Abstract
It is a fundamental property of conjugated systems to accept a proton or Lewis acid and form a stable carbonium ion. Polyenes that are protonated or add Lewis acids in this manner undergo substantial red shifts. For example, vitamin A1 acetate absorbs at 350 mµ in neutral and at 650 mµ in acidic benzene solution. The fundamental basis for absorption of polyene systems was described in detail in quantum mechanical terms. Applying the carbonium ion treatment to the visual chromophores retinal1 and retinal2 gives a very satisfactory explanation why these polyenes can be made to absorb in the visual region. Furthermore, by proper placement of the Lewis acid several absorption maxima can be gained from the carbonium ions which result. This treatment can be applied to explain experimental results. Individual cones from the frog are now known to absorb at 455, 537, and 625 mµ. If the value for the green cone (537 mµ) is used to calculate the Vo value in Kuhn's equation, the other two wave lengths may then be calculated. The calculated values are 460 and 600 mµ; this is in good agreement with the results from experiment.
Full Text
The Full Text of this article is available as a PDF (461.9 KB).
Selected References
These references are in PubMed. This may not be the complete list of references from this article.
- BROWN P. K., WALD G. VISUAL PIGMENTS IN SINGLE RODS AND CONES OF THE HUMAN RETINA. DIRECT MEASUREMENTS REVEAL MECHANISMS OF HUMAN NIGHT AND COLOR VISION. Science. 1964 Apr 3;144(3614):45–52. doi: 10.1126/science.144.3614.45. [DOI] [PubMed] [Google Scholar]
- HUBBARD R. The molecular weight of rhodopsin and the nature of the rhodopsin-digitonin complex. J Gen Physiol. 1954 Jan 20;37(3):381–399. doi: 10.1085/jgp.37.3.381. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Hubbard R., Kropf A. THE ACTION OF LIGHT ON RHODOPSIN. Proc Natl Acad Sci U S A. 1958 Feb;44(2):130–139. doi: 10.1073/pnas.44.2.130. [DOI] [PMC free article] [PubMed] [Google Scholar]
- KROPF A., HUBBARD R. The mechanism of bleaching rhodopsin. Ann N Y Acad Sci. 1959 Nov 12;74(2):266–280. doi: 10.1111/j.1749-6632.1958.tb39550.x. [DOI] [PubMed] [Google Scholar]
- MARKS W. B., DOBELLE W. H., MACNICHOL E. F., Jr VISUAL PIGMENTS OF SINGLE PRIMATE CONES. Science. 1964 Mar 13;143(3611):1181–1183. doi: 10.1126/science.143.3611.1181. [DOI] [PubMed] [Google Scholar]
- Platt J. R. Carotene-Donor-Acceptor Complexes in Photosynthesis: The predicted lowering of the excited states of carotenoids may offer a new photosynthetic pathway. Science. 1959 Feb 13;129(3346):372–374. doi: 10.1126/science.129.3346.372. [DOI] [PubMed] [Google Scholar]
- RADDING C. M., WALD G. Acid-base properties of rhodopsin and opsin. J Gen Physiol. 1956 Jul 20;39(6):909–922. doi: 10.1085/jgp.39.6.909. [DOI] [PMC free article] [PubMed] [Google Scholar]
- WALD G., BROWN P. K., GIBBONS I. R. The problem of visual excitation. J Opt Soc Am. 1963 Jan;53:20–35. doi: 10.1364/josa.53.000020. [DOI] [PubMed] [Google Scholar]
- WALD G., BROWN P. K. The role of sulfhydryl groups in the bleaching and synthesis of rhodopsin. J Gen Physiol. 1952 May;35(5):797–821. doi: 10.1085/jgp.35.5.797. [DOI] [PMC free article] [PubMed] [Google Scholar]