Fluorescence structural factors, effect

A number of factors relating to the molecular structure of an organic compound and its environment have an effect on the fluorescence quantum yield, which, as we have seen, is dependent on the relative rates of the competing processes that may occur from Si(v = 0). These molecular factors are given below. 

Besides the impressive difference in the chemiexcitation efficiency, also the fluorescence yield of the meta-pattemed emitter m-17 is by more than an order of magnitude ( ) higher than that of the para regioisomer p-17 . Evidently, crossed-conjugated emitters are advantageous for the design of efficient intramolecular CIEEL systems. In Sections V.A-V.C we shall consider additional internal (substrate structural effects) and external (medium influence) factors, which play an essential role in the development of efficient dioxetane-based analytical probes. 

Stephenson monitored the quenching of aromatic hydrocarbon singlet states by observing a decrease in the sensitizer fluorescence intensity with added diene.158 A marked effect of the structure of both the sensitizer and the quencher was noted, with values of kq ranging from 4 x 109 to 8.7 x 10s however, no quantitative correlation between k and several factors that might influence the stability of the proposed excited complex could be obtained (see below). The important observation that singlet quenching led to... 

Absorption and fluorescence spectra of aromatic hydrocarbons are not greatly affected by change of solvent, except for small solvent shifts. At low temperatures the vibrational structure of the bands sharpens up, and some peculiar solvent effects have been noted. When frozen in solution of normal paraffins coronene shows doubling of some of its vibrational bands, and the separation of the components varies with the number of carbon atoms in the solvent molecule chain. The most probable cause is some size-relationship factor between solvent and solute molecules (7). 

Raman spectroscopy has been widely used to study the composition and molecular structure of polymers [100, 101, 102, 103, 104]. Assessment of conformation, tacticity, orientation, chain bonds and crystallinity bands are quite well established. However, some difficulties have been found when analysing Raman data since the band intensities depend upon several factors, such as laser power and sample and instrument alignment, which are not dependent on the sample chemical properties. Raman spectra may show a non-linear base line to fluorescence (or incandescence in near infrared excited Raman spectra). Fluorescence is a strong light emission, which interferes with or totally swaps the weak Raman signal. It is therefore necessary to remove the effects of these variables. Several methods and mathematical artefacts have been used in order to remove the effects of fluorescence on the spectra [105, 106, 107]. 

In many spectroscopic techniques, it is not unusual to encounter baseline offsets from spectrum to spectrum. If present, these kinds of effects can have a profound effect on a PCA model by causing extra factors to appear. In some cases, the baseline effect may consist of a simple offset however, it is not uncommon to encounter other kinds of baselines with a structure such as a gentle upward or downward sloping line caused by instrument drift, or even a broad curved shape. For example, in Raman emission spectroscopy a small amount of fluorescence background signals can sometimes appear as broad, weak curves. 

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