37 research outputs found
THEORETICAL STUDIES OF BILIPROTEIN CHROMOPHORES AND RELATED BILE PIGMENTS BY MOLECULAR ORBITAL AND RAMACHANDRAN TYPE CALCULATIONS
Ramachandran calculations have been used to gain insight into steric hindrance in bile
pigments related to biliprotein chromophores. The high optical activity of denatured phycocyanin, as
compared to phycoerythrin, has been related to the asymmetric substitution at ring A, which shifts the
equilibrium towards the P-helical form of the chromophore. Geometric effects on the electronic structures
and transitions have then been studied by molecular orbital calculations for several conjugation
systems including the chromophores of phycocyanin. phytochrome P,, cations, cation radicals and
tautomeric forms. For these different chromophores some general trends can be deduced. For instance,
for a given change in the gross shape (e.g. either unfolding of the molecule from a cyclic-helical to a fully
extended geometry, or upon out-of-plane twists of the pyrrole ring A) of the molecules under study, the
predicted absorption spectra all change in a simikar way. Nonetheless, there are characteristic distinctions
between the different n-systems, both in the transition energies and the charge distribution, which
can be related to their known differences in spectroscopic properties and their reactivity
Infrared spectroscopy of phytochrome and model pigments
Fourier-transform infrared difference spectra between the red-absorbing and far-red-absorbing forms of oat phytochrome have been measured in H2O and 2H2O. The difference spectra are compared with infrared spectra of model compounds, i.e. the (5Z,10Z,15Z)- and (5Z,10Z,15E)-isomers of 2,3,7,8,12,13,17,18-octaethyl-bilindion (Et8-bilindion), 2,3-dihydro-2,3,7,8,12,13,17,18-octaethyl-bilindion (H2Et8-bilindion), and protonated H2Et8-bilindion in various solvents. The spectra of the model compounds show that only for the protonated forms can clear differences between the two isomers be detected. Since considerable differences are present between the spectra of Et8-bilindion and H2Et8-bilindion, it is concluded that only the latter compound can serve as a model system of phytochrome. The 2H2O effect on the difference spectrum of phytochrome supports the view that the chromophore in red-absorbing phytochrome is protonated and suggests, in addition, that it is also protonated in far-red-absorbing phytochrome. The spectra show that protonated carboxyl groups are influenced. The small amplitudes in the difference spectra exclude major changes of protein secondary structure