E quantum yield

A major advantage of fluorescence as a sensing property stems from the sensitivity to the precise local environment of the intensity, i.e., quantum yield (excited state lifetime (xf), and peak wavelength (Xmax). In particular, it is the local electric field strength and direction that determine whether the fluorescence will be red or blue shifted and whether an electron acceptor will or will not quench the fluorescence. An equivalent statement, but more practical, is that these quantities depend primarily on the change in average electrostatic potential (volts) experienced by the electrons during an electronic transition (See Appendix for a brief tutorial on electric fields and potentials as pertains to electrochromism). The reason this is more practical is that even at the molecular scale, the instantaneous electric... 

One of the most important features of a photoreaction is the value of the quantum yield ( )i of compound i, which is the quantifying answer to the question How effective In principle, the quantum yield is the ratio of the number of reacting molecules to the number of quanta absorbed. In praxis there are several definitions of the quantum yield true (only light absorbed by the reactant is considered) and apparent (there are other absorbers present), differential (at the moment ) and integral (mean). In the previous rate equation, ( )e and (j) are the true differential yields. The monoexponential kinetics of Equation, 1.2 or 1.4 allow one to determine the yields in systems where the starting solution is already a mixture of E- and Z-forms (which can happen easily if the E-form is not prepared under strict exclusion of light). It turns out, however, that the yalues of the Z —> E quantum yield are especially sensitive to small errors in the E values. 

V(j)g, i.e., the ratio of the E Z and Z —> E quantum yields at the two irradiation wavelengths should be equal, which is only partly true for azobenzene (see Section 1.3.2.1). Fisher s article is not easy to read one must be careful to discriminate strictly between irradiation and analysis wavelengths. 

The quantum efficiencies and photostabilities of most intrinsically fluorescent biomolecules are modest relative to those of the available fluorescent labels. There are, however, several factors that can affect these quantum yields. The ionic strength and pH of the separation conditions, as well as the presence or absence of organic additives, can have a significant effect on the fluorescent properties (i.e., quantum yields and Stokes shift) of these analytes." Thus, if sensitivity is of... 

The absorption of laser photons leads to excitation of atoms or molecules. In many cases, radiative decay of the excited state is very efficient, i.e., quantum yields of luminescence or fluorescence are very high. Measurement of the intensity of emitted photons as a function of analyte concentration is a widespread analytical method with conventional light sources. The use of intense laser sources greatly increased the sensitivity and selectivity of traditional luminescence methods. 

As reviewed in the introduction, the luminescence from polymers and bir dymers may be described in terms of spectral sh e, quantum yield of emission, decay time characteristics and polarization properties. The recent rapid increase in interest in the usefulness of luminescence tediniques to study the stmcture and prc rties of molecular systems is partly due to the now ready availability of reliable in rumentation. Although the apparatus necessary for studying the spectral characteristics of luminescence is well established and has been reviewed in detail by veral authors there have been recent rapid developments in the techniques available for time-... 

Especial attention is paid to the dependence of the azide photoactivity (i.e. quantum yield of azido group photodissociation) on the size and charge of the heteroaromatic system. Heterocyclic azides have been used as convenient model compounds for the study of charge effect, since they can be easily transformed... 

After the primary step in a photochemical reaction, the secondary processes may be quite complicated, e.g. when atoms and free radicals are fcrnied. Consequently the quantum yield, i.e. the number of molecules which are caused to react for a single quantum of light absorbed, is only exceptionally equal to exactly unity. E.g. the quantum yield of the decomposition of methyl iodide by u.v. light is only about 10" because some of the free radicals formed re-combine. The quantum yield of the reaction of H2 -f- CI2 is 10 to 10 (and the mixture may explode) because this is a chain reaction. 

The simple difhision model of the cage effect again can be improved by taking effects of the local solvent structure, i.e. hydrodynamic repulsion, into account in the same way as discussed above for bimolecular reactions. The consequence is that the potential of mean force tends to favour escape at larger distances > 1,5R) more than it enliances caging at small distances, leading to larger overall photodissociation quantum yields [H6, 117]. 

The cyclization product is thermally unstable relative to Z-stilbene and reverts to starting material unless trapped by an oxidizing agent. The extent of eyclization is solvent-dependent, with nonpolar solvents favoring cyclization more than polar ones. ° Whereas the quantum yield for Z-E isomerization is nearly constant at about 35%, the cyclization... 

Fig. 13.11. A schematic drawing of the potential energy surfaces for the photochemical reactions of stilbene. Approximate branching ratios and quantum yields for the important processes are indicated. In this figure, the ground- and excited-state barrier heights are drawn to scale representing the best available values, as are the relative energies of the ground states of Z- and E -stilbene 4a,4b-dihydrophenanthrene (DHP). [Reproduced from R. J. Sension, S. T. Repinec, A. Z. Szarka, and R. M. Hochstrasser, J. Chem. Phys. 98 6291 (1993) by permission of the American Institute of Physics.]...

The quantum yield for formation of 3-methylcyclobutene from E-ES-pentadiene is 10... 

The thermal reversal of the photochemical a-cleavage, i.e., the direct recombination of the resulting radical pair or diradical, can be recognized as such only when at least one of the a-atoms is chiral and is epimerized in the process. In fact, the frequently rather low quantum yields observed in the phototransformations of nonconjugated steroidal ketones may be largely due to the reversal of a-cleavage. 

The synthesis-driven approach towards material science can be applied to create oligomers and polymers with optimized properties, e.g. maximized carrier mobilities and electrical conductivities or high photo- and electroluminescence quantum yields. It becomes obvious, however, that the ability to synthesize structurally defined -architectures is the key to these high performance materials. 

The optical properties can be tuned by variations of the chromophores (e.g. type of side-chains or length of chromophorc). The alkyl- and alkoxy-substituted polymers emit in the bluc-gnecn range of the visible spectrum with high photolu-inincsccncc quantum yields (0.4-0.8 in solution), while yellow or red emission is obtained by a further modification of the chemical structure of the chromophores. For example, cyano substitution on the vinylene moiety yields an orange emitter. 

Fluorescence emission maximum Fluorescence quantum yield Molar absorption coefficient (e) at peak wavelengths (as monomer)... 

Name of Luciferin Molecular Formula (Mr) Absorption Max. (nm) (e value) Fluorescence Emission Max. (nm) Luminescence Max. (nm) Quantum Yield... 

Coelenterazine can be detected and measured with a coelenterazine luciferase, i.e. a luciferase specific to coelenterazine. As the coelenterazine luciferase, the luciferases from the sea pansy Renilla and the copepods Gaussia and Pleuromamma are commercially available. Certain kinds of decapod shrimps, such as Oplophoms and Heterocarpus, contain a large amount of luciferase, and the luciferases purified from them are most satisfactory for the assay of coelenterazine considering their high activities and high quantum yields. Even partially purified preparations of these luciferases are satisfactory for most measurements. The author routinely uses purified Oplophoms luciferase. 

The acyl phosphonates, acyl phosphine oxides and related compounds (e.g. 81. 82) absorb strongly in the near UV (350-400 nm) and generally decompose by rescission in a manner analogous to the benzoin derivatives.381"285 Quantum yields vary from 0.3 to 1.0 depending on structure. The phosphinyl radicals are highly reactive towards unsaturated substrates and appear to have a high specificity for addition v.v abstraction (see 3.4.3.2). 

UV spectra are, however, very useful for the determination of acid-base and ion pair formation equilibria, and for photochemical investigations (e. g., determination of quantum yield in photolytic dediazoniation, Tsunoda and Yamaoka, 1966 fluorescence and phosphorescence at low temperature, Sukigahara and Kikuchi, 1967a). 

Calibration. Many approaches have been used to calibrate flow cytometric measurements. Including the comparison of flow and nonflow techniques (radiolabels, spectrofluorometry). In recent years, commercial standards have been introduced which are calibrated in fluorescein equivalents/particle (e.g., 3,000 or 500,000). With labeled ligands, calibration requires determining the relative quantum yield of the ligand compared to pure fluorescein and using the standards to analyze the amount bound on cells. Our ligands (fluorescein isothiocyanate derivatives) are typically 50% as fluorescent as fluorescein. 

Calibration. In general, standards used for instrument calibration are physical devices (standard lamps, flow meters, etc.) or pure chemical compounds in solution (solid or liquid), although some combined forms could be used (e.g., Tb + Eu in glass for wavelength calibration). Calibrated lnstr iment parameters include wavelength accuracy, detection-system spectral responsivity (to determine corrected excitation and emission spectra), and stability, among others. Fluorescence data such as corrected excitation and emission spectra, quantum yields, decay times, and polarization that are to be compared among laboratories are dependent on these calibrations. The Instrument and fluorescence parameters and various standards, reviewed recently (1,2,11), are discussed briefly below. 

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