Phosphorescence enhancement

Cyclodextrins can solubilize hydrophobic molecules in aqueous media through complex formation (5-8). A nonpolar species prefers the protective environment of the CDx cavity to the hulk aqueous solvent. In addition, cyclodextrins create a degree of structural rigidity and molecular organization for the included species. As a result of these characteristics, these macrocycles are used in studies of fluorescence and phosphorescence enhancement (9-11), stereoselective catalysis (.12,13), and reverse-phase chromatographic separations of structurally similar molecules (14,15). These same complexing abilities make cyclodextrins useful in solvent extraction. 

Figure 19.5 Schematic diagram showing decomposition of total phosphorescence enhancement of PtOEP on silver films into absorption enhancement E X. ) and emissive rate enhancement E (%.2) based on the photophysical model described in the text and data from steady state and transient spectroscopy of PtOEP films with various thicknesses and excitation wavelengths as labeled. The lines represent the possible combinations that could explain the experimentally observed changes in photoluminescence where each position on the line represents a different choice of fQ, the fraction of the excited states that are quenched nonradiatively by interactions between the molecule and the metallic surface. The blue shaded region on the vertical axis is the range of possibilities allowed by constraints from extinction and excitation spectra as explained in the text. The dotted oval is what we believe to be the most likely decomposition for the 6 nm films characterized in Figure 19.4 as discussed in the text. Reprinted from reference 45 with permission of the American Chemical Society.

The model of the photophysics we have advocated does not take into account spin-orbit coupling effects associated with silver as a heavy atom that might affect phosphorescent and nonradiative decay rates for the triplet state. The theoretical justification for this is that heavy atom effects are quite short range since they require wavefunction overlap. Effects of the silver are in any case likely to be much smaller than those of the Pt atom embedded in the porphyrin. Experimentally, we can rule out the importance of these effects since we do not observe phosphorescence enhancement on top of uniform evaporated silver films nor on films that become essentially continuous as for the thickest films in Figure 19.4. 

Several studies on CD complexes with aromatic molecules using steady-state and nanosecond spectroscopy have been reported. These studies aimed to understand the photophysical and photochemical behavior of organic guests such as fluorescence and phosphorescence enhancement, excimer/exciplex formation, photocleavage, charge and proton transfer, energy hopping, and cis-trans photo-... 

The luminescent properties of platinum-modified DNA have also been studied, the fluorescence being quenched and phosphorescence enhanced [111]. Raman difference spectroscopy has shown that some loss of B conformation occurs on binding [124]. Competition studies with polynucleotides, using this technique confirmed the kinetic preference for guanine binding [125]. Changes in the NMR of platinated DNA show distinctive shifts, different from those obtained with intercalators [126]. 

Molecular fluorescence and, to a lesser extent, phosphorescence have been used for the direct or indirect quantitative analysis of analytes in a variety of matrices. A direct quantitative analysis is feasible when the analyte s quantum yield for fluorescence or phosphorescence is favorable. When the analyte is not fluorescent or phosphorescent or when the quantum yield for fluorescence or phosphorescence is unfavorable, an indirect analysis may be feasible. One approach to an indirect analysis is to react the analyte with a reagent, forming a product with fluorescent properties. Another approach is to measure a decrease in fluorescence when the analyte is added to a solution containing a fluorescent molecule. A decrease in fluorescence is observed when the reaction between the analyte and the fluorescent species enhances radiationless deactivation, or produces a nonfluorescent product. The application of fluorescence and phosphorescence to inorganic and organic analytes is considered in this section. 

Of interest, and occasional importance (in whiteness enhancers, for instance), are the fluorescent properties of heterocyclic compounds. Fluorescence is quite frequently found in the compounds relevant to this volume the acridines and acridones show it particularly often, but it appears in a number of very diverse systems. The fluorescence and phosphorescence of heterocyclic molecules have been reviewed by Schulman <74PMH(6)147). 

This considerable enhancement in redox properties may however remain chemically hidden. Several causes may converge to mask these properties. First of all electron transfer is an intermolecular act of reactivity even when thermodynamically feasible it may have to compete with very rapid intramolecular acts of deactivation (fluorescence, phosphorescence, internal conversion)99. The rate of electron transfer is given by the Rehm-Weller equation96,100... 

In room temperature phosphorescence, a treatment of the paper substrate with sodium dodecyl sulfate in conjunction with thallium acetate enhances the results and the technique can be used in routine environmental analysis of organic pollutants [156]. 

Emission spectra Phosphorescence Differential phase Surfactant enhancement (micelles, etc.)... 

Solid-surface room-temperature phosphorescence (RTF) is a relatively new technique which has been used for organic trace analysis in several fields. However, the fundamental interactions needed for RTF are only partly understood. To clarify some of the interactions required for strong RTF, organic compounds adsorbed on several surfaces are being studied. Fluorescence quantum yield values, phosphorescence quantum yield values, and phosphorescence lifetime values were obtained for model compounds adsorbed on sodiiun acetate-sodium chloride mixtures and on a-cyclodextrin-sodium chloride mixtures. With the data obtained, the triplet formation efficiency and some of the rate constants related to the luminescence processes were calculated. This information clarified several of the interactions responsible for RTF from organic compounds adsorbed on sodium acetate-sodium chloride and a-cyclodextrin-sodium chloride mixtures. Work with silica gel chromatoplates has involved studying the effects of moisture, gases, and various solvents on the fluorescence and phosphorescence intensities. The net result of the study has been to improve the experimental conditions for enhanced sensitivity and selectivity in solid-surface luminescence analysis. 

Au(I) in such systems should enhance the phosphorescence. The complex [AulCfiFs) (C6F4NCSPPh2)] is luminescent in the solid state at room temperature and at 77 K also in glass media at 77 K but neither in deoxygenated dichloromethane nor in acetonitrile solutions. 

S. Liu, J. Feng, and Y. Zhao, Enhanced red emission from fluorescent organic light-emitting devices utilizing a phosphorescent sensitizer, Jpn. J. Appl. Phys., 43 2320-2322 (2004). 

Of particular interest in the application of cyclodextrins is the enhancement of luminescence from molecules when they are present in a cyclodextrin cavity. Polynuclear aromatic hydrocarbons show virtually no phosphorescence in solution. If, however, these compounds in solution are encapsulated with 1,2-dibromoethane (enhances intersystem crossing by increasing spin-orbit coupling external heavy atom effect) in the cavities of P-cyclodextrin and nitrogen gas passed, intense phosphorescence emission occurs at room temperature. Cyclodextrins form complexes with guest molecules, which fit into the cavity so that the microenvironment around the guest molecule is different from that in... 

Zhang YX, Aslan K, Previte MJR, Malyn SN, Geddes CD (2006) Metal-enhanced phosphorescence Interpretation in terms of triplet-coupled radiating plasmons. J Phys Chem B 110 25108-25114... 

Inorganic ions, such as Tl+, Ag+, etc., can be incorporated as counterions on anion micelles containing the excited triplet. Spin orbit coupling ensues and enhanced phosphorescence is observed. The spin orbit coupling reaction is too inefficient to be observed in homogeneous media. 

Another possibility is deactivation through increased intersystem crossing,(1) which would occur via enhanced spin—orbit coupling.(28) If intersystem crossing is enhanced, then the phosphorescence quantum yield of a... 

The long lifetime has important consequences on the decay rates. First, we consider what affects the nonradiative rates (knr) which change the yields of fluorescence and phosphorescence. The nonradiative decay rate is often enhanced in molecules which have flexible constituents (the so-called loose-bolt effect). Therefore, both fluorescence and phosphorescence yields are generally larger for rigid molecules than flexible molecules. For the same reason, a rigid environment will increase the emission yields hence both fluorescence and phosphorescence yields often increase with increasing viscosity. 

The intersystem crossing process has opposite effects on the yields of fluorescence and phosphorescence since it depletes the singlet state and populates the triplet state. It is commonly known that heavy ions, such as iodide and bromide, increase intersystem crossing by spin-orbit coupling.(1617) For proteins, fluorescence can be quenched as phosphorescence yield is enhanced. 8,19) However, although the phosphorescence yield is increased, the lifetime is decreased. This effect arises because spin-orbit coupling, which increases the intersystem crossing rate from 5, to Tt, also increases the conversion rate from T, to S0. 

Fig. 28. Time-resolved phosphorescence spectra of quinoxaline in durene host observed at 1.38 K and at (a) 30 msec, (b) 450 msec, and (c) 1500 msec after excitation cutoff. The ordinate scale is normalized with respect to the 0 - 0" band. The numbers shown in (c) represent the vibrational frequencies (in wavenumber unit) measured from the 0 - 0" band (21639 cm r). The arrows indicate the bands whose relative intensities are remarkably enhanced at later times after the excitation cutoff. (From Yamauchi and Azumi, Ref. >)...

Protonation of (n, 7t )-nitrobenzene had been suggested earlier and later questioned I8) on account of an estimated extremely weak basicity of 3(n, tt )-nitrobenzene. Enhanced basicity of the lowest excited singlet state compared to ground and lowest excited triplet state has been derived from shifts in the phosphorescence and absorption spectra of nitrophenols ). On this basis, the increased rate of nitrobenzene photoreduction in acidic solution is formd to be thermodynamically unfeasible in the lowest excited triplet state >. Although it might be thermodynamically feasible in the excited singlet state, the short lifetime of the latter state may make this possibility unlikely. 

Luhman WA, Holmes RJ (2009) Enhanced exciton diffusion in an organic photovoltaic cell by energy transfer using a phosphorescent sensitizer. Appl Phys Lett 94 153304... 

Thymidine phosphate and cytidine phosphate do not phosphoresce in a rigid ethylene glycol-water glass at 77°K109 when directly excited, but thymidine which has lost its proton at Nx does have a triplet which phosphoresces with a decay time of 0.50 sec at high pH uridine also fluoresces with a similar decay time. The quenching of purine fluorescence and appearance of T" fluorescence in UV-irradiated DNA and poly dAT (as well as U" fluorescence in poly rAU) was attributed by Rahn et al.109 to proton transfer from thymine to adenine. This quenches adenine fluorescence and enhances thymine fluorescence. 

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