Photosensitized sensitizer

The very first use of the polarization pattern to identify the paramagnetic intermediates was in photosensitized (sensitizer, A) reactions of tertiary aliphatic amines DH, for example, triethylamine. Although the gross reaction is a one-step hydrogen abstraction... 

Phase II The pasteurization and final conditioning of a mushroom compost, phenotype The observable physical characteristics resulting from interaction between the host environment and the genotype, photosensitive Sensitive to light, phototropic Growing towards light, pileus The mushroom cap. pith The central cottony stuffing in the stems of some mushrooms. 

In the case of reactions when oxygen is present, the triplet state of these drugs (photosensitizer) sensitizes molecular oxygen, producing O2, which then reacts with the biological substrate. This has been verified by trapping tests with 2,5-dimethylfuran, furfural, and l,3-cyclohexadiene-l,4-diethanoate, as well as testing for the oxidation of histidine. 

All the silver halides are sensitive to light, decomposing eventually to silver. In sunlight, silver chloride turns first violet and finally black. The use of these compounds in photography depends on this (see below). (All silver salts are, in fact, photosensitive—the neck of a silver nitrate bottle is black owing to a deposit of silver.)... 

Dichromated Resists. The first compositions widely used as photoresists combine a photosensitive dichromate salt (usually ammonium dichromate) with a water-soluble polymer of biologic origin such as gelatin, egg albumin (proteins), or gum arabic (a starch). Later, synthetic polymers such as poly(vinyl alcohol) also were used (11,12). Irradiation with uv light (X in the range of 360—380 nm using, for example, a carbon arc lamp) leads to photoinitiated oxidation of the polymer and reduction of dichromate to Ct(III). The photoinduced chemistry renders exposed areas insoluble in aqueous developing solutions. The photochemical mechanism of dichromate sensitization of PVA (summarized in Fig. 3) has been studied in detail (13). 

Poly(vinyl cinnamate) Resists. Dichromated resists exhibit numerous shortcomings which include lot-to-lot variabiUty of the components, aging of the formulated resists in solution and in coated form, poor process stabiUty (due to a sensitivity to variations in temperature and humidity), and intrinsically low photosensitivity requiring long exposure times for adequate insolubilization. 

Deterioration. The causes of degradation phenomena in textiles (155—158, 164) are many and include pollution, bleaches, acids, alkaUes, and, of course, wear. The single most important effect, however, is that of photodegradation. Both ceUulosic and proteinaceous fibers are highly photosensitive. The natural sensitivity of the fibers are enhanced by impurities, remainders of finishing processes, and mordants for dyes. Depolymerization and oxidation lead to decreased fiber strength and to embrittlement. 

Fig. 7. Photodimerization of light-sensitive functional groups attached to polymer backbone stmctuies (a) polymer containing photosensitive cinnamic...

Although silver iodide is the least photosensitive of the three halides, it has the broadest wavelength sensitivity in the visible spectmm. This feature makes silver iodide particularly useful in the photographic industry. It resists reduction by metals, but is reduced quantitatively by zinc and iron in the presence of sulfuric acid. 

The detection of spectral sensitizing action often depends on amplification methods such as photographic or electrophotographic development or, alternatively, on chemical or biochemical detection of reaction products. Separation of the photosensitization reaction from the detection step or the chemical reaction allows selection of the most effective spectral sensitizers. Prime considerations for spectral sensitizing dyes include the range of wavelengths needed for sensitization and the absolute efficiency of the spectrally sensitized process. Because both sensitization wavelength and efficiency are important, optimum sensitizers vary considerably in their stmctures and properties. 

Natural Sensitizing Dyes and Photodynamic Therapy. The chlorophylls are, of course, among the natural sensitizers for photosynthesis. Considerable iaterest exists ia chlorophyll and related pigments as photosensitizers ia biology and medicine (75), isomeric retinal chromophores as visual pigments (76,77), and the use of synthetic photosensitizers ia neurobiology (9), hematology (78), and photodynamic therapy (79). 

In SXAPS the X-ray photons emitted by the sample are detected, normally by letting them strike a photosensitive surface from which photoelectrons are collected, but also - with the advent of X-ray detectors of increased sensitivity - by direct detection. Above the X-ray emission threshold from a particular core level the excitation probability is a function of the densities of unoccupied electronic states. Because two electrons are involved, incident and the excited, the shape of the spectral structure is proportional to the self convolution of the unoccupied state densities. 

The transfer of energy must proceed with net conservation of spin. In the usual case, the acceptor molecule is a ground-state singlet, and its reaction with the triplet state of the sensitizer will produce the triplet state of the acceptor. The mechanism for triplet photosensitization is outlined below ... 

Aromatic compounds such as toluene, xylene, and phenol can photosensitize cis-trans interconversion of simple alkenes. This is a case in which the sensitization process must be somewhat endothermic because of the energy relationships between the excited states of the alkene and the sensitizers. The photostationary state obtained under these conditions favors the less strained of the alkene isomers. The explanation for this effect can be summarized with reference to Fig. 13.12. Isomerization takes place through a twisted triplet state. This state is achieved by a combination of energy transfer Irom the sensitizer and thermal activation. Because the Z isomer is somewhat higher in energy, its requirement for activation to the excited state is somewhat less than for the E isomer. If it is also assumed that the excited state forms the Z- and -isomers with equal ease, the rate of... 

Conjugated dienes can undergo a variety of photoreactions, depending on whether excitation is direct or photosensitized. The benzophenone-sensitized excitation of 1,3-pentadiene, for example, results in stereochemical isomerization and dimerization ... 

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