1 00:00:05,829 --> 00:00:03,189 okay great uh thank you to the 2 00:00:07,990 --> 00:00:05,839 uh organizers for giving me a chance to 3 00:00:10,310 --> 00:00:08,000 give this talk and to you all for 4 00:00:12,310 --> 00:00:10,320 watching it uh my name is micah scheibel 5 00:00:14,390 --> 00:00:12,320 i'm from the georgia institute of 6 00:00:16,070 --> 00:00:14,400 technology and today i'll be talking 7 00:00:17,830 --> 00:00:16,080 about some recent measurements where we 8 00:00:20,230 --> 00:00:17,840 explore a mechanism called spin 9 00:00:23,189 --> 00:00:20,240 dichroism and its ability to form 10 00:00:24,630 --> 00:00:23,199 enantiomeric excesses in chiral amino 11 00:00:25,830 --> 00:00:24,640 acids 12 00:00:28,150 --> 00:00:25,840 so i'm sure i don't have to tell this 13 00:00:30,470 --> 00:00:28,160 crowd that chiral amino acids and and 14 00:00:33,590 --> 00:00:30,480 many other types of chiral molecules 15 00:00:36,069 --> 00:00:33,600 are uh found in in many different uh 16 00:00:38,630 --> 00:00:36,079 meteorites as well as in asteroids and 17 00:00:40,630 --> 00:00:38,640 comets uh and here i'm showing a few 18 00:00:43,030 --> 00:00:40,640 different amino acids that have been 19 00:00:45,830 --> 00:00:43,040 identified and in the parentheses is the 20 00:00:48,549 --> 00:00:45,840 largest measured enantiomeric excess of 21 00:00:51,910 --> 00:00:48,559 these chiral amino acids so these being 22 00:00:55,110 --> 00:00:51,920 the l form there's a 20 excess in the l 23 00:00:57,510 --> 00:00:55,120 over the corresponding d form 24 00:01:00,310 --> 00:00:57,520 interestingly enough when we look across 25 00:01:02,389 --> 00:01:00,320 a number of different sources for these 26 00:01:06,149 --> 00:01:02,399 chiral amino acids 27 00:01:10,149 --> 00:01:06,159 we see that very often they are 28 00:01:11,670 --> 00:01:10,159 enhanced towards the l enantiomer so 29 00:01:12,710 --> 00:01:11,680 here showing the 30 00:01:15,510 --> 00:01:12,720 measured 31 00:01:18,950 --> 00:01:15,520 excesses of l-isovalene in a number of 32 00:01:21,429 --> 00:01:18,960 different meteorite types all showing an 33 00:01:22,789 --> 00:01:21,439 excess towards the l-form and none 34 00:01:25,590 --> 00:01:22,799 really showing a statistically 35 00:01:27,109 --> 00:01:25,600 significant excess towards the d-form 36 00:01:29,190 --> 00:01:27,119 so the question that we're asking here 37 00:01:31,910 --> 00:01:29,200 is why do uh seemingly all of these 38 00:01:34,950 --> 00:01:31,920 these primitive meteorites display the 39 00:01:36,710 --> 00:01:34,960 same enantiomeric excesses or this the 40 00:01:38,630 --> 00:01:36,720 enantiomeric excesses of the same 41 00:01:40,630 --> 00:01:38,640 handedness 42 00:01:42,789 --> 00:01:40,640 so different forces in space which can 43 00:01:45,350 --> 00:01:42,799 drive enantioselectivity 44 00:01:48,069 --> 00:01:45,360 uh include several different abiotic 45 00:01:51,830 --> 00:01:48,079 mechanisms um the first being sort of 46 00:01:54,550 --> 00:01:51,840 just a chance or statistical fluctuation 47 00:01:57,030 --> 00:01:54,560 in the molecular populations which lead 48 00:01:59,670 --> 00:01:57,040 to an enhancement in one versus the 49 00:02:01,590 --> 00:01:59,680 other uh now if there's these uh 50 00:02:03,350 --> 00:02:01,600 excesses and meteorites were forming due 51 00:02:05,270 --> 00:02:03,360 to a chance mechanism we would expect 52 00:02:07,749 --> 00:02:05,280 both l and d forms 53 00:02:09,430 --> 00:02:07,759 uh alternatively amplification uh 54 00:02:12,390 --> 00:02:09,440 there's lots of different types of 55 00:02:13,750 --> 00:02:12,400 mechanisms that can drive amplification 56 00:02:17,430 --> 00:02:13,760 of a given 57 00:02:20,710 --> 00:02:17,440 chirality but all of these still require 58 00:02:22,869 --> 00:02:20,720 some initially small excess of one of 59 00:02:24,869 --> 00:02:22,879 the enantiomers versus the other so 60 00:02:27,190 --> 00:02:24,879 ultimately what we're searching for to 61 00:02:29,190 --> 00:02:27,200 explain why all of these meteorites are 62 00:02:30,710 --> 00:02:29,200 pushed in the same direction is 63 00:02:33,830 --> 00:02:30,720 something called a determinant force 64 00:02:37,350 --> 00:02:33,840 where where the excesses are at least 65 00:02:41,030 --> 00:02:37,360 initiated by some sort of physical force 66 00:02:43,190 --> 00:02:41,040 that is not dependent on the environment 67 00:02:46,150 --> 00:02:43,200 um so different determinate mechanisms 68 00:02:48,470 --> 00:02:46,160 which have been explored that uh 69 00:02:51,110 --> 00:02:48,480 induce enantiomeric excesses in organic 70 00:02:54,710 --> 00:02:51,120 molecules uh include first circularly 71 00:02:57,110 --> 00:02:54,720 polarized light uh where uh light from 72 00:03:00,710 --> 00:02:57,120 ionizing radiation such as uv light from 73 00:03:02,830 --> 00:03:00,720 distant stars can obtain a uh circular 74 00:03:05,030 --> 00:03:02,840 or actually a really unknown elliptical 75 00:03:07,110 --> 00:03:05,040 polarization as it passes through dust 76 00:03:08,309 --> 00:03:07,120 clouds on its way towards our solar 77 00:03:10,630 --> 00:03:08,319 system 78 00:03:13,830 --> 00:03:10,640 and those circularly polarized photons 79 00:03:16,390 --> 00:03:13,840 can induce an enantiomeric excess 80 00:03:19,509 --> 00:03:16,400 alternatively you can get preferential 81 00:03:21,910 --> 00:03:19,519 bonding or catalysis on chiral surfaces 82 00:03:24,309 --> 00:03:21,920 uh both of these have been explored and 83 00:03:26,710 --> 00:03:24,319 in general produce fairly small 84 00:03:29,110 --> 00:03:26,720 enantiomeric excesses 85 00:03:31,830 --> 00:03:29,120 a third mechanism which we are exploring 86 00:03:34,229 --> 00:03:31,840 in the current work is interactions of 87 00:03:36,309 --> 00:03:34,239 spin polarized electrons with chiral 88 00:03:38,630 --> 00:03:36,319 molecules uh so the question that we're 89 00:03:41,670 --> 00:03:38,640 asking is can spin polarized electrons 90 00:03:44,550 --> 00:03:41,680 create enantiomeric excesses within 91 00:03:48,229 --> 00:03:44,560 populations of chiral amino acids 92 00:03:51,670 --> 00:03:48,239 uh so first we'll just do a little bit 93 00:03:55,350 --> 00:03:51,680 about where we can expect these spin 94 00:03:57,190 --> 00:03:55,360 polarized electrons to come from um and 95 00:03:59,910 --> 00:03:57,200 what we're doing is we're 96 00:04:02,390 --> 00:03:59,920 looking at the ejection of these spin 97 00:04:05,589 --> 00:04:02,400 polarized electrons from a magnetized 98 00:04:06,470 --> 00:04:05,599 surface so you can imagine here uh our 99 00:04:09,429 --> 00:04:06,480 sort of 100 00:04:11,110 --> 00:04:09,439 schematic of an iron where all of the 101 00:04:13,509 --> 00:04:11,120 spins within the iron or at least the 102 00:04:16,229 --> 00:04:13,519 vast majority of them are pointing in 103 00:04:19,270 --> 00:04:16,239 the same direction 104 00:04:21,189 --> 00:04:19,280 and so when we have ionizing radiation 105 00:04:23,110 --> 00:04:21,199 come in it can excite one of those 106 00:04:24,310 --> 00:04:23,120 electrons which then scatters through 107 00:04:26,310 --> 00:04:24,320 the solid 108 00:04:28,469 --> 00:04:26,320 and then can escape the surface as a 109 00:04:31,670 --> 00:04:28,479 secondary electron 110 00:04:33,749 --> 00:04:31,680 so it turns out that because of the 111 00:04:36,310 --> 00:04:33,759 polarizing or the magnetization of that 112 00:04:39,030 --> 00:04:36,320 surface you have an unequal filling of 113 00:04:41,350 --> 00:04:39,040 the fermi energy levels 114 00:04:43,990 --> 00:04:41,360 within the solid and you get more or 115 00:04:46,629 --> 00:04:44,000 preferential scattering off of the prep 116 00:04:49,189 --> 00:04:46,639 slightly emptier levels so that leads to 117 00:04:51,270 --> 00:04:49,199 then a preferential polarization 118 00:04:53,830 --> 00:04:51,280 direction of the emitted secondary 119 00:04:56,950 --> 00:04:53,840 electrons from that surface 120 00:04:59,350 --> 00:04:56,960 um it turns out that a 121 00:05:01,909 --> 00:04:59,360 spin polarized electron in motion traces 122 00:05:04,230 --> 00:05:01,919 out a helical path um and that by 123 00:05:06,710 --> 00:05:04,240 reversing the substrate magnet 124 00:05:09,350 --> 00:05:06,720 uh magnetization direction we can also 125 00:05:11,990 --> 00:05:09,360 reverse the helicity of the ejected 126 00:05:13,670 --> 00:05:12,000 secondary electrons 127 00:05:17,029 --> 00:05:13,680 so the mechanism that we're exploring 128 00:05:20,230 --> 00:05:17,039 here spin dichroism consists in coupling 129 00:05:22,469 --> 00:05:20,240 between that electron helicity and the 130 00:05:25,390 --> 00:05:22,479 molecular chirality and exploring 131 00:05:27,510 --> 00:05:25,400 whether or not that coupling can lead to 132 00:05:29,510 --> 00:05:27,520 enantioselective damage and formation of 133 00:05:31,350 --> 00:05:29,520 enantiomeric excesses 134 00:05:33,510 --> 00:05:31,360 so here the idea is that we have some 135 00:05:35,909 --> 00:05:33,520 sort of ionizing radiation come in in 136 00:05:38,070 --> 00:05:35,919 these experiments we use x-rays they 137 00:05:41,270 --> 00:05:38,080 excite secondary electrons from the 138 00:05:44,629 --> 00:05:41,280 surface which then are ejected out and 139 00:05:47,110 --> 00:05:44,639 can interact with molecules absorbed 140 00:05:48,870 --> 00:05:47,120 um depending on the magnetization 141 00:05:52,469 --> 00:05:48,880 direction of that substrate you can 142 00:05:55,430 --> 00:05:52,479 either have plus or negative uh 143 00:05:57,510 --> 00:05:55,440 helicity spin polarized electrons 144 00:06:01,350 --> 00:05:57,520 and these may interact differently with 145 00:06:03,670 --> 00:06:01,360 the l or the i r car um 146 00:06:06,550 --> 00:06:03,680 enantiomers 147 00:06:09,189 --> 00:06:06,560 so the experimental setup that we 148 00:06:11,830 --> 00:06:09,199 designed was to first vapor deposit a 149 00:06:13,830 --> 00:06:11,840 molecule l-histidine uh and we used this 150 00:06:16,070 --> 00:06:13,840 one because it was well understood in in 151 00:06:17,990 --> 00:06:16,080 terms of its interactions with surfaces 152 00:06:21,029 --> 00:06:18,000 and and we knew that we could 153 00:06:22,870 --> 00:06:21,039 deposit it reliably on the surface 154 00:06:27,270 --> 00:06:22,880 and then we exposed those films of 155 00:06:28,950 --> 00:06:27,280 l-histidine to 695 ev soft x-rays uh 156 00:06:30,790 --> 00:06:28,960 that were generated by the advanced 157 00:06:32,830 --> 00:06:30,800 photon source synchrotron at argonne 158 00:06:36,469 --> 00:06:32,840 national lab 159 00:06:38,950 --> 00:06:36,479 those x-rays then interacted with our 160 00:06:41,029 --> 00:06:38,960 magnetized cobalt substrate to eject the 161 00:06:46,309 --> 00:06:41,039 spin polarized electrons 162 00:06:48,390 --> 00:06:46,319 could interact with and damage the vapor 163 00:06:50,390 --> 00:06:48,400 deposited l l-histidine 164 00:06:51,990 --> 00:06:50,400 we can then probe that damage using a 165 00:06:53,830 --> 00:06:52,000 technique called x-ray photoelectron 166 00:06:54,710 --> 00:06:53,840 spectroscopy 167 00:06:56,469 --> 00:06:54,720 and then 168 00:06:59,830 --> 00:06:56,479 determine how 169 00:07:01,909 --> 00:06:59,840 that difference in helicity 170 00:07:04,230 --> 00:07:01,919 affects the damaged cross-sections by 171 00:07:06,790 --> 00:07:04,240 reversing the magnetization of our 172 00:07:09,350 --> 00:07:06,800 substrate in situ 173 00:07:11,909 --> 00:07:09,360 what the xps measurements look like is 174 00:07:15,189 --> 00:07:11,919 shown here where i focused on the 175 00:07:17,430 --> 00:07:15,199 nitrogen uh component of our molecules 176 00:07:20,629 --> 00:07:17,440 nitrogen being uh 177 00:07:25,110 --> 00:07:20,639 very unique to the analyte molecule as 178 00:07:28,070 --> 00:07:25,120 all and also um on the chiral center so 179 00:07:29,909 --> 00:07:28,080 we see that the high resolution spectrum 180 00:07:31,909 --> 00:07:29,919 of nitrogen can be fit with five 181 00:07:35,430 --> 00:07:31,919 different peaks 182 00:07:39,029 --> 00:07:35,440 the first two uh being the largest uh 183 00:07:42,230 --> 00:07:39,039 are corresponding to the n1 and the n2 184 00:07:44,950 --> 00:07:42,240 components on the nitro uh the neutral 185 00:07:47,670 --> 00:07:44,960 histidine molecules while these smaller 186 00:07:49,670 --> 00:07:47,680 peaks out here the m3 and the n4 peaks 187 00:07:52,550 --> 00:07:49,680 correspond to nitrogen with on this 188 00:07:54,550 --> 00:07:52,560 wider ionic species 189 00:07:56,629 --> 00:07:54,560 um 190 00:07:58,390 --> 00:07:56,639 it turns out that these winter ionic 191 00:08:00,550 --> 00:07:58,400 species are important because 192 00:08:03,430 --> 00:08:00,560 depending on the thickness of our sample 193 00:08:05,830 --> 00:08:03,440 uh you you see more or less abundances 194 00:08:08,230 --> 00:08:05,840 of those of those winter ionic species 195 00:08:10,150 --> 00:08:08,240 um and so it turns out that for a thin 196 00:08:13,510 --> 00:08:10,160 film or a monolayer film sort of 197 00:08:15,670 --> 00:08:13,520 corresponding to this uh 0.3 nanometer 198 00:08:17,350 --> 00:08:15,680 thickness where the the n3 and the n4 199 00:08:18,710 --> 00:08:17,360 components of the switter ions are 200 00:08:20,950 --> 00:08:18,720 hardly there 201 00:08:23,670 --> 00:08:20,960 um you get more strongly interaction 202 00:08:26,390 --> 00:08:23,680 interactions with the molecules in the 203 00:08:29,189 --> 00:08:26,400 surface whereas with the thicker samples 204 00:08:30,390 --> 00:08:29,199 uh those those interactions aren't quite 205 00:08:31,670 --> 00:08:30,400 as strong 206 00:08:33,750 --> 00:08:31,680 so that the presence of multiple 207 00:08:35,990 --> 00:08:33,760 monolayers can weaken the molecular 208 00:08:37,269 --> 00:08:36,000 interactions between the the molecules 209 00:08:40,230 --> 00:08:37,279 and the surface 210 00:08:43,909 --> 00:08:40,240 potentially enhancing any measurement of 211 00:08:45,829 --> 00:08:43,919 this spindle dichroism in fact 212 00:08:48,790 --> 00:08:45,839 when we look at the 213 00:08:51,750 --> 00:08:48,800 abundance or the area of those peaks as 214 00:08:54,630 --> 00:08:51,760 a function of a radiation fluence or the 215 00:08:56,949 --> 00:08:54,640 cumulative electron fluence that these 216 00:08:58,870 --> 00:08:56,959 molecular films have been exposed to 217 00:09:00,710 --> 00:08:58,880 we see that they are well fit by 218 00:09:06,870 --> 00:09:00,720 exponential decays 219 00:09:09,910 --> 00:09:06,880 used to give us uh cross sections 220 00:09:12,710 --> 00:09:09,920 for the damage or what is the the damage 221 00:09:14,710 --> 00:09:12,720 cross-section for these molecules with 222 00:09:16,150 --> 00:09:14,720 the spin polarized electrons 223 00:09:17,829 --> 00:09:16,160 and so again it turns out that the 224 00:09:19,509 --> 00:09:17,839 thicker samples because there's more 225 00:09:20,949 --> 00:09:19,519 molecules there and they're less 226 00:09:22,790 --> 00:09:20,959 strongly interacting with the surface 227 00:09:25,190 --> 00:09:22,800 they give better and more precise 228 00:09:28,070 --> 00:09:25,200 exponential fits which ultimately give 229 00:09:29,990 --> 00:09:28,080 us better statistics and then we also 230 00:09:32,150 --> 00:09:30,000 see that it's pretty clear that the 231 00:09:33,750 --> 00:09:32,160 zwitter ionic species both in the thick 232 00:09:36,230 --> 00:09:33,760 and in the thinner samples those 233 00:09:40,550 --> 00:09:36,240 vitorianic species are damaged more 234 00:09:42,470 --> 00:09:40,560 readily than are the the neutral species 235 00:09:45,750 --> 00:09:42,480 so when we take measurements of these 236 00:09:48,150 --> 00:09:45,760 damaged cross sections uh at multiple 237 00:09:51,590 --> 00:09:48,160 different spots on the same sample so 238 00:09:54,150 --> 00:09:51,600 same deposition different spot uh we 239 00:09:56,790 --> 00:09:54,160 take about fifth 10 to 15 different 240 00:09:57,990 --> 00:09:56,800 spots in both of the magnetization 241 00:10:00,710 --> 00:09:58,000 conditions 242 00:10:03,030 --> 00:10:00,720 and then do a statistical comparison for 243 00:10:05,350 --> 00:10:03,040 those cross sections measured 244 00:10:07,190 --> 00:10:05,360 in both magnetization conditions and 245 00:10:08,550 --> 00:10:07,200 look for statistical significantly 246 00:10:11,030 --> 00:10:08,560 differences 247 00:10:12,870 --> 00:10:11,040 between those two populations 248 00:10:14,630 --> 00:10:12,880 and what we see that in fact the total 249 00:10:16,470 --> 00:10:14,640 cross-section and 250 00:10:18,870 --> 00:10:16,480 the cross-sections for this wider ionic 251 00:10:21,590 --> 00:10:18,880 species so strong evidence of spin 252 00:10:24,630 --> 00:10:21,600 dichroism so that the dependence that of 253 00:10:28,470 --> 00:10:24,640 the damage on that electron helicity 254 00:10:30,790 --> 00:10:28,480 for these l histidine molecules um if we 255 00:10:32,710 --> 00:10:30,800 assume that the the reverse is true for 256 00:10:35,190 --> 00:10:32,720 the d-histidine molecules which can be 257 00:10:37,590 --> 00:10:35,200 expected from previous measurements uh 258 00:10:39,910 --> 00:10:37,600 we get that if we had a racemic mixture 259 00:10:42,230 --> 00:10:39,920 of l-histidine on the surface 260 00:10:44,230 --> 00:10:42,240 we would produce actually a 17 261 00:10:45,430 --> 00:10:44,240 enantiomeric excess 262 00:10:47,509 --> 00:10:45,440 when only 263 00:10:49,670 --> 00:10:47,519 forty percent of the original molecular 264 00:10:52,069 --> 00:10:49,680 population remains uh so these are 265 00:10:54,790 --> 00:10:52,079 pretty strong effects of of this uh spin 266 00:10:57,110 --> 00:10:54,800 dichroism that we're showing here 267 00:11:00,230 --> 00:10:57,120 uh so in conclusion we've shown that uh 268 00:11:02,069 --> 00:11:00,240 elk hyrule lumentomeric excesses 269 00:11:04,470 --> 00:11:02,079 have been identified in many pretty much 270 00:11:06,710 --> 00:11:04,480 meteorites and uh although many 271 00:11:07,829 --> 00:11:06,720 mechanisms exist to explain these 272 00:11:09,990 --> 00:11:07,839 excesses 273 00:11:13,910 --> 00:11:10,000 uh ultimately the the cause of the 274 00:11:16,150 --> 00:11:13,920 symmetry breaking between y l versus d 275 00:11:18,389 --> 00:11:16,160 remains an open question 276 00:11:19,750 --> 00:11:18,399 um these experiments have shown that 277 00:11:21,590 --> 00:11:19,760 their strong and anti-selective 278 00:11:23,910 --> 00:11:21,600 preferences measured 279 00:11:26,470 --> 00:11:23,920 for spin polarized electrons ejected 280 00:11:28,790 --> 00:11:26,480 from a magnetized substrate 281 00:11:31,350 --> 00:11:28,800 in their interactions with deposited uh 282 00:11:33,350 --> 00:11:31,360 l-histidine amino acids uh it sort of 283 00:11:35,030 --> 00:11:33,360 remains to be seen how the spin 284 00:11:36,949 --> 00:11:35,040 polarized electron 285 00:11:39,350 --> 00:11:36,959 um 286 00:11:41,829 --> 00:11:39,360 molecule these spin polarized electrons 287 00:11:43,030 --> 00:11:41,839 can create these enantiomeric excesses 288 00:11:45,590 --> 00:11:43,040 are within different molecular 289 00:11:48,630 --> 00:11:45,600 populations um 290 00:11:51,190 --> 00:11:48,640 and and this is largely an unexplored 291 00:11:53,829 --> 00:11:51,200 mechanism uh within the field so with 292 00:11:55,350 --> 00:11:53,839 that i'd like to uh thank uh the the 293 00:11:58,150 --> 00:11:55,360 people who helped me out with this work 294 00:12:00,310 --> 00:11:58,160 uh tom and cermane georgia tech and 295 00:12:02,790 --> 00:12:00,320 richard at argonne as well as our 296 00:12:04,870 --> 00:12:02,800 funding from the doe and nasa post 297 00:12:07,030 --> 00:12:04,880 doctoral fellowship uh thank you all for