Electronic excitation energy migration in a photonic antenna host-guest material has been investigated by time-resolved fluorescence experiments and by Monte Carlo calculations. The host consists of a linear channel system (zeolite L). The channels are filled with energy transporting dyes (donors) in their middle section and by one or several monolayers of a strongly luminescent trapping dye (acceptors) at each end of the channels. Excitation energy is transported among the donors in a series of steps until it reaches an acceptor at one end of the channels, or it is somehow trapped on its way, or it escapes by spontaneous emission. We describe the organization of dyes in the channels by means of Monte Carlo simulation and we report time-resolved data on a variety of pyronine-, oxonine-, and oxonine, pyronine-zeolite L materials. In the latter, the pyronine acts as donor and oxonine as acceptor. We find that the luminescence decay of crystals containing only one kind of dye is single exponential for moderate loading if measured under oxygen-free conditions, but biexponential otherwise. The main characteristic of the time evolution of oxonine, pyronine-zeolite L crystals is that the acceptor intensity is first built up before it starts to decay. This intensity increase becomes faster with increasing donor loading, a fact that beautifully supports the interpretation that the crystals behave as photonic antenna in which excitation energy is transported preferentially along the channels by a Förster-type mechanism until it reaches the acceptor, where it is emitted as red luminescence.
The theory on particle distribution and exchange equilibria in a microporous material is applied to experimental ion-exchange data involving zeolite Na-A and zeolite K-A, with silver ions as the exchanging species. The presented method enables direct evaluation of the measured data and consideration of nonequivalent particle sites. The isotherms of the K+ versus Ag+ exchange in zeolite K-A rise much more steeply, at low exchange degrees, than those of the Na+ versus Ag+ exchange in zeolite Na-A. This result implies a different course of the ion-exchange reactions. Spectroscopic measurements on dehydrated, partly silver-exchanged zeolites Na-A and K-A do indeed show that in zeolite Na-A, the Na+ ions occupying four-ring positions are exchanged faster for Ag+ than the Na+ ions occupying eight- and six-ring positions, while in zeolite K-A the exchange does not start with the four-ring ion but with six-ring ions, followed by the four-ring ion. These findings are consistent with the results obtained from evaluation of the ion-exchange data. The resulting thermodynamic quantities significantly differ from published reference values, which we suggest should be revised.
The kinetics of the reaction of the amino acid epimers L-isoleucine, D-allo-isoleucine, L-threonine, and D-allo-threonine with o-phthaldialdehyde and mercaptoethanol were determined at 25 degrees C. L-Isoleucine reacts faster than its D-epimer whereas L-threonine reacts slightly slower than its D-epimer. In the case of isoleucine, the consequence can be an allo/iso ratio which in the worst case is 25% too low if these amino acids are quantified by liquid chromatography and o-phthaldialdehyde fluorescence detection. The effect on dating of fossils by amino acid racemization is discussed.
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