Emission spectra, steady state

Figure 8.11a shows steady-state absorption spectra of the CdTe quantum dots in water. Each spectrum in the figure exhibits a distinct peak at a different band corresponding to its size, indicating that all of these suspensions include mono-dispersed nanocrystals. This mono-dispersibility is also supported by their emission spectra with different peak bands corresponding to particle size, as in Figure 8.11b. 

Fig. 8. Dependence of (A) corrected diffusion coefficient (D), (B) steady-state fluorescence intensity, and (C) corrected number of particles in the observation volume (N) of Alexa488-coupled IFABP with urea concentration. The diffusion coefficient and number of particles data shown here are corrected for the effect of viscosity and refractive indices of the urea solutions as described in text. For steady-state fluorescence data the protein was excited at 488 nm using a PTI Alphascan fluorometer (Photon Technology International, South Brunswick, New Jersey). Emission spectra at different urea concentrations were recorded between 500 and 600 nm. A baseline control containing only buffer was subtracted from each spectrum. The area of the corrected spectrum was then plotted against denaturant concentrations to obtain the unfolding transition of the protein. Urea data monitored by steady-state fluorescence were fitted to a simple two-state model. Other experimental conditions are the same as in Figure 6.

Neither the electronic absorption nor the emission spectrum of Re2Cl8 changes in the presence of the quenchers, and no evidence for the formation of new chemical species was observed in flash spectroscopic or steady-state emission experiments. The results of these experiments suggest that the products of the quenching reaction form a strongly associated ion pair, Re2Cl8 D+. 

Fig. 7 Steady state excitation and emission spectra of Au25 after dansyl functionalization. Note that the emission of donor which appears 550 nm quenched significantly. Asterisks ( ) correspond to regions where higher order lines of the grating mask the spectrum [22]...

One may consider the relaxation process to proceed in a similar manner to other reactions in electronic excited states (proton transfer, formation of exciplexes), and it may be described as a reaction between two discrete species initial and relaxed.1-7 90 1 In this case two processes proceeding simultaneously should be considered fluorescence emission with the rate constant kF= l/xF, and transition into the relaxed state with the rate constant kR=l/xR (Figure 2.5). The spectrum of the unrelaxed form can be recorded from solid solutions using steady-state methods, but it may be also observed in the presence of the relaxed form if time-resolved spectra are recorded at very short times. The spectrum of the relaxed form can be recorded using steady-state methods in liquid media (where the relaxation is complete) or using time-resolved methods at very long observation times, even as the relaxation proceeds. 

A discussion on steady state fluorescent monitoring necessitates a distinction between spectroscopic and photometric measurements. The former involves a grating-based spectrofluorometer where full spectrum excitation and emission multivariate spectra are acquired. In contrast a filter photometer involves optical elements (e.g., optical Alters) to isolate excitation and emission bands thereby resulting in a univariate output emission response. 

Natural minerals may contain simultaneously up to 20-25 luminescence centers, which are characterized by strongly different emission intensities. Usually one or two centers dominate, while others are not detectable by steady-state spectroscopy. In certain cases deconvolution of the liuninescence spectra may be useful, especially in the case of broad emission bands. It was demonstrated that for deconvolution of luminescence bands into individual components, spectra have to be plotted as a function of energy. This conversion needs the transposition of the y-axis by a factor A /hc (Townsend and Rawlands 2000). The intensity is then expressed in arbitrary imits. Deconvolution is made with a least squares fitting algorithm that minimizes the difference between the experimental spectrum and the sum of the Gaussian curves. Based on the presumed band numbers and wavelengths, iterative calculations give the band positions that correspond to the best fit between the spectrum and the sum of calculated bands. The usual procedure is to start with one or... 

Two types of Cr + luminescence centers have been found in steady-state natural alexandrite, characterized by J -lines at approximately 680 and 692 nm, accompanied by very many M-lines of Cr-Cr pairs (Tarashchan 1978). Those centers have been identified as connected with substitutions of AP" in different structural sites. It was found that natural alexandrites with very rare exceptions are characterized by very low CL intensities (Ponahlo 2000). Pulse CL study revealed that the spectrum consists of a relatively broad red band peaking at 685-695 nm, accompanied by narrow lines with the strongest one at 679 nm and the weaker ones at 650,655,664,700,707 and 716 nm. All lines and bands have been ascribed to several Cr + centers (Solomonov et al. 2002). The natural chrysoberyl and alexandrite in our study consisted of six samples. The laser-induced time-resolved technique enables us to detect two different Cr and possibly Mn + and V emission centers (Figs. 4.54-4.55). 

The violet emission of the radiation-induced center (COs) " is well known in steady-state luminescence spectra of calcite (Tarashchan 1978 Kasyanenko, Matveeva 1987). The problem is that Ce also has emission in the UV part of the spectrum. In time-resolved luminescence spectroscopy it is possible to differentiate between these two centers because of the longer decay time of the radiation-induced center. Its luminescence peaking at 405 nm becomes dominant after a delay time of 100-200 ns while emission of Ce is already quenched (Fig. 4.14f). 

Fig. 5.71. a-f Unidentified emission center in apatite laser-induced time-resolved luminescence spectra of apatite, a Steady-state luminescence spectrum b Time-resolved spectrmn with narrow gate where yellow band with short decay time dominates c-d Time-resolved spectra after heating at 800 °C e-f Excitation bands of Mn and short-lived yellow band, correspondingly... 

The LIBS technique may be extremely useful for sorting of fluorite ores. Figure 8.8 clearly demonstrates the opportunities of time-resolved LIBS in comparison with the steady-state method in the case of fluorite-carbonate ores. Fluorite and calcite both has Ca as a major element and its emission lines dominate in the steady-state spectra making sorting impossible. After a delay of several ps the intensity of Ca lines is strongly diminished and a F line with a longer decay becomes visible in the fluorite spectrum. 

Fig. 23 Normalized absorption spectra of the free BSA protein (1), BSA-dye 50 conjugate (2) and steady state fluorescence emission spectrum of the BSA-dye conjugate (2 )...

The steady state absorption and emission spectra of poly(A), poly(dA), and the absorption spectrum of the ribonucleotide monomer adenosine 5 -monophosphate (AMP) are shown in Fig. 1. The absorption spectra of poly(A) and poly(dA) are essentially identical. The AMP absorption spectrum is similar to the polymer spectra, but subtle differences exist. The absorption maximum of both homopolymers is shifted to the blue by several hundred wavenumbers, while the low energy band edge is red-shifted with respect to AMP. Similar shifts are observed at 77 K [15]. 

The steady state absorption and fluorescence spectra of both dendrimer generations 1 and 2 are depicted in Fig. 2. The former are merely superpositions of the absorption spectra of both chromophores involved. In the fluorescence, however, the peryleneimide part is almost completely quenched compared to the model compound. Instead, the fluorescence at wavelengths longer than 650 nm almost completely resembles the emission spectrum of the terrylene-diimide model compound 3. This feature is a strong indication that within these dendrimers the excitation energy is efficiently transferred from the peryleneimide to the terrylenediimide. 

One of the most spectacular observations in time-resolved emission spectroscopy is the rise and decay of molecular and excimer (or exciplex) spectra, illustrated in Figure 7.35(b). The structured molecular emission decreases immediately while the excimer emission increases up to a time of tens of ns, depending on the concentration. At longer times only the broad red-shifted excimer spectrum is observed. In Figure 7.35(b) the steady-state spectrum is shown in white this represents of course the integration of all the instantaneous spectra which can be obtained only through time-resolved spectroscopy. 

Fig. I The steady-state fluorescence excitation spectrum of (1) PAQ based MIP and (2) its emission spectra in the absence and (3) in the presence of cGMP (adapted from [47])...

Steady-State Fluorescence. The fluorescence characteristics of PRODAN are extremely sensitive to the physicochemical properties of the solvent (38). As benchmarks, the steady-state emission spectra for PRODAN in several liquid solvents are presented in Figure 1. It is evident that the PRODAN emission spectrum red shifts with increasing solvent polarity. This red shift is a result of the dielectric properties of the surrounding solvent and the large excited-state dipole moment (ca. 20 Debye units) of PRODAN (38). It is the sensitivity of the PRODAN fluorescence that will be used here to investigate the local solvent composition in binary supercritical fluids. 

The time-resolved emission spectra were reconstructed from the fluorescence decay kinetics at a series of emission wavelengths, and the steady-state emission spectrum as described in the Theory section (37). Figure 4 shows a typical set of time-resolved emission spectra for PRODAN in a binary supercritical fluid composed of CO2 and 1.57 mol% CH3OH (T = 45 °C P = 81.4 bar). Clearly, the emission spectrum red shifts following excitation indicating that the local solvent environment is becoming more polar during the excited-state lifetime. We attribute this red shift to the reorientation of cosolvent molecules about excited-state PRODAN. 

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