1 00:00:00,790 --> 00:00:07,320 [Music] 2 00:00:11,310 --> 00:00:08,700 [Applause] 3 00:00:14,010 --> 00:00:11,320 I think when we conceived of this 4 00:00:16,080 --> 00:00:14,020 session we thought that we would I 5 00:00:17,970 --> 00:00:16,090 really wanted to call it weird life but 6 00:00:19,530 --> 00:00:17,980 we got kind of merged with some other 7 00:00:21,210 --> 00:00:19,540 sessions and so we had to make a more 8 00:00:24,450 --> 00:00:21,220 general term and so you guys have 9 00:00:26,520 --> 00:00:24,460 already heard about Hot Springs and sea 10 00:00:29,040 --> 00:00:26,530 floors and so I want to kind of 11 00:00:30,480 --> 00:00:29,050 transition oh and maybe even Mars and so 12 00:00:32,430 --> 00:00:30,490 I wanted to transition to some other 13 00:00:36,180 --> 00:00:32,440 locations that we could think of life 14 00:00:37,970 --> 00:00:36,190 beginning and this has been borne out of 15 00:00:40,560 --> 00:00:37,980 a project from the ideas lab which 16 00:00:43,950 --> 00:00:40,570 stemmed from can we have oil-based life 17 00:00:45,960 --> 00:00:43,960 so scientists generally think that we 18 00:00:48,180 --> 00:00:45,970 are looking for liquid water when we 19 00:00:51,060 --> 00:00:48,190 look for exoplanets and the question is 20 00:00:54,000 --> 00:00:51,070 is that a good assumption and can we get 21 00:00:58,319 --> 00:00:54,010 any interesting behaviors from polymers 22 00:01:00,119 --> 00:00:58,329 in a non-polar phase so is hydrogen 23 00:01:04,469 --> 00:01:00,129 bonding really necessary for our liquids 24 00:01:06,510 --> 00:01:04,479 and so I would like to just start by 25 00:01:08,790 --> 00:01:06,520 thanking my collaborators and that's 26 00:01:10,920 --> 00:01:08,800 Lauren Williams from Georgia Tech Paul 27 00:01:13,800 --> 00:01:10,930 bratter from University Saint Louis 28 00:01:16,080 --> 00:01:13,810 University Chris butch is at LC Tokyo 29 00:01:18,149 --> 00:01:16,090 and Mike travisano is at the University 30 00:01:20,219 --> 00:01:18,159 of Minnesota and they have all been 31 00:01:23,820 --> 00:01:20,229 instrumental in kind of shaping these 32 00:01:26,580 --> 00:01:23,830 ideas and then I work at a predominantly 33 00:01:28,320 --> 00:01:26,590 undergraduate institution so I have a 34 00:01:30,060 --> 00:01:28,330 kind of team of undergraduates who have 35 00:01:32,700 --> 00:01:30,070 participated in this research and 36 00:01:34,770 --> 00:01:32,710 evolved it to where it is today and I 37 00:01:37,920 --> 00:01:34,780 think that it's really important to 38 00:01:39,870 --> 00:01:37,930 recognize specifically brooke thompson 39 00:01:42,240 --> 00:01:39,880 who did a large amount of the amino acid 40 00:01:45,210 --> 00:01:42,250 work and then Tanner Brawl who's working 41 00:01:47,609 --> 00:01:45,220 on some of the results that I'm not 42 00:01:49,760 --> 00:01:47,619 really showing here and of course I'd 43 00:01:52,230 --> 00:01:49,770 like to thank our benevolent overlords 44 00:01:57,060 --> 00:01:52,240 NSF and NASA for supporting these 45 00:02:00,630 --> 00:01:57,070 projects so the idea of how do you even 46 00:02:03,060 --> 00:02:00,640 test if oil phases are good for life is 47 00:02:06,420 --> 00:02:03,070 is a challenging topic right how do you 48 00:02:09,749 --> 00:02:06,430 evaluate if this is possible and our 49 00:02:12,479 --> 00:02:09,759 solution was to say if we can get any 50 00:02:14,220 --> 00:02:12,489 kind of polymer into an oil phase and 51 00:02:17,670 --> 00:02:14,230 have it interact with another polymer 52 00:02:19,380 --> 00:02:17,680 that might be considered functionality 53 00:02:22,289 --> 00:02:19,390 and you know that actually turned out to 54 00:02:24,660 --> 00:02:22,299 be a pretty lofty goal and so first we 55 00:02:27,600 --> 00:02:24,670 started with analyzing how biological 56 00:02:29,940 --> 00:02:27,610 polymers enter oil phases and I wanted 57 00:02:31,530 --> 00:02:29,950 to answer the question can they and also 58 00:02:34,349 --> 00:02:31,540 when they enter those phases do they 59 00:02:35,640 --> 00:02:34,359 have any interesting structures so the 60 00:02:37,710 --> 00:02:35,650 biomolecules that I'm looking at and 61 00:02:40,890 --> 00:02:37,720 that I'm showing you here are amino 62 00:02:44,490 --> 00:02:40,900 acids and proteins specifically we have 63 00:02:46,380 --> 00:02:44,500 some amino acids and we evaluate them 64 00:02:48,149 --> 00:02:46,390 both in the acidic the neutral and the 65 00:02:50,220 --> 00:02:48,159 basic form because you can see the 66 00:02:51,930 --> 00:02:50,230 charge changes so in the acidic form we 67 00:02:55,589 --> 00:02:51,940 have a positive charge on our ammonia 68 00:02:57,449 --> 00:02:55,599 and a neutral carboxylic acid in the 69 00:02:59,699 --> 00:02:57,459 neutral form we have as whitter ionic 70 00:03:03,420 --> 00:02:59,709 situation where both the base and the 71 00:03:06,860 --> 00:03:03,430 acid are charged and then in our basic 72 00:03:10,259 --> 00:03:06,870 system our ammonia deprotonates and our 73 00:03:13,710 --> 00:03:10,269 carboxylate is deep charged negatively 74 00:03:17,009 --> 00:03:13,720 charged and we tested one charged amino 75 00:03:20,160 --> 00:03:17,019 acid glutamic acid it has a carboxylate 76 00:03:21,839 --> 00:03:20,170 on its side chain we also tested glycine 77 00:03:24,119 --> 00:03:21,849 and of course phenylalanine and 78 00:03:26,819 --> 00:03:24,129 phenylalanine was our initial choice 79 00:03:27,960 --> 00:03:26,829 because it is a little more hydrophobic 80 00:03:31,229 --> 00:03:27,970 and so we're hoping that would force 81 00:03:34,619 --> 00:03:31,239 things into our oil phase we have also 82 00:03:37,020 --> 00:03:34,629 looked at polymers oh and so we have 83 00:03:39,059 --> 00:03:37,030 looked at dye glycine and tri glycine 84 00:03:41,430 --> 00:03:39,069 and we've tried two different proteins 85 00:03:43,550 --> 00:03:41,440 so we tried BSA because it's cheap and 86 00:03:45,629 --> 00:03:43,560 it's in my lab and then we've tried 87 00:03:49,550 --> 00:03:45,639 tackle race and we were thinking that 88 00:03:51,719 --> 00:03:49,560 maybe tack would have more 89 00:03:53,849 --> 00:03:51,729 conformational stability in weird 90 00:03:55,259 --> 00:03:53,859 environments because of how it folds and 91 00:03:59,490 --> 00:03:55,269 how it stabilizes for high temperatures 92 00:04:01,439 --> 00:03:59,500 and so how we do our phase partitioning 93 00:04:02,759 --> 00:04:01,449 it's essentially I know that you might 94 00:04:05,699 --> 00:04:02,769 think this must have already been done 95 00:04:08,250 --> 00:04:05,709 by someone but we actually are cheating 96 00:04:10,680 --> 00:04:08,260 because we add something to 97 00:04:13,439 --> 00:04:10,690 counterbalance our charges so we have a 98 00:04:16,349 --> 00:04:13,449 Dessel sulfate that is in our water 99 00:04:17,370 --> 00:04:16,359 phase to counterbalance the positive 100 00:04:22,379 --> 00:04:17,380 charge on our amines 101 00:04:24,210 --> 00:04:22,389 and we have a desk dido Dessel dimethyl 102 00:04:26,820 --> 00:04:24,220 ammonium bromide so quaternary amine 103 00:04:28,330 --> 00:04:26,830 that balances the negative charge on our 104 00:04:31,450 --> 00:04:28,340 carboxylates 105 00:04:33,670 --> 00:04:31,460 and the reason that we choose DDA be is 106 00:04:36,040 --> 00:04:33,680 because it's a transaction agent so it 107 00:04:38,290 --> 00:04:36,050 can be used to pull DNA into cells and 108 00:04:39,820 --> 00:04:38,300 so it seems like you know if it can help 109 00:04:43,270 --> 00:04:39,830 permeate a cell membrane maybe it'll 110 00:04:45,760 --> 00:04:43,280 help enter an elf ace and so what 111 00:04:50,379 --> 00:04:45,770 happens when we look at just glycine or 112 00:04:52,090 --> 00:04:50,389 our monomeric amino acids oh so how this 113 00:04:54,280 --> 00:04:52,100 works is and how we how we do the 114 00:04:57,070 --> 00:04:54,290 experiment is we just vortex the water 115 00:04:59,439 --> 00:04:57,080 phase with our oil phase and we kind of 116 00:05:01,840 --> 00:04:59,449 hope that some of our biomolecules enter 117 00:05:04,540 --> 00:05:01,850 into the oil phase we also expect that 118 00:05:07,060 --> 00:05:04,550 there is some like monomer or sorry mono 119 00:05:09,550 --> 00:05:07,070 layer forming where our amphiphiles may 120 00:05:12,490 --> 00:05:09,560 actually partially partition into our 121 00:05:15,010 --> 00:05:12,500 oil phase we may have some interaction 122 00:05:18,730 --> 00:05:15,020 here and so to prevent that we actually 123 00:05:21,450 --> 00:05:18,740 separate out our molecules using HPLC so 124 00:05:24,550 --> 00:05:21,460 we're really just trying to look at our 125 00:05:26,920 --> 00:05:24,560 biomolecules and not the other products 126 00:05:28,810 --> 00:05:26,930 using HPLC and we actually use charged 127 00:05:30,430 --> 00:05:28,820 aerosol detection which is a universal 128 00:05:33,370 --> 00:05:30,440 detector so we haven't derivatives our 129 00:05:36,219 --> 00:05:33,380 amino acids at all and what we see is 130 00:05:38,260 --> 00:05:36,229 that glutamic acid has it has three 131 00:05:41,320 --> 00:05:38,270 charged States right it has the aming it 132 00:05:43,629 --> 00:05:41,330 has two carboxylates and we see that 133 00:05:46,930 --> 00:05:43,639 it's actually pretty bad at entering oil 134 00:05:49,060 --> 00:05:46,940 phases this is the just directly from 135 00:05:50,920 --> 00:05:49,070 the HPLC you can see that we get a large 136 00:05:53,110 --> 00:05:50,930 amount detected in the water phase and a 137 00:05:55,960 --> 00:05:53,120 really tiny amount regardless of our 138 00:05:57,940 --> 00:05:55,970 four PHS that we've tried and we pick 139 00:06:00,219 --> 00:05:57,950 these PHS because they are in between 140 00:06:04,770 --> 00:06:00,229 the PKS so we would expect the majority 141 00:06:08,010 --> 00:06:04,780 of our charge to be in that single state 142 00:06:11,110 --> 00:06:08,020 and so what we see with glycine is that 143 00:06:13,810 --> 00:06:11,120 at low pH we have almost no glycine in 144 00:06:15,969 --> 00:06:13,820 our oil phase but as we increase the pH 145 00:06:18,370 --> 00:06:15,979 we actually drive the glycine into the 146 00:06:21,550 --> 00:06:18,380 oil phase which is really promising it's 147 00:06:23,050 --> 00:06:21,560 possible that the Dessel sulfate that 148 00:06:24,969 --> 00:06:23,060 we're using is just not hydrophobic 149 00:06:27,339 --> 00:06:24,979 enough to cause this effect where the 150 00:06:30,070 --> 00:06:27,349 DDA B has those two hydrocarbon tails 151 00:06:32,230 --> 00:06:30,080 and so it's more effective but this begs 152 00:06:35,020 --> 00:06:32,240 the question you know we don't see any 153 00:06:37,270 --> 00:06:35,030 in our water phase at pH 10 and so 154 00:06:39,130 --> 00:06:37,280 is actually happening to the glycine 155 00:06:41,650 --> 00:06:39,140 it's possible that it's organizing at 156 00:06:44,140 --> 00:06:41,660 the interface which we're not testing or 157 00:06:45,670 --> 00:06:44,150 it's possible that it is precipitating 158 00:06:47,800 --> 00:06:45,680 out with maybe charge-charge 159 00:06:50,470 --> 00:06:47,810 interactions or something so we still 160 00:06:53,140 --> 00:06:50,480 have further testing to do and then with 161 00:06:54,550 --> 00:06:53,150 phenylalanine we see that at low pH and 162 00:06:56,620 --> 00:06:54,560 at high pH we get pretty good 163 00:06:59,170 --> 00:06:56,630 partitioning phenylalanine is pretty 164 00:07:00,670 --> 00:06:59,180 hydrophobic but then when it's doubly 165 00:07:02,440 --> 00:07:00,680 charged so at both a negative and a 166 00:07:06,100 --> 00:07:02,450 positive charge we see much less 167 00:07:08,200 --> 00:07:06,110 partitioning at the pH 7 and so I think 168 00:07:09,700 --> 00:07:08,210 you know this is a little bit predictive 169 00:07:11,410 --> 00:07:09,710 that you can kind of see that the more 170 00:07:13,090 --> 00:07:11,420 hydrophobic something is the more likely 171 00:07:17,890 --> 00:07:13,100 it is to enter an oil phase with the 172 00:07:21,100 --> 00:07:17,900 help of a phase transfer agent we also 173 00:07:23,500 --> 00:07:21,110 looked at how changing the amount of our 174 00:07:25,420 --> 00:07:23,510 phase transfer agent will change our 175 00:07:27,550 --> 00:07:25,430 partitioning so this is the 176 00:07:29,380 --> 00:07:27,560 concentration of Dessel sulfate the 177 00:07:31,510 --> 00:07:29,390 concentration of Desa salts fate indeed 178 00:07:33,550 --> 00:07:31,520 EAB or the concentration of DD a be 179 00:07:36,130 --> 00:07:33,560 alone at each of our PHS for 180 00:07:39,750 --> 00:07:36,140 phenylalanine specifically and we can 181 00:07:42,940 --> 00:07:39,760 see that as we increase our amount of 182 00:07:45,760 --> 00:07:42,950 phase transfer agent when we have equal 183 00:07:48,040 --> 00:07:45,770 molar amounts we have a about 40 percent 184 00:07:50,950 --> 00:07:48,050 partitioning but it does seem that it is 185 00:07:52,930 --> 00:07:50,960 going to reach a plateau right so this 186 00:07:55,170 --> 00:07:52,940 is not an unlimited amount that we can 187 00:07:59,740 --> 00:07:55,180 partition into an oil phase it's limited 188 00:08:01,510 --> 00:07:59,750 and interestingly at the pH 7 it 189 00:08:03,100 --> 00:08:01,520 plateaus that have really low value it's 190 00:08:08,590 --> 00:08:03,110 about 14 percent of our molecules 191 00:08:10,600 --> 00:08:08,600 actually partitioning so we also looked 192 00:08:12,490 --> 00:08:10,610 at polymers because obviously amino 193 00:08:14,920 --> 00:08:12,500 acids alone aren't super exciting and 194 00:08:18,040 --> 00:08:14,930 when we look at polymers what we see is 195 00:08:19,930 --> 00:08:18,050 that the glycine so this is just the 196 00:08:21,490 --> 00:08:19,940 data kind of reimagined from that first 197 00:08:24,640 --> 00:08:21,500 slide right so low pH we have almost 198 00:08:28,630 --> 00:08:24,650 nothing mid pH we have a small portion 199 00:08:31,420 --> 00:08:28,640 and then the high pH we see 50% of our 200 00:08:33,010 --> 00:08:31,430 starting material in the oil phase as we 201 00:08:34,510 --> 00:08:33,020 increase the length of our polymers we 202 00:08:37,630 --> 00:08:34,520 actually see that those would or ionic 203 00:08:40,360 --> 00:08:37,640 molecules are not there and you know the 204 00:08:42,640 --> 00:08:40,370 HPLC is really flat in this region it 205 00:08:44,650 --> 00:08:42,650 really seems like there are no no 206 00:08:46,450 --> 00:08:44,660 polymers entering the phase and again 207 00:08:47,210 --> 00:08:46,460 this could be a partitioning into the 208 00:08:50,210 --> 00:08:47,220 interface 209 00:08:51,890 --> 00:08:50,220 be a precipitating out of solution but 210 00:08:54,830 --> 00:08:51,900 we don't see it fully in the oil phase 211 00:08:56,900 --> 00:08:54,840 either or in the water phase either and 212 00:08:58,670 --> 00:08:56,910 a high pH we actually see that we get 213 00:09:01,970 --> 00:08:58,680 some of these polymers to enter into the 214 00:09:05,630 --> 00:09:01,980 oil phase and this may suggest that that 215 00:09:07,550 --> 00:09:05,640 the a mean is more more prone to 216 00:09:09,950 --> 00:09:07,560 preventing partitioning right when the 217 00:09:13,040 --> 00:09:09,960 it's an ammonium State it's less likely 218 00:09:14,780 --> 00:09:13,050 to partition into our oil phase and I 219 00:09:17,720 --> 00:09:14,790 have not fully characterized our 220 00:09:20,360 --> 00:09:17,730 proteins yet but we do know that we get 221 00:09:23,600 --> 00:09:20,370 some partitioning into an oil phase with 222 00:09:25,490 --> 00:09:23,610 both BSA and TAC so with BSA we try to 223 00:09:27,950 --> 00:09:25,500 have an absorbance of about 1 in our 224 00:09:30,260 --> 00:09:27,960 water phase and the difference between 225 00:09:37,160 --> 00:09:30,270 this dotted line which seems to be light 226 00:09:39,140 --> 00:09:37,170 scattering versus our BSA about 0.8 so I 227 00:09:41,150 --> 00:09:39,150 would say that we have about 50% of our 228 00:09:43,730 --> 00:09:41,160 protein looks like it actually can enter 229 00:09:46,400 --> 00:09:43,740 an oil phase and this is done with UV 230 00:09:49,160 --> 00:09:46,410 vis not with HPLC because the proteins 231 00:09:51,260 --> 00:09:49,170 are so large and if we really want to 232 00:09:52,790 --> 00:09:51,270 push it we can put a lot of tack into 233 00:09:54,860 --> 00:09:52,800 our water phase so here we're maxing out 234 00:09:58,550 --> 00:09:54,870 our detector and we see that we can get 235 00:10:01,010 --> 00:09:58,560 a pretty large tack peak we have run CV 236 00:10:02,930 --> 00:10:01,020 on these so circular dichroism can 237 00:10:05,390 --> 00:10:02,940 predict secondary structure and we 238 00:10:08,660 --> 00:10:05,400 actually see that we have no secondary 239 00:10:09,860 --> 00:10:08,670 structure in our oil phase it's likely 240 00:10:11,390 --> 00:10:09,870 that the proteins are just kind of 241 00:10:13,940 --> 00:10:11,400 turning inside out that the hydrophobic 242 00:10:16,820 --> 00:10:13,950 core is being inverted and we're losing 243 00:10:19,220 --> 00:10:16,830 all of our protein structure so I guess 244 00:10:22,070 --> 00:10:19,230 that's a downside of this this 245 00:10:24,190 --> 00:10:22,080 experiment but a result nonetheless and 246 00:10:26,840 --> 00:10:24,200 I would just like to give a brief 247 00:10:29,660 --> 00:10:26,850 preview to some of the other things that 248 00:10:31,940 --> 00:10:29,670 I've been working on so I have very 249 00:10:33,140 --> 00:10:31,950 similar to Dave Deemer and Nita so hi 250 00:10:36,200 --> 00:10:33,150 have been talking about have been using 251 00:10:37,760 --> 00:10:36,210 pH is for electron transfer and in this 252 00:10:40,940 --> 00:10:37,770 we're actually our goal is to reduce 253 00:10:43,160 --> 00:10:40,950 carbon dioxide into formate and we 254 00:10:45,920 --> 00:10:43,170 actually see that we get a pH change 255 00:10:47,960 --> 00:10:45,930 when we turn on the light so as you turn 256 00:10:51,380 --> 00:10:47,970 on the light you get an increase in pH 257 00:10:54,800 --> 00:10:51,390 and we also see if we run mass spec that 258 00:10:57,800 --> 00:10:54,810 we have a very small in this yellow peak 259 00:10:59,430 --> 00:10:57,810 a very small formic acid peak so the 260 00:11:01,140 --> 00:10:59,440 gray is our standard 261 00:11:03,450 --> 00:11:01,150 and we're it seems like we're actually 262 00:11:05,640 --> 00:11:03,460 producing formic acid in this process 263 00:11:08,880 --> 00:11:05,650 and our electron source in these 264 00:11:12,720 --> 00:11:08,890 reactions is a iron two-plus that iron 265 00:11:17,370 --> 00:11:12,730 chloride and I'll be talking more about 266 00:11:18,780 --> 00:11:17,380 this at the GRC in galveston and finally 267 00:11:20,970 --> 00:11:18,790 I just like to promote something that I 268 00:11:23,370 --> 00:11:20,980 spent a lot of time on with the help of 269 00:11:26,160 --> 00:11:23,380 many of you in this room there's an 270 00:11:27,990 --> 00:11:26,170 origins of life MOOC and it's a free 271 00:11:31,530 --> 00:11:28,000 course so if you go to complexity 272 00:11:33,510 --> 00:11:31,540 explore org you can sign up for this you 273 00:11:35,790 --> 00:11:33,520 can see your own videos if you recorded 274 00:11:37,980 --> 00:11:35,800 any additionally you can see comments so 275 00:11:41,310 --> 00:11:37,990 it's a good idea to see how the general 276 00:11:44,580 --> 00:11:41,320 public receives our kind of our kind of 277 00:11:46,530 --> 00:11:44,590 science and if you have any students who 278 00:11:48,660 --> 00:11:46,540 are entering the field that maybe need 279 00:11:50,250 --> 00:11:48,670 more of a background you can recommend 280 00:11:52,950 --> 00:11:50,260 this course for them and it gives a good 281 00:11:55,890 --> 00:11:52,960 overview of the physics the planetary 282 00:11:57,750 --> 00:11:55,900 science the chemistry the biology of 283 00:12:02,520 --> 00:11:57,760 origins of life so it's a good kind of 284 00:12:05,070 --> 00:12:02,530 primer for origins I'd be happy to take 285 00:12:05,080 --> 00:12:08,259 [Music] 286 00:12:14,109 --> 00:12:11,429 Thank You Sara we have time just for one 287 00:12:16,210 --> 00:12:14,119 question and if our men will Canadian is 288 00:12:20,350 --> 00:12:16,220 in the room I think we may need your 289 00:12:24,009 --> 00:12:20,360 slides loaded for the last slot so with 290 00:12:26,470 --> 00:12:24,019 that question is that Palmer hi I'm a 291 00:12:28,269 --> 00:12:26,480 bit confused what pH means when you're 292 00:12:30,699 --> 00:12:28,279 dealing with non aqueous solvents 293 00:12:33,100 --> 00:12:30,709 because the concentration of the H+ in 294 00:12:35,019 --> 00:12:33,110 the water won't be the same as the non 295 00:12:37,449 --> 00:12:35,029 aqueous solvent and and the ionization 296 00:12:38,949 --> 00:12:37,459 state of a molecule like an amino acid 297 00:12:42,100 --> 00:12:38,959 will change if it goes into the other 298 00:12:44,739 --> 00:12:42,110 solvent so how do you think about those 299 00:12:46,480 --> 00:12:44,749 things so I was really referring to we 300 00:12:48,460 --> 00:12:46,490 dissolve everything in water first and 301 00:12:52,809 --> 00:12:48,470 so I was referring to the starting water 302 00:12:55,299 --> 00:12:52,819 pH I don't have a good metric or a good 303 00:12:58,530 --> 00:12:55,309 system for measuring pH in an oil phase 304 00:13:01,059 --> 00:12:58,540 and so I have not really addressed that 305 00:13:04,689 --> 00:13:01,069 but you're right there is definitely a 306 00:13:11,020 --> 00:13:04,699 change in in PKA as we change our 307 00:13:12,230 --> 00:13:11,030 solvents thank you Sara