Fluorescence picosecond

Absorption spectra and decay kinetics of electron adducts of proflavin and acridine yellow in aqueous solution have been studied and the rates of transfer to different electron acceptors measured.Electron injection from xanthene dyes and tetraphenylporphines into ZnO and TiO has been shown to compete with fluorescence.Picosecond spectroscopy has been used to determine excited-state absorption spectra and decay mechanisms in photostabilizers.Fluorescence... 

Fluorescence Picosecond Time-Resolved Single Photon Counting... 

Pullerits T, Visscher K J, Hess S, Sundstrom V, Freiberg A, Timpmann K and Van Grondelle R 1994 Energy-transfer in the inhomogeneously broadened core antenna of purple bacteria-a simultaneous fit of low-intensity picosecond absorption and fluorescence kinetics Biophys. J. 66 236-48... 

Hydrogen transfer in excited electronic states is being intensively studied with time-resolved spectroscopy. A typical scheme of electronic terms is shown in fig. 46. A vertical optical transition, induced by a picosecond laser pulse, populates the initial well of the excited Si state. The reverse optical transition, observed as the fluorescence band Fj, is accompanied by proton transfer to the second well with lower energy. This transfer is registered as the appearance of another fluorescence band, F2, with a large anti-Stokes shift. The rate constant is inferred from the time dependence of the relative intensities of these bands in dual fluorescence. The experimental data obtained by this method have been reviewed by Barbara et al. [1989]. We only quote the example of hydrogen transfer in the excited state of... 

In studies of molecular dynamics, lasers of very short pulse lengths allow investigation by laser-induced fluorescence of chemical processes that occur in a picosecond time frame. This time period is much less than the lifetimes of any transient species that could last long enough to yield a measurable vibrational spectrum. Such measurements go beyond simple detection and characterization of transient species. They yield details never before available of the time behavior of species in fast reactions, such as temporal and spatial redistribution of initially localized energy in excited molecules. Laser-induced fluorescence characterizes the molecular species that have formed, their internal energy distributions, and their lifetimes. 

The LIF technique is extremely versatile. The determination of absolute intermediate species concentrations, however, needs either an independent calibration or knowledge of the fluorescence quantum yield, i.e., the ratio of radiative events (detectable fluorescence light) over the sum of all decay processes from the excited quantum state—including predissociation, col-lisional quenching, and energy transfer. This fraction may be quite small (some tenths of a percent, e.g., for the detection of the OH radical in a flame at ambient pressure) and will depend on the local flame composition, pressure, and temperature as well as on the excited electronic state and ro-vibronic level. Short-pulse techniques with picosecond lasers enable direct determination of the quantum yield [14] and permit study of the relevant energy transfer processes [17-20]. 

Brockhinke, A. and Linne, M.A., Short-pulse techniques Picosecond fluorescence, energy transfer and "quench-free" measurements, in Applied Combustion Diagnostics, Kohse-Hoinghaus, K. and Jeffries, J.B. (Eds.), Taylor Francis, New York, 2002, Chapter 5. 

Figure 6. Tempcraiure dependence of the fluorescence lifetime of BMPC in 1 1 ethanol-mcihanol. Measurements were carried out at the LENS laboratory of Florence by a picosecond apparatus using as an excitation source (at 380 nm) a dye laser pumped by a frequency-doubled cw Nd-YAG laser and recording the fluorescence time jirofiles by a streak camera. Since the overall insuumental response time was 75-80 ps, decays with t>200 ps, observed at T<130 K, were analyzed without deconvolution. At 177, 178 and 193 K, the lifetimes were roughly estimated as i=(FWHM -77 ), where FWHM was the width at half maximum of the decay. Because of the rather high sample absorbances (An,x=2), self absorption may have reduced the lifetimes to some extent.

The characterization of the laser pulse widths can be done with commercial autocorrelators or by a variety of other methods that can be found in the ultrafast laser literature. " For example, we have found it convenient to find time zero delay between the pump and probe laser beams in picosecond TR experiments by using fluorescence depletion of trans-stilbene. In this method, the time zero was ascertained by varying the optical delay between the pump and probe beams to a position where the depletion of the stilbene fluorescence was halfway to the maximum fluorescence depletion by the probe laser. The accuracy of the time zero measurement was estimated to be +0.5ps for 1.5ps laser pulses. A typical cross correlation time between the pump and probe pulses can also be measured by the fluorescence depletion method. 

Merola, R, Rigler, R., Holmgren, A., and Brochon, J-C., Picosecond tryptophan fluorescence of thioredoxin evidence for discrete species in slow exchange, Biochemistry, 28, 3383, 1989. 

Haupl T, Windolph C, Jochum T, Brede O, Hermann R (1997) Picosecond fluorescence of nucleic acid bases. Chem Phys Lett 280 520-524... 

This agrees quite well with the rate constants for intramolecular proton transfer in 2,4-bis(dimethyl-amino )-6-(2-hydroxy-5-methylphenyl)-5-triazine which had been measured by Shizuka et al. ( l6) using laser picosecond spectroscopy. The fluorescence decay constant t of (TIN) was found to be 60 20 ps. Because of the weak intensity all fluorescence lifetimes refer to the pure substance in crystalline form at room temperature. 

Using picosecond flash spectroscopy Gupta et al. 2k) reported for 2-hydroxyphenylbenzotriazole in ethanol a short-lived transient (6 ps) followed by a transient absorption whose lifetime is estimated to be 600 ps. The authors assigned the short-lived transient to the "vertical singlet" while the long-lived transient is presumably the "proton transferred species". These measurements of transient absorptions with the picosecond flash method confirm our results derived from the fluorescence emission using the phase fluorimetric method. 

Shynkar VV, Mely Y, Duportail G et al (2003) Picosecond time-resolved fluorescence studies are consistent with reversible excited-state intramolecular proton transfer in 4 -(dialkylamino)-3-hydroxyflavones. J Phys Chem A 107 9522-9529... 

Herbich J, Dobkowski J, Rulliere C, Nowacki J (1989) Low-temperature dual fluorescence in 9-morpholinoacridine picosecond TICT state formation J Lumin 44 87-95... 

Just as above, we can derive expressions for any fluorescence lifetime for any number of pathways. In this chapter we limit our discussion to cases where the excited molecules have relaxed to their lowest excited-state vibrational level by internal conversion (ic) before pursuing any other de-excitation pathway (see the Perrin-Jablonski diagram in Fig. 1.4). This means we do not consider coherent effects whereby the molecule decays, or transfers energy, from a higher excited state, or from a non-Boltzmann distribution of vibrational levels, before coming to steady-state equilibrium in its ground electronic state (see Section 1.2.2). Internal conversion only takes a few picoseconds, or less [82-84, 106]. In the case of incoherent decay, the method of excitation does not play a role in the decay by any of the pathways from the excited state the excitation scheme is only peculiar to the method we choose to measure the fluorescence (Sections 1.7-1.11). 

Kemnitz, K., Pfeifer, L. and Ainbund, M. R. (1997). Detector for multichannel spectroscopy and fluorescence lifetime imaging on the picosecond timescale. Nucl. Instrum. Meth. Phy. Res. A 387, 86-7. 

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