There is growing evidence that the remarkable ability of animals, in particular birds, to sense the direction of the Earth's magnetic field relies on magnetically sensitive photochemical reactions of the protein cryptochrome. It is generally assumed that the magnetic field acts on the radical pair [formed by the transfer of an electron from a group of three tryptophan residues to the photo-excited flavin adenine dinucleotide cofactor within the protein. ] arise from the asymmetric distribution of hyperfine interactions among the two radicals and the near-optimal magnetic properties of the flavin radical. We close by discussing the identity of Z † and possible routes for its formation as part of a spin-correlated radical pair with an FAD radical in cryptochrome.

A critical requirement in the proposed chemical model of the avian magnetic compass is that the molecules that play host to the magnetically sensitive radical pair intermediates must be immobilized and rotationally ordered within receptor cells. Rotational disorder would cause the anisotropic responses of differently oriented radical pairs within the same cell to interfere destructively, while rapid molecular rotation would tend to average the crucial anisotropic magnetic interactions and induce electron spin relaxation, reducing the sensitivity to the direction of the geomagnetic field. So far, experimental studies have been able to shed little light on the required degree of ordering and immobilization. To address this question, computer simulations have been performed on a collection of radical pairs undergoing restricted rigid-body rotation, coherent anisotropic spin evolution, electron spin relaxation and spin-selective recombination reactions. It is shown that the ordering and motional constraints necessary for efficient magnetoreception can be simultaneously satisfied if the radical pairs are uniaxially ordered with a moderate order parameter and if their motional correlation time is longer than about a quarter of their lifetime.

According to the radical pair model, the magnetic compass sense of migratory birds relies on photochemical transformations in the eye to detect the direction of the geomagnetic field. Magnetically sensitive radical pairs are thought to be generated in cryptochrome proteins contained in magnetoreceptor cells in the retina. A prerequisite of the current model is for some degree of rotational ordering of both the cryptochromes within the cells and of the cells within the retina so that the directional responses of individual molecules do not average to zero. Here, it is argued that anisotropic distributions of radical pairs can be generated by the photoselection effects that arise from the directionality of the light entering the eye. Light-induced rotational order among the transient radical pairs rather than intrinsic ordering of their molecular precursors is seen as the fundamental condition for a magnetoreceptor cell to exhibit an anisotropic response. A theoretical analysis shows that a viable compass magnetoreceptor could result from randomly oriented cryptochromes contained in randomly oriented cells distributed around the retina.

The purported effects of weak magnetic fields on various biological systems from animal magnetoreception to human health have generated widespread interest and sparked much controversy in the past decade. To date the only well established mechanism by which the rates and yields of chemical reactions are known to be influenced by magnetic fields is the radical pair mechanism, based on the spin-dependent reactivity of radical pairs. A diagnostic test for the operation of the radical pair mechanism was proposed by Henbest et al. [J. Am. Chem. Soc., 2004, 126, 8102] based on the combined effects of weak static magnetic fields and radiofrequency oscillating fields in a reaction yield detected magnetic resonance experiment. Here we investigate the effects on radical pair reactions of applying relatively strong oscillating fields, both parallel and perpendicular to the static field. We demonstrate the importance of understanding the effect of the strength of the radiofrequency oscillating field; our experiments demonstrate that there is an optimal oscillating field strength above which the observed signal decreases in intensity and eventually inverts. We establish the correlation between the onset of this effect and the hyperfine structure of the radicals involved, and identify the existence of 'overtone' type features appearing at multiples of the expected resonance field position.