Fluorescence solvents

G. van der Zwan and J. T. Hynes, Time-dependent fluorescence solvent shifts, dielectric friction and nonequilibrium solvation in polar solvents, J. Phys. Chem. 89, 418M188 (1985). 

Fluorescence Solvent Shift, Dielectric Friction, and Nonequilibrium Solvation in Polar Solvents. 

Scheme 1. Fluorescent solvent polarity probes, together with the maximum solvent-induced red shift of the long-wavelength emission band.

Xanthene Dyes. Xanthene dyes are an important class since they offer brilliant and fluorescent colors. Conversely they are only fair to good in heat and light stability. Useful xanthene dyes are Basic Violet 10, a fluorescent. Solvent Green 4, Acid Red 52, Basic Red 1, and Solvent Orange 63. 

There is some parallelism between charge/electron transfer and excimer formation. They both are two-state systems (in the simplest case), and both can occur either intra- or intermolecularly [61-69]. In this case, Scheme 15.6 is slightly modihed as for excimer formation (Scheme 15.8). The major difference between charge transfer (Scheme 15.8a) and electron transfer (Scheme 15.8b) reactions lies on the reaction product an exciplex (more or less fluorescent), resulting from partial charge transfer, and a non-fluorescent, solvent-separated radical-ion pair from (full) electron transfer, respectively. 

Note that in liquid phase chromatography there are no detectors that are both sensitive and universal, that is, which respond linearly to solute concentration regardless of its chemical nature. In fact, the refractometer detects all solutes but it is not very sensitive its response depends evidently on the difference in refractive indices between solvent and solute whereas absorption and UV fluorescence methods respond only to aromatics, an advantage in numerous applications. Unfortunately, their coefficient of response (in ultraviolet, absorptivity is the term used) is highly variable among individual components. 

Nevertheless, this type of analysis, usually done by chromatography, is not always justified when taking into account the operator s time. Other quicker analyses are used such as FIA (Fluorescent Indicator Analysis) (see paragraph 3.3.5), which give approximate but usually acceptable proportions of saturated, olefinic, and aromatic hydrocarbons. Another way to characterize the aromatic content is to use the solvent s aniline point the lowest temperature at which equal volumes of the solvent and pure aniline are miscible. 

Micellar structure has been a subject of much discussion [104]. Early proposals for spherical [159] and lamellar [160] micelles may both have merit. A schematic of a spherical micelle and a unilamellar vesicle is shown in Fig. Xni-11. In addition to the most common spherical micelles, scattering and microscopy experiments have shown the existence of rodlike [161, 162], disklike [163], threadlike [132] and even quadmple-helix [164] structures. Lattice models (see Fig. XIII-12) by Leermakers and Scheutjens have confirmed and characterized the properties of spherical and membrane like micelles [165]. Similar analyses exist for micelles formed by diblock copolymers in a selective solvent [166]. Other shapes proposed include ellipsoidal [167] and a sphere-to-cylinder transition [168]. Fluorescence depolarization and NMR studies both point to a rather fluid micellar core consistent with the disorder implied by Fig. Xm-12. 

Figure B2.1.5 Fluorescence upconversion traces obtained at two observation wavelengdis (fiill circles, 570 mn open circles, 650 mn) at room temperature with an oxazine dye, phenoxazone, in methanol solvent. Figure courtesy of Professor S Rosenthal (Vanderbilt University).

Other solubilization and partitioning phenomena are important, both within the context of microemulsions and in the absence of added immiscible solvent. In regular micellar solutions, micelles promote the solubility of many compounds otherwise insoluble in water. The amount of chemical component solubilized in a micellar solution will, typically, be much smaller than can be accommodated in microemulsion fonnation, such as when only a few molecules per micelle are solubilized. Such limited solubilization is nevertheless quite useful. The incoriDoration of minor quantities of pyrene and related optical probes into micelles are a key to the use of fluorescence depolarization in quantifying micellar aggregation numbers and micellar microviscosities [48]. Micellar solubilization makes it possible to measure acid-base or electrochemical properties of compounds otherwise insoluble in aqueous solution. Micellar solubilization facilitates micellar catalysis (see section C2.3.10) and emulsion polymerization (see section C2.3.12). On the other hand, there are untoward effects of micellar solubilization in practical applications of surfactants. Wlren one has a multiphase... 

When the ascending solvent-front has reached a convenient height, the strip is removed, the position of the solvent-front marked, and the paper strip dried. The positions of the various solutes, if they are coloured compounds, now appear as clear separate spots. Frequently however, the solutes are colourless, and the position of their spots must be determined by indirect methods, such as their fluorescence in ultraviolet light, or their absorption in such light (when the spots appear almost black), or by spraying the paper with a dilute solution of a reagent which will give a coloured insoluble derivative with the solutes. 

In fluorescent lamps, phosphors are coated on the inside of the lamp tube using a slurry containing the powder and a Hquid which is either poured down through the tube, up-flushed, or in some cases the tubes are filled and then drained. Because of concerns over having volatile organic solvents in the air, the hquid medium containing the powder is usually water with an added agent, a thickener, to increase the viscosity of the suspension, such as poly(methacryhc... 

Donoi—acceptoi chromogens in solution are often strongly affected by the nature of the solvent or the resinous substrate in which they are dissolved. The more polar the solvent or resin, the longer the wavelength of the fluorescent light emitted. Progressing from less polar to more polar solvents, the bathochromic, or reddening, effect of the solvents on the dye increases in the order of aUphatics < aromatics < esters < alcohols < amides. 

In addition to the processes that can compete with fluorescence within the molecule itself, external actions can rob the molecule of excitation energy. Such an action or process is referred to as quenching. Quenching of fluorescence can occur because the dye system is too warm, which is a very common phenomenon. Solvents, particularly those that contain heavy atoms such as bromine or groups that ate detrimental to fluorescence in a dye molecule, eg, the nitro group, ate often capable of quenching fluorescence as ate nonfluorescent dye molecules. 

A high concentration of the fluorescent dye itself in a solvent or matrix causes concentration quenching. Rhodamine dyes exhibit appreciable concentration quenching above 1.0%. Yellow dyes, on the other hand, can be carried to 5 or even 10% in a suitable matrix before an excessive dulling effect, characteristic of this type of quenching, occurs. Dimerization of some dyes, particularly those with ionic charges on the molecules, can produce nonfluorescent species. 

Soluble Fluorescent Polymers. Several pigment manufacturers have developed fluorescent polymers iatended to be used as a solution for apphcation to various substrates. These toners come ia both solvent soluble and alkaline water-soluble forms. 

In C- and T-type gravure systems where oxygenated and aromatic solvents are used, the Radiant P-1700 Series and Day-Glo GT and STX pigments are recommended. A typical formulation for an A-type gravure ink is 30% Acryloid NAD-10 (Rohm Haas), 50% fluorescent pigment, 5% toluene, and 15% heptane (as thinner). 

Flexographic Inks. Fluorescent toners such as the Radiant GF, Lawter HVT, and Day-Glo HM and HMS Series toners are used in flexographic ink formulations. These products are soluble in blends of alcohol (80%) and ester solvents (20%) and are compatible with modifying materials such as nitroceUulose resins and acryHc solution polymers. Flexographic inks of this type are used most commonly to print products such as ceUophane and polyethylene film for packaging, and also to print paper products such as gift wrap and price labels. 

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