Sensitizers cyanines

Cooper ME, Gregory S, Adie E, Kalinka S (2002) pH-Sensitive cyanine dyes for biological applications. J Fluoresc 12 425-429... 

As a final example, let us mention that Little 143,144) has discussed the possibility of obtaining organic superconductors that operate at high temperature. The first superconductive model compound to be proposed was a polymethine chain connected with highly polarizable sensitizing cyanine dyes (see e.g. Table 3). The first report on superconducting fluctuations in tetrathiafulvalene-tetra-cyanochinodimethane crystals appeared recently 145>. 2... 

In contrast to many other initiating systems based on dye sensitization, cyanine-borate complexes are ionic before electron transfer and are transformed into neutral species. Other systems are neutral before electron transfer and get ions thereafter. 

The use of sensitizing dyes in photography has been the subject of many studies and constitutes. still now. one of the most studied areas in specialized periodic publications (125, 126) or in textbooks (88. 127). It can be ascertained that one hundred years after Vogel s discovery of spectral sensitization, the basic mechanisms of action of dyes on their silver halide support still remain not fully understood. However, the theoretical reasons explaining why among many other dye families practically only cyanine methine dyes appear to be spectral sensitizers (128) are better known. 

Selenazoles and their derivatives, that is. selenazolines and selenazo-lidines. aremainh used in cyanine-type dyes and photographic sensitizers as well as in pharmacology and chemotheraphs. 

An illustration of the technological significance of the relaxation phenomenon can be taken from photographic chemistry. Dyes of the cyanine class where Y = S, 0, CH—CH— n = 0,1,2,3...X = haUde, etc, are used as spectral sensitizers to extend photochemical response of the photographic silver hahdes, which only absorb blue and ultraviolet light, into the visible spectral regime. 

The color and constitution of cyanine dyes may be understood through detailed consideration of their component parts, ie, chromophoric systems, terminal groups, and solvent sensitivity of the dyes. Resonance theories have been developed to accommodate significant trends very successfully. For an experienced dye chemist, these are useful in the design of dyes with a specified color, band shape, or solvent sensitivity. More recendy, quantitative values for reversible oxidation—reduction potentials have allowed more complete correlation of these dye properties with organic substituent constants. 

Crystal stmcture analyses of cyanine and related dyes are reviewed in Ref. 32. Most typical sensitizers are nearly planar, with angles of less than 15° between planes defined by heterocycHc rings. Distinct solvent of crystallization is present in most of the cationic dyes. X-ray crystal analyses also provide intermolecular data. Because of photographic use of cyanine and carbocyanine dyes, the cation-cation arrangements of most interest have been those for l,l -dieth5l-2,2 -quinocyanine chloride [2402-42-8] 5,5, 6,6 -tetrachloro-l,l, 3,3 -tetraethylbenzimidazolocarbocyanineiodide [3520-43-2] and 5,5 -dichloro-3,3, 9-triethylthiacarbocyanine bromide [18426-56-7] (32) (see Fig. 8). 

Fig. 8. Sensitizing dyes of the cyanine class. K. = N — alkyl or chalcogens (O, S, Se, Te) R = chloro, phenyl, or additional benzene ring R = methyl, ethyl, or hydrogen n = 0, 1, 2 and RPRIME, R " = alkyl or sulfoalkyl. Solubihty in methanol for a carbocyanine dye n = 1 X = S R = Cl R = ethyl. Cationic dye (R" = R " = ethyl anion = bromide) 9.5 mmol/T. neutral dye (R" = ethyl R " = sulfopropyl) 3.6 mmol/L anionic dye (R" = R = sulfopropyl ...

More recent research provides reversible oxidation-reduction potential data (17). These allow the derivation of better stmcture-activity relationships in both photographic sensitization and other systems where electron-transfer sensitizers are important (see Dyes, sensitizing). Data for an extensive series of cyanine dyes are pubflshed, as obtained by second harmonic a-c voltammetry (17). A recent "quantitative stmcture-activity relationship" (QSAR) (34) shows that Brooker deviations for the heterocycHc nuclei (discussed above) can provide estimates of the oxidation potentials within 0.05 V. An oxidation potential plus a dye s absorption energy provide reduction potential estimates. Different regression equations were used for dyes with one-, three-, five-methine carbons in the chromophore. Also noted in Ref. 34 are previous correlations relating Brooker deviations for many heterocycHc nuclei to the piC (for protonation/decolorization) for carbocyanine dyes the piC is thus inversely related to oxidation potential values. 

Several types of nitrogen substituents occur in known dye stmetures. The most useful are the acid-substituted alkyl N-substituents such as sulfopropyl, which provide desirable solubiUty and adsorption characteristics for practical cyanine and merocyanine sensitizers. Patents in this area are numerous. Other types of substituents include N-aryl groups, heterocycHc substituents, and complexes of dye bases with metal ions (iridium, platinum, zinc, copper, nickel). Heteroatom substituents directly bonded to nitrogen (N—O, N—NR2, N—OR) provide photochemically reactive dyes. 

Symmetrical, long-chain cyanine dyes for laser appHcations provide output from 680 to 980 nm (76). Although these dyes were obtained through early screening procedures, infrared dyes for other technologies use similar stmetures. A long-chain indolenine-type cyanine dye, general stmeture as in dye (34), has been described as the sensitizer in optical disk memories (77). 

Polymethine and Related Dyes. Cyanine dyes (qv) (46) aie the best known polymethine dyes. Nowadays, thek commeicial use is limited to sensitizing dyes for sdvei halide photogiaphy. However, derivatives of cyanine dyes provide important dyes for polyacrylonitrile. 

The anthocyanins are pH sensitive. Their color, in part, is deterrnined by the pH of the sap. Cyanin, for example, is red at pH 3, violet at 8, and blue at 11. However, there are other factors that affect the colors of the anthocyanins metallic salts, notably iron and aluminum, react with those anthocyanins containing vicinal hydroxy groups and produce highly colored complex compounds. Other factors are the colloidal condition of the cell sap and copigmentation (91). 

A useful classification of sensitizing dyes is the one adopted to describe patents in image technology. In Table 1, the Image Technology Patent Information System (ITPAIS), dye classes and representative patent citations from the ITPAIS file are Hsted as a function of significant dye class. From these citations it is clear that preferred sensitizers for silver haUdes are polymethine dyes (cyanine, merocyanine, etc), whereas other semiconductors have more evenly distributed citations. Zinc oxide, for example, is frequendy sensitized by xanthene dyes (qv) or triarylmethane dyes (see Triphenylmethane and related dyes) as well as cyanines and merocyanines (see Cyanine dyes). 

Photopolymerization reactions are widely used for printing and photoresist appHcations (55). Spectral sensitization of cationic polymerization has utilized electron transfer from heteroaromatics, ketones, or dyes to initiators like iodonium or sulfonium salts (60). However, sensitized free-radical polymerization has been the main technology of choice (55). Spectral sensitizers over the wavelength region 300—700 nm are effective. AcryUc monomer polymerization, for example, is sensitized by xanthene, thiazine, acridine, cyanine, and merocyanine dyes. The required free-radical formation via these dyes may be achieved by hydrogen atom-transfer, electron-transfer, or exciplex formation with other initiator components of the photopolymer system. 

Neady every significant class of dyes and pigments has some members that function as sensitizers. Toxicological data are often included in surveys of dyes (84), reviews of toxic substance identification programs (85), and in material safety data sheets provided by manufacturers of dyes. More specific data about toxicological properties of sensitizing dyes are contained in the Engchpedia under the specific dye classes (see Cyanine dyes Polymethine dyes Xanthene dyes). 

A reaction of mixed molybdenum polyoxometalates (POMs) with cyanine dye has been used for highly selective and sensitive spectrophotometric determination of phosphorus(V) and arsenic(V). Color of the solution is considerably changed by reaction of Keggin POMs with styrene cyanine dyes. Derivatives of l,3,3-threemethyl-3//-indol - astrazone violet (AV 3R), astrazone rose, astrazone yellow, astrazone red were investigated. 

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