ABSTRACT
With the inauguration of the small-angle instrument D11 of the Institute Laue-Langevin (ILL) in September 1972 neutron scattering revolutionized methods of contrast variation. Very soon D11 was oversubscribed by proposals relying on isotopic substitution of hydrogen isotopes. At the same time in Oxford first experiments of polarised neutron diffraction from dynamic polarised protons in lanthanum magnesium nitrate crystals demonstrated the great utility of this approach. In the early eighties a new type of polarised target material led to a boom of contrast variation by nuclear polarisation. The new samples of frozen solutions of macromolecules lent themselves to small-angle scattering. Often in collaboration with research centres of High Energy Physics various groups in Europe and Japan started experiments of polarized neutron scattering from dynamic polarised protons. Techniques of NMR and EPR considerably enlarged the spectrum of nuclear contrast variation. This is shown with time-resolved polarised neutron scattering from dynamic polarized proton spins of a free radical and of tyrosyl doped catalase using D22 at the ILL.
ABSTRACT
A tyrosyl radical, as part of the amino acid chain of bovine liver catalase, supports dynamic proton spin polarization (DNP). Finding the position of the tyrosyl radical within the macromolecule relies on the accumulation of proton polarization close to it, which is readily observed by polarized neutron scattering. The nuclear scattering amplitude due to the polarization of protons less than 10â Å distant from the tyrosyl radical is ten times larger than the amplitude of magnetic neutron scattering from an unpaired polarized electron of the same radical. The direction of DNP was inverted every 5â s, and the initial evolution of the intensity of polarized neutron scattering after each inversion was used to identify those tyrosines which have assumed a radical state. Three radical sites, all of them close to the molecular centre and the haem, appear to be equally possible. Among these is tyr-369, the radical state of which had previously been proven by electron paramagnetic resonance.
ABSTRACT
An unexpected and not always easily discernible feature in the picture of magnetic neutron scattering is widening the outlook on micromagnetic architecture [Mettus & Michels (2015). J. Appl. Cryst.48, 1437-1450].
ABSTRACT
Methods of contrast variation are tools that are essential in macromolecular structure research. Anomalous dispersion of X-ray diffraction is widely used in protein crystallography. Recent attempts to extend this method to native resonant labels like sulfur and phosphorus are promising. Substitution of hydrogen isotopes is central to biological applications of neutron scattering. Proton spin polarization considerably enhances an existing contrast prepared by isotopic substitution. Concepts and methods of nuclear magnetic resonance (NMR) become an important ingredient in neutron scattering from dynamically polarized targets.
Subject(s)
Neutron Diffraction/methods , Scattering, Small Angle , X-Ray Diffraction/methods , Bacteriorhodopsins/chemistry , HIV Reverse Transcriptase/chemistry , Hexokinase/chemistry , Magnetic Resonance Spectroscopy , Mathematics , Models, Molecular , Nucleosomes/chemistry , Phospholipids/chemistry , Purple Membrane/chemistry , RNA, Viral/chemistry , Ribosome Subunits, Small, Bacterial/chemistry , Tobacco necrosis satellite virus/chemistry , Trypsin/chemistryABSTRACT
Dynamic nuclear spin polarization (DNP) is mediated by the dipolar interaction of paramagnetic centres with nuclear spins. This process is most likely to occur near paramagnetic centres at an angle close to 45 degrees with respect to the direction of the external magnetic field. The resulting distribution of polarized nuclear spins leads to an anisotropy of the polarized neutron scattering pattern, even with randomly oriented radical molecules. The corresponding cross section of polarized coherent neutron scattering in terms of a multipole expansion is derived for radical molecules in solution. An application using data of time-resolved polarized neutron scattering from an organic chromium(V) molecule is tested.
