Scientists decipher key principle behind reaction of metalloenzymes

So-called pre-distorted states accelerate photochemical reactions too

What enables electrons to be transferred swiftly, for example during photosynthesis? An interdisciplinary team of researchers has worked out the details of how important bioinorganic electron transfer systems operate. Using a combination of very different, time-resolved measurement methods at DESY’s X-ray source PETRA III and other facilities, the scientists were able to show that so-called pre-distorted states can speed up photochemical reactions or make them possible in the first place. The group headed by Sonja Herres-Pawlis from the RWTH Aachen University  Michael Rübhausen from the University of Hamburg and Wolfgang Zinth from Munich’s Ludwig Maximilian University, is presenting its findings in the journal Nature Chemistry.

The scientists had studied the pre-distorted, “entatic” state using a model system. An entatic state is the term used by chemists to refer to the configuration of a molecule in which the normal arrangement of the atoms is modified by external binding partners such that the energy threshold for the desired reaction is lowered, resulting in a higher speed of reaction. One example of this is the metalloprotein plastocyanin, which has a copper atom at its centre and is responsible for important steps in the transfer of electrons during photosynthesis. Depending on its oxidation state, the copper atom either prefers a planar configuration, in which all the surrounding atoms are arranged in the same plane (planar geometry), or a tetrahedral arrangement of the neighbouring ligands. However the binding partner in the protein forces the copper atom to adopt a sort of intermediate arrangement. This highly distorted tetrahedron allows a very rapid shift between the two oxidation states of the copper atom.

>Read more on the PETRA III website

Image Caption: Entatic state model complexes optimize the energies of starting and final configuration to enable fast reaction rates (illustrated by the hilly ground). The work demonstrates that the entatic state principle can be used to tune the photochemistry of copper complexes.
Credit: RWTH Aachen, Sonja Herres-Pawlis

Scientists measure accelerated emission

Grazing light for rapid events

An international team, including scientists from DESY,  has verified a prediction about the quantum-mechanical behaviour of resonant systems made more than 50 years ago. In experiments at SACLA, the Japanese X-ray laser, and at the European Synchrotron Radiation Facility ESRF in France, the group led by Aleksandr Chumakov from ESRF could show a dramatic reduction in the time to emit the first X-ray photon from an ensemble of excited nuclei when the number of X-rays for the excitation was increased. This behaviour is in good agreement with one limit of a superradiant system, predicted by the US physicist Robert Dicke in 1954, as the scientists report in the journal Nature Physics.

One of the broad challenges of science is to understand the behaviour of groups of atoms based on the response of a single atom in isolation, which is usually much simpler. A facet of this is understanding the behaviour of a group of identical oscillators. An analogy is a collection of bells that all have the same tone: one can easily imagine the sound of a single bell struck once – a clear tone ringing out with a volume that decays away over time.

But what happens if one gently taps all the bells in a large collection? Will the tone be the same as a single one? What about the volume? What about the direction – does it matter where you are standing when you listen to the sound? Does it matter if you tap them all at the same time?

>Read more on the FLASH website