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[Music]

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so hi everyone I would like to thank the

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organizers for giving me the opportunity

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to present you today so my name is Moran

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Frankel painter I'm a NASA postdoctoral

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fellow working with dr. HUD dr. Williams

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and dr. Grover's here at Georgia Tech

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and in the Center for chemical evolution

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and today I will tell you about a

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reversible polymerization of periodic

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deficit cap that they will define what

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these are which allows selection of

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stable structures so as we know and as

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mentioned we know from prebiotic model

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actions and from meteorite composition

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that actually else today's the building

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blocks of today's biopolymers can be

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formed from these model periodic

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reactions and we can find these in

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meteorites but something really

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important is that we in the central

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chemical revolution we explore other

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product backbones for these by commerce

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with you today and we know that in

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addition to these building blocks that

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we see in today's biology we actually

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had very similar building blocks that

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could have been you know incorporated

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into proto backbones of these polymers

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in the pre run earth so they need are

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talked about what were possible a proto

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on nucleobases

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and water we'll be talking about today

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will be focus on today is what we think

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were the proto factoid backbones

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on a prebiotic earth and today we know

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there's these urges change of immunity

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but we think that we had some

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incorporation of other building blocks

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into them so just in general like to

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mention in the center of a chemical

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volition what is our approach for

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polymerization of these polymers and

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back you mentioned and david i weight

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cycles so just a brief overview

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Becky you said you like the Sun we also

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like the sun's though as a driving force

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for polymerization we know that all of

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today's bye

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are a result of condensation reaction so

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we lose water and that's exactly what we

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would want to mimic by these dry weight

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cycles so we can think about these let's

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say seasons on the previous curve we had

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some solutions with some monomers that

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first got we we had a dry hot face

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whatever vibrated that caused the

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condensation or polymerization of these

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monomers and then you can think about

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earth you got cold and we had some water

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coming and then we can have some

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structures and also some hydrolysis or

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degradation of non-structured polymers

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that will our some recycling and we can

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think about the cycle going on and on

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wet/dry cycles to drive selection of

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some stable moments the outline of the

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talk today is so I'm gonna start with

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some challenges with contemporary

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proteins or peptides in terms of or in

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life chemical abortion I will talk about

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what our deficit bath I doesn't know

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Trinity of bath day bathroom and I will

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also show you some selection of stable

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structures in a complex mixture so let's

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start when we think about the pros of

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peptides we know that fact that today I

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just I'm changed of amino acids but we

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also know it's pretty hard to form the

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amide bond between between the amino

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acids this is another thermodynamically

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favored reaction and we know it came

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before and if you use really high energy

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molecules or it will apply some really

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high temperature high pressure we can

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form that but then we'll run into

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another problem which is once we have

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this type oxide it can go another

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condensation into a psychic by heat up

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to Terry's name which is really stable

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and in a way it's gonna many times we'll

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call it a sink we're gonna stop

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polymerization into further

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elongate a change another problem is

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that reversibility so if we want to

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drive selection in our system we think

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that so we can think about the periodic

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step is really messy of having these

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really

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structure Spacely one sample and if we

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made this peptide and we cannot break

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them so the amide bond in addition to

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being hard to make it's also hard to

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break so we can follow these pathways

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but then they we're kind of stuck with

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what we've had so how can we have so

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action if we think about really trying

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out different sequences and give us some

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stable structures so we're gonna be able

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to be stuck we're gonna be able to not

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move forward and we'll just be

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maintaining with this certain sequence

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that we had so we will not have a

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disability so when with the search for a

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total polypeptide backbone I mentioned

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that in addition to the building blocks

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of today's talk ties the amino acids we

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had other very similar molecules in this

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case I'm gonna talk about hydroxy acids

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so in these molecules instead of the

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amine we have the alcohol away and we

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know that they result from the same

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synthesis so we had hydroxy acid in a

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really similar abundance to amino acids

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and so I will throughout the lecture I

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will just out of simplicity amino acids

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will be labeled as these blue circles

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and I mean the Drakh cepheid's will be

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represented as these red circles as I

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mentioned amino acids it's really hard

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to polymerize I mean axis into these am

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i fun but what we do know is that if you

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take hydroxy acid and you just dry them

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so you drive water off it's very easy to

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form the polymer hydroxy acid which is

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called a polyester through an ester bond

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right here so that's really easy so what

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dr. Krishnamoorthy suggested in the in

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the as part of the research in the

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Center for chemicals relation is what

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will happen if you take these both amino

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anti-drug see assets together so what

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happens is will actually get copolymers

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of both

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you know and I'd rocks the acid they are

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called ducks if a tide and briefly I

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will not go over the mechanism but I'll

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just say that once we form the Astra

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bond between I track the acid then the

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amino acid or the amine can attack and

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replace and we get a replacement of the

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ester with an amide bond so we're making

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that Zapata in support of potential

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world for adaptive baptized in origins

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of life we know that even today we have

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duck soup that is in nature they mostly

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serve as antibiotics but they also have

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different functions this one for

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instance is called Melina my same it's a

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cyclic to their capacity backside and it

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is it functions as a potassium

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transporter that facilitates the

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movement of potassium ions the lipid

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membrane so as I mentioned that see

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peptides they are readily formed under

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model prebiotic Gretchen so we just we

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can just dry it together I mean on a

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drug the acid and we can get them but

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the problem is that it's not so simple

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so if you just take these monomers we

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actually get a very complex mixture of

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deficit off site and my researchable

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focuses on understanding better

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understanding of these gaps across sites

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and if you have this complex mixture

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then how can really study the properties

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of that see baptize in terms of

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polymerization assembly this assembly so

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a way to make it more simple is really

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knowing the different stability of the

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ester versus their Maybach sophie really

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rely on chemistry and we know that

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actually the after bond so left to de to

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the red circles the ester bonds are

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really more susceptible to being

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hydrolyzed in the west face so when we

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have water so it will we're gonna break

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all these bonds and maintain the amide

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bonds

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we're gonna be left with fat guys like

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this and we know that this is what

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happens what happens in the system so to

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simplify the system what I did in my

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research is synthesizing these

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baptize which have just one hydroxy acid

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12i and me nothing and I'll show you one

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example so this is glycolic acid alanine

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so glycolic acid it's a red blue

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molecule so we have the Ajax es in

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analog of the lysine that's like our

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Kassadin alanine and then if we take

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this molecule and we just dry so we

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drive water off we try and hit it our

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expectation is that it will form an

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ester bond between the two units and

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that's exactly what happens so here you

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can see an HPLC analysis separation on a

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15 that's based on hydrophobicity you

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see absorbance a 200 meters that's gonna

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give us the absorbance of the

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Estrin amide bonds in the system over a

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tension time so the shorter the

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retention time the more hydrophilic the

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compound is so as time goes by we'll see

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the longer species which are more

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hydrophobic you can see over drying time

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this is at 65 degrees Celsius that we

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start to form these we start to stitch

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these units together and it's really

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nice because everything that we do

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really is forming these extra bonds and

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what we're making is a new backbone

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then we ask are we gonna get some

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structures once we polymerize this

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peptide so when we start with a glycolic

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acid alanine these properties are shown

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in the scanning am right here scanning

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electron microscopy these these samples

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or this path lights are really oily like

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in nature but once we put a polymer

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either once we dry them in addition to

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seeing the polymers we also start seeing

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some structures formed with gates these

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fibrils and we think that what happens

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is that once we took these two glycolic

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acid on in and we polymerize it we think

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that we're mimicking a really well-known

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motif in biology which is the glycine

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alanine repeat motif from silk fibrian's

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in which they form the glycine earlier

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form these nice Bereshit structures so

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we think that once we polymer the

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peptide some portion of it can form

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these fibrils similar to the glycine

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alanine in film the next question is can

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we go back so we have the structure

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information we have the polymerization

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that I told you reversibility is a

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really important issue so can we go back

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and hydrolyze it and go back to the

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starting material the answer is yes we

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can so if we take the preformed

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oligomers so now we have many ester

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bonds you can see incubation in water as

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65 degrees so we can actually go from a

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distribution of oligomers to a shift

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towards the lower molecular weight

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species so actually the gradation and I

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want to say that the degradation is

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again just off the ester bonds so left

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to the red molecule so we're really we

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have this unit in this case our hydroxy

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amino acid that means being stitched

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together when we draw it and it's been

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degraded as a unit when we hydrolyze it

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so we had reversibility and the next

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step was making the system a bit more

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complicated and see what happens when we

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have mixtures of of these shortstack

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tight and in collaboration with Martin

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solana is a grad students in the HUD lab

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so I showed you glycolic acid alanine

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but Martin synthesized other molecules

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and glycolic do I seem like acid alanine

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lactic acid glycine lactic acid is the

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hydroxy as an analogue of alanine so we

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just have the methyl group here in the

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force of the glycolic acid and what we

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wanted to see is what happens if we

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going to make a complicated mixture but

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first we just had to make sure that all

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of these packets polymerize when we dry

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them so you see like glycolic acid I

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mean you see the different polymers

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perhaps I did mention two means two

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units of glycolic acid I mean and so on

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so all of these packages are forming

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polymers and when we looked at the big

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red

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of these peptides as deficit bastards we

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know that the the ones with the lactic

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acid so with the metal here are much

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more stable so we said let's take the

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one one was electric I said one with

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glycolic I said put them together and

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then see if we have selection once we

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have the gradation in the West face

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towards the lactic acid containing one

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so we took glycolysis the glides near

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lactic acid I mean we dried them so in

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foreign polymers and then we hydrolyze

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after some drying time we got polymers

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so you can see in red polymers of

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glycolic of the glycine so that's two

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three four of glycolic acid glycine some

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homo polymers of lactic acid all in

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green right here and then we also got

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copolymer is composed of both glycolic

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acid glycine and lactic acid alanine

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like these ones now once we are

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hydrolyzed these ducts it back they that

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are formed we see that after hydrolysis

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or after degradation time in water we

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see that the ones that survive the most

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and the ones that are enriched with

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lactic acid so we were able to show some

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collection based on chemical stability

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of deficit baptize in your system and I

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hope I convinced you today that dr. Graf

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aid can be a plausible part of the

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peptide backbone first we're able to

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polymerize the FC package very readily

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we can even see some structures formed

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by them and last really importantly

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we're also able to recycle and really

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sample this huge asked sequence

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structural space so we'll be able to

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hopefully get some sequences this will

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give us rights to structures that might

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be functional and I don't have thanks

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for moving forward but I'd love to talk

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to you if you have any questions please

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go to see Martinez Martinez poster today

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because Marty and I have a library of

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fact ideas are tough they emphasized by

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Martine and

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we explore some interesting features on

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these making the system more complicated

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looking for some selection so without

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like

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think the piace I worked with dr. HOD

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dr. Williamson dr. Glover I would like

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to thank my lab members especially

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Martin worth work have mentioned the

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funding agencies and thank you for

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listening questions so I was wondering

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about the sort of the additional and and

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the reversibility and how the

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reversibility is really important but

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sort of the the enrichment process and

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just kind of how you know you want

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reversibility but you also want some

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sort of progress if it were and so

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what's what's sort of the balance

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between those two processes yes so we

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really need the reversibility part is

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really important for trying out

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different sequences but the premise is

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that if we have some sequences that can

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fold they can from some stable

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structures and then they will be stable

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even though if they couldn't it could be

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a reversible for immunization we think

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that if we have some structures or if we

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have a co-equal have binding to a

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cofactor for instance so we have some

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ways to stabilize the structure one so

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the ones that are not functional not

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structured they will be the grade and

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put back recycled into the prebiotic

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soup and then we can build some more and

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turn restore some that's the Baptizer

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more favorable okay great Thanks other

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00:17:27,480 --> 00:17:25,390
questions yes so sort of piggybacking on

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that idea of stabilizing the structure

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have you thought about while I'm sure

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00:17:34,010 --> 00:17:31,510
you thought about but do you have any

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plans to do things with like different

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00:17:39,930 --> 00:17:38,350
like clays or sediment or other

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00:17:43,620 --> 00:17:39,940
cofactors present those kinds of

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00:17:46,220 --> 00:17:43,630
experiments yes definitely direction

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00:17:48,660 --> 00:17:46,230
that we take we want to be able to

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select based on structure on the

384
00:18:05,159 --> 00:18:01,930
a slightly silly question why the why

385
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starting specifically from the dimer

386
00:18:09,159 --> 00:18:07,340
starting points rather than just like a

387
00:18:11,169 --> 00:18:09,169
mixture of the monomer is that just to

388
00:18:13,240 --> 00:18:11,179
sort of get things going faster or make

389
00:18:18,820 --> 00:18:13,250
the products larger or something more

390
00:18:20,830 --> 00:18:18,830
yes so we find out no no that we had a

391
00:18:22,480 --> 00:18:20,840
lot of time for a chemical of volition

392
00:18:25,270 --> 00:18:22,490
but we kind of want to speed up the

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00:18:27,610 --> 00:18:25,280
process and see and be able to speed up

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00:18:30,190 --> 00:18:27,620
things so we think that because we know

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00:18:31,930 --> 00:18:30,200
the chemistry so we know that we can

396
00:18:34,029 --> 00:18:31,940
make these peptides with a drug see an

397
00:18:36,640 --> 00:18:34,039
amino acid we know that they will be

398
00:18:40,539 --> 00:18:36,650
enriched after a wet cycle after some

399
00:18:42,549 --> 00:18:40,549
heating time we want to kind of just

400
00:18:45,159 --> 00:18:42,559
make it more simple so we'll be able to

401
00:18:47,049 --> 00:18:45,169
see things and not working with at this

402
00:18:48,850 --> 00:18:47,059
point with a complicated mixture that

403
00:18:51,640 --> 00:18:48,860
will be just they're just harder to

404
00:18:54,039 --> 00:18:51,650
analyze and so gain some insights from

405
00:18:58,779 --> 00:18:54,049
them but we just think we just want to

406
00:19:00,610 --> 00:18:58,789
speed up the things to simplify okay