It's very very pleasure like to introduce it is the single with pleasure professor. To do a special. Instruction for the day it's about two years ago I was still a post-op press room trying to get a job. But we really want to get rid of me Georgia Tech was nice enough to take me so everything worked out. Great is really going to see significant presence in the home are signs that. He's working to mark the white range of topics getting a lot of areas all of the Center for. New ways to approach making materials and making. Things work I never areas both industrial and academics spend a significant time I hear work join the Army just for work and it's really change the perspective on all of science for both don't go. Back to the tax breaks. And really does mean credible innovations all the way going all the way back to when you suppose not pushing the revolutionize the way people are on the bright colors inventors then when she would die young interesting completely new type of control radical rejection I caught sight of his age when we went to U.C. Santa Barbara very pleased with adopting new ideas of click and change the way people bought about how many materials homers use these things building blocks in themselves open up the doors and create. The most recent years to see any area like conversation with me now OK you know the selling point of calling the very. First time you are with me and I think he's really smart display or just he's been involved in a lot of different successful startup things like the looks of. But the most natural honest person country guys walked in and saw your house right here. You can tell you can touch it and feel it if you want will really like. And that's because it's what. You're all about which is actually taking the entire world but it is now over three hundred seventy thousand long. It's wonderous odds over the years it's been used by most celebrities that you know sometimes it's. For instance you could actually just we did that because. You realize just recently she went like this like crazy for yes. Character doesn't make. Any Carly you want my friend and guess what the first time for you first times free. I want to hear from. Her the same second yes it's really great to go through all the success rate you really get your first words with them all name a couple is one word on the screen for my younger son works toward. The roles I used to look at. And the list goes on. But off we see it's a pretty good guy. Using your version and like to be. Here. But soft spoken. To the everyone in the pleasure to be here today and I like. Dory will you because. You didn't know who he was by. Realizing that here. And so I like your feelings here in the land I will go back to Santa Barbara but the M.R.O. which is where we'll spend most of these time is around about here it's hidden behind this building and we have a Christmas party and the biggest while we all watch this and you can see it's true because we're starting to read. How big a soiree with the Christmas party at the M.R.O. was not whether we had enough food whether we had enough drink was what was going to do and where was will going to end up because the challenge was the. Christmas party will go into the evening and we dock outside and here are cliffs and it's cliffs down to the beach and on more than one occasion and we're not talking about fifteen twenty Christmas parties to will where I talking about three Christmas parties so he has a really good success right all disappearing dring the Christmas party and. All of this then having to look for him because we were concerned that he would he handle the Christmas parties so badly that he would just simply walk out and fall down and we'd find him on the ocean in the morning and so I'm really happy that he survived the Christmas parties and a look at him gee right in the eye and never hold the Christmas party when he's in town OK you have been warned That's right make sure there's no water body anywhere around will around the Christmas party so I'd like to tell you two short stories today in the general area of bio inspired materials but I'd first like to really think Miller Paul sigma for supporting chemical research throughout the United States and actually throughout the world. It really isn't one of the research and I will now show you how all I am by telling you exactly what I still look for from Miller pore Sigma and that's the chemical catalog for many students in the room you've probably never actually touched. The old rich catalogue but this is a very very thick book and as a student I would actually look through this and it was I really miss it he's some feedback for you guys I really miss it because you'd find the chemical that you were looking on a page and guaranteed on the next page all the opposite page they'd be another chemical that you'd see and you'd order up and so this was a great heaven you not only to discover compounds but to order even more chemicals and so. Orders chemical catalogue will always be in my hot and the other thing is I always used to love these ads from Alpha who was one of the founders of the orders chemical company and please please bother us and again this is something that Aldridge brings to the community and that's all of these unique chemical compounds that other people find extremely useful and this is going to be a theme throughout my lecture today and it really was inspired by our initial collaboration with with M.G. and Barry shoplifts was that making chemistry simple and decreasing the activation energy is really important and having Aldridge supply all of these all middle posting there I apologise all of these chemicals is really actually really tremendously useful So these are the two stories I'm going to tell you bet today the first is the development of a new class of it he's eaves and the second is instruction in a particle's again the common thing that I want the students to take away is using simple chemistry true Mike materials with application and with purpose and so both inspired by marine organisms the. First by simple muscles and the second boy cuttlefish So if we look at the first area and this is in underwater and he's eaves walk in to tell this well this was really inspired by a colleague of mine in the Marine Sciences Institute a White who's been studying muscles for the last thirty to forty years and Herb is a biochemist so he tries to understand all the biochemical underpinnings of what the muscle does and then where we come into the picture is to try and train slight those understandings into actual synthetic materials and so this is what Hood has discovered over a number of years and that is the must all prepare is two types of catatonic peptides a cat on a set of Pip tides and a separate set of Ed on it peptides both of these are water soluble but what it does next I think is really smart or I was going to make a political joke because you know this is a real genius OK. And what the muscle does is that it takes these two water soluble all you want to pick tides mixes them together in a special chimed in its body to form what's called a CO S. of eight which is Ward it insoluble so that's the first trick it's taken to water soluble materials and made a water insoluble material but from a material science viewpoint these coercive eight systems are really exceptional for that he should they share thinning the organism can easily spread it out of the orifice that it uses has low into facial energy so it's spreads readily over the surfaces that can be extremely by a fair out and then it has high frictional coefficient and secondary chemistry which we were exploited Lyta that allows you to cross link and sit here and he's Eve so comes that sticky and ends up being an extremely stable under water and he's live again starting from water soluble materials and it does this through a lot of the same really of structure in water and two key structural motifs the coalesce of that I'll go on in a second but also. Modified peptide Torah scene which is modified to dope in essence think of it as a cad a coal unit and it's this also Di phenolic unit that is really really useful from an adhesive point of view as well so these are the mind to structural motifs that muscles and a lot of other marine organisms use to survive in a hostile environment if the muscles don't get here to the surface they die there is a really strong incentive for them to actually use this chemistry and use it will as I said the other thing that I want to get across to the student is that from the simple building blocks we can assemble a large range of structures in a solution and this is something that many people here at Georgia Tech do and that is looking at the assembly of different systems in water typically a mixture of chaotic systems and on an existence allows you to create larger structures and provide more powerful properties to the systems than the single systems alone so again I just want to kind of bring out the work of else a poll Jennifer Blair in also looking at these are your own existence and so what would we like to do well we want to look at these coercive eight systems to make synthetic materials and our first test case was can we make hydrogels that have significant physical properties and mechanical properties but on. Bonding and essentially based on these Co S. of A interactions so you can think of these is similar to them a plastic elastomer as on the soles of all of our shoes these are non cross-link systems in the terms of your shoes they held together by glossy polystyrene domains in this case we're going to have hydrogels held together by the water insoluble coercive phase and so again we start with water soluble materials and we end up with water insoluble but swallow bull Hydra job and so this is some work that Jasmine and Jason did a number of years ago. And Jason I had the very smart idea to start from a common stock to try block Coppola So we have one block a central block and another terminal block so that we could really do structure properly relationships since we're going to mix two things that have share a common starting material so using chemistry that I'll go over in a minute Jasmine and Jason were able to functionalize the terminal blocks with author catatonic units or an eye on it units in such a way that we have the same number of catatonic units at both ends but also the same number of and only on it communities at both ends as the number of cattle and units and so we can really balance the charges if we want to or on balance the charges if we want to so we have a lot of structural control over these systems so again a plug for Aldrich they supplies to really useful starting with truly cheaply and so we start with polyethylene glycol as our central block how key building block is. Up which is dirt cheap we love things the cheap but it carries a lot of functionality it has the POC side and it has the alkane Typically this is used in industry put through the keen to give poly sides we're going to actually turn it around and we're going to do ring opening pluralization initiated from the polyethylene glycol all the Apoc side to give these I B I try block Coppola's in which we have terminal units that have a lot of alloy units so a lot of double bonds that we can secondarily functionalize So this is going to be a common starting material and as you can see here we can control the molecular weight we get low poly dispersed the materials the polyethylene glycol is cheap and the. Thing is also very cheap we can actually make this on multi gram Scouse I think our largest scale is about two hundred grams because you don't need solvent for this pluralization And so this is a bad is easy to get you simply take your SIL ether add it to peg in the Plumber zation the Shiites when you have the potential potassium salt. And so this is where chemistry comes in because now we have all of these Hello units along the backbone we need highly efficient chemistry to functionalize those we want to put a lot of function different functionalities on without protecting the protecting chemistry we also cannot purify these functionalize try book Coppola miss so we need efficient chemistry that's compatible for a lot of functional units and again this is where the concept of click chemistry comes in and I took this from the total of M.G.'s two thousand and one paper where he and Barry introduced this concept of chemistry and this pipe I don't know whether you've looked it up recently has been signed to approaching ten thousand times and so you know this is probably one of the highest cited pipe in the last twenty to thirty years and so this is really impacted a lot of people in this really impacted all of the work that I'm going to show you the softer noone has also used other click type reactions to put together the materials it really is so simple that I am hoping now that Natalie has left Imperial College that she will become a synthetic chemist and stop making all who materials with chemistry OK And so we exploit thought Eileen chemistry as you can appreciate to functionalize all of these units and again it's a quantitative reaction and as I show you we can introduce a wide variety of functional units with that protection D protection chemistry so to cut a long story short we made a whole lot of different materials where we had different cattle ya Nick units and different and ionic units and then we start to mix these to see whether we see any impact from not only the number of groups but also the night of the on the ON IT groups and so again cutting a long story short when we have these tribal Coppola misfunction Elias with primary amino groups all come to groups you mix these together in water nothing happens you don't get any increase in viscosity and so there may be some association but it's not leading to any useful properties. When we swap the casket with the SO FUNNY tested you get a slight increase in the scar city but still it really is not a useful increase in performance and so it's only when we go to the going to do any M and the cupboard Cassatt that we actually start to get so we're making a hard job but in this case it's really soft. Has the mechanical properties similar to Jell-O. and so it's not it's but again it's not going to give us any of the mechanical performance that we want only when we go to the GO ON A Deanie M and the SO FUNNY Cassatt do we get a tough Jill that actually is I'll show you in a second is so tough it's actually hard to cut it with a rise of blight and so the difference in physical properties simply biased by choosing the groups is really actually significant and we will stop to see that we can go from something that has the scarcity of water to something that you can't cut with the rights of blood and so the other thing that was really surprising about all of this in retrospect maybe we should have expected it we didn't expect all was how quickly this. Is And so this is an experiment the Jasmine was doing we have one wait percent solutions of the Caddo on it try block and the an eye on it try block in water there's simply different colors because they have Ph indicated in them Jasmine sucks up the gun a dinny a material and by the time she squirted it in to the end on a try block and mixed it it's jailed these things exceptionally quickly and in retrospect this is understandable from two reasons. The muscle is not going to wait around for die for it's coercive to form it needs to survive so it needs to do it quickly and we're talking about ionic bones and so they're going to associate very quickly as well and so we were surprised that this form so quickly but the thing that was even more surprising was one when Katie looked at the structure of the system so this is the you can think of it as the crude Hydra Joe that we form when we mix either end on a concurrent try blocks that have a middle polyethylene glycol of ten K. twenty K. or thirty five K. together and then looking at the structure that you get that is immediately form so there's no one kneeling here this is the structure that you get and you can see that for the ten K. and the twenty K. especially we get very long range water out of these systems and so we get these assembling into these spherical done mines and then those domains assemble many many orders of repeats so that we have this cross-linked but not chemically cross-link hydrogen where the matrix is ninety five percent water it's wall and polyethylene glycol and it's held together by the spherical CO S of a domains which interesting really somewhat hard to fill it. Somewhat hydrophobic there about thirty five percent water obviously not saw a balloon water but so show you they do have enough hundred felicity to soluble lies small organic molecules which again we've used for drug delivery system so this was really surprising that they form with such a high degree of long range order the other thing that was interesting was that these samples extremely robust not only to temperature but to also on it content so many systems use ionic screening to stop coercive bone formation in this case you can see that as we prepare these hydrogels we can choose in their performance by choosing the number of oil on it groups in each domain but also by swelling them in this sodium chloride or hot water we see very little change expression as we go to D.P. thirty and forty and so seawater is much less than one mole a sodium chloride but this shows you that even with that high degree of salt that these coercive domains are stable under these conditions and we don't screen on a CLI the bonds that form the bonded interactions that stabilize these hydrogels So the one thing I insinuated a number of times already is the degree of control that we have in these systems so as I said before we have a common starting material so that we can match the number of oil and groups but we don't have to do that we can actually do a mismatch so that in this case we have had on it try block and we mix it with. Really decreased amount of the and ionic try block and then some I honestly will and ironically chacha small molecule Kaga with the idea that hopefully these will form a hydrogen but incorporate our desire. Into the CO S. of A domains and release that over time so think of this as a delivery system for a range of different charge materials the other thing that this in C. This implies is that if we could make this into a mock or Jill it may actually be more easily implanted into the body or taken through the G.I. track and so that's exactly what we wanted to do in this piece of work we wanted to answer these two questions can we include go and can we make something other than a slab of hard to chill and so to look at that we turn to. Michael fluidics. The idea being that we have night Paul and it dissolved in water going to Denny and Palmer dissolved in water and in a model fluidic device and taking advantage of the really fast speed these things jail can we simply make spherical particles that during the residence time in the model fluidic device will actually Jill and become stable and again I want to really cut a long story short and in a mixing channel that has arisen this time of less than a minute you can make these spherical particles that you can collect in the outlet and these are now stable they are held together by the CO S. of a bonding they do not clump and this stable for long periods of time and we can also form these in the presence of various Cod goes I. Cast the. Self on a castle and a tryst so funny casts that you can see here that the model for the way the device actually really does allow us to control the diameter all of the big pot of coals and in the and then our skull Picco S. about domains we can get fairly high loading all of these. Up to twenty percent and then these Cod goes can be released over time and they release right as you express it is really dictated by this structure the more I own it groups the slower that there were at least so funny classes are released slower than comp oxalic acid so you can really showing your release profile based on the structure of your car go and the structure of your original try block. And so that was the stories I wanted to tell you using direct mimic of the CO S. of a formation where instead of peptides way using synthetic Palmas but night is somewhat limited the muscles can use peptides pick tides or peptides but as synthetic chemists we're not limited to organic materials so this is one project that we did in collaboration with. At the University of Tokyo where we asked a simple question. KNIGHT You cannot use inorganic materials they limited to peptides as I said can we actually start to use in only inorganic materials and actually Mike hydrogen that has significantly different properties to the organic one and it's actually quite simple to do here we have the same carry on to try block that I showed you before polyethylene glycol made block one a D.M. groups at the end and instead of using the corresponding N.O.I. on it try block we're going to use an eye on it client in a sheet and so the idea is that we're going to have the trouble of Palma essentially act like a bind up binding to the surface of the clay sheets and bridging the clay sheets to again give us. Cross-linked hydrogen but you can now think of this is being plated since instead of purely organic systems we now have these very stiff clay Nana sheets in these materials they are transparent because of the dimensions of the client in a sheet but we do see a significant improvement in performance for the all organic system we have G. prime and D. double prime a random ten to the three tenths of the four in this case we got about a two orders of magnitude to three orders of main chute increased in G. prime and double prime by simply using the client in a sheets instead of the polyethylene glycol based try block Coppola as I said before you know these things stream Lia robust This is actually a rise of blade and you can see that you can put a significant degree of force on the rise of blade and it's not cutting the hydrogen even though the hydrogels about ninety seven percent water the other nice feature is that these materials still have the robustness that you would expect from a organic harder job and so these are really interesting materials one of the things that your highness and Jeff was able to show is that these are robust These are tough but remember these are not covered systems so they should sail heal and that's exactly what they did they looked at the mixture of these catatonic try blocks the client in a sheets and it's a real study where they look at the real they then. Put a lot of stress on the system we get Strine we get recovery we constrain and again it recovers we constrain it again and it recovers and you can see that the self healing or the recovery time is again very short that's tracking the quickness that these materials are formed by and we recover to approximately the same properties that we saw before this is really kind of easy to understand again biased on the fact that we're using on it Bones which if you pull them the pot will find each other again and really heal and reform and so we did a number of cute little studies with to KUSA where we cut things we put them back together we D. swelled and then REESE Well and so again these have really good self healing properties driven by the fact they're not bad not based on cross links that based on physical cross links and on and on. And so that was the first structural motif that I really wanted to tell you about today the second structural motif is really based on some chemistry that that will brought to the table and so again very cheap starting with truth about Yes So so this is the this is the before picture. This is the after all flicks picture OK so I won't be selling it outside off of the lecture and if you just feel you if you buy one you get the second one free OK and we'll throw in shipping so so if you look at that cattle call group a really nice functional functionality but doper itself is extremely expensive and so we wanted a much cheaper functionality that allowed us to access these cattle call units and huge an all or clove oil is as you can see really very very cheap also makes the lab smell on believed to be good and so this was the starting material that we wanted but from a synthetic chemist viewpoint you know it's a bit of a challenge we have one free phenolic group one protected is the metal ether it does have the a little like double bone that we want so it's almost there but it's not really there and if you look at all the protection the protection chemistry is a valuable nothing really worked very well but will come along. And took out the next slide OK So we'll come along and I was going to promote some of what Will's other would just looking at again using cheap styling materials in this case saccharin to build quite complex macromolecules but since Will's been nasty to me I'm going to pos over this work and show you again a photo of the younger will and so this is the chemistry the Will brought to the table that we can take you to know and treat this with a variety of different sidelines in the presence of this Boron trist pencil Fluor fennel catalyst is a room temperature reaction no solvent Natalie could do this really easily and get very very good yields of a protected derivative so we've not only got rid of that method which is rube although we've protected it we've got a quantitative yield we can do this on very high scale it's a room temperature reaction and now we're perfectly set up to start incorporating this building block into a variety of different poll America's systems and have the. Catacomb very easily obtainable by simply as a deep protecting the SOL. So again one of the chemistry's that we've used a lot is the thought I'll addition to this double bond with a lot of these sawlog same derivatives that have thought all groups off the back burner again we can vary the number of catacombs along the backbone the molecular weight of the backbone this is all quantitative chemistry that works very well and now we can start to use the excess thought well to cover cross-link these systems so in this case we use some thought I lean cross-linking chemistry these are all well studied materials and if we add shootable amounts of this thought derivative that has the chemical units we can actually functionalize silicones where we have controllable amounts of catacombs just waiting there to be exploited. We treat this one facet we protect and now we have these that he is the groups that I told you about before that who was able to show really had he had strongly to surfaces and so just to prove this if we look at these catacombs surfaces and compare them on so essentially we make a pure chemical surface and then deposit these gold squares on top if we go across this and measure the IT HE Asian to a silicon dioxide probe as we go across it really correlates very nicely we get stronger he Asian where we had to catapult we get no wood he's in where we have the gold we can do a similar experiment way instead of gold these Nandi protected had a coals and they get very similar behavior only when you have to cut a cold do you have the to the oxide surface and so these are just some pretty experiments that we decided to try where we take silica we functionalize them a stamp with the chemical units and see whether we can pick up these beads and how strongly these beads are and he had to the surface so these are silica be aides and we've fabricated these little. Cylinders and we can either have protected catacombs at the surface or non protected free catacombs and just to cut a long story short when the chemicals are protected you can't pick things up but I was very very easily because you just use ing Vanda Wells forces to pick it up but there's nothing really sticking the beads to the Pillas But when we have the freak out a cause even when we all just on the Cape these the beads a stuck to the catacombs units that are on the solid sign pillars. This actually then starts to allow you to think about capturing things so imagine you have a surface where we have predefined areas that we have had a coast and other areas that we don't have had a cold can we simply flow a solution of silicon beads over the top and start to capture the silicon what is delicacy of capture does it happen everywhere we have Cata calls or only occasionally so that was the experiments that decided to look at this is has stamps if you can capture the beads with really high fidelity and even very very small structures so these pillars that as you can see are about five mark crones in diameter the surface of these have the free Cata calls and again these capture the silica be by simply flowing over the top very very easily so the final thing I want to show is that we can actually now use these Catacomb as well as the CO S. of chemistry to actually make some and he's lived very much mimic a marine organism and the marine organism the sandcastle wombs which are found off the coast of Santa Barbara and they're fascinating creatures that form the habitat to protect themselves from predators and so what the animal does and you can see it here it makes these choose by simply taking sang grains rubbing it on all going in the chest and that organ then puts a little bit of it he. That is based on coercive chemistry as well as Quetta calls and then sticks those saying grains together so that they have a little Ahmed helps in amongst all of the end of the animals that want to kill it. So. And I should say I was not involved in these experiments at all but. Stressed the same cost a woman out by making them build their houses out of spherical silica B. instead of saying grains this really stresses the sand castle rooms and they want these irregular. Sand grains if you give them the choice they will never pick a spherical silica particle might have something to do with the mechanics into locking but you can get them to use spherical particles and you can see here the little bit of glue that they put and used to stick the silica particles together so this is how the same castle works and this is the set of experiments that in June why did she talk to silica bees that I showed you before and then the Cata called Paula again that I showed you before and simply had a solution of the two so that the silica particles had here some of the catacombs which undergo deep protection in solution to the surface and now she has the silica particles that have these cattle call groups that have additional Cata calls as well as freeze thaw oils attach to the surface she then takes these B. and one by one puts them with the surface coating into a solution that let me get. That has ten million dollars of sodium pariah date and this is two. Stott cross-linking chemistry that night she uses nature uses an oxidative chemistry as I'll show you a second to cross-link up the particles and the chemistry that we've put on the surface and so she does this one by one and slowly but surely builds up the cylindrical habitat that is very similar to what the same kus a worm does and again you can see here the secondary chemistry that the sodium Polaroid they initiate that allows us to stick the chains together which in turn stuck to the surface of the silica particles and cross-linking is absolutely key for the stability as is the presence of the free Catacomb unit so this just shows you an image of the cylindrical habitat that gene while was able to make the same class a womb is actually happy to live in there but the key is that in the absence of pariah date or if you get used protect the catacombs you cannot make this habitat at all. With just the slightest knowledge and the same Casa womb will also as it goes in and out will destroy it and so this was really nice example of not only using secondary chemistry but was an absolute expert with chopsticks and I tried that with that was how she placed the be in the solution I tried to do this and I could get up to a bet to lie and everything just fell apart and so this was really nice use of that chemistry again inspired by the marine organism so in the last five to ten minutes I'm just going to tell you a very short story about some structured nanoparticles again inspired by marine organisms in this case the cuttlefish again that's a strength of Georgia take looking at structured in a particle and structured and functional particles we're going to take advantage of particles that is somewhat similar to what Todd looks at with respect to having lie is in this case these generous particles we're going to try and make particles that have more than one law is and so this was inspired by a collaboration with Dan Morse who's also in the Marine Sciences Institute and then has been studying for a number of years cuttlefish which are absolutely unbelievable with respect to camouflage this is what the cuttlefish looks like when it swims normally when it settles down on the surface you can see that it mimics what's underneath that. Almost perfectly Hal these animals do this no one really knows but what they do know is how they choose the color on this surface and it's done using these specialized sales called really a full cells which I'm showing you here and if I just showed you this photo with that telling you that these are Radio four cells and you are in the poem a science community you'd say well that's a Lamell a die block obviously they're not what they are protein platelets that a separated boy extracellular space there's a small we frac to in the difference between the protein and the extra So you'll fluid and what the organism does is it just swells the protein platelets by a very small amount but that amount is enough to impact the brag reflection which allows it to choose the color so if it wants a dock it colors a little bit more light a color it doesn't swell as much and so these this is how these cuttlefish and a lot of other marine organisms actually do camouflage and so again we wanted to see with that we could learn anything by translating this to synthetic systems so I'm going to go over this relatively quickly as I said when we look at this we don't see Radio four cells we see the M L A die block Coppola MS So when we wanted to make instant that equivalent of this we thought can we make spherical or ellipsoid shaped particles from a block of Palmas have them face separate to give us the M L a dog walker problem is and then we can can we swell those. Block of pollen is one of the biggest challenges that we initially had was to make ellipsoids an ellipsoid. Orientation of the dog. For a number of years and not lying a number of years we looked at taking solutions of dog block of polymers evaporating them down to give us and in every case we've got spherical particles and as you can see they have a structure like an onion exactly what we don't want and so we were stuck in onion land for a long long time and everything we tried gave us onions and SFI is and so at the same time we were doing some work with crime up and a post-doc of he is looking at the control of block a poem is in thin films and we found that specifically functionalize gold nanoparticles really aligned at the interface between the die block a poem is and allowed us to control the orientation of those dog but cupola as in thin films and so our idea was pretty simple can we use the sign tile of gold nanoparticles and turn these onions into these Lamell of footballs. To cut a long story short it works we get not only our lips oids but we also get this Lamell orientation of the die block PALMER The problem is that not everyone wants to work with gold and it gets pretty darn expensive but this did showed that not only could we get the ellipsoid but it was really about this interface between the surrounding solution and the two Diable Coppola MS because you can see that the golden in a particle's all at the surface at this interface so that told us that we only need a small amount of material to turn it from being a sphere into an ellipsoid and so traditional So fact and don't work this was an absolute disaster until Daniel and Cynthia asked the simple question well it's probably because we're using once a fact that we should use a mixture of so fact it's one that locks polystyrene and one that locks Poly to volatile period in the mines in polymer if we do that maybe we will get this preferential interactions and again we stop with the c tab commercially available we get on humans if we make a very small structural modification so we have a hydroxy group at the end of now I die Ethel version of C. tab we still get onions but we get the opposite. So in this Anya we have polystyrene as the external layer in this case we have poly too volatile period in the external layer so think of this as white and think of this as black hopefully by using a mixture of the suspect and we can get some color of gray in which we don't have. We have these ellipsoids And there's actually exactly what Cynthia and Daniel did we start with onions somewhere around about fifty percent we get these really funny odd structures and then between about seventy and eighty five percent we get footballs and we only get footballs and they were thrilled and I was actually even more thrilled since it actually worked out that when we go even higher we get back to onions so this logical argument that I've told you before that a version of grey. Is exactly what we want and we get that grey by mixing two relatively simple so fact insta get that we can do this with a variety of different molecular whites so we can choose the thickness of these. The next and final thing that we needed to do was to swell and contract the spacing so that we could start to choose the Bragg reflection and this is where a good friend of will burn came in handy because burnout again brought very simple chemistry to this which solve this problem and so this is the problem that we have these ellipsoid particles that composed of polystyrene and Poly to volatile period thing if we swell these in acid they fall apart because the poly Tuvan appear again is predicated it becomes water soluble and so these water and saw uble ellipsoids that we spent so much time making full of pot and give us the individual polystyrene this that made up this for so we've just disassembled the whole structure so this was not good but the solution is really quite simple what we need to do is to cross-link Cavalli cross-link the poly Tuvan appear again to stop this total destruction of the particle the cross-linking chemistry is very easy we borrowed it from Karen willies group you simply expose these ellipsoid particles to a viper one for dive Bromo butane it outta lights the volatile period in units we can control the level of. Aggregation and cross-linking to control the chemistry and now we have. As you can see in this example ninety five percent of the vinyl period in units free that are available for proto nation and hopefully by proto ending that and the fact that we've now cross-link these to make a hydrogen will be out a swale and D. swell these and these are my last few slides this is what we get from twenty five percent cross-linking you can see that we start to change shape and then if we go down in cross-linking level to five mile percent now we have a much better ellipsoid shape we take these materials we add acid and we swell the Poly to volatile purity and law is but because across linked they don't fall apart and so what you're seeing here all those poly starring disks that I showed you before that it's now just like an accordion nice way O. and contract swell and contract by simply predicating the vinyl period anes or the proto naming the Vaio vinyl perience we can go from ellipsoid to very elongated ellipsoid and back by simply controlling the ph out Plimer area work does show that you can control the brag this is about as basic as you can do and compared to the cuttlefish I hope you appreciate that if we relied on this for Kemah Flash movie did in about thirty seconds but it does show you that we can take a lot of the inspiration from marine organisms and translate that into synthetic systems the key is efficient and orthogonal chemistry and hopefully I've demonstrated to you today how we can use simple chemistry to really affect the physical properties of a water variety of synthetic systems I like to acknowledge whole host of people who supported this work the National Science Foundation through our materials research lab down and mystic bitchy chemical was also a big supporters and contributors to this research I took to our talk a lot about collaboration and really driven by Kramer and Glen Frederickson who Dan Morse to Koos and Knight And finally I'd like to think Miller pour sigma one more time and all of you for your attention the soft and thank you. So let me repeat in paraphrase the question I made the point of the fact that we had the same starting material so we could have the right same number of an eye on a groups that was so that we could really understand the system so we when we went from you know twenty to thirty to be forty we really knew what we were doing if you don't critically balance you get materials that have properties that are slightly less than the ones that have the correct matching. And so you can think of is as almost a bell shaped if you too far off you start not forming the CO S. of eight or and an extreme examples you get a precipitate And so it's important to balance it but it doesn't have to be balance perfectly and that's what also allowed us to have cod go in there and so these co estimates do have a significant amount of leeway you can't push it too far but you don't have to have perfect balance we just like this system because it really allowed us to compare apples with apples rather than apples with oranges. So again let me repeat and paraphrase the question when we made the micro particles using Michael fluidics And again you know using some cargo How did we stop. And clogging of the market fluidic channels and so you might have noticed they would. Fourth five things coming into the mixing chamber there was some water the cut on it polymer the palm and then some silicon fluid and so we were forming the. Droplets surrounded by silicon fluid and so by having that done correctly you can get individual droplets and then by having the residence time being approximately a minute you gave time for those droplets to solidify. Fully cross-link So when they came out the end they didn't Glaum up together and also by having the individual droplets He also stopped. Cross-linking in the channels when we didn't do it correctly so that instead of individual droplets we might have had a little bit more you know tool three droplets connect together that clogged very rapidly because then it just formed this mass and that mass wouldn't go through the mixing channel mode so I didn't point this out but you use your silicon fluid to actually isolate the individual who is droplets so all of the assembly. In that droplets and that droplet can travel through. Charge complementarity is yours yes. Yes. Thermally. Rapidly is that. Why you range. Things together because it. Is able to relax. You know that's the way the less was that I know I saw again the question and what was. You know how do we get this long range order and is that the fact that these groups you know reach a thermodynamic minimum easily is that what gives us the long range order naively as a synthetic chemist and add in Glyn would probably argue with me but I that's the way that I think of it that it's enough freedom for all of these Chinas to find the time and then at minimum and space each other because they want to get all these Co S. about domains want to get away from each other and so it gives it enough time to actually. Achieve the long run short and my and also if you notice it at thirty five thousand molecular Whitehall you think like it didn't really get long range order and we think that may be due to the fact that now we have enough spacing so that the domains are not influencing each other as they do when there's a shorter polyethylene glycol or it might be. Changed. But the dynamics of that system. So. You can see one in which. The So So the comment was do you get exchange. All of so if we do a thought experiment I make my hide to Joe with normal catatonic try block and ionic trouble then add a solution of a fluorescent Lee labeled catatonic try block and let it cool a bright will I see the migration of that catatonic try block into the system the answer is yes but it happens incredibly slowly and that right of exchange is dictated by the number of groups in the little in the mines and so if you have short enough ones the exchange is somewhat rapid as you get to say D.P. thirty forty this almost becomes glacial time frames and so you do get exchanged but I like to think of it as as Velcro if my velcro strip is long enough it's really high to pull it all off that wants but if it's short enough you can do it. Later. What. You're. So the. Question was when we looked at the cargo release. You saw almost a bush just release and then a much slower release we're not sure exactly what's going on there we think there may be some cargo that is more on this on the interface all of the quests evade the mines and some that are more interior to the domains I'm not so sure I'm a big believer in that because these a very small done mines and so. It. Yeah and so from a from a dragon release viewpoint. I don't think these at the present point in time have the right release characteristics to be of any great potential use. It's. All. Right. So. QUESTION Was We can think of a lot of really interesting other sofa same beliefs strategies braced on both the catacombs as well as a on in groups we haven't done much work in the area but Rohan has done an enormous amount of work in this area and you know if you look at some of his work you know you can exchange a lot of interesting things into these type of systems. Now. It's just. A little more that happened Bill. Like you this beautiful blue crystal thing. Thank you everyone.