Liquid phosphorescence

More importantly, the use of heavy metal anionic micellar media has been shown to allow for observation of analytically useful room-temperature liquid phosphorescence (RTLP) (7.484.487). There are several examples in which phosphorescence has been employed as a LC detector with the required micellar assembly being present as part of the LC mobile phase (482) or added post column (485). More recently, metal ions have been determined in a coacervate scum by utilizing the micellar-stabilized RTLP approach (498). Thus, the future should see further development in RTLP detection of metal ions in separation science applications. 

D.W. Armstrong, W. Hinze, K.H. Bui and H.N. Singh, Enhanced Fluorescence and Room Temperature Liquid Phosphorescence Detection in Pseudophase LC, Anal Lett., 14 1659 (1981). 

Armstrong D W, Hinze W L, Bui K H, Singh H N 1981 Enhanced fluorescence and room temperature liquid phosphorescence detection in pseudophase liquid chromatography (PLC). Anal Lett 14 1659-1667... 

Typical singlet lifetimes are measured in nanoseconds while triplet lifetimes of organic molecules in rigid solutions are usually measured in milliseconds or even seconds. In liquid media where drfifiision is rapid the triplet states are usually quenched, often by tire nearly iibiqitoiis molecular oxygen. Because of that, phosphorescence is seldom observed in liquid solutions. In the spectroscopy of molecules the tenn fluorescence is now usually used to refer to emission from an excited singlet state and phosphorescence to emission from a triplet state, regardless of the actual lifetimes. 

On the average, one part of radon is present ot 1 x IO21 part of air. At ordinary temperatures radon is a colorless gas when cooled below the freezing point, radon exhibits a brilliant phosphorescence which becomes yellow as the temperature is lowered and orange-red at the temperature of liquid air. It has been reported that fluorine reacts with radon, forming a fluoride. Radon clathrates have also been reported. 

The commonest form of phosphorus, and the one which is usually formed by condensation from the gaseous or liquid states, is the waxy, cubic, white form o -P4 (d 1.8232 gcm at 20°C). This, paradoxically, is also the most volatile and reactive solid form and thermodynamically the least stable. It is the slow phosphorescent oxidation of the vapour above these crystals that gives white phosphorus its most characteristic property. Indeed, the emission of yellow-green light from the oxidation of P4 is one of the earliest recorded examples of chemiluminescence, though the details of the reaction... 

Certain features of light emission processes have been alluded to in Sect. 4.4.1. Fluorescence is light emission between states of the same multiplicity, whereas phosphorescence refers to emission between states of different multiplicities. The Franck-Condon principle governs the emission processes, as it does the absorption process. Vibrational overlap determines the relative intensities of different subbands. In the upper electronic state, one expects a quick relaxation and, therefore, a thermal population distribution, in the liquid phase and in gases at not too low a pressure. Because of the combination of the Franck-Condon principle and fast vibrational relaxation, the emission spectrum is always red-shifted. Therefore, oscillator strengths obtained from absorption are not too useful in determining the emission intensity. The theoretical radiative lifetime in terms of the Einstein coefficient, r = A-1, or (EA,)-1 if several lower states are involved,... 

James Dewar observed in 1894 phosphorescence from frozen solutions utilizing liquid air [5], Jean Becquerel discovers in 1907 that samples frozen at liquid air temperatures considerably narrow the spectral shape and increased information is obtained from the luminescence spectra [26],... 

Finally, and apart from the importance of micelles in the solubilization of chemical species, mention should also be made of their intervention in the displacement of equilibria and in the modification of kinetics of reactions, as well as in the alteration of physicochemical parameters of certain ions and molecules that affect electrochemical measurements, processes of visible-ultraviolet radiation, fluorescence and phosphorescence emission, flame emission, and plasma spectroscopy, or in processes of extraction, thin-layer chromatography, or high-performance liquid chromatography [2-4, 29-33],... 

Strip lighting in a classroom, hospital, business hall or kitchen is often called fluorescent lighting, although in fact it is a phosphorescent process, as above. Each bulb consists of a thin, hollow glass tube that is sealed at both ends. It contains gas such as helium, argon or krypton, and a drop of liquid mercury (about 0.5 mg of mercury per kilogram of lamp, or 0.5 parts per million). Like the neon and sodium lamps above, the pressure inside the tube is about 30 Pa, so the mercury evaporates to become a vapour. It is the mercury that yields the light, albeit indirectly. 

FIGURE 10.7 Power consumption simulation for a 2.2-in. full-color OLED display using Universal Display s phosphorescent OLEDs, small-molecule fluorescent devices, and polymer OLEDs along with a comparison of the power consumed by an active-matrix liquid crystal display backlight. R G B= 3 6 1, 50% polarizer efficiency, and 30% of pixels lit. (From Mahon, J.K., Adv. Imaging, June, 28, 2003. With permission.)... 

Several methods are employed to allow the observation of phosphorescence. One of the most common techniques is to supercool solutions to a rigid glass state, usually at the temperature of liquid nitrogen... 

Essentially nothing is known about tyrosine phosphorescence at ambient temperatures. In frozen solution, tyrosine residues have a phosphorescence decay of seconds. We would expect, however, a decay of milliseconds or shorter at ambient temperature. Observation of tyrosine phosphorescence from proteins in liquid solution will undoubtedly require efficient removal of oxygen. Nevertheless, it could be fruitful to explore ambient temperature measurements, since the phosphorescence decay could extend the range of observation of excited-state dynamics into the microsecond, or even millisecond, time range. 

T. Horie and J. M. Vanderkooi, Phosphorescence of tryptophan from parvalbumin and actin in liquid solutions, FEBS Lett. 147, 69-73 (1982). 

Notwithstanding the excellent analytical features inherent in molecular phosphorimetric measurements, their use has been impeded by the need for cumbersome cryogenic temperature techniques. The ability to stabilize the "triplet state" at room temperature by immobilization of the phosphor on a solid support [69,70] or in a liquid solution using an "ordered medium" [71] has opened new avenues for phosphorescence studies and analytical phosphorimetry. Room-temperature phosphorescence (RTF) has so far been used for the determination of trace amounts of many organic compounds of biochemical interest [69,72]. Retention of the phosphorescent species on a solid support housed in a flow-cell is an excellent way of "anchoring" it in order to avoid radiationless deactivation. A configuration such as that shown in Fig. 2.13.4 was used to implement a sensor based on this principle in order to determine aluminium in clinical samples (dialysis fluids and concen-... 

Phosphorescence is observed when the dry sheet is dipped in a container with liquid nitrogen and illuminated by a UV lamp. Purine derivatives phosphoresce light blue pyrimidines are not visible. 

Phosphorimetric methods have been used to determine such substances as nucleic acids, amino acids, and enzymes. However, this is not a widely used method since it cannot be run at room temperature. Measurements are usually performed with liquid nitrogen to prevent degradation due to collision deactivation. Fluorometric methods are used to determine both inorganic and organic species. Instruments used for measuring fluorescence and phosphorescence are fluorometers and spectrofluorometers, respectively. These instruments are similar to ultraviolet and visible spectrometers,... 

Luminescence spectrocopy is potentially a powerful technique for studying chromium(III) complexes and a series of fluoro and aqua complexes have been studied.1066 The luminescence correlates well with ligand field strength and, at. liquid air temperatures, the lifetime of the doublet state from which phosphorescence originates is 2 x 1CT7 s 1. 

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