Thermal Interconversions Among 15-cis-, 13-cis-, and All-trans-β-carotene: Kinetics, Arrhenius Parameters, Thermochemistry, and Potential Relevance to Anticarcinogenicity of All-trans-β-carotene
Rates of thermal, cis-trans rearrangement among all-trans-, 15-cis-, and 13-cis-β-carotene have been measured at temperatures in the range 37-69°C. From the resulting specific rate constants, Arrhenius and Eyring parameters are derived. Positions of equilibrium are estimated experimentally and by force field calculations based on the Allinger MM2 program as improved by Roth (MM2-ERW), while enthalpies of activation for cis-trans isomerization to 11-, 9-, and 7-cis-β-carotenes are estimated by application of the Roth program augmented by the inclusion of the quantum mechanical program of Malrieu et al., EVBH (effective valence-bond Hamiltonian), expanded to encompass longer polyenes. Implications of the interaction of strain and delocalization in the rotation about the 7,8 double bond are presented. A procedure has been developed for the small scale preparation of 13-cis-β-carotene by heating all-trans-β-carotene at 80°C for 8 h. Kinetically and thermodynamically accessible at 37°C, 15-cis- or 13-cis-β-carotene or both become candidates for the role of true anticarcinogenic agent, where upon all-trans-β-carotene would be relegated to the role of reservoir for the active species.
W. V. Doering et al., "Thermal Interconversions Among 15-cis-, 13-cis-, and All-trans-β-carotene: Kinetics, Arrhenius Parameters, Thermochemistry, and Potential Relevance to Anticarcinogenicity of All-trans-β-carotene," Journal of the American Chemical Society, American Chemical Society (ACS), Jan 1995.
The definitive version is available at http://dx.doi.org/10.1021/ja00115a010
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© 1995 American Chemical Society (ACS), All rights reserved.