Quenching complexes

The methods of anion detection based on fluorescence involve quenching, complex formation, redox reactions and substitution reactions (Fernandez-Gutierrez and Munoz de la Pena, 1985). This chapter will be restricted to anion molecular sensors based on collisional quenching (in general, they exhibit a poor selectivity) and on recognition by an anion receptor linked to a fluorophore (fluoroionophore). 

By comparing time-resolved and steady-state fluorescence parameters, Ross et alm> have shown that in oxytocin, a lactation and uterine contraction hormone in mammals, the internal disulfide bridge quenches the fluorescence of the single tyrosine by a static mechanism. The quenching complex was attributed to an interaction between one C — tyrosine rotamer and the disulfide bond. Swadesh et al.(()<>> have studied the dithiothreitol quenching of the six tyrosine residues in ribonuclease A. They carefully examined the steady-state criteria that are useful for distinguishing pure static from pure dynamic quenching by consideration of the Smoluchowski equation(70) for the diffusion-controlled bimolecular rate constant k0,... 

Two kinds of quenching are distinguished. In static quenching, complexation between the potentially luminescent molecule and the quencher takes place in the ground state. The complex, when excited, fails to luminesce. The efficiency of quenching is governed by the formation constant of the complex as well as by the concentration of the quencher. The quenching of the fluorescence of doxorubicin by Fe(III) is an example. 

Gilmore AM, Hazlett TL and Govindjee (1995) Xanthophyll cycle dependent quenching of Photosystem II chlorophyll a fluorescence Formation of a quenching complex with a short lifetime. Proc Nat Acad Sd USA 92 2273-2277... 

Normalized rates are given with respect to quenching by [FefCNis], which preferentially quenches complexes bound in a mode more accessible to solvent. 

Laser ablation Reactive quenching complex, multicomponent materials produced Low production rate, vacuumed unit required... 

In addition, the capacity of the large outlet tube coil is greater than that of the short coil and as such, the quench complexity and costs are reduced. The capacity of the large diameter coil compared to the small diameter coil studied in the selectivity experiment was 4.3 times greater for the same operating selectivity. This higher coil capacity and simpler overall system result in a pyrolysis reaction module of a much lower cost for a fixed production of olefins. 

Kolubayev T, Geacintov N E, Paillotin G and Breton J 1985 Domain sizes in chloroplasts and chlorophyll-protein complexes probed by fluorescence yield quenching induced by singlet-triplet exciton annihilation Biochimica Biophys. Acta 808 66-76... 

E. Vedejs (1978) developed a general method for the sterically controlled electrophilic or-hydroxylation of enolates. This uses a bulky molybdenum(VI) peroxide complex, MoO(02)2(HMPTA)(Py), which is rather stable and can be stored below 0 °C. If this peroxide is added to the enolate in THF solution (base e.g. LDA) at low temperatures, oneO—O bond is broken, and a molybdyl ester is formed. Excess peroxide is quenched with sodium sulfite after the reaction has occurred, and the molybdyl ester is cleaved to give the a-hydroxy car-... 

Quench. Attempts have been made to model this nonisotherma1 process (32—35), but the complexity of the actual system makes quench design an art. Arrangements include straight-through, and outside-in and inside-out radial patterns (36). The optimum configuration depends on spinneret size, hole pattern, filament size, quench-chamber dimensions, take-up rate, and desired physical properties. Process continuity and final fiber properties are governed by the temperature profile and extension rate. 

S. M. Complex, ia B. Cantor, ed.. Proceedings of the 3rd International Conference on Rapidly Quenched Metals Vol. 1, The Metals Society, London, 1978, p. 

Alkali metal haHdes can be volatile at incineration temperatures. Rapid quenching of volatile salts results in the formation of a submicrometer aerosol which must be removed or else exhaust stack opacity is likely to exceed allowed limits. Sulfates have low volatiHty and should end up in the ash. Alkaline earths also form basic oxides. Calcium is the most common and sulfates are formed ahead of haHdes. Calcium carbonate is not stable at incineration temperatures (see Calcium compounds). Transition metals are more likely to form an oxide ash. Iron (qv), for example, forms ferric oxide in preference to haHdes, sulfates, or carbonates. SiHca and alumina form complexes with the basic oxides, eg, alkaH metals, alkaline earths, and some transition-metal oxidation states, in the ash. 

Design of explosion suppression systems is clearly complex, since the effectiveness of an explosion suppression system is dependent on a large number of parameters. One Hypothesis of suppression system design identifies a limiting combustion wave adiabatic flame temperature, below which combustion reactions are not sustained. Suppression is thus attained, provided that sufficient thermal quenching results in depression of the combustion wave temperature below this critical value. This hypothesis identifies the need to deliver greater than a critical mass of suppressant into the enveloping fireball to effect suppression (see Fig. 26-43). 

It is well known, that in aqueous solutions the water molecules, which are in the inner coordination sphere of the complex, quench the lanthanide (Ln) luminescence in result of vibrations of the OH-groups (OH-oscillators). The use of D O instead of H O, the freezing of solution as well as the introduction of a second ligand to obtain a mixed-ligand complex leads to either partial or complete elimination of the H O influence. The same effect may be achieved by water molecules replacement from the inner and outer coordination sphere at the addition of organic solvents or when the molecule of Ln complex is introduced into the micelle of the surfactant. 

Fluorescence quenching methods wits ai omatic complexing reagents are often recommended for copper (II) determination in water. 

In the above scheme A represents the excited polymer, Q the quenching agent and [A.Q] an excited complex. 

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