Fluorescence quenching rate constants, kq, ranging from 106 to 2 × 1010 M−1 sec−1, of more than 60 typical electron donor-acceptor systems have been measured in de-oxygenated acetonitrile and are shown to be correlated with the free enthalpy change, ΔG23, involved in the actual electron transfer process

in the encounter complex and varying between + 5 and −60 kcal/mole. The correlation which is based on the mechanism of adiabatic outer-sphere electron transfer requires ΔG≠23, the activation free enthalpy of this process to be a monotonous function of ΔG23 and allows the calculation of rate constants of electron transfer quenching from spectroscopic and electrochemical data.

A detailed study of some systems where the calculated quenching constants differ from the experimental ones by several orders of magnitude revealed that the quenching mechanism operative in these cases was hydrogen-atom rather than electron transfer.

The conditions under which these different mechanisms apply and their consequences are discussed.

Kinetics of Fluorescence Quenching by Electron and H‐Atom Transfer

Quenching of the fluorescence of various fluorophores by molecular oxygen has been studied in aqueous and nonaqueous solutions equilibrated with oxygen pressures up to 100 atm. Temperature dependence of quenching, agreement with the Stern–Volmer equation, and fluorescence lifetime measurements indicate that essentially all the observed quenching is dynamic and close to the diffusion-controlled limits. Studies of charged polyamino acids containing tryptophan show that oxygen quenching, in contrast to I−, is completely insensitive to charge effects. Ethidium bromide, when intercalated into double helical DNA, is quenched with 1/30th of the efficiency of the free dye in solution. Three dyes bound to bovine serum albumin were also found to be relatively protected from the free diffusion of oxygen. Quenching of intrinsic or bound fluorophores by molecular oxygen is therefore an appropriate method to determine the accessibility to oxygen of regions of the macromolecule surrounding the fluorophore and indirectly the structural fluctuations in the macromolecule that permit its diffusion to the fluorophore.

Quenching of fluorescence by oxygen. A probe for structural fluctuations in macromolecules.

Fluorographic detection of radioactivity in polyacrylamide gols with the water-soluble fluor, sodium salicylate

The use of standards for the measurement of photoluminescence quantum yields (QYs) in dilute solutions is reviewed. Only three standards can be considered well estab- lished. Another group of six standards has been investigated by several independent researchers. A large group of standards is frequently used in recent literature, but the valid- ity of these is less certain. The needs for future development comprise: (i) confirmation of the validity of the QY values of many commonly used standard materials, preferably in the form of SI traceable standards; (ii) extension of the set of standard materials to the UV and near-IR spectral ranges; and (iii) good standards or robust protocols for the measurements of low QYs.

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Standards for photoluminescence quantum yield measurements in solution (IUPAC Technical Report)

A phenomenological description, or “conceptual model,” of how direct-injection (DI) diesel combustion occurs has been derived from laser-sheet imaging and other recent optical data. To provide background, the most relevant of the recent imaging data of the author and co-workers are presented and discussed, as are the relationships between the various imaging measurements. Where appropriate, other supporting data from the literature is also discussed. Then, this combined information is summarized in a series of idealized schematics that depict the combustion process for a typical, modern-diesel-engine condition. The schematics incorporate virtually all of the information provided by our recent imaging data including: liquidand vapor-fuel zones, fuel/air mixing, autoignition, reaction zones, and soot distributions. By combining all these elements, the schematics show the evolution of a reacting diesel fuel jet from the start of fuel injection up through the first part of the mixing-controlled burn (i.e. until the end of fuel injection). In addition, for a “developed” reacting diesel fuel jet during the mixingcontrolled burn, the schematics explain the sequence of events that occurs as fuel moves from the injector downstream through the mixing, combustion, and emissions-formation processes. The conceptual model depicted in these schematics also gives insight into the most likely mechanisms for soot formation and destruction and NO formation during the portion of the DI diesel combustion event discussed.

Isadore B. Berlman

Papers

Handbook of Fluorescence Spectra of Aromatic Molecules