Comment on "The Jones-Hore theory of radical-ion-pair reactions is not self-consistent" (arXiv:1010.3888v3)

A short comment on "The Jones-Hore theory of radical-ion-pair reactions is not self-consistent" (arXiv:1010.3888v3) is presented. In the comment, it is pointed out that the paper includes a misconception about the Jones-Hore approach in Chem. Phys. Lett. 488 (2010) 90-93. The re-formulation is presented and it is demonstrated that the Jones-Hore theory is consistent at least on the point claimed by I. K. Kominis in the paper

Chemically amplified ¹⁹F-¹H nuclear Overhauser effects

Chemically induced dynamic nuclear polarisation (CIDNP) is explored as a source of nuclear hyperpolarisation in heteronuclear Overhauser effect experiments. A photochemical reaction proceeding through a radical pair intermediate is used to enhance 19F nuclear magnetisation in 3-fluorotyrosine by more than an order of magnitude with a corresponding increase in the amplitudes of 19F–1H cross-relaxation and cross-correlation effects. The reactions employed are cyclic and leave the sample chemically unchanged. The potential for enhancing the sensitivity of heteronuclear NOEs in 19F-labelled proteins is discussed

Uniform illumination of optically dense NMR samples

We demonstrate a simple, inexpensive method for in situ laser illumination of NMR samples using a stepwise tapered optical fibre to deliver light uniformly along the axis of a 5 mm NMR tube. The optical path length of the incident light inside the sample is about 3 mm, allowing efficient illumination of optically dense samples. The degradation in spectral resolution and the reduction in filling factor are both minimal. Probe modifications are not required

Increasing the sensitivity of time-resolved photo-CIDNP experiments by multiple laser flashes and temporary storage in the rotating frame

Pulse sequences have been developed that add up time-resolved photo-CIDNP signals from n successive laser flashes not in the acquisition computer of the NMR spectrometer but in the experiment itself, resulting in a greatly improved signal-to-noise ratio. For this accumulation, CIDNP is first stored in the transverse plane and then on the z axis, and finally superimposed on CIDNP produced by the next flash. These storage cycles also result in a very efficient background suppression. Because only one free induction decay is acquired for n flashes, the noise is digitized only once. The signal gain is demonstrated experimentally and analyzed theoretically. Losses are mostly due to nuclear spin relaxation, and to a small extent to instrument imperfections. With 10 laser flashes, a signal increase by a factor of about 7.5 was realized. As their main advantage compared to signal averaging in the usual way, these sequences yield the same signal-to-noise ratio with fewer laser flashes; the theoretical improvement is by a factor of √n

A light-dependent magnetoreception mechanism insensitive to light intensity and polarization

Billions of migratory birds navigate thousands of kilometres every year aided by a magnetic compass sense the biophysical mechanism of which is unclear. One leading hypothesis is that absorption of light by specialised photoreceptors in the retina produces short‐lived chemical intermediates known as radical pairs whose chemistry is sensitive to tiny magnetic interactions. A potentially serious but largely ignored obstacle to this theory is how directional information derived from the Earth’s magnetic field can be separated from the much stronger variations in the intensity and polarization of the incident light. Here we propose a simple solution in which these extraneous effects are cancelled by taking the ratio of the signals from two neighbouring populations of magnetoreceptors. Geometric and biological arguments are used to derive a set of conditions that make this possible. We argue that one likely location of the magnetoreceptor molecules would be in association with ordered opsin dimers in the membrane discs of the outer segments of double‐cone photoreceptor cells

Bloch-Redfield-Wangsness theory engine implementation using symbolic processing software

We describe a general method for the automated symbolic processing of Bloch-Redfield-Wangsness relaxation theory equations for liquid-phase spin dynamics in the algebraically challenging case of rotationally modulated interactions. The processing typically takes no more than a few seconds (on a contemporary single-processor workstation) and yields relaxation rate expressions that are completely general with respect to the spectral density functions, relative orientations, and magnitudes of the interaction tensors, with all cross-correlations accounted for. The algorithm easily deals with fully rhombic interaction tensors, and is able, with little if any modification, to treat a large variety of the relaxation mechanisms encountered in NMR, EPR, and spin dynamics in general

Polynomially scaling spin dynamics simulation algorithm based on adaptive state-space restriction

We report progress with an old problem in magnetic resonance—that of the exponential scaling of simulation complexity with the number of spins. It is demonstrated below that a polynomially scaling algorithm can be obtained (and accurate simulations performed for over 200 coupled spins) if the dimension of the Liouville state space is reduced by excluding unimportant and unpopulated spin states. We found the class of such states to be surprisingly wide. It actually appears that a majority of states in large spin systems are not essential in magnetic resonance simulations and can safely be dropped from the state space. In restricted state spaces the spin dynamics simulations scale polynomially. In cases of favourable interaction topologies (sparse graphs, e.g. in protein NMR) the asymptotic scaling is linear, opening the way to direct fitting of molecular structures to experimental spectra

Spin relaxation effects in photochemically induced dynamic nuclear polarization spectroscopy of nuclei with strongly anisotropic hyperfine couplings

We describe experimental results and theoretical models for nuclear and electron spin relaxation processes occurring during the evolution of 19F-labeled geminate radical pairs on a nanosecond time scale. In magnetic fields of over 10 T, electron-nucleus dipolar cross-relaxation and longitudinal HFC-g (hyperfine coupling anisotropy - g-tensor anisotropy) cross-correlation are shown to be negligibly slow. The dominant relaxation process is transverse HFC-g cross-correlation, which is shown to lead to an inversion in the geminate 19F chemically induced dynamic nuclear polarization (CIDNP) phase for sufficiently large rotational correlation times. This inversion has recently been observed experimentally and used as a probe of local mobility in partially denatured proteins (Khan, F.; et al. J. Am. Chem. Soc. 2006, 128, 10729-10737). The essential feature of the spin dynamics model employed here is the use of the complete spin state space and the complete relaxation superoperator. On the basis of the results reported, we recommend this approach for reliable treatment of magnetokinetic systems in which relaxation effects are important

Novel pulse sequences for time-resolved photo-CIDNP

The properties of a new class of pulse sequences for photo-CIDNP (photochemically induced dynamic nuclear polarization) are analysed in detail, and guidelines for their optimization and applicability are derived. Sensitivity is a central problem with time-resolved photo-CIDNP experiments. By using multiple laser flashes per acquisition and storing the polarizations temporarily in the spin system, a significant improvement is achieved. An alternative application is the reduction of the absorbed light needed to attain a given sensitivity. Compared to conventional signal averaging with the same number n of flashes, a maximum additional improvement by a factor of slightly more than 0.5?n can be achieved in both cases. By an analysis of the transfer pathways, it is shown that multiplet signals and CIDNP multiplet effects can also be investigated in this way, even for strongly coupled spin systems. Experimental examples are given