Thursday, June 01, 2017

Nick Lane on Proto-Ech

Nick Lane has a few more downloadable papers available on his website, two of which focus on ideas I've thought a lot about. Here are a few quotes:

Iron Catalysis at the Origin of Life

"Why does the reduction of ferredoxin via Ech depend on the proton-motive force? The answer is as yet unknown, but cannot relate to reverse electron flow [as originally proposed (49)] as these methanogens do not possess an electron-transport chain (37,38). A more pleasing possibility is that pH modulates reduction potential at the active site of the enzyme. The flux of protons through Ech from the relatively acidic exterior could lower the pH at the active site of the enzyme, which should facilitate reductions that depend on protons, including CO2 as well as some ferredoxins (50)".

My italics. Next:

Proton gradients at the origin of life

Aside: If you read the full text of Lane's paper you will take note of Jackson JB (2016) Natural pH gradients in hydrothermal alkali vents were unlikely to have played a role in the origin of life. And this passed scrutineering. Nick Lane does not seem impressed. End aside.

"One possibility is that prebiotic carbon and energy metabolism entailed the synthesis of reactive thioesters analogous to acetyl CoA, such as methyl thioacetate, coupled to substrate-level phosphorylation, generating acetyl phosphate and ultimately ATP [1, 17, 27, 60–63] as still happens in bacteria [14, 31]".

"Across the barrier, in acidic conditions, CO2 is more easily reduced, and so is more likely to be reduced by Fe2+ in the barrier. The semiconducting barrier should transfer electrons from Fe2+ on the alkaline side to Fe3+ on the acidic side. The thickness of the barrier does not matter, so long as it is semiconducting. The two phases do not come into direct contact - H2 and CO2 do not react directly (Fig. 3)".

This is really neat, it puts in to a published paper many of the logical concepts that went in to the Life series. I really like the pre biotic ideas of electron transfer across any-thickness FeS barriers. No need for membranes, indeed insulating "crud" membranes would hinder electron transfer from the FeS wall to the enzyme, necessitating the generation of a pore like structure (ancestor to NuoH) to get the voltage generating acidic pH to the active enzyme's site.

This ferredoxin reduction plus subsequent substrate-level phosphorylation is where it should all start. NuoH starts as a pH channel, not part of a nano machine. That comes later with reversal of proton flow and the development of complex I, a true advanced nano machine.

I still don't buy ATP synthase (another very complex nano machine) as running on the primordial vent proton gradient as Nick Lane holds to. Later developing Na+ energetics look much more likely, these following on from Proto-Ech's pore duplication to form a Na+/H+ antiporter, giving a usable Na+ gradient. That clearly post-dates some sort of membrane, which ferredoxin based metabolism must precede when using a geochemical proton gradient. NuoH becomes essential only after a crude membrane forms to impede this process of ferredoxin reduction.

Nice papers.



cavenewt said...

This stuff is fascinating even though most of it is way over my high-school-chemistry head.

One question regarding "I really like the pre biotic ideas of electron transfer across any-thickness FeS barriers. No need for membranes, indeed insulating "crud" [crude?] membranes would hinder electron transfer..."

In this context, there appears to be a technical difference between a barrier and a membrane. What would that difference be?

Peter said...

This is a matter of semantics, it's one of the big arguments Lane has with Jackson. Jackson seems to switch between the two to build straw men. A barrier is all you need, FeS does the job. "Crud" is (in my mind) a non structured mix of hydrocarbons, amino acids and carbohydrates acting as a sludge which stops the reaction site of the proto-enzyme easily reaching the charged FeS surface needed to provide high energy electrons. An FeS barrier comes first. A "crud" proto-membrane lines that barrier. A pore is needed to make a hole in the proto-membrane to allow supply of low potential electrons to the active site of the Proto Ech. Ferredoxin is such a simple protein it might have been a pre genome construct. I love that Lane quotes the ferredoxin paper in his recent discussions. Obviously ferredoxin is a transporter which allows the actual CO2 reduction to be well away from the site of electron supply to the interior of the "cell"...