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.Graphical abstract