So today it's a pleasure to welcome Professor Paul Rousseau Paul got his bachelor's degree at the University of Wisconsin and then did his Ph D. at the University of Minnesota in chemistry and then did a post stuck at U. Mass in polymer physics he spent thirty years at the State University before coming to Georgia Tech in two thousand and fourteen were he is the Hightower chair in materials science and engineering with an adjunct position in chemistry and biochemistry and. Generally his research areas but I would say broadly soft materials. But you'll see his title in abstract do not mention the word nanotechnology nano anything but don't be fooled there's plenty of nanotechnology I promise said Paul. We'll talk about that a minute this week. We're. Good. OK that pocket. Well thank you for attending I have come to these lunches a lot of times and I often wonder why why talks why come to them why give them we'll talk about that a little bit if you didn't get one of the little handouts try to grab one I apologize that they're on such so much paper I forgot to ask the secretary to print on double sided she could have reduced the font too but anyway that's a good thing and we're going to talk about that a little bit. So. Of course the work I'll show you isn't anything that I do. I don't know what I do I would say that I answer email but my students would say no it doesn't. So anyway singling out probably that what you'll see today the people have done the most are DR CONY Rose who and John who will be Ph D. here I don't know within the year certainly I hope. But why go to talks Why do you go to these talks of course there's the free pizza that's a good thing but I think mostly I go to get away. And to be alone with my thoughts and you know maybe something off most is through just accidentally and I learn something and leads to some new thought I don't know. But this handout that I've given you is article by David Mirman anybody know who mermen is. MIRMAN is sort of like the Richard Feynman of upstate New York he is the National Academy member in physics and he has a whole series of wonderful articles. And they often start with what's wrong with I Want To my favorites is what's wrong with those awards you know and that's really funny because you can read it if you don't know who he is you never figure out is he an award winning guy or not he is. But this one is about what wrong with those talks and what he says is you know every talk I've ever attended in forty years of going to talks has been too hard so we'll endeavor not to do that so there's no point in telling you try to make it simple because if somebody could have done it they would've. So will it will still try OK. And your your goal is to strive to place as far as possible from the beginning of the of the talk of the grim moment when more than ninety percent of the audience is able to make sense out of less than ten percent of what you're saying. That's. Kind of a bad thing so the best reason to lecture on your work is that it affords you the opportunity to rediscover why you did it you know we forget why that is we forget in the middle of what's going on you know the order that didn't come the instrument that's broken. Filling out for the fourth time my. Request to pay the things and I say we've paid it and they say no you have it stuff like that happens anyway so you know you do have the opportunity to sort of rediscover why you did it why we got excited in the first place and he says this is funny there's always a risk you will not find an answer why you're doing it what is there to capture the imagination. Of somebody who lacks your specialized skills and he says Give yourself a week well I gave myself a weekend but I spent most of it skiing so and I have a sore knee the only reason I'm able to do this is all of my knee was to store to ski the third day and so I was able to quote unquote prepare. All right so what I will do at the beginning since I think some of you don't know too much molecular things is talk about proteins just in the most general of terms so you have something to go on at least to get imparted a little bit of knowledge about that and then we'll move on to an example of a particular protein that is somehow affiliated with elm wilt we have one that I know of beautiful American elm tree on this campus and it seems to still be healthy but a lot of them are suffering then we'll talk about how that protein has to be used to encapsulate P three H. T. which is one of the polymers used for semiconductors of type applications and then we'll talk about mimicking that kind of response. Using synthetic type polymers OK. So very quickly a little bit about proteins. So. You know when the I remember when the Nano revolution came was mid ninety's right. Now Gar invented nanotechnology. Just ask him he did so well the rest of us many of us in the polymer field in the protein field was like big deal and it's always been about nanotechnology. It to get all these functions that you see up there enzyme could tell us a storage movement munity OK to get the ninety percent of what cells do takes a molecule of a certain size and sophistication and that size happens Biggins happening really at the national level. OK so I don't know if. This was my slide from one of my former colleagues insula kata back at Alice who I was and like his slides were going to use them. But. You know says that they perform a greater than ninety percent of the work of the cell the only other thing I can think of that's not there is replication. And so I don't know about you guys but if you're spending more than ten percent of your time replicating good for you. But anyway I don't think cells do either I think it's really closer to ninety nine percent of what cells do is proteins OK The rest is the replication part with D.N.A.. OK so the only reason for example to highlight one of these things enzyme could tell us if you're eating this pizza and you're going to burn it and nobody is going to self-immolating nobody's going to go up in flames we don't have to have a spark plug we don't have to have any energy and that's because the enzymes in your body are lowering that energy of activation to the point where you can burn that fuel at a comfortable thirty seven degrees centigrade. Very handy All right so just a little bit about the proteins they're made up of amino acids OK which are chiral molecules which means they don't have to have a certain symmetry we don't go into that and they are so I don't know some twenty of them naturally occurring once more than that. And they're all the same molecules at the backbone level across the backbone they're all the same but the side chain see this thing here is a hydrogen Whereas you look over on this one it's a mouthful group and that's a different thing totally hydrogen versus metal so you have like these you know twenty twenty five whatever choices of amino acids. That you can put together and to make a protein you do have to put them together and form a peptide link so there's a peptide link one of them being formed a bond being four minutes a pretty strong bond has a particular kind of geometry to it. And that's just a dime or that's two amino acids together if you want a little bit more function. You can make this here's a pen to peptide with Terri saying single I seen Lucy and I guess. Anyway so. You can make these and if you start thinking about it. If you have said that you say twenty natural Mino acid just to make the math easy each of those could be a choice of twenty twenty for the first times twenty for the second times twenty but I could make a lot of different. Different proteins just by varying the sequence OK in fact basically it's an infinite night I'm of possibilities of what you could make and that's what attracts me to this kind of field this possibility the possibilities are endless Of course nature has made a lot of the ones that you need already right but we could make other ones additional ones if we wanted so that's kind of interesting so the language of it is that you know if they're usually call in. Peptides if they're less than about fifty OK And that's you know you can make that on a machine we can now make those in the machine. Proteins are usually you know if they're bigger than fifty repeat units fifty different amino acids or fifty repeat units and then we start calling it a protein for sure that's kind of a gray area there when they convert from peptides to proteins who cares. Primary sequence is what really determines the sequence of the amino acids. Well one of the other things that can happen is that chain can grow to a certain size and it can have this this group here is cysteine on it with the ends and SH If you oxidise that Sistine you wind up with the steam and you have this dye sulfide link and so that lets you cross link to change so you can actually connect to growing chains like that and in fact they could be the same strand that has kind of came back onto itself and then gets cross thing that could happen OK so here's an example of insulin which was sequenced about the time I was born. Little before that I guess and so we've known how to make the sequel how to determine these sequences for a long time and you can see example here. In try and sulfite link and interview to enter strand planes right. The other thing you need to know is that these things fold in a certain way they fold in a certain way so these strands grow and they fold and people worked out the energy map for what's likely to happen and one of the things likely to happen is helix and the other is called beta shit which we'll talk about now so here's the helix OK so one of the things that the chains can do is sort of wrap themselves into the spiral staircase type structure of course that's a sort of extended structure once you do that it's a sort of long extended structure in terms. It's very rigid too in terms of bending rigidity it doesn't have much. Extensional modulus but the bending modulus So that is pretty high as molecules go. And differ Eppie's intentions of it are shown here here's the same thing basically this is looking down the helix from one end it's wraps around it around. So one of the things that the other thing that you can get is the thing called a beta sheet OK So this is come Times called a pleated sheet as in you know pleaded means it means like you've sort of iron in folds like a pleated skirt or something like that for those who remember wearing skirts. Anyway not that I ever wore one myself but anyway. It's sort of a pleated structure can be obtained in this way so here is a chain growing off in this direction and it has this kind of connections here which are held and here's one that just sort of loops around and makes a fold and these things are kind of stiff and rigid and difficult to dissolve in. So if you take bovines Fairmount human and you are to make it into an alpha helix take the five hundred eighty four residues this is a high protein that's very common in cows you have it in You Tube but yours is human serum I'll be human. And anyway if you were to take it in stretch it out put it in the helix it would be about ninety nanometer so long if you were to take make up beta sheet one way and then pleat down the other way just up here and then just fold it back two hundred enemies what it actually is is much more compact Actually I think this numbers wrong I got a pocket recalculate that but but it's certainly possible to have it be a much more common compact structure and I know a lot of you metals you know I was surprised coming to Georgia Tech I'm trained as a chemist now I'm in this material science department and the amount of effort they put into things like crystallography just blows my mind you know studying a barium die for items studying trying to get the magnetic properties out of this and all these other things with these tiny little crystals OK but it's not often realized that you know a big things make crystals too and proteins can be crystallized at least some of them it's not an easy thing the ones that we'll talk about it pretty difficult but this is an example of a diffraction pattern so imagine that your unit contains not something simple like barium in a couple of forums but hundreds and hundreds of atoms Thousands of that it's OK And so you can actually work out the locations of all of those OK and obtain structures. All right so we're bready that's your introduction to proteins we're ready now to talk about this example of one particular protein Elm welt protein. OK And it's actually a member of a class of proteins called hydrophobic. And hydrophobic we think our major is most surface active proteins OK So surface active means that they go to the surface and they do that to minimize the interaction energy of one part of the molecule with water OK so the hydrophobic ends there seemed to be about sixty or seventy of them I am not sure we have an exact count. One of them that has been crystallized as only a few that have been crystallize one of them is shown and what you need to know is that there are groups. Down at the bottom of it are hydrophobic means that they don't want to be near water and the rest of them are hard to fill it meaning that they do want to be water and you see some die sulfide links in here holding this thing together this is not a very large protein and molecular weight so a ten thousand for the hydrophone that's not very big OK but they all have this conserved pattern of the dice all fly by two. Hundred sixteen Fordyce all findings and in a small molecule all that much stuff holding things together is kind of. So they're very rugged little molecules you can heat them you can beat them you can let's let them sit in solution in the presence of other bugs that don't eat them you can do all sorts of stuff and they just remain functional for a very long time and they always have one side hydrophobic and the other side how to fill it. OK And so the way they're like little natures Jane is nature's little Janus particle some of you work very hard to get one side of a particle different than the other side but nature does it in these hydrophobia ins. Like I said they're they're made of mushrooms and mushrooms make them other things make them. From that family. This is a picture of some mushrooms in a New York store I just took to send to my son because he gets he's revolted at the sight of mushrooms actually. And this one speaking of revolting I came out of the first center you know first place George's idea of dining. And. Well I saw this piece of insulation from I thought it was some construction foam they left over on the ground I was going to go pick it up and throw it into the garbage because it looked like a piece of that Great Stuff foam you know you've seen construction foam I thought I just picked it up it looked trashy on the campus and I got there it was a mushroom and that's my foot in the image there you get an icy idea of the size of these things well one thing you know about mushrooms is they really struggled up a boom they just grow right so that much growth creates the need for a lot of surface quickly OK when you grow something that fast you're creating a lot of new surface so one of the reasons people think that mushrooms make hydrophobic is to lower the surface tension and make it easier for the surface to be generated there are other reasons that people think they are formed but OK so I already kind of told you this there are actually two two kinds of hydrophobia So this is just showing the conserved pattern of I saw five links OK. This one is a picture of where I used to spend my summers. In Minnesota let's see Protestants buried on this side and Catholics buried on that side that's you know they have a segregation issue there too. But anyway look at the trees these are all elm trees and they're not healthy you see him at the top of that there canopy is greatly diminished and it looks like the Protestants are suffering more in this case. Anyway. The fact that this protein his made and it's actually carried to the tree. On a fungus in the fungus is carried to the tree on a beetle that's the problem and it's been implicated in the death of these trees there are other factors that intervene but it's definitely true if you take this hydrophobic protein the one that we deal with is called Serato omen Means Elm OK So Serato omen. In is implicated in if you take purified throughout omen and just place it near growing and almost seedling it will die so I mean it's definitely lethal to the trees it's not clear that that means it's the only thing that's involved in the disease. I'll draw your attention to the way the wind is blowing here you know obviously it's summer in the summer the wind blows like that from the south it was winter be blowing just as hard from the north and be really cold. All right. Well if you take some of this strata Ohman protein and you purify it and you just. It doesn't really dissolve in the usual sense but you can put it in the presence of water and you agitate slightly you'll see that there are all these misshapen structures OK sort of cylindrical type structures here this is in the presence of just you know water solution of the air on the top and you disorder of mist agitates like you get these things. OK And so actually those are bubbles. And you all know that bubbles around bubbles around to minimize the surface tension right but these are bubbles that clearly are not round and it seems like a really remarkable thing until you think differently imagine a straw plastic straw all right and I pinch off both ends I've made a bubble right but it's still not going to be round why because the surface of it is a solid basically it's plastic solid So what this is really telling us is that the. So I don't know molecules go to a surface the air water interface and get to be solid like solid like at that interface OK now you could go instead to in water oil interface and here we've taken oil I think cycle hexane I can't remember and we've added a little dye to make it very visible. OK And you again get these sort of misshapen structures OK this so if this route a woman was behaving as a fluid interface that would have to be around well you can force it to be round you can sort of Kheta and then that adds enough energy and it makes it around and this case we've actually trapped the polymer in the polymer has jelled if you can see carefully enough here you can see that these structures are really round but one half of them is filled with polymer that's kind of the face separated out in Joe. All right so that understanding these bubbles has been sort of a lot of fun to for us to try to do. And let's see I think here if I can I think I have to his game and then if I'm very lucky I'll be able to make this go. Let's assume that it's going to go when I get there I've got to set up for us this is a picture of some of these air bubbles cylindrical air bubbles and what's being plotted here is the pressure over the solution so this is starting off at atmospheric pressure and we're going to go down. In pressure OK So what happens to a bubble if I reduce the air pressure above it. It should expand right so you'll see that they expand and then we're going to go down down down and then we'll come back up and you'll see some funny things happen. Let's hope that it really plays it's playing OK good now we're going down in pressure see the plot of the right is going down and a lot of them have converted to round bubbles some of them are staying. And the pressure is now we're going to start the pressure coming back up all right. And these ones are about the little ones are about to disappear look at this one here that I can't see look at the top watch very closely and see if you don't get a familiar shape don't it's right there. OK airfield doing it it's a dream come true very few calories. So I always have trouble stopping it at the right point so I will discard it in the slide which shows it see an air filter don't it. Now sometimes you go I know what you call a little done it sort of like figure eight you know the taste at a crawl or something anyway the sometimes you can get those it's kind of interesting. That's a new structure that we do not know why that happens and some people here are trying to help us understand that from a mechanical engineering point of view. Why that can happen and about I would appreciate especially from you guys who all have you know in creative minds most of you. What the hell would we do with a national gun OK it's an interesting natural phenomenon and we have some ideas certainly it's a high surface area compared to most other shapes that's nice possibly is image contrast I was talking to somebody this weekend on the ski throws about filling these here with a reactive gas and solidifying them OK you can talk about jelling things outside of them and then they would have sort of a different property in terms of acoustic transparency that might be interesting to some people but we just need more applications all turns out Susan John has gotten pretty good at making these things in their stable for pretty long time day they are more. And so now it becomes incumbent upon us to try to understand the mechanical properties of that surface so this is a picture from a paper that's just been accepted. That shows how we go about measuring the mechanical properties of those bubbles OK And let me set this up a little bit here on the left there's a pump and they can awfully you know pulsing pump pressure less pressure pressure blast pressure the pressure and it feeds a kind of a syringe you could think of it as with a very fine tip about forty microns I think and you push that inside this reservoir that has the solution that contains the proteins the proteins are in the solution and you can see there the. The bubble and here is an actual picture of it taken under Mike all this is under a microscope OK And you can just sit there and the bubble will change its shape because the protein is coming to it OK it's diffusing to it from the solution or you can oscillate and make the bubble expand and contract and expand and contract and it's you sort of perturbing it just like you would in a reality so this is really a surface for ya meter to measure of the properties of this film. OK this is a sort of another picture of what's going on here so here's a picture of a hydrophobia in the egg shaped particles with green hydrophobic regime those are going to align near air or oil I forgot to tell you back on this one here we've got it filled with air but you can just as easily put oil in there. And here's a picture of the bubble at the tip and you're going along and you're not you just sitting there letting the bubble sit there and then we turn on and off the oscillations and you can see pressure Australasia and size oscillations that go with it and you can back out from all of this information about the mechanical properties of this tiny little bubble. So here his example of static mode no oscillating the pump is switched off it's just sitting there and we're just observing changes to the shape of the bubble and this is the surface energy here it's right in line here we go. Wow OK We're looking at the surface energy. And it just goes down over a period of about an hour it takes zero proteins about an hour to diffuse to the surface there and change the shape and that's how we get the of the information about the surface tension and the inset here this little inset up here the inset shows you what would happen what happens if you reduce all the protein out of the solution remember the protein is in this reservoir and you can rinse it out just put in water and if you do that at early times after it's only been maybe. Eight hundred seconds there something like that it's reversible the surface tension bounces back up a little bit. But if you wait and try to that later it doesn't happen it doesn't come back up so what happens is that the proteins go to this interface and somehow strengthen and become solids OK. This is a kind of a compound picture of the sort of what else goes on here. Just to give you an idea of how this works the black trace up there is the. That is the. Surface tension and you can think about it that is the pressure being applied to the system if you want. And the pink trace is the radius and what we show down here at the lower left is a zoom we just zoom that you can see the oscillations that are turned on during this time and you. And what you see is that at early times. Very small surface pressures. Result in very big. Radius changes so small black curve oscillations are big pink curve oscillations so. You know even a little bit of pressure change results in a great big change in the radius of the bubble which means that it's soft right and then over a period of time it hardens at the end of this curve here we find that large. Pressure oscillations are no longer able to produce anything that we can see in terms of site change in size and now the material is has got hard. And you can back out from this the dilatation will modulus of this protein see the solid like character of this protein. OK well you can repeat all that in the presence of oil or in air OK so you can have air bubbles or oil bubbles or blobs. And what you see is that there are different in the presence of air there's a sort of long gestation period here where nothing really happens and then boom starts to solidify. Whereas in the presence of oil. Sort of immediately you start getting an increase and sort of slowly solidifies and it never gets a strong C. there's a different scale here for the red curve than there is for the blue curve so that oil films just never seem to get as strong. As the. Blue curse but having said that I will tell you that we think. Either these are sort of a lower bound on the actual strike and people have done this with other proteins a lot but these are record setting results these are the stiffest proteins that people have measured they are really quite amazing. So we could start asking things like. Is there a mint molecular explanation for this is there something going on in the confirmation of a protein that changes in that confirmation so you could ask that question and it turns out that one way to interpret the results is that you know we can we can expose a protein to ethanol we can heat it we do different salts and do all these things but the one thing that really seems to get its attention is to give it a while OK so it's almost as if the oil is there in sort of lubricating the surface so this is a protein that's going to surface in creating a kind of a rigid type structure and in the presence of oil it's a little bit lubricated and starts happening right away without the longest Haitian period and this seems also to a SO that be associated with conformational changes in the protein This is circular dye crew as a result of this is one way that we used to follow pretty well can any of this be used for material science OK. One thing that you can do is you can put in as your oil compo knit some simple polymer like polystyrene So if you wanted to have polystyrene particles with a very high surface area you could do I'm completely risin inside of these bubbles and that's what's going on there OK. This one is application to the oil film OK so here we left the meat I think that's actually engine oil there at the interface and you get an idea of how strong these little surfaces are that they bag of the oil almost they just bag it up like that OK. So that's not a normal thing to happen inside of oil meets water. OK so now I've come around to this part of the talk I've talked about protein So one example of a natural protein could we do something material science see with it OK and in particular we do something of interest to others at Georgia Tech so there's a big effort here in the semi conducting polymers OK and the model polymer that's always used is often used this puff piece three H.D. five feet and there it is up there that structure and it likes to you we would like it to line up OK The goal is to get them to line up because if they can line up then the electrons can be conducted in particular in this direction here OK So the goal is to line them up. So about the time I was coming to Georgia Tech I had some students make this picture which I call a sausage and it contains a solution of P three H T in it and the idea would be that the solvent would slowly evaporate from that and force the polymers to coalesce into longing and so then when we got here we chose solvency easier softer more more relevant solvent actually a more difficult solvent to work with but a more relevant solvent and this cartoon was drawn and what it shows is these sort of like potato shaped structures containing a polymers dissolved in solution drying out and hopefully leading to alignment and so our hypothesis at this point is that when you do that you haven't. That's properties for the material and one of the ways that they used to follow this is just good old U.V. absorption spectroscopy and so people who are in the conducting polymer field know that this band here and particular it's racial with other bands is an indicator of the alignment and this is very good alignment. If you need to see that at a more molecular scale than that becomes G. Sachs experiment and that also works but is a little bit of a surprise that we also found out. That you can have these polymers dissolved polymers or dissolves in solution that's all this red stuff here and you see all these little specks and these little arms coming out here look like neurons right so if you thinking that the polymers are you know conducting all that's sighting have the sort of neuron looking thing here but the thing that's really catches my attention is all these little dots and little things that are blood being off of this thing they contained polymer two and they give us the opportunity to process it really for the first time like a lake effects dispersion you know latex that you paint on your wall the reason do that instead of the old fashioned oil based paints is use a lot less volatile organic solvents I really would like to live in a volatile organic solvents So what you do is you make a part of the oil part that you want in the paint into a little clay will particle when you disperse it in water in the water dries and you have this nice film and so it's interesting to think about that kind of possibility for P three H. T. and other semi conducting polymers this place has more semi conducting polymers and anywhere All right so now what about mimicking this kind of action with a synthetic polymer Here's a poly peptide that. Can mimic it and we're just going to talk about some simple ones P B L G is a classic polymer it's the first synthetic polymer that people made that exhibited some of the important properties of. Naturally occurring proteins in particular it's very prone to make he will cease to he local shape and so it's a rod like polymer and that's the one that we use we use that one here and this talk only this one group here it's been solving hanging off there so ours. But you see there and it's prone to make jobs OK so if you treat it right it will make shells and I've never been clear that this is the best image of these gels but it's a very famous image of these gels that P.B. L.G. makes. And you can see that somehow the rods are aligned in kind of a parallel arrangement and so the basic hypothesis that committee arose who happened was that it would somehow and trap or template the knot trap is not very Some how you would template on to this linear structure from the P B A G You would somehow get the piece three H. T. to follow along with that structure in such a way as to enhance its conduct Hippity OK So that was basically the idea. So in a cartoon form that looks like this I'm not sure the scales here tire Lee meaningful or accurate but the idea is that they have the heel a C. shaped from the P.B. L.G. and then you have these poly five things with their rings hanging off of them in red here which should be there and we will get them to line up OK. So if the hypothesis that you get that lining up is true then we would expect to see changes in the U.V. Bactrim just as I've seen showed you before. Now you'd expect to see a difference in the D.S.E. the CAT scan in calorimetry response to change there's a technique out there which we don't have in Georgia Tech which is rare that we don't have something here but we don't seem to have a F. M.R.I. Our which is atomic force microscope e where you also get an infrared spectrum right at the tip OK where the F.M. probe goes put that as close as you want to the molecule of interest and you see well what really is there OK So F. M.R.I. are that should show that the P three H.T. in the P.B.S. are colocated and then supposed to be able to use Saxon G. Sachs to see some changes in the system too but that's a difficult one because everything scatters you don't really have very much contrast in those experiments Well the slide just basically tells you I mean you're not going to step through this but you to the rear of the paper did so in any way. The the vailable data support the hypothesis that there's an interaction OK a long way to go to optimize that and you can't use for way but I think it points in the direction generally of taking rod like polymers and using them as templates for the saw the rub like. OK So actually I have now come to the end of my talk you see the little circle is empty and if you chose to read the handout that I gave you from N David Mirman instead of listening to the talk will bully for you good choice OK. And you would realize that he said this and mermen is controversial he's physicist so he's entitle to be controversial right he says you don't even need a conclusion there's war and peace have a conclusion no but there are book reviews will have a conclusion slide in a minute OK But anyway I'm basically I'm done if you insist on a conclusion here it is basically that the proteins in Pike have ties maybe they can be harnessed to do useful things this is an example of a protein that actually you know insults and damages trees we could try to get money by curing trees but will be the point of that other people are doing that here we would like to actually use that kind of protein to do something in a material science way and then be inspired to make other polypeptides and other materials to do the same and so with that I've hit the end and I'll take your questions. This. To you the question is to use it as a tag of what to tag some some link or what should I tag with it. I said. No I we haven't it's a great idea I like that because you know you if you're going to. Do that it should it should want to go and you know sit on a surface of VESA go particularly we have sort of a hydrophobic comp maybe list Barry in there a little bit maybe but one of the problems with doing it is doing anything with this protein that one travel in particular is very hard to label it so we would like to fluorescent label that and we've tried that for years I mean literally years and I think all of the reactive groups it has groups that are react but we haven't been able to get them to react in any large amount so it's a little bit disappointing in terms of fluorescence. Probably be good to make that protein and just include something else on it that's even more reactive otherwise I really like that suggestion Yeah. Yeah. No So your question is you know they they go to the interface and lower the surface tension we clearly see the strengthening What's the mechanical reason right. I don't think that they're forming more deisel five bonds that's over OK. The. I can only offer you sort of pitifully we cancers about that what I would say is that they are probably jammed on the surface in some way. We've been thinking can we are something we can pick up in the spectroscopy that shows conformational change no not really. There are things you can do to get to get them out of there you can reduce persimmon ethanol. You can think about circular diagram experiments where you just a temperature and watch for conformational changes and we haven't done those things yet and so we really don't have a very good. Explanation that we do know that it is reversible eventually you can agitate them and get them off the surface. By the way if you get these on a tough one coated surface God help you there are very hard to clean off. What is there what. Is. I don't know if I included it in the talk amigo I sometimes take the slide and let's see what else I got here there it is there it is. I don't think it's got anything to do with a minute Alex OK if so one of the I teach the embassy two thousand and one class and one of things I teach them is thermodynamics is grossly overrated OK and almost nothing is a terminator Thank God we would all none of us are thermodynamically stable right or wrong so this is just an image of our a wave curling on the way so what we could imagine is that the height of problems are here on the surface of the same make this much smaller than a real way and we think they just roll up like cigars OK but why that always that that particular shape I do not know. OK I really do not know but it's a mechanical thing I don't think it's really a thermodynamic thing because when we pull on with a vacuum they go to a ground shape of density you can make them go. And they will they won't they don't snap back to this shape after that and so what. Difference. Yeah what a good idea to mix different hydrophobic to see if this happens so often asked what that's just one hydrophobic do their sixty of them do them do some more right well we don't have that kind of money and resources but we have got really two others that we've looked at and neither of them are as prone to make these extended shapes. One of them will do it but not very high not high acceleration shapes and with much more effort so we think there's something special about this one but we need to do a whole study of them to see and something's gotta pay so hopefully it'll be a material science application that pays for that. Thank you.