Luminescence fluorescence and phosphorescence

TGA, iodometric, mid-IR, luminescence (fluorescence and phosphorescence) and colour formation (yellowness index according to standard method ASTM 1925) were all employed in a study of aspects of the thermal degradation of EVA copolymers [67], Figure 23 compares a set of spectra from the luminescence analysis reported in this work. In the initial spectra (Figure 23(a)) of the EVA copolymer, two excitation maxima at 237 and 283 nm are observed, which both give rise to one emission spectrum with a maximum at 366 nm weak shoulders... 

Emission of a photon from an electronically excited state is referred to as luminescence. Fluorescence and phosphorescence can be differentiated depending on whether the transition is between states of equal or different multiplicity and hence spin-allowed or spin-forbidden. (Cf. Section 5.1.1.) Thus, for molecules with singlet ground states fluorescence constitutes a pathway for deactivating excited singlet states whereas phosphorescence is observed in the deactivation of triplet states. 

Fig. 4. Relative position of lower excited singlet state (S,), triplet state (Tt) and metal ions (Mi), electronic levels, and transitions between them in metal ion complexes with organic ligands, (A) luminescence (fluorescence and phosphorescence) with levels of metal ion located above Sr levels, (B) phosphorescence with metal ion levels located between S,- and Trlevels, (C) sensitized (native) luminescence with metal ion levels located below Ti-levels...

T uminescence studies of commercial polymers have provided valuable -L information on the nature of some of the light absorbing chromophoric impurities believed to be responsible for sunlight-induced oxidation (1-13). The luminescence (fluorescence and phosphorescence) from commercial polyolefins has been attributed to the presence of impurity carbonyl groups (1,2,5,6,8), and recent work on polypropylene has indicated that these groups are conjugated with ethylenic unsaturations... 

Luminescence is the emission of light from any substance occurring when an electron returns from an electronically excited state to ground state. Luminescence can be caused by a number of factors, most commonly chemical or biochemical changes, electrical energy, or subatomic motions. There are two main categories of luminescence, fluorescence and phosphorescence, and these are dependent on the nature of the excited state. 

The basic idea underlying the physical labelling approach is the modification of the chosen sites of the object in question by specific compounds, which are boimd covalently (labels) and/or non-covalently (probes), whose properties make it possible to trace the state of the surrounding biological matrix by appropriate physical methods. The following main types of compounds are used as labels and probes to monitor the dynamic parameters of proteins (1) centers with unpaired electrons (stable nitroxide radicals, radical pairs and paramagnetic complexes) exhibit electron spin resonance (ESR), (2) luminescent fluorescence and phosphorescence chromophores, and (3) Mossbauer atoms (e.g. Pe) which gives the nuclear y-resonance (NGR) spectra. 

Selectivity The selectivity of molecular fluorescence and phosphorescence is superior to that of absorption spectrophotometry for two reasons first, not every compound that absorbs radiation is fluorescent or phosphorescent, and, second, selectivity between an analyte and an interferant is possible if there is a difference in either their excitation or emission spectra. In molecular luminescence the total emission intensity is a linear sum of that from each fluorescent or phosphorescent species. The analysis of a sample containing n components, therefore, can be accomplished by measuring the total emission intensity at n wavelengths. 

Fluorescence and phosphorescence are types of luminescence, ie, emission attributed to selective excitation by previously absorbed radiation, chemical reaction, etc, rather than to the temperature of the emitter. Laser-iaduced and x-ray fluorescence are important analytical techniques (see... 

Fluorescent and phosphorescent substances are excited into an unstable energy state by UV light. When they return to the ground state they release a part of the energy taken up in the form of radiation. The emitted radiation is less energetic than the light absorbed and usually lies in the visible part of the spectrum. Since absorption (excitation) and emission obey a linear relationship over a certain range a reduction in absorption leads to a reduction in the luminescence, too. 

Fluorescence and phosphorescence are both forms of luminescence [3]. If the emission of radiation has decayed within 10 s after the exciting radiation is cut off it is known as fluorescence [4], if the decay phase lasts longer (because the electrons return to the ground state from a forbidden triplet state (Fig. 5), then the phenomenon is known as phosphorescence. A distinction is also made between... 

Solid-surface room-temperature phosphorescence (RTF) is a relatively new technique which has been used for organic trace analysis in several fields. However, the fundamental interactions needed for RTF are only partly understood. To clarify some of the interactions required for strong RTF, organic compounds adsorbed on several surfaces are being studied. Fluorescence quantum yield values, phosphorescence quantum yield values, and phosphorescence lifetime values were obtained for model compounds adsorbed on sodiiun acetate-sodium chloride mixtures and on a-cyclodextrin-sodium chloride mixtures. With the data obtained, the triplet formation efficiency and some of the rate constants related to the luminescence processes were calculated. This information clarified several of the interactions responsible for RTF from organic compounds adsorbed on sodium acetate-sodium chloride and a-cyclodextrin-sodium chloride mixtures. Work with silica gel chromatoplates has involved studying the effects of moisture, gases, and various solvents on the fluorescence and phosphorescence intensities. The net result of the study has been to improve the experimental conditions for enhanced sensitivity and selectivity in solid-surface luminescence analysis. 

Solid-surface luminescence analysis involves the measurement of fluorescence and phosphorescence of organic compounds adsorbed on solid materials. Several solid matrices such as filter paper, silica with a polyacrylate binder, sodium acetate, and cyclodextrins have been used in trace organic analysis. Recent monographs have considered the details of solid-surface luminescence analysis (1,2). Solid-surface room-temperature fluorescence (RTF) has been used for several years in organic trace analysis. However, solid-surface room-temperature phosphorescence (RTF) is a relatively new technique, and the experimental conditions for RTF are more critical than for RTF. 

Interactions in Solid-Surface Luminescence Temperature Variation. Solid-surface luminescence analysis, especially solid-surface RTF, is being used more extensively in organic trace analysis than in the past because of its simplicity, selectivity, and sensitivity (,1,2). However, the interactions needed for strong luminescence signals are not well understood. In order to understand some of the interactions in solid-surface luminescence we recently developed a method for the determination of room-temperature fluorescence and phosphorescence quantum yields for compounds adsorbed on solid surfaces (27). In addition, we have been investigating the RTF and RTF properties of the anion of p-aminobenzoic acid adsorbed on sodium acetate as a model system. Sodium acetate and the anion of p-aminobenzoic acid have essentially no luminescence impurities. Also, the overall system is somewhat easier to study than compounds adsorbed on other surfaces, such as filter paper, because sodium acetate is more simple chemically. 

Most dyes and pigments owe their colour to the selective absorption of incident light. In some compounds, colour can also be observed as a result of the emission of visible light of specific wavelengths. These compounds are referred to as luminescent. The most commonly encountered luminescent effects are fluorescence and phosphorescence. The transitions which can occur in a molecule exhibiting either fluorescence... 

The original stabilizer (HBC) was modified as the rapid radiationless deactivation of the stabilizer is (at least partly) due to the intramolecular hydrogen bond, the H-atom was substituted by a methyl group (MBC). This "probe molecule" showed fluorescence and phosphorescence and enabled us to demonstrate the energy transfer to the stabilizer, simply by studying its sensitized luminescence. 

Dependencies of luminescence bands (both fluorescence and phosphorescence), anisotropy of emission, and its lifetime on a frequency of excitation, when fluorescence is excited at the red edge of absorption spectrum. Panel a of Fig. 5 shows the fluorescence spectra at different excitations for the solutes with the 0-0 transitions close to vI vn, and vra frequencies. Spectral location of all shown fluorescence bands is different and stable in time of experiment and during lifetime of fluorescence (panel b)... 

Radiative transitions (Chapter 4), which involve the emission of electromagnetic radiation as the excited molecule relaxes to the ground state. Fluorescence and phosphorescence are known collectively as luminescence. 

Generally speaking, luminescence spectra (fluorescence and phosphorescence) provide more information about excited states than do absorption spectra. This is because luminescence measurements are much more sensitive than absorption measurements, and the two types of emission can be studied separately due to their widely differing lifetimes. 

Fluorescence and phosphorescence are particular cases of luminescence (Table 1.1). The mode of excitation is absorption of a photon, which brings the absorbing species into an electronic excited state. The emission of photons accompanying deexcitation is then called photoluminescence (fluorescence, phosphorescence or delayed fluorescence), which is one of the possible physical effects resulting from interaction of light with matter, as shown in Figure 1.1. 

The fluorescence and phosphorescence of luminescent materials are modulated by the characteristics of the environment to which these materials are exposed. Consequently, luminescent materials can be used as sensors (referred also as transducers or probes) to measure and monitor parameters of importance in medicine, industry and the environment. Temperature, oxygen, carbon dioxide, pH, voltage, and ions are examples of parameters that affect the luminescence of many materials. These transducers need to be excited by light. The manner in which the excited sensor returns to the ground state establishes the transducing characteristics of the luminescent material. It is determined by the concentration or value of the external parameter. A practical and unified approach to characterize the luminescence of all sensors is presented in this chapter. This approach introduces two general mechanisms referred as the radiative and the nonradiative paths. The radiative path, in the general approach, is determined by the molecular nature of the sensor. The nonradiative path is determined by the sensor environment, e.g., value or concentration of the external parameter. The nonradiative decay rate, associated with the nonradiative path, increases... 

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