-spectroscopic method. Oligomerization was observed to be an important SOA formation pathway in all cases; however, the nature of the oligomers depends strongly on the NO(x) level, with acidic products formed under high-NO(x) conditions only. We present, to our knowledge, the first evidence of particle-phase esterification reactions in SOA, where the further oxidation of the isoprene oxidation product methacrolein under high-NO(x) conditions produces polyesters involving 2-methylglyceric acid as a key monomeric unit. These oligomers comprise approximately 22-34% of the high-NO(x) SOA mass. Under low-NO(x) conditions, organic peroxides contribute significantly to the low-NO(x) SOA mass (approximately 61% when SOA forms by nucleation and approximately 25-30% in the presence of seed particles). The contribution of organic peroxides in the SOA decreases with time, indicating photochemical aging. Hemiacetal dimers are found to form from C(5) alkene triols and 2-methyltetrols under low-NO(x) conditions; these compounds are also found in aerosol collected from the Amazonian rainforest, demonstrating the atmospheric relevance of these low-NO(x) chamber experiments.     

Trennung des Mono- Di- und Triaethylamins

Analytical and Bioanalytical Chemistry -     

Reactionen auf Pikrins?ure

Ohne Zusammenfassung     

Untersuchung von Fetten

Ohne Zusammenfassung     

The relationship between DEA efficiency and the type of production function, the degree of homogeneity, and error variability

In this paper, we use simulations to investigate the relationship between data envelopment analysis (DEA) efficiency and major production functions: Cobb-Douglas, the constant elasticity of substitution, and the transcendental logarithmic. Two DEA models were used: a constant return to scale (CCR model), and a variable return to scale (BCC model). Each of the models was investigated in two versions: with bounded and unbounded weights. Two cases were simulated: with and without errors in the production functions estimation. Various degrees of homogeneity (of the production function) were tested, reflecting a constant increasing and decreasing return to scale. With respect to the case with errors, three distribution functions were utilized: uniform, normal, and double exponential. For each distribution, 16 levels of the coefficient of variance (CV) were used. In all the tested cases, two measures were analysed: the percentage of efficient units (from the total number of units), and the average efficiency score. We applied a regression analysis to test the relationship between these two efficiency measures and the above parameters. Overall, we found that the degree of homogeneity has the largest effect on efficiency. Efficiency declines as the errors grow (as reflected by larger CV and of the expansion of the probability distribution function away from the centre). The bounds on the weights tend to smooth the effect, and bring the various DEA versions closer to one other. The type of efficiency measure has similar regression tendencies. Finally, the relationship between the efficiency measures and the explanatory variables is quadratic.     

Light-induced structural changes in chiral liquid crystals

Novel light-sensitive chiral dopants are studied as a light-sensitive component in chiral liquid crystals which may be used in tunable optical devices. Light-induced cis-trans- isomerization of chiral dopants results in changes of helical twisting power which translates into variations of helical pitch. Due to the light absorption in the liquid crystal cell the pitch variation is non-uniform across the cell, which leads, at first, to a deformation of cholesteric layers, and then to the formation of cholesteric bubbles. The sequence of structural changes has a distinct visual pattern and occurs at the surface close to the UV light source. Small deformations of cholesteric layers and bubbles are unstable and disappear after removing UV irradiation. The increasing size of the cholesteric bubbles results in better stability; large bubbles do not disappear after removing UV light. A theoretical model is suggested to describe the undulations of cholesteric layers.