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The fluorescence properties and the fluorescence quenching by Tb3+ of substituted benzoic acid were investigated in solution at different pH. The substituted benzoic acids were used as simple model compounds for chromophores present in humic substances (HS). It is shown that the fluorescence properties of the model compounds resemble fluorescence of HS quite well. A major factor determining the fluorescence of model compounds are proton transfer reactions in the electronically excited state. It is intriguing that the fluorescence of the model compounds was almost not quenched by Tb3+ while the HS fluorescence was decreased very effectively. From our results we concluded that proton transfer reactions as well as conformational reorientation processes play an important role in the fluorescence of HS. The luminescence of bound Tb3+ was sensitized by an energy transfer step upon excitation of the model compounds and of HS, respectively. For HS the observed sensitization was dependent on its origin indicating differences 1) in the connection between chromophores and binding sites and 2) in the energy levels of the chromophore triplet states. Hence, the observed sensitization of the Tb3+ luminescence could be useful to characterize structural differences of HS in solution. Interlanthanide energy transfer between Tb3+ and Nd3+ was used to determine the average distance R between both ions using the well-known formalism of luminescence resonance energy transfer. R was dependent on the origin of the HS reflecting the difference in structure. The value of Rmin seemed to be a unique feature of the HS. It was further found that upon variation of the pH R also changed. This demonstrates that the measurement of interlanthanide energy transfer can be used as a direct method to monitor conformational changes in HS.
We give a necessary and sufficient condition for the existence of an increasing coupling of N (N >= 2) synchronous dynamics on S-Zd (PCA). Increasing means the coupling preserves stochastic ordering. We first present our main construction theorem in the case where S is totally ordered; applications to attractive PCAs are given. When S is only partially ordered, we show on two examples that a coupling of more than two synchronous dynamics may not exist. We also prove an extension of our main result for a particular class of partially ordered spaces.
In this paper, we consider families of time Markov fields (or reciprocal classes) which have the same bridges as a Brownian diffusion. We characterize each class as the set of solutions of an integration by parts formula on the space of continuous paths C[0; 1]; R-d) Our techniques provide a characterization of gradient diffusions by a duality formula and, in case of reversibility, a generalization of a result of Kolmogorov.