Biochemical reactions sometimes have to handle dangerous things in a safe way. New work from researchers at UC Davis and Stanford University shows how cyanide（氰化物） and carbon monoxide are safely bound to an iron atom to construct an enzyme¹ that can generate hydrogen gas. The work is published Jan. 24 in the journal Science. Producing hydrogen with catalysts³ based on abundant metals, such as iron, is key to hopes of using hydrogen to replace carbon-based fuels. But before you can make hydrogen, you have to make the catalyst² that enables the reaction -- something bacteria have been able to do for millennia⁴.

 

Jon Kuchenreuther, a postdoctoral researcher working with Professor Dave Britt, project scientist Simon George and colleagues at the UC Davis Department of Chemistry, with James Swartz and colleagues at Stanford, used a variety of analysis techniques to study the chain of chemical reactions that assembles these catalysts based on clusters of iron and sulfur⁵ atoms adorned⁶ with cyanide (CN) and carbon monoxide (CO) molecules⁷.

 

"How does biology make these complicated active sites?" Britt said. "You can't release cyanide or carbon monoxide into the cell. It turns out that it's formed and kept on iron throughout."

 

In work published in Science last year, the researchers showed that the amino acid tyrosine first binds⁸ to the iron/sulfur cluster, and is then split by the enzyme HydG to create a radical⁹. The new paper picks up the story from there, showing that carbon monoxide and cyanide derived¹⁰ from the splitting of tyrosine（酪氨酸）, remain bound to the same iron atom as the tyrosine radical is removed. This iron/cyanide/carbon monoxide structure becomes part of the final cluster.

 

The team principally used a technique called Fourier Transform Infra Red spectroscopy to follow the process. FTIR measures vibrations¹¹ in bond length, and both cyanide and carbon monoxide show strong signals with this method.

 

Metal atoms in biological molecules are usually bound to large structures, like amino acids or heme groups, Britt said. For metals to be bound to small molecules, like carbon monoxide and cyanide, is "some unusual chemistry by itself," he said.

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