Retinitis

So far we have exclusively discussed time-resolved absorption spectroscopy with visible femtosecond pulses. It has become recently feasible to perfomi time-resolved spectroscopy with femtosecond IR pulses. Flochstrasser and co-workers [M, 150. 151. 152. 153. 154. 155. 156 and 157] have worked out methods to employ IR pulses to monitor chemical reactions following electronic excitation by visible pump pulses these methods were applied in work on the light-initiated charge-transfer reactions that occur in the photosynthetic reaction centre [156. 157] and on the excited-state isomerization of tlie retinal pigment in bacteriorhodopsin [155]. Walker and co-workers [158] have recently used femtosecond IR spectroscopy to study vibrational dynamics associated with intramolecular charge transfer these studies are complementary to those perfomied by Barbara and co-workers [159. 160], in which ground-state RISRS wavepackets were monitored using a dynamic-absorption technique with visible pulses. [Pg.1982]

The first study in which a full CASSCE treatment was used for the non-adiabatic dynamics of a polyatomic system was a study on a model of the retinal chromophore [86]. The cis-trans photoisomerization of retinal is the primary event in vision, but despite much study the mechanism for this process is still unclear. The minimal model for retinal is l-cis-CjH NHj, which had been studied in an earlier quantum chemisti7 study [230]. There, it had been established that a conical intersection exists between the Si and So states with the cis-trans defining torsion angle at approximately a = 80° (cis is at 0°). Two... [Pg.305]

The multiple spawning method described in Section IV.C has been applied to a number of photochemical systems using analytic potential energy surfaces. As well as small scattering systems [36,218], the large retinal molecule has been treated [243,244]. It has also been applied as a direct dynamics method. [Pg.306]

Isralewitz et eil., 1997] Isralewitz, B., Izrailev, S., and Schulten, K. Binding pathway of retinal to bacterio-opsin A prediction by molecular dynamics simulations. Biophys. J. 73 (1997) 2972-2979... [Pg.62]

FIGURE 17 11 Imine formation between the aldehyde function of 11 as retinal and an ammo group of a protein (opsin) is involved in the chemistry of vision The numbering scheme in retinal is specifically developed for carotenes and related compounds... [Pg.729]

Retinal trans-Retinal [116-31-4] Retinaldehyde [116-31-4] Retinitis pigmentosa Retinoblastoma Retinoic acid... [Pg.851]

High power lasers also can cause serious skin bums (53,54). The ha2ard is less than that of retinal bums, because the power per unit area is not increased by focusing, but the high power lasers in use for industrial appHcations could inflict extremely serious skin bums. [Pg.12]

Because of the presence of an extended polyene chain, the chemical and physical properties of the retinoids and carotenoids are dominated by this feature. Vitamin A and related substances are yellow compounds which are unstable in the presence of oxygen and light. This decay can be accelerated by heat and trace metals. Retinol is stable to base but is subject to acid-cataly2ed dehydration in the presence of dilute acids to yield anhydrovitamin A [1224-18-8] (16). Retro-vitamin A [16729-22-9] (17) is obtained by treatment of retinol in the presence of concentrated hydrobromic acid. In the case of retinoic acid and retinal, reisomerization is possible after conversion to appropriate derivatives such as the acid chloride or the hydroquinone adduct. Table 1 Hsts the physical properties of -carotene [7235-40-7] and vitamin A. [Pg.96]

Work at Rhc ne-Poulenc has involved a different approach to retinal and is based on the paHadium-cataly2ed rearrangement of the mixed carbonate (41) to the aHenyl enal (42). Isomerization of the aHene (42) to the polyene (43) completes the constmction of the carbon framework. Acid-catalyzed isomerization yields retinal (5). A decided advantage of this route is that no by-products such as triphenylphosphine oxide or sodium phenylsulfinate are formed. However, significant yield improvements would be necessary for this process to compete with the current commercial syntheses (25—27) (Fig. 9). [Pg.99]

In the BASF synthesis, a Wittig reaction between two moles of phosphonium salt (vitamin A intermediate (24)) and C q dialdehyde (48) is the important synthetic step (9,28,29). Thermal isomerization affords all /ra/ j -P-carotene (Fig. 11). In an alternative preparation by Roche, vitamin A process streams can be used and in this scheme, retinol is carefully oxidized to retinal, and a second portion is converted to the C2Q phosphonium salt (49). These two halves are united using standard Wittig chemistry (8) (Fig. 12). [Pg.100]

In nature, vitamin A aldehyde is produced by the oxidative cleavage of P-carotene by 15,15 - P-carotene dioxygenase. Alternatively, retinal is produced by oxidative cleavage of P-carotene to P-apo-S -carotenal followed by cleavage at the 15,15 -double bond to vitamin A aldehyde (47). Carotenoid biosynthesis and fermentation have been extensively studied both ia academic as well as ia iadustrial laboratories. On the commercial side, the focus of these iavestigations has been to iacrease fermentation titers by both classical and recombinant means. [Pg.101]

The distribution of rods and cones is shown in Figure 3b centered about the fovea, the area of the retina that has the highest concentration of cones with essentially no rods and also has the best resolving capabiUty, with a resolution about one minute of arc. The fovea is nominally taken as a 5° zone, with its central 1° zone designated the foveola. There are about 40 R and 20 G cones for each B cone in the eye as a whole, whereas in the fovea there are almost no B cones. A result of this is that color perception depends on the angle of the cone of light received by the eye. The extremely complex chemistry involved in the stimulation of opsin molecules, such as the rhodopsin of the rods, and the neural connections in the retinal pathway are well covered in Reference 21. [Pg.407]

The trichromatic theory, subsequendy confirmed by the existence of the three sets of cones, must be combined with the opponent theory, which is involved in the retinal pathway. A third approach, the appearance theory (2) or the retinex theory, must be added to explain color constancy and other effects. As one example of this last, consider an area perceived as red in a multicolored object such as a Mondrian painting when illuminated with white... [Pg.407]

Fig. 1. Representative spectral sensitivities of the human retinal receptors, (-) scotopic (rod) vision, and P, y, and p cone sensitivities. The wavelengths of...

Fig. 23. An example of fundus (retinal) photography, widely used for diagnosis in opthamology. The photograph is on Polaroid Type 779, a professional...

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). [Pg.437]

Retinal (vitamin A aldehyde), alcohol) see entries in Chapter 6. [Pg.348]

Retinal (Vitamin A aldehyde). Retinoic acid (Vitamin A acid), Retinyl acetate, Retinyl palmitate see entries in Chapter 4. [Pg.564]

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