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hello welcome to the next in our webinar

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series just a few announcements to start

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with there was a slight mix-up on the

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email that went out today so just in

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case you haven't seen it the email and

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the calendar we're out of date we are

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starting off with Greg's presentation

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today tomorrow is going to be the to

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Eric's on stretching time and space

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those things are we are now also up to

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date with all of our video recordings so

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if you want to go back through any of

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the presentations using to go to the

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astrobiology future website and select

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any of the events and the associated

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YouTube video will be linked in there

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the slides for this event are also on

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each of the event entry so if you

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connect to this and you're only

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listening to the audio you can download

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the slides directly from the website and

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finally the meeting is being recorded so

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at this point let me pass over to Greg

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take it away thanks daddy so my name is

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Greg Springsteen as one of the

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participants in the astrobiology roadmap

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meeting and what are they talking about

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today is the synthesis and assembly of

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populations of stable oligomers now the

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text that we plan or at least that is

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currently in the paper will be

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highlighted in red like this this text

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this document will be opened quite soon

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maybe right after the presentation okay

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so first are justifications for this

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topic why are we interested in this is

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part of the astrobiology roadmap and so

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our group came up with three primary

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justifications one polymers are uniquely

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capable of selective catalytic and

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janette genetic functions necessary to

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life on so we've got the large size of a

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polymer incorporating a transition state

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and a poly dentate fashion giving some

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selectivity

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to the catalysis also these polymers or

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linear polymers can we can generate

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libraries with quite a bit of structural

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variability with an extraordinary

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limited set of reaction types for

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example we could just do the addition of

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the monomer if we have multiple monomers

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to generate all sorts of structural

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variability on in an environment of

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which just monomer coupling is the only

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available synthetic reaction type

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additionally chemical and phylogenetic

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evidence suggests that both extant and

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ancestral ancestral metabolisms as far

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as we are aware at the moment are

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dependent on polymers for structural

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catalytic and genetic functions it makes

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a lot of sense to go after an

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understanding of how polymers or

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oligomers were generated prebiotic ly so

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as a broad overview of the topic topic

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explanation we have in most plausible

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prebiotic hypotheses abiotic monomers

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and we're keeping that very broad amino

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acids nucleotides monosaccharides we're

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condensed by abiotic dehydration

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condensation reactions to form oligomers

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life evolved from within this milieu of

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reversible polymerization is a plausible

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prebiotic hypothesis however

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condensation reactions are

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thermodynamically problematic in aqueous

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media of course because we are

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generating water in these condensation

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reactions additionally carboxylate and

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phosphate astera fication / amidation

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reactions suffer from large connect

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barriers and near neutral aqueous

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environments primarily because of the

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poor leaving groups under neutral

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conditions from these carboxylic acids

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and these phosphate efforts as well so

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mechanisms by which dehydration and

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condensation reactions may have been

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thermodynamically driven and or kinetic

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excel data include incorporation of high

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potential energy activating groups to

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polymer growth and non-aqueous or dry

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down environments

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potentially three non-covalent

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pre-assembly if monomers either with or

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without a template that template being

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broadly defined and for some polymer

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properties that inhibit degradation of

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the polymers of the larger complex are

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selectively of one complex over other

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complexes and so we've broken up each of

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these topics into a number of self

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questions so to hit these really one by

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one so the first we talked about it on

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the previous slide is chemical

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activation so what's polymerization

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driven in here i'm just going to broadly

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speak of thermodynamically or

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kinetically by chemical coupling agents

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and then what is the source and

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persistence of these agents and that is

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often a particularly problematic

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question now it's not hard to envision

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what these agents might have been a look

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at carbon diameter carbodiimide

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chemistry is very well known for

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coupling chemistry diamino maleo nitrile

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that not only leads nucleobases but it's

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a reasonable dehydrating reagent iron

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cyanide is a dehydrating reagent also

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the phosphates try meta phosphate is a

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dehydrating reagent so we can imagine

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all of these catalyzing the coupling of

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monomers they are in themselves just

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dehydrated reagents so in that sense

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we're just pushing the question back to

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what was the source of the dehydration

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to generate these monomers excuse me

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these agents and and why were they not

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hydrolyzed in their environments

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question 2 what is the role of phosphate

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in early dehydration polymerization I

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think this is a reasonable separate

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question from the first one in that

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extent biology is driven by triphosphate

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catalysis in terms of a dehydration and

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so what was the origin of that that that

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phosphate driven dehydration and if it

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wasn't the first dehydrating reagents

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what were the Meccan

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ism's to move from a say car mode I

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timid based dehydration environment to a

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nucleotide triphosphate on driven

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environment additionally so or what say

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alternatively if we don't have these

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high potential energy dehydrating

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reactions we're we potentially doing

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these condensation polymerization in

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alternative solvents or environments so

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what are potential non aqueous

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environments we can think of things like

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a form of my which will be seen in the

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literature hydrocarbons deep eutectic

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environments potentially in the

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membranes of myself if the legalization

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reactions occurred within these solvents

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flash environments of this dehydration

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Stefan may have been thermodynamically

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favorable and kinetically feasible one

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of the other or more um so investigation

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of alternative solvent systems with

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respect to accumulation in geochemical

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and cost melodica context may justify

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these environments as prebiotic ly

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plausible and additionally what's

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polymerization driven by water activity

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cycling so are we talking about

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conditions that are a dry um whether

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we're talking about dry down conditions

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or just our solvents becoming dry in in

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cycling conditions weather temperature

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day night title and on um so below we

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just have just some structures to

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exemplify kind of things that we're

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thinking of they become in urea based

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deep eutectics the formatted for my

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excuse me ammonium formate non-aqueous

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alright a third question what about

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polymer sustainability so were these

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early polymers that gave rise to

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biopolymers a thermodynamically

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advantage door

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ethically trapped what polymer

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properties could potentially confer

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resistance to hydrolysis or other

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degradation leading to a kinetic

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trapping and what roles do polymer

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solubility salvation and hydrophobicity

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play in the evolution of functional

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polymers so we imagine that polymer

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folding polymer solubility are going to

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be on important questions in our

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understanding of how these first

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oligomers / polymers arose on an evolved

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function all right next up reassembly of

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monomers so if we look at biopolymers

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right there's a strong sense of

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non-covalent interactions whether we're

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looking at the beta sheets of peptides

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which I got in the upper left or we're

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looking at the hydrogen bonding patterns

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of nucleic acids which I got in the top

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right there's this non covalent

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association so one could ask did this

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non covalent association precede the

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covalent polymerization and so that's

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the first question we have down below so

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was this polymerization dynamic or

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templated before that the covalent bonds

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formed we can also ask one other

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mechanisms promote high effective

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concentrations of monomers preceding

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covalent bond formation thermal

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convection service absorption

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permeability lots of other potential

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ideas and if we are imagining scenarios

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at which these monomers were laid down

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noncovalently before non covalent bond

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formation can we imagine scenarios in

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which this homo chirality arose not

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because of a preference of monomers but

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because of a preference of how these

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monomers interacted in their local

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a big part of this question is also what

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what can we infer from extant

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biopolymers since our X and biology is

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so polymer based so what does the

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mechanisms of polymerization in extant

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biology so besides lipids primarily

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dehydrated polymerization tell us about

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the early biotic environment as far as

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the early biotic environment may

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potentially dehydrated are irregular or

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branched polymers horrible precursors to

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functional biopolymers so we see

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primarily linear polymers now besides

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some notable exceptions with disulfide

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bonds for example um but in a prebiotic

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sense it's very hard to limit polymers

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to just linear right there if we look at

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peptides for example or the two prime

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three prime ribose right there are lots

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of opportunities to branch out in our

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pre bio polymeric systems and uh when

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did the primacy of polyphosphate driven

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condensation arise and if it wasn't the

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first what were the mechanisms of

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transferring that dehydrated potential

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from earlier precursors and then our

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last light is connections to other Road

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mech topics and there are a lot what

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what is our library of potential

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monomers and what was the synthesis of

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these monomers that might give us some

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clues as to what the environment was on

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that led to the dehydration of these

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monomers once generated what are the

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common attributes of X living systems

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and what can they tell us about all

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living systems so what was the driver

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was with their redox driver for example

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of these dehydrated conditions how did

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my bro molecules gain functions of

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course how do we link the folding of

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macromolecules into some functional

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catalyst genetic polymer what does that

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tell us about the environment at which

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the covalent bond formation of those

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macromolecules happened what

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environmental factors are coupled to the

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emergence of life so there's got to be a

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non-equilibrium driving here

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particularly if we're reading to aqueous

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conditions again it brings us back to

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redox and dehydrated conditions or what

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environment where we end laboratory

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models of earliest cellular life again

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if we are imagining that we are arising

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in aqueous conditions how do we justify

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that in terms of the the thermodynamics

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and the kinetics of this polymerization

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and how the polypeptide meet Polly

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nucleotide there's anything that we

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learn about the polymerization of one

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system our polypeptide system is likely

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going to play a large role in our

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understanding of the condensation

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polymerization in the other system so

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there's going to be a lot of cross talk

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between these two worlds at least the

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study of these two systems once we

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understand in one or the other how this

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dehydrated condensation polymerization

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may have arisen um so I would happily

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take any questions and you can certainly

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look at the road map document and I

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would love to see anybody suggestions on

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that document as well of how we're going

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to potentially take this paper forward

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thanks for your time and attention and I

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look forward to hearing from you okay so

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we have a select group that appears in

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the in the participant list here I'm not

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sure if we have other people who are

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also dialed in just to say to our

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participants were right partway through

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obviously this is being recorded so you

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can run back and see the beginning of it

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as well but let me just throw it open

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because our our audio lines are now open

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legal Alyssa

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or even Lindsey because you there do you

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have any questions that observations

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that you want to make now and actually

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just before you do that let me just

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respond to gregs point the document is

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currently in read-only mode that in a

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few minutes it will be flipped over so

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that you'll be able to add comments to

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it so by all means and your thoughts

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directly in the document as well but

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come back to our participants or any

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questions or observations that you'd

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like to make at this one hello this is

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Melissa no comments from me but thank

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you Greg hey this is Lindsay um can you

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all hear me hey yes okay I apologize

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that I came in a bit late but I actually

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would actually sort of like to direct

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the same question to you that I directed

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to the last group which was you know for

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if we're looking at things that we can

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think about working on in the next 10

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years etc I mean that's sort of the

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general concept of this whole program

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this whole astrobiology strategy but is

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there anything specific that you would

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want to point to about that you know

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sort of specific questions you know in a

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in a more in a less general sense in a

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more directed sense that you think we're

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going to we're going to get you yeah you

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know you said not general and then I'm

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going to answer generally but I the idea

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of drivers of non-equilibrium

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environments and how they were coupled

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to polymer synthesis I think it's very

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fascinating and I think whether the

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answer comes directly from this question

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or from others that we pertained to hear

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this tremendous amount of crosstalk

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right if we're talking about a redox

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driver for example of polymerization um

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you know as we see now it's quite calm

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next in biology how we couple redox

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energy to ATP synthesis and then to this

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dehydrate of polymerization and so which

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way did that occur if prebiotic lee was

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it with a dehydration first or redox

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coupling first so i think what is

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fascinating about this concept is we are

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either going to teach or learn from a

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great deal of other questions ok any

365
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other hopes of the vendors that answer i

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think your question specifically enough

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we'll go with that you're very

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interested specifically on in realistic

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coupling reagent sorry we see a lot of

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those in the literature can we imagine

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environments at which they persist and

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our effective generators of polymers and

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you know I would like to see that

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explored in the very near term great any

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other thoughts questions that people

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want to pose this point okay uh we will

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go and flip the switch on your document

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great thank you very much for doing this

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appreciate that and if I can encourage

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everyone whether you are live now or

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catching missin and at the recording

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please go and put your thoughts and

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comments directly in the document the

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documents link strength from the front

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page of the site and it will help the

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team enormously if you can just add

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anything to help them strengthen the

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paper that will be wonderful thank you

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very much okay I'm document thanks dear