Ultrafast excited-state intermolecular proton transfer of cyanine fluorochrome dyes

Steady-state and time-resolved emission spectroscopy techniques were employed to study the excited-state proton transfer (ESPT) to water and D(2)O from QCy7, a recently synthesized near-infrared (NIR)-emissive dye with a fluorescence band maximum at 700 nm. We found that the ESPT rate constant, k(PT), of QCy7 excited from its protonated form, ROH, is ~1.5 × 10(12) s(-1). This is the highest ever reported value in the literature thus far, and it is comparable to the reciprocal of the longest solvation dynamics time component in water, τ(S) = 0.8 ps. We found a kinetic isotope effect (KIE) on the ESPT rate of ~1.7. This value is lower than that of weaker photoacids, which usually have KIE value of ~3, but comparable to the KIE on proton diffusion in water of ~1.45, for which the average time of proton transfer between adjacent water molecules is similar to that of QCy7.     

Theoretical Photodynamic Study of the Photoprotolytic Cycle of Firefly Oxyluciferin

Firefly oxyluciferin presents a pH‐sensitive fluorescence in aqueous solutions. Its fluorescence spectra are composed of two green peaks at different pH values, despite the enolate anion being the only emitter. A computational approach was used to further elucidate the photoprotolytic cycle of oxyluciferin and investigate its pH sensitivity. It was found that oxyluciferin forms π–π stacking complexes both in the ground and excited states, at basic and acidic/neutral pH. However, at different pH values, these complexes adopt a different conformation, which explains the lower energy of the emission at acidic/neutral pH, in comparison with the emission at basic pH.     

High Reynolds number gravity currents along V-shaped valleys

The motion of saline gravity currents propagating horizontally in a tank of rectangular upper cross section and lower V-shaped valley is investigated both by lock-exchange experiments and a box model. The experiments were performed for equal depths of heavy and light fluid on both sides of the lock gate. The density ratio of the heavy fluid to the light fluid was in the range 1.04–1.13 and the lock height to length aspect ratios ranged from 0.5 to 1.6. We show that a box model with the Froude number of the head defined using the distance from the top of the current to the bottom of the valley predicts the position of the head in close agreement with the experiments. The presence of the valley results in three major differences in the gravity current compared to that flowing along a flat bottom. These are (a) the front of the current is approximately parabolic with radius of curvature proportional to the initial depth of the current, (b) for sufficiently large time t, the velocity of the current in the V-shaped valley varies as t^−1/5 compared to t^−1/3 in the flat bottom case, and (c) the width of the current in the V-shaped valley decreases with time t according to t^−2/5. Based on the box model, we predict that the steeper the flanks of the valley the faster the flow.     

Ueber die saure Reaction des Harns

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Ueber den Nachweis des Paralbumins

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Eiereiweiss

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Ueber den Nachweis des Urobilins im Harn

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Untersuchungen über die Veresterung unsymmetrischer zwei- und mehrbasischer Säuren

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