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radley berker I'm a NASA post doctoral

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fellow at Georgia Tech I work at the

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Center for chemical evolution where our

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main focus is to look at basic prebiotic

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chemical systems and see how those can

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grow and evolve and develop complexity

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over time these view think about it if

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you look at biology and you really

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tunnel down to its basics it's all just

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chemistry at its heart so as a prebiotic

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chemist looking at the origins of life I

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back when you have a primordial soup

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perhaps maybe of hydrothermal vents

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maybe have these small little warm

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little ponds and lagoons on the surface

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the earth where all sorts of interesting

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and chemical complexity can happen so

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eventually the complexity grows you

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develop membranes RNA DNA proteins all

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of the fundamental parts of life

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eventually transition from this sort of

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system to a living system of modern

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earth full of life but you have to go

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back to the basic fundamentals and

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figure out how those systems came to be

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in the first place so my current project

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is focusing on trying to synthesize a

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very basic monomer so for this case you

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look at RNA or perhaps DNA and it's

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possible that this was not the very

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first informational carrying molecule

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but its components are quite informative

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of what the first informational very

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molecule could have been so we don't

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necessarily at the CC think that this is

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the first monomer but you can look at

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the bases and look at that as

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information carrying unit and you can

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replace with something else like Matt's

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talk earlier today with Barbra tarek

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acid or other sorts of derivatives but

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the main thing is something that does

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hydrogen bonding to carry information

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you also look at ribose which is

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just a component that can tie all of the

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different parts of the monomer together

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into one system it doesn't have to be

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ribose maybe it could be glycerol maybe

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it could be something more complex

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glucose who knows but as long as it can

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branch the different parts of the system

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together that's the important part as a

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trifunctional connector and my specific

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part I working on this project is

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looking at this ionized linker and a

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modern life uses a phosphate as its

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source it makes very energetically

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favorable bonds that can be formed and

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broken quite reasonably and it provides

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a basic amount of celula tea and water

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very valuable properties to have for

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life as we know it for polymers and

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monomers that have to exist in an

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aqueous environment so it's not

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essential that phosphate was the source

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and in my group we look at a lot of

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different possibilities for what it

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could be for phosphate but phosphate is

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so helpful is has such good properties

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that would be really great if it could

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be the source and so I'm specifically

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trying to find reactions that could help

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to incorporate phosphate into early

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organics but this has been a problem for

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a long time the prebiotic

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phosphorylation problem which is why

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people are even looking for other

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informational linkers as it is a hot did

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yep alright so the basic fundamental

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question is how phosphorylated nucleus

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sides or organic phosphates came to be

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in the first place there's two

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fundamental problems first of all if you

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have phosphate it reacts with divalent

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cations like magnesium or calcium in

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solution and it just precipitates out

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you can have a nice bed of appetite so

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this makes it largely inaccessible for

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prebiotic chemistry which is the main

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reason why a lot of prebiotic chemistry

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so long also if you're making organic

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phosphates it's a condensation reaction

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it gives off water it is incredibly

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thermodynamically unfavorable to try to

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give off water for a chemical reaction

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in a water-based environment so these

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are two big problems trying to make

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phosphate be incorporated into organics

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so a lot of research has been done

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starting in the late 60s to figure out

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what can work how can you incorporate

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how can you take a nucleobase or any

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organic incorporate phosphate and make

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organic phosphates so a lot of work has

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shown that urea is a very key component

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for this if you have urea and soluble

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phosphate like sodium phosphate in

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solution in a dry reaction it can add a

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phosphate as low 65 degrees or if you

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really ratchet up the temperatures to

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100 degrees you can take in soluble

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minerals like appetite and also

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phosphorylate also if you just remove

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water completely from the equation and

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use something like toluene or formamide

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you can do low temperature reactions

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also using soluble phosphate as low as

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70 degrees but it's kind of a cheat

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because you removed water from the

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equation and then you have all sorts of

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arguments to make about formamide on a

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prebiotic earth also they have

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pretreated some of the insoluble

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minerals and have used that as a

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phosphate source to phosphorylate so

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that's one way to deal with the

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insoluble mineral problem but these this

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pretreatment took place at 150 degrees

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Celsius which is very high temperature

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and recently

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they're novel solvent systems have been

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explored particularly this choline

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chloride urea eutectic solution so this

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is also a water free solution and

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eutectics are interesting

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multi-component systems in which you can

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mix them together and you have a lower

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melting point than either the components

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so in this case you take two solids at

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room temperature mix them together and

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you create a liquid this is actually

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quite abundant in plants and a lot of

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biological life so it has been

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investigated a lot in modern

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biochemistry and if you use one of these

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interesting novel solvent it's been

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shown that you can phosphate those those

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65 degrees it's problematic because it

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reacts with your solvent in this case

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which is not great but it works and i'll

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reiterate this part here because this is

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apparently a very important fundamental

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reaction in prebiotic chemistry so this

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is the urea catalyzed phosphorylation so

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you can take your phosphate group take a

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urea and create this high energy

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intermediate in a water free solution so

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in fact you're activating the phosphate

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if you can create this then you can

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bring in any alcohol that we've tested

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so far and create an organo phosphate so

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it's a great way in urea is a very

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powerful chemical for doing this and the

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biologists in the group might notice

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that this looks like a EDC activated

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intermediate which is used for a ton of

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modern biochemical reactions so we've

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been investigating a phosphorylation can

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take place in this in a eutectic made of

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urea ammonium wat ammonium formate and

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water well this last part is key because

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it allows this to be created on a

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prebiotic earth in a water-based soluble

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system so the great things about this

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eutectic all of these components are

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very abundant on a prebiotic earth we

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saw earlier the serpent in ization

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reactions can lead to a lot of ammonium

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formate for example and urea can be

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abundantly made from miller early type

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reactions in fact a lot of prebiotic

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scientists think that like the Salt

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Flats in Utah

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you would have had your reah flats on a

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pre-bout occurs so both of these would

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have been very available also after some

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slight heating driving off the excess

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volatile from the solution you have a

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fluidic environment that can promote

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chemical interactions so you don't have

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to have a completely dry system anymore

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and a lot of chemistry can take place a

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lot more readily in fluidic environments

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it's made from urea also upon heating

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these chemicals actually do form form ID

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which creates a four-part system and

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then we have this solvent which has been

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shown to do phosphorylation before and

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some other prebiotic reactions so it's a

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great easy pathway to developing for

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moment the high viscosity environment

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promotes chemical interactions and it's

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a low enough water environment that it

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can actually still do dehydration

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condensation reactions and one of the

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first things that we discovered through

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our work with them our collaborators at

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USF is just by taking different

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phosphate sources struvite which is a

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mildly soluble phosphate source

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hydroxyapatite which is calcium

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phosphate which is a very insoluble

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phosphate source in Vivian 8 which is an

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iron phosphate which is also Clinton

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soluble and mixing it in the eutectic

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comparing it at 70 degrees to water we

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could see that just initially in the

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eutectic there's a marked increase in

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solubility of these highly insoluble

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phosphate species so one good check for

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the eutectic to start with is great you

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can now sell you buy some phosphate also

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thermodynamically we ran some

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calculations and showed in a urea rich

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environment that's slightly acidic like

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the eutectic is if you have magnesium

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and sulfates in there with this in

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soluble phosphate source you can just

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generate struvite a much more soluble

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mineral at a very thermodynamically

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favorable rate so you can just mix it

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with eutectic and it just can

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the phosphate right into solution and

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this is shown we've ran some xrd and

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some Robin actually testing this

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experimentally on some hydroxyapatite

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and it's invisible but there's a red

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line down here that's for the

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hydroxyapatite which is this didn't come

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out at all anyway what this shows is

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that it works you mix it together and

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you create struvite you can separate all

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the minerals that you want and see that

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it has worked greatly for transferring

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hydroxyapatite to other sources Oh max

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so this allows allows us to create a

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very fundamental prebiotic model so you

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could take calcium magnesium and

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phosphate on a prebiotic earth which

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come together and formed this bed of

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insoluble minerals the water can be

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removed and then you can get a nearby

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hydrothermal sources and volcanoes or

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other surface Mets that can create this

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interest this suite of organic molecules

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and in organics to create the beds of

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urea ammonium formate water will come

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wash them into solution you now have a

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nice warm lagoon rich in magnesium

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sulfate urea ammonium formate which will

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then convert all of these minerals to

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the much more usable struvite and

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soluble phosphate i'll go through my

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reaction conditions very quickly it's

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very simple you mix of adenosine with

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the eutectic in a phosphate source in

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heated and those are the reactions that

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go forth and make phosphorylation so

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this is an HPLC trace showing the

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different phosphorylated species that

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are made five prime a and P some

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psychics to prime and three prime and

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this these chromatograms down here

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compare reactions with soluble phosphate

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in the eutectic to soluble phosphate in

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just a urea solution alone so you can

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see the area of the peak is important

278
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it's related to how much you have in

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solution so the eutectic works it makes

280
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great phosphorylated products comparing

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00:12:38,750 --> 00:12:36,570
it to the urea controls which are up

282
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here we got a total of seven percent

283
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phosphorylation at 65 degrees but

284
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fifty-eight percent running in the

285
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eutectic at a higher temperature of 85

286
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degrees we just see a mild increase so

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this works really great at lower

288
00:12:54,770 --> 00:12:53,250
temperatures when you're comparing the

289
00:12:59,080 --> 00:12:54,780
different phosphate sources that you

290
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have we get a up to thirty two percent

291
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phosphorylation with sodium phosphate

292
00:13:06,260 --> 00:13:03,960
struvite in Newberry eight which are

293
00:13:09,920 --> 00:13:06,270
very similar minerals of mildly

294
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phosphate solubility give a little bit

295
00:13:16,250 --> 00:13:11,640
decrease but still a great amount and

296
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then we synthesized some struvite

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00:13:20,150 --> 00:13:18,540
ourself in the lab and it's a mixture of

298
00:13:22,070 --> 00:13:20,160
Bruce Shannon's through vide and other

299
00:13:23,720 --> 00:13:22,080
mixtures and it still works great if

300
00:13:25,070 --> 00:13:23,730
they very dirty make sure that still

301
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produces a decent amount of

302
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phosphorylation and we process some

303
00:13:34,310 --> 00:13:32,220
hydroxyapatite showing that model that I

304
00:13:36,560 --> 00:13:34,320
had before with the washing and the

305
00:13:39,020 --> 00:13:36,570
magnesium sulfate in the drying and

306
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converting and showed an increase in

307
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phosphorylation compared to just

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hydroxyapatite by itself and this is

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really emphasized when we do some wet

310
00:13:53,150 --> 00:13:50,550
dry cycles where we continually add in

311
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magnesium sulfate try it added in more

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to really drive the equilibrium forward

313
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so this is particularly noticeable at 85

314
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degrees when we get a decent amount of

315
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phosphorylation as sodium phosphate and

316
00:14:09,170 --> 00:14:05,190
servite hardly any with hydroxyapatite

317
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at 65 and 85 and it really jumps up and

318
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we get fifteen percent phosphorylation

319
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by treating these mixtures with the

320
00:14:20,060 --> 00:14:18,180
magnesium sulfate so we can follow that

321
00:14:22,580 --> 00:14:20,070
one pot scenario to generate that lake

322
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and cellulose phosphate and bring it

323
00:14:28,580 --> 00:14:26,220
into reactions and also it doesn't just

324
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work with the denisita nucleosides we

325
00:14:35,800 --> 00:14:32,210
have done this with a glycerol so we get

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phospho glycerol this is a

327
00:14:42,170 --> 00:14:38,880
phosphodiester bond of to glycerol zin

328
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phosphate and two phosphates and to

329
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glycerol so this is showing the mass

330
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spec so we can great higher or

331
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phosphorylated species and create

332
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phosphodiester bonds if you're really

333
00:14:54,100 --> 00:14:51,860
paying attention to a couple talks ago

334
00:14:56,079 --> 00:14:54,110
can think that this might work with

335
00:14:59,980 --> 00:14:56,089
fatty acids and maybe you can make some

336
00:15:04,750 --> 00:14:59,990
lipids and some protocells so all sorts

337
00:15:07,269 --> 00:15:04,760
of interesting possibilities so overall

338
00:15:09,160 --> 00:15:07,279
these results have shown that it that

339
00:15:11,579 --> 00:15:09,170
the eutectic liberate the sequestered

340
00:15:14,560 --> 00:15:11,589
phosphate promotes phosphorylation and

341
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for the future work what other reactions

342
00:15:18,370 --> 00:15:16,339
will work we're taking this off in

343
00:15:20,440 --> 00:15:18,380
different angles and seeing maybe this

344
00:15:23,590 --> 00:15:20,450
is a great solvent to make all sorts of

345
00:15:25,060 --> 00:15:23,600
different prebiotic chemistry can it

346
00:15:27,880 --> 00:15:25,070
make long change polymerization

347
00:15:30,250 --> 00:15:27,890
reactions we saw the to glycerol xin the

348
00:15:32,470 --> 00:15:30,260
two phosphates so that made a polymer

349
00:15:35,949 --> 00:15:32,480
there we've seen up to three informers

350
00:15:38,680 --> 00:15:35,959
with the Deniz een maybe we can make 10

351
00:15:40,449 --> 00:15:38,690
verse 20 MERS maybe there's some magical

352
00:15:43,090 --> 00:15:40,459
chemical equilibrium that can happen in

353
00:15:47,170 --> 00:15:43,100
there to make the information carrier

354
00:15:50,710 --> 00:15:47,180
polymers that we need and this paper has

355
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just been accepted for publication on

356
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Yvonne take mea so you can see a more

357
00:15:56,949 --> 00:15:55,490
detailed version of our work if you

358
00:16:00,790 --> 00:15:56,959
check out that general in the next

359
00:16:03,370 --> 00:16:00,800
couple months here's the group that I

360
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work with and my funding sources from

361
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the nasa astrobiology program I'm

362
00:16:13,630 --> 00:16:11,149
supported by the nasta post doctoral

363
00:16:16,509 --> 00:16:13,640
program and we are funded by a grant

364
00:16:21,380 --> 00:16:16,519
from the ni as well so I'll take any

365
00:16:36,980 --> 00:16:32,090
thank you I'll ask one over I got the

366
00:16:38,270 --> 00:16:36,990
mic I got the power yeah so the wet/dry

367
00:16:40,130 --> 00:16:38,280
cycles you were showing where was like

368
00:16:42,080 --> 00:16:40,140
raining off and then refilling and

369
00:16:44,120 --> 00:16:42,090
drying out again yeah so is your

370
00:16:46,220 --> 00:16:44,130
thinking this is like a marginal coastal

371
00:16:49,190 --> 00:16:46,230
type of environment where you're having

372
00:16:50,690 --> 00:16:49,200
some terrestrial exposure yes ok so our

373
00:16:53,000 --> 00:16:50,700
fundamental thing you're looking at

374
00:16:55,100 --> 00:16:53,010
either small islands or very small proto

375
00:16:56,810 --> 00:16:55,110
continents I'm sure yeah and so we're

376
00:16:58,520 --> 00:16:56,820
not looking at both water systems at all

377
00:17:04,130 --> 00:16:58,530
it is very hard to do chemistry in the

378
00:17:06,650 --> 00:17:04,140
bulk water Hey yeah enjoy yeah I'm just

379
00:17:09,290 --> 00:17:06,660
curious can this also work with ammonia

380
00:17:11,000 --> 00:17:09,300
oceans as well as it is over just only

381
00:17:14,840 --> 00:17:11,010
considering just water oceans at this

382
00:17:17,660 --> 00:17:14,850
point so ammonia ammonia is a key

383
00:17:20,180 --> 00:17:17,670
component of it so urea will convert to

384
00:17:22,730 --> 00:17:20,190
you Mona ammonia I'm only a four mate

385
00:17:24,650 --> 00:17:22,740
has ammonia in it so you do need ammonia

386
00:17:26,360 --> 00:17:24,660
to drive these reactions so ammonia

387
00:17:28,670 --> 00:17:26,370
oceans will work ammonia lagoons will

388
00:17:36,910 --> 00:17:28,680
work but you need some source of ammonia

389
00:17:39,050 --> 00:17:36,920
yes in a prebiotic setting could this

390
00:17:40,970 --> 00:17:39,060
phosphorylation should be nonspecific

391
00:17:43,190 --> 00:17:40,980
like you could end up phosphorylating

392
00:17:46,250 --> 00:17:43,200
your amino acids to or would this be

393
00:17:49,190 --> 00:17:46,260
somewhat specific at least so we have

394
00:17:51,680 --> 00:17:49,200
shown a small amount of specific Regis

395
00:17:54,320 --> 00:17:51,690
Rijo specific reactions so if you look

396
00:17:55,820 --> 00:17:54,330
at the adenosine you form far more five

397
00:17:59,270 --> 00:17:55,830
prime than the two prime of the three

398
00:18:01,400 --> 00:17:59,280
prime if you put in glycerol is going to

399
00:18:03,470 --> 00:18:01,410
react with that I don't know how it's

400
00:18:05,390 --> 00:18:03,480
going to react with a whole mixture of

401
00:18:07,820 --> 00:18:05,400
alcohols in there and what will be

402
00:18:09,850 --> 00:18:07,830
specifically phosphorylated over there

403
00:18:16,509 --> 00:18:09,860
it looks like it's a pretty nonspecific

404
00:18:22,029 --> 00:18:19,719
how much water is too much water before

405
00:18:24,489 --> 00:18:22,039
the dehydration doesn't work very well

406
00:18:26,619 --> 00:18:24,499
anymore so I mean that's a good question

407
00:18:30,099 --> 00:18:26,629
this is actually problematic to quantity

408
00:18:31,839 --> 00:18:30,109
to quantify an NMR because in this

409
00:18:33,399 --> 00:18:31,849
eutectic you get so many interactions we

410
00:18:37,839 --> 00:18:33,409
just get a broad peak instead of a nice

411
00:18:40,419 --> 00:18:37,849
sharp water peak it is what it is but

412
00:18:43,029 --> 00:18:40,429
there is still water present in there it

413
00:18:45,699 --> 00:18:43,039
takes three days of heating at 85 before

414
00:18:47,949 --> 00:18:45,709
South passports phosphorylate if I riad

415
00:18:50,440 --> 00:18:47,959
water it stops and then happens like a

416
00:18:54,249 --> 00:18:50,450
day to two days later but I don't know

417
00:18:58,989 --> 00:18:54,259
how much is in there but it is still in