Theoretical study on the protonation of AZA-aromatics

The protonation of azanaphthalenes and azabenzenes has been studied theoretically using CNDO/2 wavefunctions and perturbation theory in order to examine the correlation between pKa values and quantum-mechanical quantities

Diazanaphthalenes: A 13C NMR investigation on the site of protonation and pKa values

The pH dependence of the 13C chemical shifts (δ) of the diazanaphthalenes has been recorded. From this dependence the pKa values have been determined using the Henderson-Hasselbach equation. The change in 13C chemical shifts under the influence of nitrogen protonation (Δδ) has been predicted using the Δδ values of quinoline and isoquinoline. The correlation between observed and expected Δδ values of the symmetric diazanaphthalenes is very good. Assuming these changes in chemical shifts to be of general validity, the site of protonation in the asymmetric diazanaphthalenes has been determined by comparison of the expected Δδ values for α- and ß-nitrogen protonation with the observed ones. The site of protonation for 1,6- and 1,7-naphthyridine is the ß-nitrogen atom, whereas for cinnoline both monoprotonated species are present in a significant amount

Liquid-grain mixing suppresses droplet spreading and splashing during impact

Would a raindrop impacting on a coarse beach behave differently from that impacting on a desert of fine sand? We study this question by a series of model experiments, where the packing density of the granular target, the wettability of individual grains, the grain size, the impacting liquid, and the impact speed are varied. We find that by increasing the grain size and/or the wettability of individual grains the maximum droplet spreading undergoes a transition from a capillary regime towards a viscous regime, and splashing is suppressed. The liquid-grain mixing is discovered to be the underlying mechanism. An effective viscosity is defined accordingly to quantitatively explain the observations

Crater formation during raindrop impact on sand

After a raindrop impacts on a granular bed, a crater is formed as both drop and target deform. After an initial, transient, phase in which the maximum crater depth is reached, the crater broadens outwards until a final steady shape is attained. By varying the impact velocity of the drop and the packing density of the bed, we find that avalanches of grains are important in the second phase and hence, affect the final crater shape. In a previous paper, we introduced an estimate of the impact energy going solely into sand deformation and here we show that both the transient and final crater diameter collapse with this quantity for various packing densities. The aspect ratio of the transient crater is however altered by changes in the packing fraction.Comment: 9 pages, 9 figure

Exploring droplet impact near a millimetre-sized hole: comparing a closed pit with an open-ended pore

We investigate drop impact dynamics near both closed pits and open- ended pores experimentally. The resulting impact phenomena differ greatly for a pit or a pore. For the first, we observe three phenomena: a splash, a jet and an air bubble, whose appearance depends on the distance between impact location and pit. Furthermore, we found that splash velocities can reach up to seven times the impact velocity. Drop impact near a pore, however, results solely in splashing. Surprisingly, two distinct and disconnected splashing regimes occur, with a region of plain spreading in-between. For pores, splashes are less pronounced than in the pit case. We state that, for the pit case, the presence of air inside the pit plays a crucial role: it promotes splashing and allows for air bubbles to appear.Comment: 17 pages, 11 figures, 1 supplementary movie, submitted to JF

Dramatic effect of fluid chemistry on cornstarch suspensions: linking particle interactions to macroscopic rheology

Suspensions of cornstarch in water exhibit strong dynamic shear-thickening. We show that partly replacing water by ethanol strongly alters the suspension rheology. We perform steady and non-steady rheology measurements combined with atomic force microscopy to investigate the role of fluid chemistry on the macroscopic rheology of the suspensions and its link with the interactions between cornstarch grains. Upon increasing the ethanol content, the suspension goes through a yield-stress fluid state and ultimately becomes a shear-thinning fluid. On the cornstarch grain scale, atomic force microscopy measurements reveal the presence of polymers on the cornstarch surface, which exhibit a co-solvency effect. At intermediate ethanol content, a maximum of polymer solubility induces high microscopic adhesion which we relate to the macroscopic yield stress

Inquiry into the diagnostic workup of patients with fever of unknown origin

Contains fulltext : inqiinthd.pdf (publisher's version ) (Open Access

Einselection and Decoherence from an Information Theory Perspective

We introduce and investigate a simple model of conditional quantum dynamics. It allows for a discussion of the information-theoretic aspects of quantum measurements, decoherence, and environment-induced superselection (einselection).Comment: Proceedings of the Planck constant centenary meeting. Uses annalen.cls and fleqn.st

In vitro proliferation of mononuclear phagocytes from murine and human bone marrow

Contains fulltext : 4339.pdf (publisher's version ) (Open Access