ABSTRACT
Night-migratory songbirds are remarkably proficient navigators1. Flying alone and often over great distances, they use various directional cues including, crucially, a light-dependent magnetic compass2,3. The mechanism of this compass has been suggested to rely on the quantum spin dynamics of photoinduced radical pairs in cryptochrome flavoproteins located in the retinas of the birds4-7. Here we show that the photochemistry of cryptochrome 4 (CRY4) from the night-migratory European robin (Erithacus rubecula) is magnetically sensitive in vitro, and more so than CRY4 from two non-migratory bird species, chicken (Gallus gallus) and pigeon (Columba livia). Site-specific mutations of ErCRY4 reveal the roles of four successive flavin-tryptophan radical pairs in generating magnetic field effects and in stabilizing potential signalling states in a way that could enable sensing and signalling functions to be independently optimized in night-migratory birds.
Subject(s)
Animal Migration , Cryptochromes/genetics , Magnetic Fields , Songbirds , Animals , Avian Proteins/genetics , Chickens , Columbidae , RetinaABSTRACT
Modulated magnetically altered reaction yield (ModMARY) spectroscopy is a derivative variant of fluorescence detected magnetic field effect measurement, where the applied magnetic field has both a constant and a modulated component. As in many derivative spectroscopy techniques, the signal to noise ratio scales with the magnitude of the modulation. High modulation amplitudes, however, distort the signal and can obscure small features of the measured spectrum. In order to detect weak magnetic field effects (including the low field effect) a balance of the two has to be found. In this work we look in depth at the origin of the distortion of the MARY signal by field modulation. We then present an overtone detection scheme, as well as a data analysis method which allows for correct fitting of both harmonic and overtone signals of the modulation broadened MARY data. This allows us to robustly reconstruct the underlying MARY curve at different modulation depths. To illustrate the usefulness of the technique, we show measurements and analysis of a well known magnetosensitive system of pyrene/1,3-dicyanobenzene (Py/DCB). The measurements of first (h1) and second (h2) harmonic spectra are performed at different modulation depths for both natural isotopic abundance (PyH10), and perdeuterated (PyD10) pyrene samples.
ABSTRACT
Certain pairs of paramagnetic species generated under conservation of total spin angular momentum are known to undergo magnetosensitive processes. Two prominent examples of systems exhibiting these so-called magnetic field effects (MFEs) are photogenerated radical pairs created from either singlet or triplet molecular precursors, and pairs of triplet states generated by singlet fission. Here, we showcase confocal microscopy as a powerful technique for the investigation of such phenomena. We first characterise the instrument by studying the field-sensitive chemistry of two systems in solution: radical pairs formed in a cryptochrome protein and the flavin mononucleotide/hen egg-white lysozyme model system. We then extend these studies to single crystals. Firstly, we report temporally and spatially resolved MFEs in flavin-doped lysozyme single crystals. Anisotropic magnetic field effects are then reported in tetracene single crystals. Finally, we discuss the future applications of confocal microscopy for the study of magnetosensitive processes with a particular focus on the cryptochrome-based chemical compass believed to lie at the heart of animal magnetoreception.
