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[Music]

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Thank You Irina

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that's a great question George and so

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what actually they're sort of core of

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what I'm going to try to talk about here

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so I gave this I think it's kinda like a

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Harry Potter s sort of title dynamic

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organic reaction networks and where to

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find them it's kind of like magical

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beasts and how to feed them and I think

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a bunch of different collaborators are a

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highlight show a ohhara I'm going to

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show quite a bit of his work that he did

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with along with Vijay that was actually

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inspired by some ideas a Harold marwat's

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had are very consistent with what we

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just heard before really pretty cool

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stuff so I think to me a statement of

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the obvious is that for life to emerge

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on this planet there had to be

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environments that we're capable of

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continuous synthesis of reactive organic

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molecules I think that's probably the

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simplest requirement so that's an

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obvious question now I'll refer to this

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in a very general sense it's dynamic

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organic reaction networks I think you're

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self-explanatory we get to it what's not

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at all obvious from a geochemical

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perspective is how and where could these

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naturally occur I think this speaks

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somewhat to exactly what George was

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asking at this stage of what we do we're

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generally not worried so much about

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yield we're worried about pathway can we

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show pathway connectivity between one

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state systems to nuts but at some point

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we do have to worry about yield in some

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way we have to at some point we have to

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worry about control functions and I will

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point to that so when one puts it

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together a talk like this one generally

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likes to look at sort of big idea papers

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and and you can't really go wrong or I

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think you can't go wrong by looking at

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big idea of papers from norms sleep

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he always has very interesting

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perspective so I hadn't read this

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particular paper if his but I did just

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to kind of get myself energized for

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putting this talk together and and he

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says some statements that make me feel

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really good like life probably

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originated here and definitely evolved

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here that's a great statement and if you

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know norm he he is very very careful

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about what he says and then I game since

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I said was probably unproductive to

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precisely define when auto catalysis

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became life and from norms perspective

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this an absolutely relevant point

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because he's focused on life on Earth

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and the evolution of both life and the

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earth in

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interactive sort of way so he he can

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take that question off the table

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but we can hey we really have to address

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this issue about the broader context of

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life how that reflects to Swiss self in

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an exoplanets and the possibility of

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life elsewhere so again going back to

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norm sleeps key requirements

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he says temperatures key here we really

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don't we've got a narrow band of

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temperature to play with it has to be

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warmer than in solid water so you could

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have Bryan's that are colder than zero

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but but a certain point waters gonna

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solidify and it has to be probably he

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argues less than 122 degrees centigrade

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and then the second requirement is

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straightforward there has to be energy

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and I like the fact that he said there

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have always been hydrothermal systems to

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promote this chemical D security regime

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and the earth throughout Earth history

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he also argues that then came

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phototropism I think everybody agree

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with that so in a norm kind of grounds

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the questions rather nicely and both the

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requirements that seem very reasonable

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to me so then I went off and I said well

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you know at this point 2018 we must have

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a pretty clear view of what the Earth's

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early atmosphere looked like and I was

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surprised that the first figure you get

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when you google it is very Harold Urey

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--is-- sort of view of the earth even in

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2018 so don't think that that's

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particularly likely so another person

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that's always kind of fun to go visit is

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Kevin's on LI and apparently this must

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have been a really interesting meeting I

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think Jack szostak put it together at

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Cold Spring Harbor and what Kevin does

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of course is he takes her the same

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perspective that norm does perhaps a

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little bit more if you know Kevin work

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Kevin like way it is very complicated

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diagram the bottom line is is Kevin

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would argue that that the surface of the

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earth itself became a very climate place

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for life remarkably quickly so in this

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axis of time he would argue that that

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oceans had completely started to

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condense at about a million years and at

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that point like we go on he also argues

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against things like an ammoniated or or

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methane ated atmosphere atmosphere based

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on on photochemistry so so if you you

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think Kevin's --only esque way you're

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really talking about co2 so that gets us

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to ask about Hadean sources of fuels and

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oxidants

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so we condensed a planet from

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interstellar material

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course one of those abundant molecules

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in in the universe is hydrogen but I

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doubt very severely than any of that

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hydrogen made it way into the accretion

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of the earth that was left so we need

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the earth to generate the hydrogen

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that's going to be probably the most

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dominant fuel this is a model reaction

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of certain ization reaction which is a

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very efficient hydrogen generator my

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Kressel has considered this for many

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many years many people do so it's a very

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reliable source of a fuel maybe there

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was methane maybe there was ammonium

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hydrogen sulfides a good fuel that would

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be more of a URI askes thing so we

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include that for oxidants it would

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appear that co2 is really the only solid

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oxidant we have things appear to be Mike

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could speak to this much more eloquently

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and I but but sulfate doesn't seem to be

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reasonable in the beginning although

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I'll talk to you about this and make

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some arguments that there may have been

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some other interesting oxidants that we

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don't normally take an account so

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starting with co2 and hydrogen it's good

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place to start with sitting organic

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synthesis and life's origins and so the

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key is of course co2 reductions we just

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heard now thermodynamically carbon

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dioxide and hydrogen can do two things

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they can do the water gas shift reaction

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it's basically a very fast equilibrium

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between co2 and hydrogen carbon monoxide

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water the problem is almost any

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temperature any pressure you can think

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of the reaction is always strongly in

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charge use chips to the co2 side of

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things so so it's it's a fast reaction

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it doesn't require a catalyst but it's

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it's it's not particularly interesting

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as the previous speaker noted carbon

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monoxide is a great molecule for

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chemistry co2 is not now the methanogens

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this reaction is very very strongly

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thermodynamically driven at low

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temperatures so co2 plus hydrogen goes

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to methane and water so this is a great

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game and it senses start at least it's

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not making carbon-carbon bonds but it's

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a start for basically building something

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however it's interesting to go back

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through the literature particularly

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amongst experimental geochemist they

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were quickly surprised when they started

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studying this reaction that they could

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never see any methane even though

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thermodynamically it was the most stable

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species by far and they didn't recognize

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at the time that that without a catalyst

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you'll form no methane so you can verify

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that yourself in fact when you do seem

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Thayne using gold reactors where gold is

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effectively non catalytic you'll find

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that it's due to trace metal

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contaminants in the gold because there's

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always you know entropy will never allow

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you to have pure gold pure words you

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might think it might be will always be a

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little bit platinum iridium and some

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kind of sicyon so any methane that you

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do generate can be attributed we had a

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postdoc in my lab who did a very careful

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experiment showing just that fact and

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important but not particularly exciting

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so we do the reaction and this is this

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is scaled so that you can see all the

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products but you get mostly methane you

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get a subordinate amount of ethane

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that's the two-threes propane you get

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your butane and your pentane and your

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hexane so this is fine I'll talk about

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the kinetics but I'll highlight one

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thing you do form a bunch of other

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little molecules and it turns out these

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are really going to be the source altom

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utley if your dynamic organic reaction

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networks so these are branched and

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partially unsaturated but they're very

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subordinate to to the main reduce

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products now kinetics you know this is a

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if theoretically if you had homogeneous

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kinetics you'd predict this sort of

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behavior decay of co2 so we're starting

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with formic acid so you only form 25%

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methane so co2 and hydrogen decay

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exponentially and then one minus

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exponent production of water and methane

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is what is expected but of course I said

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you can't do this without a catalyst so

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with heterogeneous catalysis you end up

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with essentially 0th order kinetics so

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this is what you would predict to see if

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you did this reaction as a function of

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time and that little blue box shows you

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why you get 0th order kinetics in fact

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we can show this in a really funny

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reaction for chemists because we did a

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reaction to butane Thyle which is one of

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the most foul-smelling molecules could

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possibly imagine except for the product

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of the reaction which is pentanoic or

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villi Eric acid which is about the most

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horrendously smelly compound you can so

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it's like gifs go for bad too costly

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worse but it shows beautiful 0th order

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kinetics and its yield so so what we saw

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in this reaction this is a funny story

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to this so I wasn't particularly

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interested in this reaction but I had a

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summer research intern and I wanted to

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give them a

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experiment to do and I wanted to get

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them from bothering me so I thought I

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could teach them how to weld gold tubes

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and I would give this very simple

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reaction I said just take form of gas to

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decompose it over iron and gold tubes

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and just show me that co2 is decaying

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linearly and hydrogens decaying linearly

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and methane is increasing linearly and

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then you'll be done for your summer

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research and so he came back in and he

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and he showed me this plot and I said

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that's ridiculous to go back and do it

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again this doesn't make any sense and so

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he did it over and over again so of

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course this is what we predicted and

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this is what we see that in the first

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couple hours there's no co2 at all co2

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is just disappears from the system half

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of the hydrogen you'd expect to see is

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there and it just sort of floats there

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and then miraculously about four to six

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hours also there's an explosion of co2

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and product hydrocarbons this is the

274
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distribution I showed you so again it

275
00:09:58,769 --> 00:09:55,779
looks very Fischer troph like in its

276
00:10:00,780 --> 00:09:58,779
distribution so methane propane is

277
00:10:02,550 --> 00:10:00,790
abundant over at more abundant of ethane

278
00:10:03,930 --> 00:10:02,560
and so on and so forth but a decay and

279
00:10:06,120 --> 00:10:03,940
the relative yield as a function of

280
00:10:10,050 --> 00:10:06,130
chain length the blue are branched

281
00:10:11,610 --> 00:10:10,060
compounds and when you do a mass balance

282
00:10:13,199 --> 00:10:11,620
you see the carbon budget doesn't make

283
00:10:15,530 --> 00:10:13,209
any sense so for the first four hours

284
00:10:18,180 --> 00:10:15,540
100% of your carbon is just not

285
00:10:19,920 --> 00:10:18,190
detectable analytically it's there right

286
00:10:22,010 --> 00:10:19,930
it's in a sealed gold tube but but you

287
00:10:26,100 --> 00:10:22,020
just can't see it using gas phase

288
00:10:27,960 --> 00:10:26,110
analysis headspace-gc similarly it

289
00:10:29,970 --> 00:10:27,970
reappears about four hours but it's now

290
00:10:32,100 --> 00:10:29,980
quite important the black line down

291
00:10:33,300 --> 00:10:32,110
below is about the amount of hydrocarbon

292
00:10:34,740 --> 00:10:33,310
so you would predict you have made so

293
00:10:36,449 --> 00:10:34,750
you're making more hydrocarbons and you

294
00:10:37,680 --> 00:10:36,459
had hydrogen to make with so it tells

295
00:10:39,630 --> 00:10:37,690
you that you've got hydrogen generation

296
00:10:43,530 --> 00:10:39,640
going on that's not a surprise the

297
00:10:45,150 --> 00:10:43,540
hydrogen budget also and then we did we

298
00:10:47,730 --> 00:10:45,160
looked at stable isotopes and again you

299
00:10:49,860 --> 00:10:47,740
can see at low times the co2 both the

300
00:10:51,569 --> 00:10:49,870
co2 and methane are actually more

301
00:10:52,920 --> 00:10:51,579
depleted relative to the starting

302
00:10:54,689 --> 00:10:52,930
material which is the dashed line which

303
00:10:56,189 --> 00:10:54,699
is just the carbon your four mate so

304
00:11:00,269 --> 00:10:56,199
that's your missing carbon reservoir

305
00:11:01,829 --> 00:11:00,279
somewhere and the same thing happens

306
00:11:04,560 --> 00:11:01,839
over here there's a bottom line what I'm

307
00:11:05,939 --> 00:11:04,570
saying is so then interact Sharma was

308
00:11:07,500 --> 00:11:05,949
working out loud and he's very handy

309
00:11:09,120 --> 00:11:07,510
with a hydrothermal diamond anvil cell

310
00:11:10,710 --> 00:11:09,130
which is a beautiful device to allow you

311
00:11:12,660 --> 00:11:10,720
to look into the reactor to see what's

312
00:11:13,980 --> 00:11:12,670
actually going on and what you can see

313
00:11:15,630 --> 00:11:13,990
is complete mayhem

314
00:11:19,170 --> 00:11:15,640
so you're seeing all sorts of different

315
00:11:20,880 --> 00:11:19,180
phases here the absolute cake phases are

316
00:11:23,370 --> 00:11:20,890
your residual iron there's at least two

317
00:11:25,050 --> 00:11:23,380
different liquids but apparently even

318
00:11:27,420 --> 00:11:25,060
three different liquid phases that are

319
00:11:29,220 --> 00:11:27,430
immiscible and if you look closely in

320
00:11:31,380 --> 00:11:29,230
the rommel inspector you see abundant

321
00:11:33,660 --> 00:11:31,390
transition metal carbonyls so the bottom

322
00:11:36,360 --> 00:11:33,670
line is in this particular super simple

323
00:11:39,240 --> 00:11:36,370
system or organometallic chemistry x' is

324
00:11:41,220 --> 00:11:39,250
very abundant it highlights the fact

325
00:11:43,620 --> 00:11:41,230
that even simple experiments are rarely

326
00:11:45,300 --> 00:11:43,630
simple and the hidden mineral chemistry

327
00:11:46,890 --> 00:11:45,310
that drives the system towards sorts

328
00:11:50,220 --> 00:11:46,900
very rapid Hodge a thermo-pile

329
00:11:52,050 --> 00:11:50,230
hydrocarbon synthesis the kinetics are

330
00:11:53,370 --> 00:11:52,060
completely unusual we don't really quite

331
00:11:55,530 --> 00:11:53,380
understand them there they're almost

332
00:11:56,790 --> 00:11:55,540
explosive so you know you would have

333
00:11:58,380 --> 00:11:56,800
thought I would have thought the system

334
00:12:00,480 --> 00:11:58,390
would have established one state or the

335
00:12:02,400 --> 00:12:00,490
other what special at four or six hours

336
00:12:03,720 --> 00:12:02,410
it causes a system to all us and shift

337
00:12:07,440 --> 00:12:03,730
from one state to another

338
00:12:08,610 --> 00:12:07,450
is not at all obvious to us I don't know

339
00:12:10,520 --> 00:12:08,620
if it's a profitable thing to really

340
00:12:12,930 --> 00:12:10,530
worry about but it's very reproducible

341
00:12:15,300 --> 00:12:12,940
but either way I wanted to highlight for

342
00:12:17,340 --> 00:12:15,310
this talk that even though we can do

343
00:12:19,890 --> 00:12:17,350
very easily all this carbon-carbon bond

344
00:12:22,020 --> 00:12:19,900
formation simple hydrocarbons are not

345
00:12:24,030 --> 00:12:22,030
reactive and are not capable of

346
00:12:25,440 --> 00:12:24,040
sustaining a dynamic organic reaction

347
00:12:27,780 --> 00:12:25,450
network so even though this is how you

348
00:12:29,700 --> 00:12:27,790
have to start the system the main

349
00:12:32,010 --> 00:12:29,710
product distribution is not something

350
00:12:36,180 --> 00:12:32,020
that's going to be in my view beneficial

351
00:12:38,010 --> 00:12:36,190
for a emergent living system as George

352
00:12:42,120 --> 00:12:38,020
talked about this morning and others

353
00:12:43,290 --> 00:12:42,130
have talked about so just this figure is

354
00:12:45,030 --> 00:12:43,300
kind of screwed up but obviously there's

355
00:12:47,550 --> 00:12:45,040
a carbon valence state from minus 4 to

356
00:12:51,350 --> 00:12:47,560
plus 4 and then hydrogen redox over here

357
00:12:54,000 --> 00:12:51,360
and it highlights the fact that if you

358
00:12:56,610 --> 00:12:54,010
if you're just making simple

359
00:13:00,090 --> 00:12:56,620
hydrocarbons as a macro moly ethylenes

360
00:13:02,820 --> 00:13:00,100
and alkanes through -4 minus 2 or

361
00:13:04,650 --> 00:13:02,830
methane Thyle which is a molecule that's

362
00:13:06,990 --> 00:13:04,660
fine but all of life exists essentially

363
00:13:10,140 --> 00:13:07,000
much more at sort of a carbon neutral

364
00:13:13,980 --> 00:13:10,150
valence state and if our Trebor were

365
00:13:17,010 --> 00:13:13,990
here he would go on quite convincingly

366
00:13:18,630 --> 00:13:17,020
and and I think rightly so and the

367
00:13:19,920 --> 00:13:18,640
benefit of being at around 0 valence

368
00:13:21,630 --> 00:13:19,930
carbon for the kind of chemistry you

369
00:13:23,400 --> 00:13:21,640
want to do but the bottom line is you

370
00:13:25,260 --> 00:13:23,410
see all amino acids are sort of sitting

371
00:13:26,910 --> 00:13:25,270
back and forth around the zero valence

372
00:13:27,630 --> 00:13:26,920
state and all the T C intermediates are

373
00:13:31,080 --> 00:13:27,640
relatively

374
00:13:32,610 --> 00:13:31,090
sighs when it comes to organic

375
00:13:34,470 --> 00:13:32,620
polymerization which is something we're

376
00:13:36,420 --> 00:13:34,480
always interested in this becomes

377
00:13:38,010 --> 00:13:36,430
critical so even if you if you wanted to

378
00:13:39,870 --> 00:13:38,020
make a compelling physical argument that

379
00:13:41,550 --> 00:13:39,880
polyethylene was your polymer of choice

380
00:13:44,040 --> 00:13:41,560
for emergence systems I don't think

381
00:13:46,410 --> 00:13:44,050
anybody would the problem is is that

382
00:13:48,060 --> 00:13:46,420
this catalytic chemistry is is strongly

383
00:13:50,130 --> 00:13:48,070
quenched by the presence of water and

384
00:13:51,510 --> 00:13:50,140
and so you're not going to go very far

385
00:13:54,120 --> 00:13:51,520
with regards to the activity water

386
00:13:56,580 --> 00:13:54,130
before if things fall apart now my

387
00:13:59,130 --> 00:13:56,590
colleague Irina she does some beautiful

388
00:14:00,930 --> 00:13:59,140
work with you know cyclic drying heating

389
00:14:03,480 --> 00:14:00,940
wetting drying wetting drying white

390
00:14:05,160 --> 00:14:03,490
wedding to do polymerization but she

391
00:14:06,600 --> 00:14:05,170
would also agree at a certain point the

392
00:14:08,550 --> 00:14:06,610
activity of water is going to shut

393
00:14:10,890 --> 00:14:08,560
things down just simple thermodynamics

394
00:14:12,990 --> 00:14:10,900
condensation and that's the beauty is

395
00:14:14,730 --> 00:14:13,000
art Weber would talk to you about is the

396
00:14:16,500 --> 00:14:14,740
idea of what sugars can do in aldol

397
00:14:18,630 --> 00:14:16,510
polymerization so they're not

398
00:14:20,490 --> 00:14:18,640
condensation polymerization and and in

399
00:14:22,650 --> 00:14:20,500
fact you can show that sugars will

400
00:14:24,780 --> 00:14:22,660
polymerize themselves I'll be it into a

401
00:14:27,480 --> 00:14:24,790
mess so there's your messy chemistry

402
00:14:29,190 --> 00:14:27,490
like that but but it you know you can go

403
00:14:30,450 --> 00:14:29,200
down to millimolar concentrations and

404
00:14:32,130 --> 00:14:30,460
give it enough time and the stuff will

405
00:14:34,650 --> 00:14:32,140
polymerize and precipitate out I'll show

406
00:14:36,030 --> 00:14:34,660
you an example of that so so there's

407
00:14:37,560 --> 00:14:36,040
something to be said is what I'm getting

408
00:14:40,140 --> 00:14:37,570
at maybe the core of this entire

409
00:14:42,480 --> 00:14:40,150
argument is getting a system to sit

410
00:14:48,630 --> 00:14:42,490
around sort of equivalently carbon 0

411
00:14:50,850 --> 00:14:48,640
valence so we kind of got re-energized

412
00:14:53,960 --> 00:14:50,860
by this ism it's a different difficult

413
00:14:55,920 --> 00:14:53,970
segue to make but I'm going to it is

414
00:14:57,030 --> 00:14:55,930
independent of this I've been studying

415
00:14:58,380 --> 00:14:57,040
the organic matter and carbonaceous

416
00:15:00,180 --> 00:14:58,390
chondrite meteorites and I've been

417
00:15:01,530 --> 00:15:00,190
focusing on the in cell insoluble

418
00:15:03,750 --> 00:15:01,540
organic matter and I'm not going to talk

419
00:15:05,160 --> 00:15:03,760
about that specifically but others have

420
00:15:07,530 --> 00:15:05,170
a dominantly been focusing on small

421
00:15:09,000 --> 00:15:07,540
molecules they can extract now the neat

422
00:15:10,650 --> 00:15:09,010
thing about carbonaceous chondrites

423
00:15:12,690 --> 00:15:10,660
is they tell you about chemistry and

424
00:15:15,270 --> 00:15:12,700
planet parent body interiors these are

425
00:15:17,340 --> 00:15:15,280
planetesimals that existed for tens to

426
00:15:20,640 --> 00:15:17,350
hundreds of millions of years they had

427
00:15:22,710 --> 00:15:20,650
interesting disequilibrium systems that

428
00:15:24,690 --> 00:15:22,720
were warm but not hot they were wet but

429
00:15:25,860 --> 00:15:24,700
not soaked they initially started very

430
00:15:28,200 --> 00:15:25,870
far from equilibrium

431
00:15:30,270 --> 00:15:28,210
very rich in carbon predominantly co2

432
00:15:32,150 --> 00:15:30,280
and perhaps some carbon monoxide and

433
00:15:36,900 --> 00:15:32,160
catalytic phases iron nickel metal

434
00:15:39,330 --> 00:15:36,910
kemacite and correlate as a iron

435
00:15:40,950 --> 00:15:39,340
sulphide is very very abundant

436
00:15:41,519 --> 00:15:40,960
relatively speaking and potentially

437
00:15:43,530 --> 00:15:41,529
millions

438
00:15:45,809 --> 00:15:43,540
years of mild hydrothermal reaction and

439
00:15:49,170 --> 00:15:45,819
the possibility perhaps of chemical

440
00:15:50,850 --> 00:15:49,180
evolution so but up to this point most

441
00:15:52,499 --> 00:15:50,860
people have focused on amino acids there

442
00:15:53,699 --> 00:15:52,509
been detection of nucleobases there's

443
00:15:56,929 --> 00:15:53,709
certainly some interesting chemistry in

444
00:16:01,710 --> 00:15:56,939
there George Cooper published a paper in

445
00:16:03,600 --> 00:16:01,720
2011 which astounded me he is a very

446
00:16:06,660 --> 00:16:03,610
careful analyst and he's been studying

447
00:16:09,030 --> 00:16:06,670
the Murchison meteorite and he detected

448
00:16:10,920 --> 00:16:09,040
and on the biggest identified all sorts

449
00:16:12,360 --> 00:16:10,930
of interesting compounds that are very

450
00:16:17,610 --> 00:16:12,370
familiar to us as metabolic

451
00:16:21,360 --> 00:16:17,620
intermediates and so he finds pyruvate

452
00:16:22,980 --> 00:16:21,370
and citrate and alpha ketoglutarate and

453
00:16:27,059 --> 00:16:22,990
some and so forth lactic acids over

454
00:16:28,679 --> 00:16:27,069
there alanine glycolic acid and some and

455
00:16:30,449 --> 00:16:28,689
so forth there's even a can con at eight

456
00:16:33,989 --> 00:16:30,459
somewhere here

457
00:16:35,429 --> 00:16:33,999
yeah down in the corner and but he's you

458
00:16:37,350 --> 00:16:35,439
know he focuses primarily at doing

459
00:16:39,449 --> 00:16:37,360
really precise analytical chemistry and

460
00:16:42,809 --> 00:16:39,459
using isotopic analysis to verify the

461
00:16:45,449 --> 00:16:42,819
you know JIT a'mma C of these compounds

462
00:16:47,100 --> 00:16:45,459
with respect to their origin but when it

463
00:16:48,809 --> 00:16:47,110
came time to proposing what their

464
00:16:51,360 --> 00:16:48,819
formation mechanism was he said well

465
00:16:54,119 --> 00:16:51,370
maybe they came from Keene and we get to

466
00:16:56,069 --> 00:16:54,129
pyruvate and then we can add potassium

467
00:17:00,119 --> 00:16:56,079
cyanide to the system and all this

468
00:17:01,920 --> 00:17:00,129
chemistry occur and you know possibly

469
00:17:07,350 --> 00:17:01,930
possibly that's okay

470
00:17:09,630 --> 00:17:07,360
but the thing that struck me was if you

471
00:17:12,090 --> 00:17:09,640
looked at all his molecules citric acid

472
00:17:13,919 --> 00:17:12,100
and the previous speaker highlighted his

473
00:17:16,110 --> 00:17:13,929
early study I did looking at the hydro

474
00:17:18,809 --> 00:17:16,120
thermal decomposition such a gas is a

475
00:17:20,250 --> 00:17:18,819
fairly tough molecule it's it's you have

476
00:17:21,929 --> 00:17:20,260
to go to temperatures on the order of

477
00:17:24,720 --> 00:17:21,939
about 200 Gries centigrade to start to

478
00:17:26,360 --> 00:17:24,730
see it decompose in a reasonable way you

479
00:17:28,710 --> 00:17:26,370
know at a hundred degrees I haven't

480
00:17:30,990 --> 00:17:28,720
bothered to determine what the half-life

481
00:17:33,029 --> 00:17:31,000
is as a function of temperature but it's

482
00:17:34,169 --> 00:17:33,039
it's a tough molecule in fact one of the

483
00:17:35,639 --> 00:17:34,179
reasons that people got interested in

484
00:17:37,680 --> 00:17:35,649
getting rid of it is it turns out that

485
00:17:39,240 --> 00:17:37,690
it's a byproduct of the molasses

486
00:17:41,070 --> 00:17:39,250
industry and we generate more citric

487
00:17:42,419 --> 00:17:41,080
acid than we know what to do with and if

488
00:17:43,649 --> 00:17:42,429
you could find an easy way of getting

489
00:17:45,659 --> 00:17:43,659
rid of it this would be a really good

490
00:17:48,899 --> 00:17:45,669
thing to do so it's tough enough that

491
00:17:51,539 --> 00:17:48,909
people worry about this toughness but

492
00:17:53,370 --> 00:17:51,549
nevertheless it will go away and if you

493
00:17:55,020 --> 00:17:53,380
give something like 10 to 100 million

494
00:17:57,300 --> 00:17:55,030
years of hydrothermal chemistry

495
00:17:58,530 --> 00:17:57,310
a hundred to even maybe fifty two

496
00:18:00,690 --> 00:17:58,540
hundred great it's gonna decompose

497
00:18:01,860 --> 00:18:00,700
here's just showing the decomposition a

498
00:18:04,020 --> 00:18:01,870
two hundred grease integrated and within

499
00:18:06,240 --> 00:18:04,030
two hours you dropped a concentration of

500
00:18:09,630 --> 00:18:06,250
citric acid by three orders of magnitude

501
00:18:12,450 --> 00:18:09,640
which tells you so good something even

502
00:18:14,730 --> 00:18:12,460
as robust as citric acid less a million

503
00:18:16,050 --> 00:18:14,740
years not possible and that's probably

504
00:18:17,130 --> 00:18:16,060
one of the toughest molecules and all

505
00:18:20,460 --> 00:18:17,140
the molecules that George Cooper

506
00:18:21,750 --> 00:18:20,470
detected so the key here is that none of

507
00:18:24,570 --> 00:18:21,760
the molecules that George Cooper

508
00:18:26,760 --> 00:18:24,580
identified have ever been proposed to

509
00:18:28,770 --> 00:18:26,770
form prior to planetesimals accretion

510
00:18:30,510 --> 00:18:28,780
alright so so these things had to form

511
00:18:32,760 --> 00:18:30,520
in the parent body due to whatever

512
00:18:34,110 --> 00:18:32,770
process of occurring and he said many of

513
00:18:36,090 --> 00:18:34,120
these molecules have not all of them are

514
00:18:38,760 --> 00:18:36,100
academic acid if you don't freeze it

515
00:18:39,720 --> 00:18:38,770
decomposes on the shelf right so so

516
00:18:41,070 --> 00:18:39,730
there's no way you're gonna have a

517
00:18:42,990 --> 00:18:41,080
commit a gas for the last thing for a

518
00:18:44,460 --> 00:18:43,000
couple of days let alone you know a

519
00:18:46,950 --> 00:18:44,470
millions of years in wet water

520
00:18:49,050 --> 00:18:46,960
conditions so so these things will not

521
00:18:50,670 --> 00:18:49,060
suffice oh we require in my view that

522
00:18:52,260 --> 00:18:50,680
the only way you could find these things

523
00:18:54,990 --> 00:18:52,270
in a meteorite if they were continuously

524
00:18:57,540 --> 00:18:55,000
regenerated and so in essence George

525
00:18:59,610 --> 00:18:57,550
Cooper detected the core evidence we

526
00:19:01,830 --> 00:18:59,620
were hoping to find and probably try to

527
00:19:03,720 --> 00:19:01,840
do in a laboratory of a natural dynamic

528
00:19:06,150 --> 00:19:03,730
organic reaction operating in

529
00:19:07,680 --> 00:19:06,160
planetesimals interiors so it raises the

530
00:19:10,920 --> 00:19:07,690
question how did this start and how did

531
00:19:12,660 --> 00:19:10,930
it operate so key here is planetesimals

532
00:19:14,490 --> 00:19:12,670
in crete from rapid collation of

533
00:19:16,470 --> 00:19:14,500
ice-covered interstellar silicate grains

534
00:19:18,210 --> 00:19:16,480
and ice is predominantly water that's

535
00:19:20,820 --> 00:19:18,220
why we call it ice but there's a fair

536
00:19:22,460 --> 00:19:20,830
amount of co2 carbon monoxide methanol

537
00:19:24,810 --> 00:19:22,470
formaldehyde my favorite molecule

538
00:19:27,150 --> 00:19:24,820
ammonia h2s and all about the same

539
00:19:29,550 --> 00:19:27,160
abundance and the silicates are in Hydra

540
00:19:31,940 --> 00:19:29,560
iron hydras hi I'm bearing silicates and

541
00:19:34,590 --> 00:19:31,950
amorphous iron bearing classes

542
00:19:35,940 --> 00:19:34,600
radiogenic elements provide the heat so

543
00:19:37,350 --> 00:19:35,950
in the core of a reasonably sized

544
00:19:39,180 --> 00:19:37,360
planetesimals and will get warm enough

545
00:19:41,580 --> 00:19:39,190
to melt the ices and start to react the

546
00:19:43,020 --> 00:19:41,590
iron to generate hydrogen so you have an

547
00:19:45,210 --> 00:19:43,030
environment that's capable of producing

548
00:19:47,340 --> 00:19:45,220
fuels and it has the oxidants you might

549
00:19:51,420 --> 00:19:47,350
like to do but what else has struck me

550
00:19:53,310 --> 00:19:51,430
about George Cooper's work is that all

551
00:19:56,160 --> 00:19:53,320
of these compounds much like our

552
00:19:57,480 --> 00:19:56,170
previous speaker was showing we've been

553
00:19:58,890 --> 00:19:57,490
able to make in our hydrothermal

554
00:20:01,710 --> 00:19:58,900
experiments in our laboratories so

555
00:20:04,350 --> 00:20:01,720
everyone in blue we made now the pathway

556
00:20:05,970 --> 00:20:04,360
unlike George's pathway coming from from

557
00:20:08,700 --> 00:20:05,980
this key team to to pyruvate and

558
00:20:11,370 --> 00:20:08,710
everywhere else the pathway we saw it

559
00:20:13,889 --> 00:20:11,380
doing something more like that in terms

560
00:20:16,470 --> 00:20:13,899
of connectivity of molecular species

561
00:20:19,230 --> 00:20:16,480
micro species and I highlight the methyl

562
00:20:21,210 --> 00:20:19,240
cynic acid there so this really struck

563
00:20:23,250 --> 00:20:21,220
me because these molecules we can make

564
00:20:23,909 --> 00:20:23,260
in our little gold reactors and we see

565
00:20:25,380 --> 00:20:23,919
them all the time

566
00:20:27,240 --> 00:20:25,390
however we had never been able to make

567
00:20:29,880 --> 00:20:27,250
fumaric acid and we never could find a

568
00:20:31,560 --> 00:20:29,890
pathway to that alpha keto glue turret

569
00:20:33,960 --> 00:20:31,570
and so that really intrigued me that

570
00:20:37,769 --> 00:20:33,970
clearly this is occurring at Murchison

571
00:20:39,149 --> 00:20:37,779
how come we can't do it now one of the

572
00:20:40,710 --> 00:20:39,159
things we've always been focusing on not

573
00:20:42,539 --> 00:20:40,720
worrying at all about yields but we're

574
00:20:44,519 --> 00:20:42,549
just worrying about topology pathways

575
00:20:46,049 --> 00:20:44,529
--is is how would you start with co2 and

576
00:20:48,480 --> 00:20:46,059
hydrogen get to interesting molecules

577
00:20:51,299 --> 00:20:48,490
and so the pathway we like is going say

578
00:20:52,980 --> 00:20:51,309
through propane to acrylic acid through

579
00:20:55,950 --> 00:20:52,990
a carbonyl addition reaction and so and

580
00:20:57,899 --> 00:20:55,960
so forth level by level up the core to

581
00:20:59,669 --> 00:20:57,909
this chemistry is I'll show you later is

582
00:21:01,350 --> 00:20:59,679
that you can't just do this in a

583
00:21:03,180 --> 00:21:01,360
reductive sense you have to be playing

584
00:21:07,740 --> 00:21:03,190
both oxidative and reductive chemistry

585
00:21:10,019 --> 00:21:07,750
simultaneously which is tricky so a bit

586
00:21:12,630 --> 00:21:10,029
of history we got involved in this game

587
00:21:14,580 --> 00:21:12,640
when Harold Warwick's came to our lab 20

588
00:21:16,769 --> 00:21:14,590
years ago and he asked if I could do an

589
00:21:19,590 --> 00:21:16,779
experiment adding co2 to pyruvic acid to

590
00:21:21,210 --> 00:21:19,600
make oxaloacetate and I didn't think

591
00:21:23,580 --> 00:21:21,220
that that would work at the time and it

592
00:21:25,139 --> 00:21:23,590
didn't and I thought would happen would

593
00:21:27,389 --> 00:21:25,149
be nothing but trouble and I was right

594
00:21:29,730 --> 00:21:27,399
is that the pyruvate would just react

595
00:21:31,889 --> 00:21:29,740
with itself forming this gooey tar which

596
00:21:34,200 --> 00:21:31,899
is what it does and or it just

597
00:21:38,340 --> 00:21:34,210
spontaneously decomposes to acetate

598
00:21:39,810 --> 00:21:38,350
releasing his reductive potential there

599
00:21:41,460 --> 00:21:39,820
are some interesting intermediates but

600
00:21:43,049 --> 00:21:41,470
but if you did this reactions as we did

601
00:21:45,029 --> 00:21:43,059
them in water that they're very low

602
00:21:46,620 --> 00:21:45,039
abundance but the only product that you

603
00:21:48,750 --> 00:21:46,630
do detected sort of builds up in the

604
00:21:54,510 --> 00:21:48,760
system is methyl 6na so I was really

605
00:21:56,010 --> 00:21:54,520
struck in when when it George Cooper

606
00:21:57,570 --> 00:21:56,020
called that out because that again

607
00:22:02,450 --> 00:21:57,580
looked like a lot of our aldol

608
00:22:10,620 --> 00:22:08,430
so any case so but that was as far as we

609
00:22:13,380 --> 00:22:10,630
went with the aldol reaction effect I

610
00:22:15,419 --> 00:22:13,390
used to say I know I'm sort of a little

611
00:22:17,010 --> 00:22:15,429
jet lag here I apologize for this one of

612
00:22:20,250 --> 00:22:17,020
the things I like about this system is

613
00:22:22,410 --> 00:22:20,260
the power of the retro aldol component

614
00:22:23,880 --> 00:22:22,420
to give you reactive compound

615
00:22:25,590 --> 00:22:23,890
when and possibly you need it so for

616
00:22:28,470 --> 00:22:25,600
example on the right side Citroen malic

617
00:22:30,300 --> 00:22:28,480
acid turned out to be the best pyruvic

618
00:22:32,700 --> 00:22:30,310
acid generator I've ever seen and so in

619
00:22:35,850 --> 00:22:32,710
terms of high yield for example if you

620
00:22:37,620 --> 00:22:35,860
have ammonia and pyruvate as its own

621
00:22:40,710 --> 00:22:37,630
self reductant you can get almost the

622
00:22:42,420 --> 00:22:40,720
full yield of alanine one to one out of

623
00:22:45,480 --> 00:22:42,430
sitri moly under a aquatherm oolitic

624
00:22:47,760 --> 00:22:45,490
conditions i contrast that with my first

625
00:22:49,680 --> 00:22:47,770
and only first author science paper

626
00:22:51,810 --> 00:22:49,690
where I made some yield at point zero

627
00:22:54,360 --> 00:22:51,820
one percent pyruvate over Iron Mountain

628
00:22:55,920 --> 00:22:54,370
sulfate sulphide and at the time and we

629
00:22:57,210 --> 00:22:55,930
were really excited about that but but

630
00:22:59,310 --> 00:22:57,220
when you can see what you can do with

631
00:23:01,680 --> 00:22:59,320
the retro aldol reaction with something

632
00:23:03,180 --> 00:23:01,690
like Citra malate it's just incredible

633
00:23:05,940 --> 00:23:03,190
it's almost a hundred percent of the

634
00:23:10,860 --> 00:23:05,950
potential pyruvate generation will give

635
00:23:13,110 --> 00:23:10,870
you and so in keys but Harold had been

636
00:23:16,890 --> 00:23:13,120
starting to read some interesting papers

637
00:23:20,030 --> 00:23:16,900
by I wouldn't say his wasn't his nemesis

638
00:23:25,350 --> 00:23:23,550
but Leslie or gal it was the chemist

639
00:23:27,420 --> 00:23:25,360
chemist if my view in this business and

640
00:23:29,010 --> 00:23:27,430
and Harold as a biophysicist who was

641
00:23:31,290 --> 00:23:29,020
coming into this and just throwing out

642
00:23:33,770 --> 00:23:31,300
possible ideas and it I used to drive I

643
00:23:37,530 --> 00:23:33,780
think's fair to say Leslie a little bit

644
00:23:38,640 --> 00:23:37,540
crazy and so Harold came to me one time

645
00:23:41,040 --> 00:23:38,650
he said you know I just was reading

646
00:23:43,230 --> 00:23:41,050
Leslie's book on on ligand theory he

647
00:23:44,370 --> 00:23:43,240
says it's really very very good we

648
00:23:46,140 --> 00:23:44,380
should just start working with

649
00:23:47,430 --> 00:23:46,150
transition metal cations search as

650
00:23:50,420 --> 00:23:47,440
you've seen the previous talk turned out

651
00:23:53,220 --> 00:23:50,430
to be very fortuitous and so fine so

652
00:23:55,860 --> 00:23:53,230
showy O Hara and VJ who was a postdoc

653
00:23:57,870 --> 00:23:55,870
with Harold at the time we're in my lab

654
00:24:00,840 --> 00:23:57,880
and they just had a bunch of different

655
00:24:02,700 --> 00:24:00,850
transition metal chlorides and decided

656
00:24:04,140 --> 00:24:02,710
they'd start with they said well we've

657
00:24:05,220 --> 00:24:04,150
got to build something from something so

658
00:24:07,020 --> 00:24:05,230
it's gonna have to be the alwah

659
00:24:09,120 --> 00:24:07,030
condensation so they started with

660
00:24:11,160 --> 00:24:09,130
glyoxylate and pyruvate moderate

661
00:24:13,290 --> 00:24:11,170
conditions so on and so forth and some

662
00:24:15,540 --> 00:24:13,300
really really cool pathways emerged so

663
00:24:17,460 --> 00:24:15,550
they found a not particularly high yield

664
00:24:21,150 --> 00:24:17,470
but a very elegant pathway to alpha key

665
00:24:23,010 --> 00:24:21,160
to glue to rate unambiguously and due to

666
00:24:25,170 --> 00:24:23,020
some other issues we reran all these

667
00:24:27,770 --> 00:24:25,180
experiments Irena reran all of them to

668
00:24:30,450 --> 00:24:27,780
verify that you know it wasn't just

669
00:24:32,250 --> 00:24:30,460
magic that show hey Vijay could do that

670
00:24:34,050 --> 00:24:32,260
it's magic that anybody can do well not

671
00:24:36,780 --> 00:24:34,060
anybody but Irene Irene

672
00:24:38,640 --> 00:24:36,790
I had no problem doing this they also

673
00:24:40,350 --> 00:24:38,650
found a really novel pathway to

674
00:24:42,690 --> 00:24:40,360
isocitrate I was intrigued by the

675
00:24:44,520 --> 00:24:42,700
previous talk because we had tried to

676
00:24:47,520 --> 00:24:44,530
look at the conversion of citrate to

677
00:24:49,380 --> 00:24:47,530
isocitrate and we could easily get the

678
00:24:50,760 --> 00:24:49,390
conversion from isocitrate to citrate

679
00:24:53,460 --> 00:24:50,770
but we could never get around the

680
00:24:55,110 --> 00:24:53,470
Markoff knockoffs or propensity to put

681
00:24:57,990 --> 00:24:55,120
the hydroxyl on that particular carbon

682
00:25:00,090 --> 00:24:58,000
so it's isocitrate instantaneously goes

683
00:25:02,400 --> 00:25:00,100
to citrate but we couldn't get the

684
00:25:06,210 --> 00:25:02,410
slightest amount of isocitrate to form

685
00:25:08,190 --> 00:25:06,220
in the opposite direction but here you

686
00:25:10,170 --> 00:25:08,200
can form isocitrate in a very novel way

687
00:25:11,550 --> 00:25:10,180
so if you take glass light and succinate

688
00:25:13,650 --> 00:25:11,560
the way you think it might work nothing

689
00:25:15,390 --> 00:25:13,660
happens but if you take black slate now

690
00:25:17,420 --> 00:25:15,400
if a key to glitter 8 you go through

691
00:25:19,860 --> 00:25:17,430
this pathway generate co2 and hydrogen

692
00:25:22,620 --> 00:25:19,870
it's really slick Toledo's yields are

693
00:25:24,060 --> 00:25:22,630
not particularly low now if you just

694
00:25:26,370 --> 00:25:24,070
start with your product alpha-keto

695
00:25:29,460 --> 00:25:26,380
glitter 8 and in the presence of cobalt

696
00:25:32,520 --> 00:25:29,470
nickel or st. cation you form

697
00:25:34,410 --> 00:25:32,530
Arisa some succinate through the metal

698
00:25:37,190 --> 00:25:34,420
producted you know and control the cells

699
00:25:41,670 --> 00:25:37,200
to produced oxidative decarboxylation

700
00:25:44,250 --> 00:25:41,680
glittery but if you put iron and copper

701
00:25:46,710 --> 00:25:44,260
in the system you get considerable loss

702
00:25:49,350 --> 00:25:46,720
at off key to glue rate any form malate

703
00:25:51,930 --> 00:25:49,360
and oxalate and fumarate and ultimately

704
00:25:55,350 --> 00:25:51,940
pyruvate and then a lot of acetate is a

705
00:25:57,150 --> 00:25:55,360
product so so some interesting things

706
00:25:59,730 --> 00:25:57,160
are going on in the system as a previous

707
00:26:03,840 --> 00:25:59,740
speaker talked it's it's almost like a

708
00:26:05,310 --> 00:26:03,850
classic Maxwell demon you you the

709
00:26:07,800 --> 00:26:05,320
frustrating thing about this chemistry

710
00:26:09,390 --> 00:26:07,810
is you you really I can't convey man

711
00:26:11,520 --> 00:26:09,400
Eric Smith used to sit we would sit

712
00:26:13,170 --> 00:26:11,530
there in discuss what might become

713
00:26:16,400 --> 00:26:13,180
possible going on at the molecular level

714
00:26:20,160 --> 00:26:16,410
and it it's it's really tricky business

715
00:26:22,140 --> 00:26:20,170
but what it is tricky or not is it turns

716
00:26:23,700 --> 00:26:22,150
out that these different metals are do a

717
00:26:25,560 --> 00:26:23,710
lot of interesting different things I

718
00:26:27,450 --> 00:26:25,570
think at the molecular level what's

719
00:26:30,180 --> 00:26:27,460
actually going on is hyper complex and

720
00:26:32,400 --> 00:26:30,190
perhaps unknowable at the core level but

721
00:26:35,840 --> 00:26:32,410
clearly these metal cations are doing

722
00:26:38,010 --> 00:26:35,850
some very interesting molecular

723
00:26:39,930 --> 00:26:38,020
coordination based chemistry that

724
00:26:43,230 --> 00:26:39,940
enhances certain aldol polymerization

725
00:26:46,080 --> 00:26:43,240
suppresses other net reactions minimizes

726
00:26:47,799 --> 00:26:46,090
almost no polymerization and as clearly

727
00:26:50,200 --> 00:26:47,809
as I would say physical chemical

728
00:26:53,349 --> 00:26:50,210
it's a very high loss system but it's a

729
00:26:55,659 --> 00:26:53,359
very dynamic system and so for example

730
00:26:58,299 --> 00:26:55,669
you can start with glyoxylate pyruvate

731
00:27:00,339 --> 00:26:58,309
up here you can wander along you can get

732
00:27:01,359 --> 00:27:00,349
as far as Auto key of glue to rate you

733
00:27:04,180 --> 00:27:01,369
can go from alpha ketoglutarate

734
00:27:06,459 --> 00:27:04,190
isocitrate and so on and so forth but

735
00:27:08,589 --> 00:27:06,469
you can also start to fall backwards

736
00:27:11,379 --> 00:27:08,599
through oxidation reactions to Foom rate

737
00:27:13,149 --> 00:27:11,389
back to malate hydration Mount alight

738
00:27:14,649 --> 00:27:13,159
over Docs I'll acetates and ultimately

739
00:27:16,659 --> 00:27:14,659
decomposition very rapid decomposition

740
00:27:18,909 --> 00:27:16,669
regenerating pyruvate here and

741
00:27:21,789 --> 00:27:18,919
generating or regenerating glyoxylate

742
00:27:28,119 --> 00:27:21,799
there in all cases acetate becomes your

743
00:27:30,009 --> 00:27:28,129
predominant product so where I'm getting

744
00:27:31,989 --> 00:27:30,019
with this is that as I said in the

745
00:27:33,430 --> 00:27:31,999
beginning it seems like all life

746
00:27:35,829 --> 00:27:33,440
chemistry and the interesting chemistry

747
00:27:38,469 --> 00:27:35,839
where you want to go with this sits at

748
00:27:42,009 --> 00:27:38,479
around sort of the zero valence carbon

749
00:27:44,379 --> 00:27:42,019
level equivalent yet you're started you

750
00:27:46,419 --> 00:27:44,389
start out with a system that tends to

751
00:27:48,940 --> 00:27:46,429
give you a predominance of methane

752
00:27:51,310 --> 00:27:48,950
followed by propane than ethane and then

753
00:27:54,849 --> 00:27:51,320
so on and so forth really far away from

754
00:27:55,599 --> 00:27:54,859
that and if everything this previous

755
00:27:57,249 --> 00:27:55,609
talk

756
00:28:00,159 --> 00:27:57,259
presents brilliantly and then it gets

757
00:28:01,629 --> 00:28:00,169
factors into what also Leslie Orgel and

758
00:28:03,729 --> 00:28:01,639
Dave Ross were talking about right that

759
00:28:05,289 --> 00:28:03,739
the idea of if you got a system that's

760
00:28:07,029 --> 00:28:05,299
really great for reductive chemistry

761
00:28:09,519 --> 00:28:07,039
you're gonna get stuck this has always

762
00:28:11,619 --> 00:28:09,529
been our concern and so it cruelly came

763
00:28:13,869 --> 00:28:11,629
clear to us and actually in that 2001

764
00:28:15,609 --> 00:28:13,879
paper we had identified an area where

765
00:28:17,829 --> 00:28:15,619
you had a couple reduction and then

766
00:28:19,839 --> 00:28:17,839
partial oxidation that you have to have

767
00:28:21,779 --> 00:28:19,849
both going on and and the question for

768
00:28:23,709 --> 00:28:21,789
us became and how how could that be

769
00:28:25,089 --> 00:28:23,719
particularly in the early Earth where

770
00:28:29,109 --> 00:28:25,099
everybody would presume that things were

771
00:28:32,079 --> 00:28:29,119
so reducing how am i doing time was you

772
00:28:34,839 --> 00:28:32,089
just I'm almost done okay I'm rocketing

773
00:28:36,759 --> 00:28:34,849
along with Hostin the simple fact that

774
00:28:37,810 --> 00:28:36,769
is DNA source was two scoops again in

775
00:28:40,060 --> 00:28:37,820
our lab was doing an interesting

776
00:28:41,289 --> 00:28:40,070
experiment and this is a complicated

777
00:28:43,509 --> 00:28:41,299
diagram so I won't waste time with it

778
00:28:45,219 --> 00:28:43,519
but the point is if you think in

779
00:28:49,349 --> 00:28:45,229
equilibrium considerations and

780
00:28:52,180 --> 00:28:49,359
particularly in hydrogen oxidation then

781
00:28:54,549 --> 00:28:52,190
you don't worry things too much but but

782
00:28:56,979 --> 00:28:54,559
it turns out hot water you see the

783
00:28:58,239 --> 00:28:56,989
equilibrium from h2o goes to H 2 plus O

784
00:29:00,669 --> 00:28:58,249
2 is favored at higher and higher

785
00:29:01,210 --> 00:29:00,679
temperatures and when you start to

786
00:29:02,770 --> 00:29:01,220
quench that

787
00:29:04,000 --> 00:29:02,780
hot water down the actually the

788
00:29:06,190 --> 00:29:04,010
oxidation kinetics could be pretty

789
00:29:08,500 --> 00:29:06,200
sluggish and so you can have situations

790
00:29:11,919 --> 00:29:08,510
where in fact hydrogen and oxygen will

791
00:29:14,830 --> 00:29:11,929
persist even an in height in a you know

792
00:29:18,490 --> 00:29:14,840
a net redox neutral systems where I'm

793
00:29:21,549 --> 00:29:18,500
getting at so ultimately what we're

794
00:29:23,919 --> 00:29:21,559
doing is saying if you can get a dynamic

795
00:29:25,720 --> 00:29:23,929
or functional dynamic organic reaction

796
00:29:27,909 --> 00:29:25,730
network to occur you can get an awful

797
00:29:29,799 --> 00:29:27,919
lot from a little so this is an example

798
00:29:31,090 --> 00:29:29,809
is just playing around on paper but if

799
00:29:33,909 --> 00:29:31,100
you start with something like butanoic

800
00:29:35,380 --> 00:29:33,919
acid and IC butanoic acid and you allow

801
00:29:37,330 --> 00:29:35,390
for these following reactions to occur

802
00:29:39,580 --> 00:29:37,340
and every one of these has been verified

803
00:29:42,310 --> 00:29:39,590
right so carbonyl certain partial

804
00:29:44,230 --> 00:29:42,320
oxidation Retro aldol aldol lamination

805
00:29:46,980 --> 00:29:44,240
and reductive amination you can easily

806
00:29:49,620 --> 00:29:46,990
generate over 350 different molecules

807
00:29:51,970 --> 00:29:49,630
starting with saturated and olefinic

808
00:29:53,890 --> 00:29:51,980
including a broad range of things so the

809
00:29:57,220 --> 00:29:53,900
question is but to get to that you'd

810
00:29:58,510 --> 00:29:57,230
have to have unusual controls but the

811
00:30:00,250 --> 00:29:58,520
bigger problem and this is the very end

812
00:30:02,140 --> 00:30:00,260
of the talk is the following said if you

813
00:30:04,000 --> 00:30:02,150
start out with a system and catalysts

814
00:30:07,149 --> 00:30:04,010
where you can go from carbon dioxide

815
00:30:08,740 --> 00:30:07,159
hydrogen most your products are going to

816
00:30:10,360 --> 00:30:08,750
be very reduced methane and alkanes

817
00:30:12,310 --> 00:30:10,370
you're going to produce a small amount

818
00:30:13,630 --> 00:30:12,320
of these potentially reactive molecules

819
00:30:16,390 --> 00:30:13,640
that are going to be your dynamic

820
00:30:18,789 --> 00:30:16,400
organic rational network that system is

821
00:30:20,289 --> 00:30:18,799
a very efficient acetate generator so

822
00:30:22,600 --> 00:30:20,299
carbon is just going to flux through

823
00:30:24,880 --> 00:30:22,610
there into an acetate and some of it is

824
00:30:28,149 --> 00:30:24,890
going to polymerize and the bottom line

825
00:30:29,409 --> 00:30:28,159
is that's going to grow and that's going

826
00:30:30,760 --> 00:30:29,419
to grow and this is going to say the

827
00:30:32,440 --> 00:30:30,770
same so everything that you don't want

828
00:30:35,320 --> 00:30:32,450
is going to grow but the dynamic or get

829
00:30:37,990 --> 00:30:35,330
organic reaction network does not now

830
00:30:40,750 --> 00:30:38,000
this is just a picture of the polymer

831
00:30:42,610 --> 00:30:40,760
that you can make very easily so what

832
00:30:44,799 --> 00:30:42,620
you want to do is you want to find a way

833
00:30:46,060 --> 00:30:44,809
of doing this so one of these you want

834
00:30:48,669 --> 00:30:46,070
to see a system that can direct

835
00:30:49,960 --> 00:30:48,679
catalytically co2 directly into the into

836
00:30:52,600 --> 00:30:49,970
the dynamic organic reaction that we're

837
00:30:54,909 --> 00:30:52,610
suppressing methane and alkanes you'd

838
00:30:56,529 --> 00:30:54,919
like to find a way of using your acetate

839
00:30:59,110 --> 00:30:56,539
so it isn't constantly being rejected

840
00:31:00,669 --> 00:30:59,120
from the system and you don't mind the

841
00:31:02,110 --> 00:31:00,679
organic polymer growing because I might

842
00:31:03,430 --> 00:31:02,120
be useful you don't mind the dynamic

843
00:31:05,230 --> 00:31:03,440
organic reaction that we're growing

844
00:31:06,899 --> 00:31:05,240
because that's what you want so the

845
00:31:09,070 --> 00:31:06,909
question is how in the world to do that

846
00:31:09,639 --> 00:31:09,080
this is where we get into a complete

847
00:31:12,580 --> 00:31:09,649
fantasy

848
00:31:14,169 --> 00:31:12,590
but perhaps the cord all of this is the

849
00:31:14,740 --> 00:31:14,179
idea of start thinking about reactive

850
00:31:16,810 --> 00:31:14,750
Nano and

851
00:31:18,580 --> 00:31:16,820
and one of the areas is to actually move

852
00:31:21,909 --> 00:31:18,590
your dynamic organic reaction Network

853
00:31:25,270 --> 00:31:21,919
and your entire system into the organic

854
00:31:27,070 --> 00:31:25,280
polymer system so now you have a system

855
00:31:29,529 --> 00:31:27,080
that's generating all of this and

856
00:31:31,120 --> 00:31:29,539
everything is growing the acetate is

857
00:31:34,960 --> 00:31:31,130
following the dynamic organic reaction

858
00:31:36,820 --> 00:31:34,970
Network and so the problem is is solved

859
00:31:38,350 --> 00:31:36,830
if you could do it so what I'm getting

860
00:31:40,120 --> 00:31:38,360
at is that the problem of life's origins

861
00:31:41,830 --> 00:31:40,130
is not in my mind a chemistry problem

862
00:31:42,970 --> 00:31:41,840
the chemistry is not the problem we know

863
00:31:44,440 --> 00:31:42,980
how to do that kind of see the question

864
00:31:46,570 --> 00:31:44,450
is how to harness that chemistry were to

865
00:31:48,430 --> 00:31:46,580
direct that chemistry through some sort

866
00:31:50,799 --> 00:31:48,440
of control function and we'll hear more

867
00:31:53,260 --> 00:31:50,809
about that in Christophe lambs talk and

868
00:31:56,529 --> 00:31:53,270
and this is where I think theory really

869
00:31:58,120 --> 00:31:56,539
has to jump into this so the question is

870
00:32:00,250 --> 00:31:58,130
what a special environment so so key

871
00:32:01,450 --> 00:32:00,260
here is we need an environment the only

872
00:32:02,919 --> 00:32:01,460
way you're gonna get acetate back in the

873
00:32:04,899 --> 00:32:02,929
systems you have to activate it the

874
00:32:07,480 --> 00:32:04,909
simplest way of activating it is through

875
00:32:08,799 --> 00:32:07,490
phosphorylation there's nothing

876
00:32:10,390 --> 00:32:08,809
difficult about doing it if you can get

877
00:32:11,740 --> 00:32:10,400
the activity in pyrophosphate high

878
00:32:13,210 --> 00:32:11,750
enough how do you do that you can do

879
00:32:14,289 --> 00:32:13,220
that in a nano environment you can't do

880
00:32:15,820 --> 00:32:14,299
that in open water

881
00:32:18,010 --> 00:32:15,830
the same is true we have to affect

882
00:32:19,299 --> 00:32:18,020
enhance the control of ammonia activity

883
00:32:21,430 --> 00:32:19,309
and this is again if you dilute

884
00:32:23,860 --> 00:32:21,440
everything and George Whitesides to do

885
00:32:26,770 --> 00:32:23,870
critically nothing's going to happen so

886
00:32:28,240 --> 00:32:26,780
so at some level environments have to

887
00:32:29,919 --> 00:32:28,250
develop and these environments are not

888
00:32:31,149 --> 00:32:29,929
living systems but in my view our

889
00:32:33,610 --> 00:32:31,159
systems where you can start to control

890
00:32:35,380 --> 00:32:33,620
the activities of things you have to

891
00:32:36,760 --> 00:32:35,390
control oxidative decarboxylation you

892
00:32:38,740 --> 00:32:36,770
don't if you keep throwing away your

893
00:32:40,539 --> 00:32:38,750
Redoute potential and you have to

894
00:32:44,230 --> 00:32:40,549
control partial oxidation if you don't

895
00:32:46,180 --> 00:32:44,240
have some oxidation nothing interesting

896
00:32:48,220 --> 00:32:46,190
is going to occur but it has to be

897
00:32:51,010 --> 00:32:48,230
balanced with the idea of high loss to

898
00:32:52,690 --> 00:32:51,020
the system so the requirement of a

899
00:32:54,909 --> 00:32:52,700
dynamic organic reaction I think remains

900
00:32:57,610 --> 00:32:54,919
obvious precisely where and how it

901
00:32:59,620 --> 00:32:57,620
occurs I don't know potential for at

902
00:33:01,450 --> 00:32:59,630
least a stable dynamic organic reaction

903
00:33:03,310 --> 00:33:01,460
network is I would argue probably proven

904
00:33:06,070 --> 00:33:03,320
for chondritic environments so it works

905
00:33:09,220 --> 00:33:06,080
I think that's a remarkable result and I

906
00:33:10,690 --> 00:33:09,230
and I just got me really excited re

907
00:33:13,120 --> 00:33:10,700
excited if you will about this entire

908
00:33:14,799 --> 00:33:13,130
field so experimental evidence supports

909
00:33:16,750 --> 00:33:14,809
the potential chemical topology that

910
00:33:18,130 --> 00:33:16,760
would do this but both redox and

911
00:33:20,350 --> 00:33:18,140
oxidative chemistry have to operate

912
00:33:21,700 --> 00:33:20,360
simultaneously this is not classically

913
00:33:23,440 --> 00:33:21,710
the kind of chemistry that you might

914
00:33:24,789 --> 00:33:23,450
think about doing in the laboratory but

915
00:33:26,710 --> 00:33:24,799
it may be that we have to start thinking

916
00:33:28,420 --> 00:33:26,720
about that perhaps chemistry along

917
00:33:30,430 --> 00:33:28,430
gradients and so on and so forth

918
00:33:32,110 --> 00:33:30,440
and a true lab demonstration of a

919
00:33:33,550 --> 00:33:32,120
dynamic organic reaction network I would

920
00:33:35,530 --> 00:33:33,560
say remains elusive

921
00:33:37,600 --> 00:33:35,540
but we saw snapshots of pictures and

922
00:33:39,130 --> 00:33:37,610
pieces of what you can be done by

923
00:33:42,400 --> 00:33:39,140
setting up a system that actually would

924
00:33:44,800 --> 00:33:42,410
grow would be the de facto it's not a

925
00:33:46,600 --> 00:33:44,810
criteria for life but it is a criteria

926
00:33:49,270 --> 00:33:46,610
that I would say would be very very

927
00:33:57,490 --> 00:33:49,280
interesting to see and that's all I have

928
00:34:04,720 --> 00:33:57,500
to say on that topic got a little jet

929
00:34:06,790 --> 00:34:04,730
lag either you with the blue box already

930
00:34:08,740 --> 00:34:06,800
to do this twice but I want to ask about

931
00:34:10,300 --> 00:34:08,750
a general theme because this morning in

932
00:34:12,399 --> 00:34:10,310
George Whitesides is talk one of the

933
00:34:15,100 --> 00:34:12,409
conceptual pillars he brought up was the

934
00:34:16,570 --> 00:34:15,110
essential role of kinetic traps and in

935
00:34:18,460 --> 00:34:16,580
biochemistry that's clear this is the

936
00:34:21,399 --> 00:34:18,470
thing ever it has emphasized in

937
00:34:22,330 --> 00:34:21,409
geochemical contexts for ever you know

938
00:34:26,860 --> 00:34:22,340
forever

939
00:34:27,760 --> 00:34:26,870
yeah apologies but it's been hard to get

940
00:34:31,600 --> 00:34:27,770
out systematically

941
00:34:33,190 --> 00:34:31,610
so if I look at what Joseph showed by

942
00:34:35,680 --> 00:34:33,200
controlling for the fact that when you

943
00:34:37,149 --> 00:34:35,690
scrub you can find these complexity

944
00:34:38,530 --> 00:34:37,159
generating intermediates but if you put

945
00:34:42,430 --> 00:34:38,540
them into the solution you get nothing

946
00:34:45,060 --> 00:34:42,440
and then your black hole for carbon

947
00:34:48,159 --> 00:34:45,070
which then suddenly comes up right I

948
00:34:50,530 --> 00:34:48,169
think ok it looks like we have surface

949
00:34:53,350 --> 00:34:50,540
associated traps we have something that

950
00:34:55,780 --> 00:34:53,360
is has a time lag it's in a transition

951
00:34:58,390 --> 00:34:55,790
from being a metal to being an oxide and

952
00:35:00,280 --> 00:34:58,400
it's in that intermediate State it's

953
00:35:01,420 --> 00:35:00,290
band structure is changing its site

954
00:35:03,910 --> 00:35:01,430
density on the surface is changing

955
00:35:05,830 --> 00:35:03,920
possibly its morphology is changing and

956
00:35:07,930 --> 00:35:05,840
we have overwhelming evidence that it's

957
00:35:09,550 --> 00:35:07,940
a kinetic trap that's crucial to the

958
00:35:10,600 --> 00:35:09,560
distinction between going into one of

959
00:35:12,790 --> 00:35:10,610
these dead ends and going into

960
00:35:14,530 --> 00:35:12,800
complexity how do we study that

961
00:35:17,650 --> 00:35:14,540
systematically that is the grand

962
00:35:18,910 --> 00:35:17,660
challenge because what we want to see so

963
00:35:20,410 --> 00:35:18,920
getting back to the idea of this being a

964
00:35:21,700 --> 00:35:20,420
constraint at all and I think in some

965
00:35:23,170 --> 00:35:21,710
ways the best we could hope for right

966
00:35:25,270 --> 00:35:23,180
now I was talking to George this morning

967
00:35:27,400 --> 00:35:25,280
you know in the nice thing about this

968
00:35:28,720 --> 00:35:27,410
field this is so wide open and it's so

969
00:35:31,210 --> 00:35:28,730
wide open because we're so close all

970
00:35:32,200 --> 00:35:31,220
ignorant we can't we have difficulties I

971
00:35:33,940 --> 00:35:32,210
think George's talked this morning

972
00:35:36,700 --> 00:35:33,950
perfect week we can't even really

973
00:35:38,470 --> 00:35:36,710
clarify what we think is life what is

974
00:35:39,470 --> 00:35:38,480
semi life of what is dead and was semi

975
00:35:42,500 --> 00:35:39,480
dead

976
00:35:44,570 --> 00:35:42,510
so so we at least I feel that we can try

977
00:35:46,100 --> 00:35:44,580
to play some emphasis on constraints and

978
00:35:48,830 --> 00:35:46,110
that's where the geochemistry becomes so

979
00:35:52,250 --> 00:35:48,840
critical because it evidently occurred

980
00:35:54,410 --> 00:35:52,260
on this planet subject to the laws of

981
00:35:57,380 --> 00:35:54,420
chemistry has defined by this planet at

982
00:36:01,160 --> 00:35:57,390
the same token there's a lot that has to

983
00:36:02,420 --> 00:36:01,170
happen so for example this explosive

984
00:36:04,040 --> 00:36:02,430
effect that you saw in this one

985
00:36:06,140 --> 00:36:04,050
so-called simple experiment I showed

986
00:36:08,090 --> 00:36:06,150
that as a demonstration of that that

987
00:36:09,920 --> 00:36:08,100
simple experiments aren't simple but I

988
00:36:12,860 --> 00:36:09,930
also had to say that if that was a

989
00:36:14,240 --> 00:36:12,870
useful state then you'd have to say on

990
00:36:17,510 --> 00:36:14,250
this planet would have to be a

991
00:36:18,950 --> 00:36:17,520
continuously regenerating state so so

992
00:36:20,630 --> 00:36:18,960
what one this is two always been the

993
00:36:22,550 --> 00:36:20,640
problem whatever one experiment we set

994
00:36:23,960 --> 00:36:22,560
up is set up in a sense intrinsically

995
00:36:25,910 --> 00:36:23,970
thermodynamically to move in the

996
00:36:27,650 --> 00:36:25,920
direction thermodynamics required to go

997
00:36:29,590 --> 00:36:27,660
and it goes as far as the energy

998
00:36:31,730 --> 00:36:29,600
available to it does and then it stops

999
00:36:34,180 --> 00:36:31,740
but we know that that's not sufficient

1000
00:36:36,230 --> 00:36:34,190
to get us for where we need to go I

1001
00:36:37,280 --> 00:36:36,240
don't know if I'm articulated as well so

1002
00:36:39,650 --> 00:36:37,290
that's why I got so interested about

1003
00:36:41,420 --> 00:36:39,660
George Cooper's results because clearly

1004
00:36:44,000 --> 00:36:41,430
in this planetesimals

1005
00:36:46,310 --> 00:36:44,010
somehow this system was able to make

1006
00:36:48,890 --> 00:36:46,320
pyruvate it went away makes it again it

1007
00:36:50,720 --> 00:36:48,900
goes away make aconite and you know and

1008
00:36:52,700 --> 00:36:50,730
it makes it enough so finally when the

1009
00:36:54,470 --> 00:36:52,710
system freezes out it's able to freeze

1010
00:36:56,120 --> 00:36:54,480
out at least some signature that those

1011
00:36:59,360 --> 00:36:56,130
molecules were being regenerated from

1012
00:37:01,220 --> 00:36:59,370
millions of years so constantly I'm

1013
00:37:02,390 --> 00:37:01,230
trying to think about what's experiment

1014
00:37:05,330 --> 00:37:02,400
and getting back to what George was

1015
00:37:07,370 --> 00:37:05,340
asking if you could do the experiment

1016
00:37:10,370 --> 00:37:07,380
you could start to show the components

1017
00:37:12,830 --> 00:37:10,380
of the network growing in perhaps

1018
00:37:14,660 --> 00:37:12,840
through cycles that you could develop

1019
00:37:17,150 --> 00:37:14,670
and this is where Christophe lambs

1020
00:37:21,350 --> 00:37:17,160
approach is critical here I don't know

1021
00:37:23,300 --> 00:37:21,360
yet how I want to control the system and

1022
00:37:26,480 --> 00:37:23,310
whether so he might look at this network

1023
00:37:27,830 --> 00:37:26,490
idea answer to say as you said knobs and

1024
00:37:29,540 --> 00:37:27,840
buttons and things like this that's K

1025
00:37:31,580 --> 00:37:29,550
and start playing around with them and

1026
00:37:34,280 --> 00:37:31,590
then can you find that geochemical set

1027
00:37:36,380 --> 00:37:34,290
of conditions that allow you to tweak

1028
00:37:37,610 --> 00:37:36,390
the knobs in a way that makes sense such

1029
00:37:39,620 --> 00:37:37,620
that the chemical system you're

1030
00:37:42,650 --> 00:37:39,630
interested in grows as opposed to decays

1031
00:37:44,960 --> 00:37:42,660
and what I tried to show you was I why

1032
00:37:48,080 --> 00:37:44,970
we see the topology this network growing

1033
00:37:49,700 --> 00:37:48,090
it's it's a lossy system right most of

1034
00:37:50,450 --> 00:37:49,710
the stuff is going to acetate so fast

1035
00:37:50,950 --> 00:37:50,460
make your head spin

1036
00:37:51,940 --> 00:37:50,960
so

1037
00:37:54,310 --> 00:37:51,950
nothing that we've done in the

1038
00:37:56,920 --> 00:37:54,320
laboratory shows us anything other than

1039
00:37:59,260 --> 00:37:56,930
the connectivity of molecular states and

1040
00:38:01,450 --> 00:37:59,270
we have to go that next level of playing

1041
00:38:03,760 --> 00:38:01,460
around with the knobs in a dynamical

1042
00:38:08,460 --> 00:38:03,770
system and then seeing does that take us

1043
00:38:17,010 --> 00:38:12,730
you mentioned dhunda has been proven for

1044
00:38:20,860 --> 00:38:17,020
kinetic planetesimals to me yes yeah

1045
00:38:25,450 --> 00:38:20,870
yeah I'd believe that but I also want to

1046
00:38:29,110 --> 00:38:25,460
point out Don may also be a proven for

1047
00:38:32,140 --> 00:38:29,120
this small moon of Saturn this Enceladus

1048
00:38:35,980 --> 00:38:32,150
because from the prune we can measure

1049
00:38:39,520 --> 00:38:35,990
this array of organics which are

1050
00:38:43,180 --> 00:38:39,530
obviously be manufactured and inside and

1051
00:38:45,070 --> 00:38:43,190
they have been preserved over certainly

1052
00:38:49,330 --> 00:38:45,080
the over long period of times like

1053
00:38:51,220 --> 00:38:49,340
millions of years yes I agree with you

1054
00:38:52,570 --> 00:38:51,230
actually in solid solidus is becoming

1055
00:38:54,820 --> 00:38:52,580
one of the more interesting objects in

1056
00:38:59,350 --> 00:38:54,830
our solar system and I hope we study it

1057
00:39:00,940 --> 00:38:59,360
much more closely yes a question that

1058
00:39:03,670 --> 00:39:00,950
comes up listening to the several

1059
00:39:07,360 --> 00:39:03,680
fascinating last talks and listening to

1060
00:39:10,240 --> 00:39:07,370
my colleagues I formed no judgments

1061
00:39:13,570 --> 00:39:10,250
publicly at least is that the kind of

1062
00:39:15,540 --> 00:39:13,580
chemistry that you do is you know Co

1063
00:39:18,460 --> 00:39:15,550
hydrogen high temperature

1064
00:39:21,190 --> 00:39:18,470
hydroformylation that kind of thing and

1065
00:39:24,310 --> 00:39:21,200
what many of my colleagues think is that

1066
00:39:26,050 --> 00:39:24,320
it's all done in space it's HCN and co

1067
00:39:28,420 --> 00:39:26,060
and stuff that forms there and

1068
00:39:30,550 --> 00:39:28,430
particularly HCN maybe acetylene and

1069
00:39:33,280 --> 00:39:30,560
sano acetylene so you've done all the

1070
00:39:34,900 --> 00:39:33,290
reactivation chemistry there right and

1071
00:39:36,880 --> 00:39:34,910
so there's that approach there's also

1072
00:39:38,800 --> 00:39:36,890
the approach that says why work with co2

1073
00:39:40,930 --> 00:39:38,810
which is a horrible reaction for

1074
00:39:42,760 --> 00:39:40,940
anything except nucleophiles work with

1075
00:39:45,580 --> 00:39:42,770
cs2 because there's an enormous amount

1076
00:39:47,260 --> 00:39:45,590
of cs2 around and there's h2s and

1077
00:39:50,110 --> 00:39:47,270
there's a lot of h2s and that's a great

1078
00:39:52,030 --> 00:39:50,120
nucleophile in an activating agent or do

1079
00:39:54,280 --> 00:39:52,040
you consider these as independent themes

1080
00:39:57,670 --> 00:39:54,290
or is one going to turn out to be better

1081
00:40:00,760 --> 00:39:57,680
than the others well that's that's an

1082
00:40:02,080 --> 00:40:00,770
excellent question so HCN is a fantastic

1083
00:40:04,150 --> 00:40:02,090
molecule in chemistry

1084
00:40:09,310 --> 00:40:04,160
and I don't have anything against it

1085
00:40:11,620 --> 00:40:09,320
personally but you're laughing but but

1086
00:40:13,600 --> 00:40:11,630
but it does have a problem which is it

1087
00:40:15,190 --> 00:40:13,610
hydrolyzes really quickly so I recall

1088
00:40:16,770 --> 00:40:15,200
when people were worried about terrorist

1089
00:40:19,120 --> 00:40:16,780
threats and things like this and I I

1090
00:40:20,560 --> 00:40:19,130
knew Quabbin Reservoir really well and

1091
00:40:21,970 --> 00:40:20,570
people say well oh my god what if

1092
00:40:24,520 --> 00:40:21,980
somebody sneaks up one night and they

1093
00:40:26,770 --> 00:40:24,530
dump you know tons of potassium cyanide

1094
00:40:28,720 --> 00:40:26,780
in Quabbin Reservoir and people like

1095
00:40:32,020 --> 00:40:28,730
well we'll have a lot of formate then

1096
00:40:35,800 --> 00:40:32,030
because it hydrolyzes so quickly so in

1097
00:40:37,480 --> 00:40:35,810
my view and this is partly my bias in

1098
00:40:42,040 --> 00:40:37,490
terms of trying to place constraints on

1099
00:40:42,910 --> 00:40:42,050
my own set of questions for you to get

1100
00:40:44,440 --> 00:40:42,920
to the point where you have a dynamic

1101
00:40:46,900 --> 00:40:44,450
organic reaction network you know

1102
00:40:48,070 --> 00:40:46,910
carbonaceous chondrite whatever hydrogen

1103
00:40:50,290 --> 00:40:48,080
cyanide might have done for you in the

1104
00:40:52,420 --> 00:40:50,300
very beginning has been over printed by

1105
00:40:54,820 --> 00:40:52,430
millions of years of hydrothermal

1106
00:40:56,680 --> 00:40:54,830
recurrence so unless you have a

1107
00:40:59,260 --> 00:40:56,690
mechanism in the interior of the planet

1108
00:41:01,600 --> 00:40:59,270
to regenerate some of these interstellar

1109
00:41:03,790 --> 00:41:01,610
molecules I would take a lot of them off

1110
00:41:05,890 --> 00:41:03,800
the table I love carbonyl carbon

1111
00:41:07,870 --> 00:41:05,900
disulphide but it also is it's very

1112
00:41:10,570 --> 00:41:07,880
strongly prone to hydrolysis to co2

1113
00:41:13,690 --> 00:41:10,580
ultimately it's a great molecule or

1114
00:41:15,010 --> 00:41:13,700
Leslie or gal I was sitting a meeting he

1115
00:41:16,690 --> 00:41:15,020
was getting really really excited and

1116
00:41:18,370 --> 00:41:16,700
kept asking me have you ever worked with

1117
00:41:20,080 --> 00:41:18,380
carbonyl sulfide carbon eel sulfide and

1118
00:41:22,300 --> 00:41:20,090
it turns out it became a wonderful

1119
00:41:23,440 --> 00:41:22,310
polymerization reagent for amino acids

1120
00:41:27,280 --> 00:41:23,450
for the work that he did with Reis

1121
00:41:31,780 --> 00:41:27,290
Agadir so these are great molecules but

1122
00:41:33,730 --> 00:41:31,790
I fear that so I looted to this so there

1123
00:41:36,670 --> 00:41:33,740
is a big problem with ammonia and the

1124
00:41:39,670 --> 00:41:36,680
problem is the following if you allow me

1125
00:41:42,790 --> 00:41:39,680
all the ammonia or equivalent ammonia

1126
00:41:44,830 --> 00:41:42,800
equivalent that I could have then making

1127
00:41:46,720 --> 00:41:44,840
things like nucleobases is very very

1128
00:41:49,300 --> 00:41:46,730
easy to do and I can do them in the

1129
00:41:55,090 --> 00:41:49,310
laboratory I like urea which is

1130
00:41:56,980 --> 00:41:55,100
equivalently ammonia plus co2 but the

1131
00:42:00,010 --> 00:41:56,990
biggest race I have when I do this for

1132
00:42:01,180 --> 00:42:00,020
example making uracil very easy to do

1133
00:42:02,320 --> 00:42:01,190
the yields are really low the only

1134
00:42:04,780 --> 00:42:02,330
reason the yields are low is because

1135
00:42:06,910 --> 00:42:04,790
it's I'm competing with hydrolysis urea

1136
00:42:09,880 --> 00:42:06,920
as fast as I'm making the uracil

1137
00:42:11,200 --> 00:42:09,890
it's just it hydrolyzes so quickly if I

1138
00:42:14,740 --> 00:42:11,210
could crank that so I don't know how to

1139
00:42:15,670 --> 00:42:14,750
deal with that that and there so it's a

1140
00:42:18,040 --> 00:42:15,680
really getting back

1141
00:42:19,510 --> 00:42:18,050
it's really interesting I think I don't

1142
00:42:20,950 --> 00:42:19,520
have to worry about HCN I think I don't

1143
00:42:22,630 --> 00:42:20,960
have to worry about carbonyl sulfide I

1144
00:42:25,059 --> 00:42:22,640
know I have to worry about ammonia it

1145
00:42:26,740 --> 00:42:25,069
just doesn't seem to be a easy way of

1146
00:42:29,020 --> 00:42:26,750
generating enough ammonia or keeping the

1147
00:42:30,880 --> 00:42:29,030
activity high enough and this again I

1148
00:42:34,809 --> 00:42:30,890
think factors into the idea that that

1149
00:42:37,599 --> 00:42:34,819
one has to have some sort of nano

1150
00:42:40,120 --> 00:42:37,609
environment where you can enhance the

1151
00:42:42,670 --> 00:42:40,130
effective molarity of ammonia way higher

1152
00:42:44,799 --> 00:42:42,680
than perhaps the ambient would be and I

1153
00:42:46,329 --> 00:42:44,809
like the idea Polly electrolyte gels or

1154
00:42:48,790 --> 00:42:46,339
probably electrolyte polymers that might

1155
00:42:51,069 --> 00:42:48,800
actually enhance the the molar

1156
00:42:52,599 --> 00:42:51,079
concentration of ammonia even if it's an

1157
00:42:54,400 --> 00:42:52,609
equilibrium with less concentration

1158
00:42:57,520 --> 00:42:54,410
ammonium in a solution it's an

1159
00:43:01,359 --> 00:42:57,530
equilibrium with it's like effective

1160
00:43:05,109 --> 00:43:01,369
molarity with proteins may be similar

1161
00:43:07,270 --> 00:43:05,119
questions so thank you for the very

1162
00:43:12,640 --> 00:43:07,280
interesting alpha ketoglutarate since

1163
00:43:15,250 --> 00:43:12,650
this reaction my question is that if the

1164
00:43:18,099 --> 00:43:15,260
green oxalate is replaced though is

1165
00:43:20,200 --> 00:43:18,109
hollom hardline so for my heart height

1166
00:43:23,349 --> 00:43:20,210
and pyruvate reaction what happens so

1167
00:43:26,680 --> 00:43:23,359
this is why probably so formal

1168
00:43:29,140 --> 00:43:26,690
aldehyde would be much more abundant in

1169
00:43:34,539 --> 00:43:29,150
solar system compared with gree oxide

1170
00:43:36,609 --> 00:43:34,549
right we mean my god so long for from

1171
00:43:39,400 --> 00:43:36,619
aldehyde it's very abundant molecules is

1172
00:43:42,430 --> 00:43:39,410
one from a library hundred waters it's

1173
00:43:45,880 --> 00:43:42,440
like what's the other calamari hide on

1174
00:43:48,400 --> 00:43:45,890
pyruvate oh oh yeah from a time far away

1175
00:43:50,650 --> 00:43:48,410
versus glyoxylate power of eight if

1176
00:43:54,760 --> 00:43:50,660
you're saying yes the problem is from

1177
00:43:56,710 --> 00:43:54,770
aldehyde is it's a great molecule to so

1178
00:43:59,410 --> 00:43:56,720
then that's we're getting back to

1179
00:44:02,799 --> 00:43:59,420
George's question formaldehyde is stable

1180
00:44:07,089 --> 00:44:02,809
enough that it can hang around and

1181
00:44:08,230 --> 00:44:07,099
polymerize now usually there are great

1182
00:44:09,099 --> 00:44:08,240
stories and all these things I remember

1183
00:44:10,539 --> 00:44:09,109
the first time I was trying to do

1184
00:44:12,819 --> 00:44:10,549
formaldehyde polymerization and it just

1185
00:44:15,039 --> 00:44:12,829
never worked and I was on a train with

1186
00:44:16,120 --> 00:44:15,049
Leslie Orgel and I asked him why you

1187
00:44:17,920 --> 00:44:16,130
know why doesn't this work and he said

1188
00:44:19,539 --> 00:44:17,930
it's because you're doing it right he

1189
00:44:20,920 --> 00:44:19,549
said if you do it right it doesn't work

1190
00:44:22,690 --> 00:44:20,930
they said the trick to making it

1191
00:44:24,069 --> 00:44:22,700
polymerizes you you give it some glycol

1192
00:44:27,069 --> 00:44:24,079
and hide and then the thing takes off

1193
00:44:28,510 --> 00:44:27,079
very Auto catalytically and so so the

1194
00:44:29,500 --> 00:44:28,520
trick is let's say fortunately we can

1195
00:44:31,810 --> 00:44:29,510
say there's glycol

1196
00:44:33,070 --> 00:44:31,820
in these interstellar ices as well it

1197
00:44:34,840 --> 00:44:33,080
turns out and this I'm not going to

1198
00:44:36,070 --> 00:44:34,850
divulge I'm very bad at showing data

1199
00:44:37,420 --> 00:44:36,080
before I publish it so I'm not gonna

1200
00:44:39,340 --> 00:44:37,430
mention what we have found a way of

1201
00:44:41,290 --> 00:44:39,350
making formaldehyde polymerize with

1202
00:44:43,120 --> 00:44:41,300
itself without giving a clack all died

1203
00:44:45,700 --> 00:44:43,130
this is really cool and I'm not gonna

1204
00:44:47,590 --> 00:44:45,710
say worried about it but but it's

1205
00:44:50,950 --> 00:44:47,600
interesting for but formaldehyde will

1206
00:44:53,080 --> 00:44:50,960
eventually through the countess our

1207
00:44:54,670 --> 00:44:53,090
reaction decomposed so what limits the

1208
00:44:56,590 --> 00:44:54,680
yield of polymer that you ultimately get

1209
00:44:59,380 --> 00:44:56,600
from from a light anyway is the fact

1210
00:45:02,200 --> 00:44:59,390
that it will decompose to form a gas and

1211
00:45:05,380 --> 00:45:02,210
methanol and that's an e recoverable

1212
00:45:07,210 --> 00:45:05,390
irreversible formaldehyde it's a great

1213
00:45:09,550 --> 00:45:07,220
molecule I like it because I don't think

1214
00:45:11,770 --> 00:45:09,560
that is no one has ever advocated that

1215
00:45:13,690 --> 00:45:11,780
you could make it hydrothermally it sits

1216
00:45:15,580 --> 00:45:13,700
on the very very top of an energetic

1217
00:45:17,440 --> 00:45:15,590
mountain so there's only two ways to

1218
00:45:19,210 --> 00:45:17,450
know that we make it either do it with

1219
00:45:22,240 --> 00:45:19,220
you know photochemistry

1220
00:45:24,340 --> 00:45:22,250
or you do it with interstellar ices and

1221
00:45:27,490 --> 00:45:24,350
again photochemistry or hi molecule

1222
00:45:33,700 --> 00:45:27,500
reactions so it is sort of the one thing

1223
00:45:35,680 --> 00:45:33,710
that's interstellar I believe thank you

1224
00:45:39,609 --> 00:45:35,690
i I want to go back to your comment

1225
00:45:42,430 --> 00:45:39,619
about ammonia so what how did we make

1226
00:45:44,290 --> 00:45:42,440
ammonium so we you you started off your

1227
00:45:46,000 --> 00:45:44,300
talk with a discussion of early Earth's

1228
00:45:48,640 --> 00:45:46,010
atmosphere and we haven't changed much

1229
00:45:51,609 --> 00:45:48,650
since Yuri but I think that's not true

1230
00:45:54,070 --> 00:45:51,619
yeah I agree me or Yuri advocated for a

1231
00:45:55,690 --> 00:45:54,080
reducing atmosphere that's right I think

1232
00:45:57,670 --> 00:45:55,700
now we think it's more oxidized more

1233
00:46:01,030 --> 00:45:57,680
oxidized so you had you had another

1234
00:46:03,040 --> 00:46:01,040
oxidant you had n2 gas that's right and

1235
00:46:05,800 --> 00:46:03,050
we don't treat it as an oxidant we

1236
00:46:09,960 --> 00:46:05,810
almost ignore it okay so right and so

1237
00:46:12,340 --> 00:46:09,970
why is it that we get ammonia at

1238
00:46:14,080 --> 00:46:12,350
standard pressure and in fact it was

1239
00:46:16,660 --> 00:46:14,090
point eight bar probably even lower

1240
00:46:18,280 --> 00:46:16,670
pressure and we don't get it from

1241
00:46:21,580 --> 00:46:18,290
hydrothermal vents nope

1242
00:46:25,780 --> 00:46:21,590
so how do we make ammonia on the planet

1243
00:46:27,820 --> 00:46:25,790
before life that is that is very much in

1244
00:46:29,470 --> 00:46:27,830
my view in elephant Mike Mike Mike this

1245
00:46:31,450 --> 00:46:29,480
so the simplest way to do it that I

1246
00:46:34,090 --> 00:46:31,460
could you know if he said George you

1247
00:46:36,160 --> 00:46:34,100
know I'm holding a gun to you what I

1248
00:46:38,200 --> 00:46:36,170
would say said well he wants nitrate so

1249
00:46:39,370 --> 00:46:38,210
so nitrate is the easiest way to do and

1250
00:46:41,500 --> 00:46:39,380
the easiest way to get nitrate is

1251
00:46:43,300 --> 00:46:41,510
through Auto chemistry with water and

1252
00:46:46,150 --> 00:46:43,310
die nitrogen in the upper atmosphere and

1253
00:46:49,870 --> 00:46:46,160
you rain it out then then hydrate then

1254
00:46:52,420 --> 00:46:49,880
you can make very high quantitative

1255
00:46:53,920 --> 00:46:52,430
yields if you take that off the table I

1256
00:46:55,930 --> 00:46:53,930
think you've got a real problem so I

1257
00:46:57,430 --> 00:46:55,940
don't want to strongly put myself into

1258
00:46:59,470 --> 00:46:57,440
what the source is

1259
00:47:02,380 --> 00:46:59,480
but I'm strongly advocating that we have

1260
00:47:04,480 --> 00:47:02,390
I believe in a nitrogen problem that has

1261
00:47:06,099 --> 00:47:04,490
to be solved and currently on earth we

1262
00:47:08,230 --> 00:47:06,109
have a nitrogen problem because we are

1263
00:47:10,240 --> 00:47:08,240
using right we're using more ammonia

1264
00:47:12,970 --> 00:47:10,250
than we can actually fix through

1265
00:47:15,700 --> 00:47:12,980
nitrogenase so it's it's a problem now

1266
00:47:17,500 --> 00:47:15,710
and it was a bigger problem then and so

1267
00:47:19,180 --> 00:47:17,510
I went through this calculation with

1268
00:47:22,060 --> 00:47:19,190
canfield a few years ago in a paper in

1269
00:47:24,880 --> 00:47:22,070
science and and if we appeal to nitrate

1270
00:47:26,740 --> 00:47:24,890
as a source without a molecular oxygen

1271
00:47:28,390 --> 00:47:26,750
in the planet so we're doing it with

1272
00:47:31,120 --> 00:47:28,400
lightning right right

1273
00:47:35,590 --> 00:47:31,130
you all get approximately 10 to the

1274
00:47:38,290 --> 00:47:35,600
minus tenth molar concentration 10 to

1275
00:47:40,300 --> 00:47:38,300
the minus 10 this is I mean your sub

1276
00:47:42,340 --> 00:47:40,310
nano molar oh yeah it's really really

1277
00:47:44,950 --> 00:47:42,350
really low it's it's a huge so that's

1278
00:47:47,470 --> 00:47:44,960
why I was saying that again I think we

1279
00:47:50,710 --> 00:47:47,480
all know this in too intellectually this

1280
00:47:52,630 --> 00:47:50,720
idea of I think John barrows pointed

1281
00:47:55,210 --> 00:47:52,640
initially that one kilometer cell the

1282
00:47:56,800 --> 00:47:55,220
idea that that that life as a system

1283
00:48:00,490 --> 00:47:56,810
could ever have been occurring in a

1284
00:48:02,500 --> 00:48:00,500
dilute ocean is impossible so one has to

1285
00:48:04,720 --> 00:48:02,510
say okay even that tiny amount of

1286
00:48:06,580 --> 00:48:04,730
ammonia if you could find a physical

1287
00:48:10,960 --> 00:48:06,590
chemical mechanism by which you could

1288
00:48:12,520 --> 00:48:10,970
concentrate it in a way that doesn't you

1289
00:48:14,950 --> 00:48:12,530
know violate the laws of physics and

1290
00:48:16,540 --> 00:48:14,960
particularly the loss of entropy the

1291
00:48:17,230 --> 00:48:16,550
best way I can think of doing that is

1292
00:48:22,200 --> 00:48:17,240
through

1293
00:48:25,990 --> 00:48:24,609
might about thesis and cult chemistry

1294
00:48:27,940 --> 00:48:26,000
strangely enough and one of the things I

1295
00:48:29,770 --> 00:48:27,950
do is I would automatically dilate calls

1296
00:48:32,560 --> 00:48:29,780
to measure viscoelastic properties and

1297
00:48:34,030 --> 00:48:32,570
what happens there is that you achieve a

1298
00:48:36,160 --> 00:48:34,040
thermodynamic equilibrium where the

1299
00:48:39,190 --> 00:48:36,170
molarity of your compounds can be very

1300
00:48:41,740 --> 00:48:39,200
high inside this gel relative to their

1301
00:48:44,890 --> 00:48:41,750
concentration in a medium stay outside

1302
00:48:46,630 --> 00:48:44,900
so it was kind of where I was leading

1303
00:48:48,250 --> 00:48:46,640
people I think that you have to be able

1304
00:48:50,530 --> 00:48:48,260
to create micro environments that at

1305
00:48:52,480 --> 00:48:50,540
least locally take a small amount of

1306
00:48:55,030 --> 00:48:52,490
ammonia and Hance that to the point

1307
00:48:56,230 --> 00:48:55,040
where you can start to because the way I

1308
00:48:58,690 --> 00:48:56,240
like you know the way I look at it

1309
00:49:01,690 --> 00:48:58,700
living system right so for example ATP

1310
00:49:03,250 --> 00:49:01,700
synthesis synthesis from a living system

1311
00:49:05,470 --> 00:49:03,260
point of view it's just a mechanical way

1312
00:49:07,030 --> 00:49:05,480
of locally getting the concentration of

1313
00:49:10,240 --> 00:49:07,040
phosphates so high that making the

1314
00:49:12,130 --> 00:49:10,250
phosphate diester banas is cost you

1315
00:49:13,300 --> 00:49:12,140
nothing right but then you then you send

1316
00:49:14,920 --> 00:49:13,310
it off to a system where else and that's

1317
00:49:24,820 --> 00:49:14,930
not the case and now you got a really

1318
00:49:27,940 --> 00:49:24,830
energetic molecule I agree I completely

1319
00:49:29,680 --> 00:49:27,950
agree it's a huge problem yeah I hate to

1320
00:49:32,050 --> 00:49:29,690
be the one to interrupt this all this

1321
00:49:32,920 --> 00:49:32,060
fascinating debate which we do need to

1322
00:49:36,410 --> 00:49:32,930
move on

1323
00:49:55,160 --> 00:49:36,420
[Applause]