1 00:00:05,510 --> 00:00:02,659 good morning or good afternoon everyone 2 00:00:08,360 --> 00:00:05,520 welcome to the continuation of the 3 00:00:11,570 --> 00:00:08,370 series of seminars by each of the NAI 4 00:00:14,780 --> 00:00:11,580 teams this is origins of life week here 5 00:00:17,180 --> 00:00:14,790 at nai central plaza and we're going to 6 00:00:20,090 --> 00:00:17,190 hear today from John Peters for the 7 00:00:21,679 --> 00:00:20,100 Montana State team John got his BS in 8 00:00:24,859 --> 00:00:21,689 microbiology at the university of 9 00:00:26,779 --> 00:00:24,869 oklahoma in norman and a PhD in 10 00:00:30,109 --> 00:00:26,789 biochemistry from Virginia Tech and then 11 00:00:33,410 --> 00:00:30,119 was a postdoc at Caltech before moving 12 00:00:37,010 --> 00:00:33,420 on to msu john is also the director of 13 00:00:40,430 --> 00:00:37,020 the thermal biology institute at msu in 14 00:00:43,160 --> 00:00:40,440 addition to being the pi/4 the NAI team 15 00:00:45,590 --> 00:00:43,170 and the thermal biology Institute 16 00:00:48,709 --> 00:00:45,600 investigates the geothermal environments 17 00:00:51,799 --> 00:00:48,719 of yellowstone national park which the 18 00:00:54,080 --> 00:00:51,809 NAIA ec will have the privilege of 19 00:00:57,110 --> 00:00:54,090 seeing and being shown by John in 20 00:01:00,860 --> 00:00:57,120 September at our next in person ec 21 00:01:03,200 --> 00:01:00,870 meeting after the asu workshop and we're 22 00:01:06,020 --> 00:01:03,210 all looking forward to that and without 23 00:01:17,450 --> 00:01:06,030 any further ado I will turn the floor 24 00:01:22,760 --> 00:01:17,460 over to John god I think your 25 00:01:27,080 --> 00:01:22,770 microphones muted that's right I'm 26 00:01:32,960 --> 00:01:27,090 hopeful ok ok ok thanks Carl can you can 27 00:01:36,710 --> 00:01:32,970 they hear me now Margo yes ok you know 28 00:01:38,630 --> 00:01:36,720 you said about the delay if if if I'm 29 00:01:46,280 --> 00:01:38,640 not observing the delay can you reel me 30 00:01:48,230 --> 00:01:46,290 in Marco please sir ok thanks ok so I'm 31 00:01:50,510 --> 00:01:48,240 going to talk about our project it's 32 00:01:52,460 --> 00:01:50,520 really centered on structure and 33 00:01:54,950 --> 00:01:52,470 reactivity at iron sulfur motifs I've 34 00:01:57,830 --> 00:01:54,960 got the number of my p.i is here with me 35 00:02:01,700 --> 00:01:57,840 so if and I'm going to try to feel the 36 00:02:04,200 --> 00:02:01,710 whole centers threats by myself but if I 37 00:02:05,760 --> 00:02:04,210 see them wave in their arms or 38 00:02:08,540 --> 00:02:05,770 role in their eyes or something like 39 00:02:12,330 --> 00:02:08,550 that I make Paul on some of my pee is to 40 00:02:16,410 --> 00:02:12,340 clarify some things that all be 41 00:02:17,880 --> 00:02:16,420 disgusting okay so our team is a number 42 00:02:20,760 --> 00:02:17,890 of investigators here at Montana State 43 00:02:23,010 --> 00:02:20,770 University Martin skinnin and John 44 00:02:28,559 --> 00:02:23,020 previous Stony Brook University and damn 45 00:02:32,490 --> 00:02:28,569 strong in at Temple University and it's 46 00:02:35,330 --> 00:02:32,500 a disciplinary team of different flavors 47 00:02:38,930 --> 00:02:35,340 of chemists mainly and so we have 48 00:02:41,880 --> 00:02:38,940 metallic a biochemist or biochemists and 49 00:02:44,790 --> 00:02:41,890 all the way to a computational and 50 00:02:48,690 --> 00:02:44,800 physical chemists or were spanning that 51 00:02:51,479 --> 00:02:48,700 range of chemistry so John Broderick and 52 00:02:54,390 --> 00:02:51,489 I are our expertise is in the tallow 53 00:02:59,190 --> 00:02:54,400 biochemistry Martin student in 54 00:03:01,430 --> 00:02:59,200 geochemistry and John Parise in 55 00:03:04,410 --> 00:03:01,440 geochemistry as well being strong in 56 00:03:06,900 --> 00:03:04,420 surface science Trevor Douglas in nano 57 00:03:09,870 --> 00:03:06,910 material science that Tim mitten in 58 00:03:12,350 --> 00:03:09,880 molecular beam science mark young 59 00:03:14,880 --> 00:03:12,360 molecular biologist and neurologist 60 00:03:17,420 --> 00:03:14,890 Roberts loggia spectroscopy and 61 00:03:21,870 --> 00:03:17,430 computational chemist and a philosopher 62 00:03:26,370 --> 00:03:21,880 prashanta baba bhai pretty good job with 63 00:03:28,650 --> 00:03:26,380 that one I say okay so so it's a fairly 64 00:03:30,030 --> 00:03:28,660 focused center where we're probing the 65 00:03:34,650 --> 00:03:30,040 relationships between structure and 66 00:03:37,050 --> 00:03:34,660 reactivity of iron sulfur motifs and the 67 00:03:39,479 --> 00:03:37,060 role of iron sulfur motifs in prebiotic 68 00:03:41,970 --> 00:03:39,489 chemistry and the origin of blood so 69 00:03:45,440 --> 00:03:41,980 there's been a lot of ideas about the 70 00:03:48,479 --> 00:03:45,450 origin of life and those have evolved 71 00:03:50,729 --> 00:03:48,489 with time so to speak and I think 72 00:03:54,780 --> 00:03:50,739 without going through this slide you 73 00:03:58,470 --> 00:03:54,790 know our project is really can be tied 74 00:04:00,539 --> 00:03:58,480 to metabolism first ideas for the 75 00:04:03,750 --> 00:04:00,549 original life that are really focused 76 00:04:09,800 --> 00:04:03,760 more on prebiotic chemistry so relevant 77 00:04:13,530 --> 00:04:09,810 to RNA world with the world making proto 78 00:04:15,840 --> 00:04:13,540 biomolecules of any kind but I think you 79 00:04:18,060 --> 00:04:15,850 know vodka Hauser's ideas on 80 00:04:20,940 --> 00:04:18,070 sofa world and Mike Russell's ideas I 81 00:04:24,090 --> 00:04:20,950 think that our project is in line mostly 82 00:04:25,740 --> 00:04:24,100 with those out here so what we're 83 00:04:28,560 --> 00:04:25,750 interested in we're interested in the 84 00:04:31,220 --> 00:04:28,570 reactions of raw materials important for 85 00:04:33,450 --> 00:04:31,230 the production of proto biomolecules or 86 00:04:38,730 --> 00:04:33,460 prebiotic chemistry and I've listed some 87 00:04:45,200 --> 00:04:38,740 of the those molecules those small 88 00:04:48,180 --> 00:04:45,210 molecules here and in the hypothetical 89 00:04:51,030 --> 00:04:48,190 origin alive broken into four stages 90 00:04:54,450 --> 00:04:51,040 here a Hadean stage in which we have 91 00:04:57,020 --> 00:04:54,460 inter conversion of small molecules to 92 00:04:59,370 --> 00:04:57,030 increase the pool of raw materials for 93 00:05:00,540 --> 00:04:59,380 condensation reactions in the second 94 00:05:03,500 --> 00:05:00,550 stage which is followed by 95 00:05:07,350 --> 00:05:03,510 polymerization reactions and then 96 00:05:11,250 --> 00:05:07,360 organization and so enough I haven't 97 00:05:12,870 --> 00:05:11,260 drawn a line here where life emerges but 98 00:05:15,450 --> 00:05:12,880 we all know that you know at this stage 99 00:05:18,120 --> 00:05:15,460 when we have cells and organization we 100 00:05:20,790 --> 00:05:18,130 have luck so the interconversion between 101 00:05:24,090 --> 00:05:20,800 small molecules these molecules that 102 00:05:26,370 --> 00:05:24,100 I've shown above maintaining the pool of 103 00:05:28,410 --> 00:05:26,380 raw materials for condensation reaction 104 00:05:30,650 --> 00:05:28,420 the second stage that result the 105 00:05:33,210 --> 00:05:30,660 formation of proto biomolecules is 106 00:05:35,640 --> 00:05:33,220 critical for the original so again we're 107 00:05:39,600 --> 00:05:35,650 talking about hating chemistry of his 108 00:05:42,510 --> 00:05:39,610 first stage so when Dave Desmarais gave 109 00:05:46,890 --> 00:05:42,520 his talk he presented this slide from 110 00:05:49,400 --> 00:05:46,900 Andrew portillo about the integration of 111 00:05:52,950 --> 00:05:49,410 original life research across the 112 00:05:57,380 --> 00:05:52,960 Institute which includes the studies at 113 00:06:00,780 --> 00:05:57,390 Goddard origin and evolution of organic 114 00:06:04,170 --> 00:06:00,790 studied that wrestler that got catalytic 115 00:06:06,000 --> 00:06:04,180 potential of clays and then to Carnegie 116 00:06:09,810 --> 00:06:06,010 the geochemical steps leading to the 117 00:06:12,180 --> 00:06:09,820 emergence of catalysis then our project 118 00:06:15,780 --> 00:06:12,190 origin and evolution of iron sulfur of 119 00:06:18,429 --> 00:06:15,790 protein enzyme the aims groups research 120 00:06:21,320 --> 00:06:18,439 on that foraging and evolution of in 121 00:06:24,559 --> 00:06:21,330 then the Georgia Tech group looking at 122 00:06:27,080 --> 00:06:24,569 the ribosome and RNA and protein 123 00:06:29,689 --> 00:06:27,090 translation I think you know now that I 124 00:06:32,029 --> 00:06:29,699 have this in my hands I can say that you 125 00:06:34,040 --> 00:06:32,039 know i think our project really in 126 00:06:37,520 --> 00:06:34,050 addition to focusing on this area really 127 00:06:39,709 --> 00:06:37,530 expands from these studies on the 128 00:06:42,709 --> 00:06:39,719 catalytic potential of things through 129 00:06:47,059 --> 00:06:42,719 the origin and evolution of the 130 00:06:49,300 --> 00:06:47,069 influence ok so in biology hating 131 00:06:52,040 --> 00:06:49,310 chemistry or the like is catalyzed by 132 00:06:53,990 --> 00:06:52,050 iron sulfur enzymes and some complex 133 00:06:56,600 --> 00:06:54,000 iron sulfur enzymes and iron sulfur 134 00:07:00,100 --> 00:06:56,610 proteins and enzymes are ubiquitous in 135 00:07:03,980 --> 00:07:00,110 life almost all organisms have these 136 00:07:05,860 --> 00:07:03,990 smaller simpler versions to iron sulfur 137 00:07:10,879 --> 00:07:05,870 clusters four on four so four clusters 138 00:07:13,189 --> 00:07:10,889 three iron for sulfur clusters in many 139 00:07:15,769 --> 00:07:13,199 cases those clusters involved in 140 00:07:17,749 --> 00:07:15,779 electron transfer reactions are involved 141 00:07:20,899 --> 00:07:17,759 in photosynthesis in respiration 142 00:07:22,939 --> 00:07:20,909 involved in many other processes but we 143 00:07:25,670 --> 00:07:22,949 also have these more complex versions 144 00:07:28,129 --> 00:07:25,680 like the metal clusters associated with 145 00:07:31,279 --> 00:07:28,139 nitrogenase the key cluster iron origina 146 00:07:35,149 --> 00:07:31,289 sofa the metal cluster associated with 147 00:07:38,329 --> 00:07:35,159 the iron iron hydrogen aah cluster and 148 00:07:40,730 --> 00:07:38,339 these costs are associated with the 149 00:07:43,899 --> 00:07:40,740 carbon monoxide dehydrogenase acetyl co 150 00:07:46,790 --> 00:07:43,909 raise synthase complex which has nickel 151 00:07:50,409 --> 00:07:46,800 iron sulfur clusters in a couple 152 00:07:53,589 --> 00:07:50,419 different terms so those reactions 153 00:07:57,019 --> 00:07:53,599 catalyzed by these complex iron-sulfur 154 00:07:58,999 --> 00:07:57,029 cluster containing enzymes again these 155 00:08:01,369 --> 00:07:59,009 are reactions hey team chemistry 156 00:08:04,939 --> 00:08:01,379 reactions that would have been important 157 00:08:07,730 --> 00:08:04,949 in the early Earth or at least reactions 158 00:08:09,260 --> 00:08:07,740 that are very similar to the reactions 159 00:08:12,429 --> 00:08:09,270 that would have been important in her 160 00:08:15,890 --> 00:08:12,439 life the hydrogen AIDS reaction the 161 00:08:18,079 --> 00:08:15,900 reversible oxidation of hydrogen the 162 00:08:18,900 --> 00:08:18,089 nitrogenase reaction the reduction of 163 00:08:22,050 --> 00:08:18,910 nitrogen 164 00:08:25,500 --> 00:08:22,060 ammonia the inter conversion between co 165 00:08:29,060 --> 00:08:25,510 and co2 or the condensation of CO and 166 00:08:32,460 --> 00:08:29,070 methyl groups to form activated absolute 167 00:08:34,230 --> 00:08:32,470 so iron sulfur mineral and other 168 00:08:37,770 --> 00:08:34,240 derivatives have interesting structural 169 00:08:40,110 --> 00:08:37,780 relationships with enzymes and have also 170 00:08:42,540 --> 00:08:40,120 been able to have been shown to catalyze 171 00:08:46,410 --> 00:08:42,550 these type of reaction well this is a 172 00:08:50,610 --> 00:08:46,420 fired from unintentionally created a 173 00:08:53,970 --> 00:08:50,620 strange animation hibbett this this is a 174 00:08:56,370 --> 00:08:53,980 fired from my Brussels work that Mike 175 00:09:00,270 --> 00:08:56,380 Russell bill bill martin just looking at 176 00:09:02,340 --> 00:09:00,280 the similarities between the clusters 177 00:09:04,410 --> 00:09:02,350 the active site clusters co 178 00:09:08,940 --> 00:09:04,420 dehydrogenase and sedo cow attentive and 179 00:09:12,840 --> 00:09:08,950 the structure of a nickel containing ray 180 00:09:16,890 --> 00:09:12,850 got mineral lattice and so you have 181 00:09:20,550 --> 00:09:16,900 nickel the themes the nickel and iron 182 00:09:22,560 --> 00:09:20,560 sulfur clusters and association and you 183 00:09:24,630 --> 00:09:22,570 know we would assert that the 184 00:09:26,970 --> 00:09:24,640 relationship between aerosol for mineral 185 00:09:29,700 --> 00:09:26,980 and iron sulfur enzyme structure 186 00:09:32,520 --> 00:09:29,710 function and reactivities just too 187 00:09:36,050 --> 00:09:32,530 strong to be coincidental and especially 188 00:09:38,820 --> 00:09:36,060 with the you know what we know the 189 00:09:44,690 --> 00:09:38,830 abundance of iron supplemental at the 190 00:09:46,860 --> 00:09:44,700 origin okay another that's an example of 191 00:09:51,480 --> 00:09:46,870 structural relationships here's a couple 192 00:09:55,350 --> 00:09:51,490 reaction or examples of reactivity in 193 00:09:57,330 --> 00:09:55,360 iron sulfur minerals or the why this is 194 00:10:00,260 --> 00:09:57,340 an example from good good job octa 195 00:10:04,320 --> 00:10:00,270 Hauser looking at the formation of 196 00:10:08,880 --> 00:10:04,330 activated after cake under primordial 197 00:10:12,450 --> 00:10:08,890 conditions with small molecule small 198 00:10:16,020 --> 00:10:12,460 molecule precursors and a nickel iron 199 00:10:19,320 --> 00:10:16,030 sulfur amalgam as a catalyst forming an 200 00:10:22,650 --> 00:10:19,330 activated a potato thursday miss 201 00:10:26,569 --> 00:10:22,660 proposed mechanism this is an example 202 00:10:29,419 --> 00:10:26,579 from our kopi I Martin student where 203 00:10:31,460 --> 00:10:29,429 been able to show that he can get 204 00:10:33,619 --> 00:10:31,470 nitrogen reduction under hydrothermal 205 00:10:35,660 --> 00:10:33,629 vent conditions are really know if 206 00:10:37,400 --> 00:10:35,670 you're compared to that predict the 207 00:10:39,949 --> 00:10:37,410 conditions where we produce nitrogenous 208 00:10:44,090 --> 00:10:39,959 fertilizers milder conditions and 209 00:10:47,960 --> 00:10:44,100 temperature and pressure and so this on 210 00:10:52,150 --> 00:10:47,970 this flawed just showings it that the 211 00:10:57,169 --> 00:10:52,160 rate of nitrogen reduction to ammonia 212 00:11:01,429 --> 00:10:57,179 with oxygen sulfide is increased in the 213 00:11:03,350 --> 00:11:01,439 presence of pyrite and Martin and a 214 00:11:07,600 --> 00:11:03,360 number of under other investigators have 215 00:11:10,369 --> 00:11:07,610 been able to show that defects in 216 00:11:12,919 --> 00:11:10,379 mineral structure actually enhance the 217 00:11:17,689 --> 00:11:12,929 reactivity or enhance the catalytic 218 00:11:21,639 --> 00:11:17,699 activity I'll get back to the so those 219 00:11:24,739 --> 00:11:21,649 that three examples really implicate a 220 00:11:27,769 --> 00:11:24,749 iron sulfur or the Royal of iron simple 221 00:11:30,710 --> 00:11:27,779 mineral in these two stages of the 222 00:11:35,449 --> 00:11:30,720 original life in the fourth stage model 223 00:11:39,109 --> 00:11:35,459 that I've already shown and know when 224 00:11:45,530 --> 00:11:39,119 you think about a marker am i doing okay 225 00:11:47,720 --> 00:11:45,540 with the delay yes I'm okay um so you 226 00:11:50,569 --> 00:11:47,730 know if you think about it iron so for 227 00:11:52,460 --> 00:11:50,579 minerals serving as catalysts for these 228 00:11:54,889 --> 00:11:52,470 varying reactions than you have to think 229 00:11:57,109 --> 00:11:54,899 of a variety of iron sulfur minerals it 230 00:11:59,720 --> 00:11:57,119 showed you know the Greg I'd example 231 00:12:01,639 --> 00:11:59,730 that's one modification nickel 232 00:12:05,329 --> 00:12:01,649 association with iron sulfur minerals 233 00:12:07,549 --> 00:12:05,339 but you know to catalyze nitrogen 234 00:12:08,960 --> 00:12:07,559 reduction or reversible hydrogen 235 00:12:10,850 --> 00:12:08,970 oxidation have to take a variety of 236 00:12:13,039 --> 00:12:10,860 different minerals and I think that you 237 00:12:15,919 --> 00:12:13,049 know hydrothermal vent systems or the 238 00:12:17,479 --> 00:12:15,929 effluence of iron soulful rich thermal 239 00:12:20,150 --> 00:12:17,489 springs are really inspiration for this 240 00:12:25,239 --> 00:12:20,160 idea to get gradients of temperature and 241 00:12:28,579 --> 00:12:25,249 pressure and different gas solubility 242 00:12:30,590 --> 00:12:28,589 mineral solubility really combinatorial 243 00:12:32,780 --> 00:12:30,600 chemistry with respect to the types of 244 00:12:37,670 --> 00:12:32,790 iron sulfur minerals that you could 245 00:12:39,860 --> 00:12:37,680 right in these systems ok so our project 246 00:12:41,810 --> 00:12:39,870 overall it's really asking this question 247 00:12:43,430 --> 00:12:41,820 can we think about the active sites of 248 00:12:45,740 --> 00:12:43,440 iron sulfur enzymes of highly evolved 249 00:12:48,170 --> 00:12:45,750 derivatives that aren't a tremendous and 250 00:12:50,570 --> 00:12:48,180 from that we have and I'm showing here 251 00:12:55,130 --> 00:12:50,580 the active site of unit h cluster of 252 00:12:57,440 --> 00:12:55,140 hydrogen a and the Armos and cofactor of 253 00:12:59,890 --> 00:12:57,450 nitrogenase a couple of our favorite 254 00:13:02,450 --> 00:12:59,900 model systems with the structure of 255 00:13:05,210 --> 00:13:02,460 minerals and a mineral lattice and you 256 00:13:06,800 --> 00:13:05,220 know from that overarching question the 257 00:13:10,940 --> 00:13:06,810 number of different questions that we 258 00:13:12,410 --> 00:13:10,950 can attach experiments to including g 259 00:13:15,200 --> 00:13:12,420 mineral modifications enhanced 260 00:13:17,060 --> 00:13:15,210 reactivity to minerals be modified in a 261 00:13:20,900 --> 00:13:17,070 manner inspired by the biochemistry to 262 00:13:22,520 --> 00:13:20,910 enhance reactivity what is the influence 263 00:13:26,120 --> 00:13:22,530 of organic nesting or the protein 264 00:13:27,890 --> 00:13:26,130 environment on structuring cell what are 265 00:13:30,620 --> 00:13:27,900 the structural determinants totality 266 00:13:33,020 --> 00:13:30,630 catalysis and how they're derived our 267 00:13:34,970 --> 00:13:33,030 modifications chemically conferred what 268 00:13:37,130 --> 00:13:34,980 is the evolutionary history and origin 269 00:13:39,830 --> 00:13:37,140 of violence such an engine and so this 270 00:13:41,180 --> 00:13:39,840 really these list of questions that I 271 00:13:43,280 --> 00:13:41,190 just rattled off where you really 272 00:13:47,540 --> 00:13:43,290 represent sort of a continuum that's 273 00:13:50,420 --> 00:13:47,550 going across scare and that's really in 274 00:13:53,390 --> 00:13:50,430 a way how our project is set up in three 275 00:13:55,280 --> 00:13:53,400 thrusts series the first thrust area of 276 00:13:57,470 --> 00:13:55,290 focusing on iron sulfur mineral and 277 00:14:00,310 --> 00:13:57,480 modified arms of a mineral structure and 278 00:14:02,630 --> 00:14:00,320 reactivity that's our mineral thrust a 279 00:14:04,520 --> 00:14:02,640 bridging thrust and the medic 280 00:14:07,100 --> 00:14:04,530 iron-sulfur cluster synthesis and 281 00:14:11,060 --> 00:14:07,110 organic nesting thrust probing the 282 00:14:14,420 --> 00:14:11,070 transition between abiotic and biotic or 283 00:14:16,490 --> 00:14:14,430 the relationship between abiotic and 284 00:14:18,860 --> 00:14:16,500 biotic iron sulfur catalysis and that's 285 00:14:20,980 --> 00:14:18,870 our mimetic thrust and then iron super 286 00:14:25,640 --> 00:14:20,990 enzyme structure reactivity and 287 00:14:27,770 --> 00:14:25,650 biosynthesis our enzyme threats so are 288 00:14:30,640 --> 00:14:27,780 our mineral thrusts really the 289 00:14:33,290 --> 00:14:30,650 hypothesis the overarching hypothesis 290 00:14:36,230 --> 00:14:33,300 metal centers in enzymes are more likely 291 00:14:38,360 --> 00:14:36,240 related to mineral defects and ideal 292 00:14:41,050 --> 00:14:38,370 mineral structural motifs and really 293 00:14:43,970 --> 00:14:41,060 sort of probing the effects of defined 294 00:14:44,950 --> 00:14:43,980 modifications or defect I hate it and I 295 00:14:46,360 --> 00:14:44,960 work on these 296 00:14:49,480 --> 00:14:46,370 enzymes that have these beautiful 297 00:14:52,050 --> 00:14:49,490 iron-sulfur clusters I have a reluctance 298 00:14:57,730 --> 00:14:52,060 to connect them to defects so their 299 00:15:00,940 --> 00:14:57,740 modification but you know examining the 300 00:15:03,340 --> 00:15:00,950 relationship between defects the 301 00:15:06,460 --> 00:15:03,350 structure of Defense and the effects on 302 00:15:09,240 --> 00:15:06,470 reactivity and so within that we have 303 00:15:12,670 --> 00:15:09,250 three different levels of which we're 304 00:15:15,970 --> 00:15:12,680 looking at minerals one is to synthesize 305 00:15:21,400 --> 00:15:15,980 these mineral surfaces modify those 306 00:15:25,630 --> 00:15:21,410 mineral surfaces or if we must introduce 307 00:15:29,140 --> 00:15:25,640 defined defects in that characterize the 308 00:15:30,490 --> 00:15:29,150 nature of the defects use a combination 309 00:15:33,970 --> 00:15:30,500 of advanced experimental and theoretical 310 00:15:36,840 --> 00:15:33,980 techniques to develop insight into the 311 00:15:39,700 --> 00:15:36,850 reactions look at the reactivity 312 00:15:42,250 --> 00:15:39,710 directly and the intermediates in those 313 00:15:44,230 --> 00:15:42,260 reactions and then and looking at 314 00:15:46,110 --> 00:15:44,240 defining the energy barriers of 315 00:15:49,120 --> 00:15:46,120 processes connecting the reaction 316 00:15:52,660 --> 00:15:49,130 intermediate together really defining 317 00:15:55,260 --> 00:15:52,670 the reaction mechanism for mineral a lot 318 00:16:00,700 --> 00:15:55,270 of this mineral trust has focused on 319 00:16:04,000 --> 00:16:00,710 reactivity dinitrogen reduction it's 320 00:16:07,950 --> 00:16:04,010 sort of the tour de force you mean this 321 00:16:11,080 --> 00:16:07,960 one is the most challenging reactivity 322 00:16:13,510 --> 00:16:11,090 ok so for from the slide I've already 323 00:16:16,840 --> 00:16:13,520 shown you the real what the mineral 324 00:16:18,850 --> 00:16:16,850 thrust is focusing on is these two 325 00:16:21,490 --> 00:16:18,860 questions here de mineral modifications 326 00:16:24,790 --> 00:16:21,500 enhancer activity and communal be 327 00:16:27,640 --> 00:16:24,800 modified inspired by the biochemistry to 328 00:16:32,880 --> 00:16:27,650 enhance reactivity aurelia driven ligand 329 00:16:36,210 --> 00:16:32,890 accelerated catalysis okay so the first 330 00:16:38,350 --> 00:16:36,220 generating these mineral surfaces or 331 00:16:41,320 --> 00:16:38,360 defective mineral surfaces and 332 00:16:44,170 --> 00:16:41,330 characterizing those that's really a 333 00:16:48,130 --> 00:16:44,180 thrust that damn strong and spearheading 334 00:16:53,020 --> 00:16:48,140 and so we introduces defects and you can 335 00:16:55,780 --> 00:16:53,030 see here hydrogen and barting hydrogen 336 00:16:56,670 --> 00:16:55,790 on this mineral surface hydrogen sulfide 337 00:17:03,690 --> 00:16:56,680 in 338 00:17:05,699 --> 00:17:03,700 defects eyes by six town-based 339 00:17:11,220 --> 00:17:05,709 photoemission or even photoelectron 340 00:17:14,549 --> 00:17:11,230 spectroscopy in the last the next part 341 00:17:17,340 --> 00:17:14,559 of the mineral thrust is looking at 342 00:17:19,770 --> 00:17:17,350 reactivity directly spearheaded by 343 00:17:23,610 --> 00:17:19,780 Martin skinnin who's looking at nitrogen 344 00:17:29,060 --> 00:17:23,620 reduction reactivity but also nitrate 345 00:17:31,850 --> 00:17:29,070 and nitrite sources for abiotic ammonia 346 00:17:36,210 --> 00:17:31,860 reduction of those molecules as well 347 00:17:39,750 --> 00:17:36,220 he's in this first part of grammar 348 00:17:42,240 --> 00:17:39,760 developed a system to in a very 349 00:17:45,380 --> 00:17:42,250 sensitive way detect nitrogen reduction 350 00:17:49,080 --> 00:17:45,390 or of sensitive method for analyzing 351 00:17:51,480 --> 00:17:49,090 ammonia using this making this 352 00:17:56,940 --> 00:17:51,490 fluorescence derivative and has a flow 353 00:17:59,549 --> 00:17:56,950 system where he can analyze the same he 354 00:18:01,860 --> 00:17:59,559 and Dan strong in our team not to look 355 00:18:05,280 --> 00:18:01,870 at intermediates in those reactions 356 00:18:08,760 --> 00:18:05,290 using IR spectroscopy and a significant 357 00:18:11,910 --> 00:18:08,770 challenge with these as was or a barrier 358 00:18:15,299 --> 00:18:11,920 that had to be over time was just with 359 00:18:18,090 --> 00:18:15,309 the sample apparatus having hydrogen 360 00:18:21,210 --> 00:18:18,100 sulfide around very corrosive there was 361 00:18:29,490 --> 00:18:21,220 some problems with the sample apparatus 362 00:18:31,530 --> 00:18:29,500 now and now this feeling the support by 363 00:18:33,870 --> 00:18:31,540 gold plating is actually allowed them to 364 00:18:41,310 --> 00:18:33,880 overcome those challenges and you're 365 00:18:43,770 --> 00:18:41,320 generating results so the third part of 366 00:18:45,630 --> 00:18:43,780 this defining energy barriers of the 367 00:18:47,940 --> 00:18:45,640 processes and connecting reaction 368 00:18:51,270 --> 00:18:47,950 intermediates is the thrust that 369 00:18:53,600 --> 00:18:51,280 spearheaded by Tim Minton and involves 370 00:18:57,440 --> 00:18:53,610 molecular beam songs and here's the 371 00:19:00,030 --> 00:18:57,450 instrument that Tim uses for these 372 00:19:02,070 --> 00:19:00,040 studies that like Labine studies in 373 00:19:03,210 --> 00:19:02,080 attempt to jump to me that if you 374 00:19:04,650 --> 00:19:03,220 wouldn't have become a physical chemist 375 00:19:05,820 --> 00:19:04,660 he would have become a plumber and I 376 00:19:07,200 --> 00:19:05,830 think they've killed is the plumber 377 00:19:10,070 --> 00:19:07,210 really come in handy 378 00:19:12,750 --> 00:19:10,080 terms of maintaining the instrumentation 379 00:19:18,180 --> 00:19:12,760 after I did get my trophy eyes to roll 380 00:19:21,240 --> 00:19:18,190 their eyes advanced Africa ok so what 381 00:19:23,100 --> 00:19:21,250 ten is looking at models of prebiotic 382 00:19:25,320 --> 00:19:23,110 chemical transformations mechanisms for 383 00:19:27,510 --> 00:19:25,330 hydrogen and nitrogen reactions at iron 384 00:19:30,960 --> 00:19:27,520 supplemental services so really bringing 385 00:19:34,340 --> 00:19:30,970 together the results from Dan and 386 00:19:38,430 --> 00:19:34,350 Martin's work and focusing on energy so 387 00:19:40,169 --> 00:19:38,440 what a mark to a level description of 388 00:19:41,820 --> 00:19:40,179 the mechanism nitrogen production and 389 00:19:46,289 --> 00:19:41,830 guide our understanding what kinds of 390 00:19:48,180 --> 00:19:46,299 services are likely to be react and so 391 00:19:50,539 --> 00:19:48,190 these studies will provide an input for 392 00:19:52,620 --> 00:19:50,549 theory and experiments by other groups 393 00:19:55,039 --> 00:19:52,630 explanation of the observed phenomenon 394 00:19:57,480 --> 00:19:55,049 and complex experimental system and 395 00:20:00,930 --> 00:19:57,490 insight in the structural motifs that 396 00:20:01,889 --> 00:20:00,940 have been seen in nature and so really 397 00:20:04,080 --> 00:20:01,899 what we're talking about is 398 00:20:09,149 --> 00:20:04,090 understanding reaction at the molecular 399 00:20:11,549 --> 00:20:09,159 level with these studies and well what 400 00:20:13,950 --> 00:20:11,559 Tim has is you know really it's 401 00:20:16,380 --> 00:20:13,960 basically a closed system where you can 402 00:20:18,090 --> 00:20:16,390 modulate a lot of different variables 403 00:20:20,880 --> 00:20:18,100 and the variables some of the variables 404 00:20:23,159 --> 00:20:20,890 are shown here and look at what comes 405 00:20:25,799 --> 00:20:23,169 out at the end with mass spec and then 406 00:20:30,510 --> 00:20:25,809 from that infer what's going on at the 407 00:20:34,100 --> 00:20:30,520 surface you can look at inelastic 408 00:20:37,740 --> 00:20:34,110 scattering which will be indicative of 409 00:20:41,880 --> 00:20:37,750 energy related to bond breakage and bond 410 00:20:45,299 --> 00:20:41,890 formation okay and here's an example of 411 00:20:48,690 --> 00:20:45,309 experiment here bombarding or using a 412 00:20:51,860 --> 00:20:48,700 molecular beam deuterium atoms on pyrite 413 00:20:58,289 --> 00:20:51,870 surface and looking at the formation of 414 00:21:02,340 --> 00:20:58,299 d2f which looking at d2s and that's 415 00:21:05,159 --> 00:21:02,350 shown here and the maxwell-boltzmann 416 00:21:08,190 --> 00:21:05,169 distribution indicates that the 417 00:21:11,580 --> 00:21:08,200 formation is in thermal equilibrium and 418 00:21:13,500 --> 00:21:11,590 then here is a set of images showing 419 00:21:16,390 --> 00:21:13,510 what happens to the mineral surface 420 00:21:18,400 --> 00:21:16,400 after exposure five minutes and 421 00:21:22,090 --> 00:21:18,410 three hundred twenty minutes here and 422 00:21:26,140 --> 00:21:22,100 these are fpm images of that searches 423 00:21:29,410 --> 00:21:26,150 and Robert who's not with us today 424 00:21:32,010 --> 00:21:29,420 Robert szilágyi one of our co p oz is 425 00:21:34,750 --> 00:21:32,020 actually at the synchrotron source 426 00:21:38,350 --> 00:21:34,760 analyzing what's happening at this 427 00:21:40,000 --> 00:21:38,360 mineral surface using excess so what's 428 00:21:43,240 --> 00:21:40,010 happening to the bonding of iron and 429 00:21:45,160 --> 00:21:43,250 Soviet businesses so tim is also going 430 00:21:47,760 --> 00:21:45,170 to show that the evolution of nitrogen 431 00:21:53,350 --> 00:21:47,770 scattering on these surfaces the 432 00:21:57,040 --> 00:21:53,360 modified surfaces is affected by the 433 00:21:58,840 --> 00:21:57,050 surface roughness and so this may tie us 434 00:22:03,300 --> 00:21:58,850 back to what we were saying earlier 435 00:22:10,690 --> 00:22:03,310 about the that the defect stocks or 436 00:22:12,160 --> 00:22:10,700 defects affecting reactivity okay I got 437 00:22:16,660 --> 00:22:12,170 through that one that one's actually the 438 00:22:20,830 --> 00:22:16,670 toughest women and on to the next dress 439 00:22:22,570 --> 00:22:20,840 the mimetic thrust and this is Trevor 440 00:22:24,670 --> 00:22:22,580 Douglas the leader of that threaten both 441 00:22:27,880 --> 00:22:24,680 Trevor Douglas mark young and John 442 00:22:31,060 --> 00:22:27,890 trivia Stoney group and so this is 443 00:22:33,400 --> 00:22:31,070 iron-sulfur cluster synthesis or organic 444 00:22:36,520 --> 00:22:33,410 nesting so this is really looking at the 445 00:22:38,140 --> 00:22:36,530 effect in a controlled way of a protein 446 00:22:40,920 --> 00:22:38,150 environment on the physical and 447 00:22:44,440 --> 00:22:40,930 catalytic properties of metal clusters 448 00:22:48,370 --> 00:22:44,450 and what you know the systems that use 449 00:22:50,770 --> 00:22:48,380 our protein cages as templates templates 450 00:22:53,980 --> 00:22:50,780 for the synthesis of clusters and they 451 00:22:56,500 --> 00:22:53,990 can do this in a controlled way this is 452 00:22:59,530 --> 00:22:56,510 one example of the ferritin molecule 453 00:23:02,680 --> 00:22:59,540 from pyrococcus furiosus is it done a 454 00:23:04,360 --> 00:23:02,690 stable template you're breaking news for 455 00:23:07,360 --> 00:23:04,370 synthesis which is you know greater 456 00:23:11,890 --> 00:23:07,370 flexibility and so do these syntheses 457 00:23:14,170 --> 00:23:11,900 under hydrothermal vent conditions okay 458 00:23:17,530 --> 00:23:14,180 so that's thrust the mimetic thrust 459 00:23:19,630 --> 00:23:17,540 spans these questions in our continuum 460 00:23:22,180 --> 00:23:19,640 of questions looking at the relation 461 00:23:25,810 --> 00:23:22,190 between iron silver kingdoms and iron 462 00:23:30,400 --> 00:23:25,820 super minions and so the simple system 463 00:23:34,240 --> 00:23:30,410 and showing that the synthesis of or the 464 00:23:38,110 --> 00:23:34,250 protection of iron oxide clusters here 465 00:23:41,350 --> 00:23:38,120 in this mineral pad so in this in this 466 00:23:46,060 --> 00:23:41,360 end picture we have and cage and you can 467 00:23:48,550 --> 00:23:46,070 see this is abstained stained image 468 00:23:50,380 --> 00:23:48,560 where you can see the protein here and 469 00:23:52,570 --> 00:23:50,390 then these are unstained images we're 470 00:23:55,060 --> 00:23:52,580 looking at the density of the metal 471 00:23:58,780 --> 00:23:55,070 clusters here I are not Cyrus and even 472 00:24:00,910 --> 00:23:58,790 here iron sulphide then iron oxide can 473 00:24:04,240 --> 00:24:00,920 be produced by the procedure shown here 474 00:24:09,970 --> 00:24:04,250 and iron sofa or iron oxide can then be 475 00:24:12,100 --> 00:24:09,980 converted to iron hopefully these 476 00:24:15,240 --> 00:24:12,110 clusters it can be characterized in a 477 00:24:17,230 --> 00:24:15,250 number of ways and this is an example of 478 00:24:19,780 --> 00:24:17,240 characterization by small-angle x-ray 479 00:24:22,810 --> 00:24:19,790 scattering and pear distribution 480 00:24:24,790 --> 00:24:22,820 function which allows us to look at you 481 00:24:27,310 --> 00:24:24,800 know these clusters there really they 482 00:24:29,380 --> 00:24:27,320 don't have a well-defined mineral 483 00:24:33,010 --> 00:24:29,390 lattice and so that the bonding is a 484 00:24:35,970 --> 00:24:33,020 uniform ensue this approach which gives 485 00:24:39,310 --> 00:24:35,980 a similar information to the excess on 486 00:24:43,260 --> 00:24:39,320 someone and that we can get the the 487 00:24:45,520 --> 00:24:43,270 bonding of iron and sulfur in these 488 00:24:51,730 --> 00:24:45,530 somewhat heterogenous that when our 489 00:24:54,790 --> 00:24:51,740 closest and also control and monitor the 490 00:24:58,150 --> 00:24:54,800 cluster size and again you know this is 491 00:25:00,460 --> 00:24:58,160 really an organic template we're growing 492 00:25:04,180 --> 00:25:00,470 mineral clusters and then looking at the 493 00:25:06,610 --> 00:25:04,190 effect of cluster size and the protein 494 00:25:09,670 --> 00:25:06,620 environment what the protein environment 495 00:25:13,660 --> 00:25:09,680 imposes on the clusters in terms of its 496 00:25:18,790 --> 00:25:13,670 physical properties and reactivity this 497 00:25:21,370 --> 00:25:18,800 is one example of effect of the protein 498 00:25:24,550 --> 00:25:21,380 environment on the properties of these 499 00:25:27,370 --> 00:25:24,560 mineral clusters and this is looking at 500 00:25:30,130 --> 00:25:27,380 magnetism and this is showing here a 501 00:25:32,020 --> 00:25:30,140 cluster with the protein environment 502 00:25:34,930 --> 00:25:32,030 here showing that in the presence of the 503 00:25:37,170 --> 00:25:34,940 protein environment in this particle all 504 00:25:40,000 --> 00:25:37,180 the spindle on but if we remove the 505 00:25:43,600 --> 00:25:40,010 protein environment here the spins at 506 00:25:45,550 --> 00:25:43,610 the surface randomized and then can 507 00:25:49,960 --> 00:25:45,560 introduce that protein environment and 508 00:25:52,180 --> 00:25:49,970 restore that the alignment so the 509 00:25:53,970 --> 00:25:52,190 protein environment impacting the 510 00:25:57,160 --> 00:25:53,980 physical property of those clusters 511 00:25:59,920 --> 00:25:57,170 another example here is looking at the 512 00:26:01,720 --> 00:25:59,930 effect of size on the physical 513 00:26:04,690 --> 00:26:01,730 properties of those clusters and this is 514 00:26:07,210 --> 00:26:04,700 again a an example of magnetism with 515 00:26:08,740 --> 00:26:07,220 particle five nanometers eight 516 00:26:11,350 --> 00:26:08,750 nanometers and twenty nanometers 517 00:26:14,320 --> 00:26:11,360 applying a magnetic field for those 518 00:26:18,310 --> 00:26:14,330 particles and working as a change in 519 00:26:21,070 --> 00:26:18,320 momentum and can see in this 5 nanometer 520 00:26:24,640 --> 00:26:21,080 particle in the 8th animator particle it 521 00:26:28,000 --> 00:26:24,650 returns to the same moment here but the 522 00:26:30,460 --> 00:26:28,010 larger particle actually has some memory 523 00:26:34,870 --> 00:26:30,470 so there's a difference in the physical 524 00:26:38,950 --> 00:26:34,880 property that larger partisan so size 525 00:26:42,000 --> 00:26:38,960 affects the physical properties that the 526 00:26:44,710 --> 00:26:42,010 particle or the cluster in this state 527 00:26:46,840 --> 00:26:44,720 another example to influence of the 528 00:26:50,050 --> 00:26:46,850 protein environment on catalytic 529 00:26:56,220 --> 00:26:50,060 activity and this is an example of epic 530 00:26:59,130 --> 00:26:56,230 03 in ferritin and looking at that that 531 00:27:01,120 --> 00:26:59,140 cluster terms of its reactivity as a 532 00:27:04,120 --> 00:27:01,130 photocatalyst and actually be enough to 533 00:27:08,620 --> 00:27:04,130 measure this as a photo carry and so 534 00:27:10,480 --> 00:27:08,630 that that's a an example of reactivity 535 00:27:13,210 --> 00:27:10,490 of reactivity that we can measure them 536 00:27:16,570 --> 00:27:13,220 and that's a an objective and the thrust 537 00:27:22,450 --> 00:27:16,580 and now you know we've lips go back to 538 00:27:26,500 --> 00:27:22,460 that flood we have a facile means to 539 00:27:29,890 --> 00:27:26,510 convert these iron oxide clusters to 540 00:27:32,560 --> 00:27:29,900 iron-sulfur clusters and you know of the 541 00:27:33,190 --> 00:27:32,570 parallel analysis is now on going for 542 00:27:37,299 --> 00:27:33,200 the iron 543 00:27:41,649 --> 00:27:37,309 clusters and then they have some data on 544 00:27:44,470 --> 00:27:41,659 that and that will see the ready for 545 00:27:45,639 --> 00:27:44,480 prime time okay so that's the second 546 00:27:47,649 --> 00:27:45,649 thrust and I'm actually doing pretty 547 00:27:50,919 --> 00:27:47,659 good on time animes but I think I'm 548 00:27:53,529 --> 00:27:50,929 going like a mile event here and I can 549 00:27:58,870 --> 00:27:53,539 go into our iron sulfur ends on dress 550 00:28:01,029 --> 00:27:58,880 and so this is that John Broderick and 551 00:28:02,470 --> 00:28:01,039 and I are spearheading and what we're 552 00:28:05,049 --> 00:28:02,480 doing is rubbing the structural 553 00:28:07,090 --> 00:28:05,059 determinants with developers were 554 00:28:09,759 --> 00:28:07,100 probing complex called the biosynthesis 555 00:28:12,120 --> 00:28:09,769 and the evolutionary origin and history 556 00:28:15,220 --> 00:28:12,130 of iron sulfur proteins in England 557 00:28:19,180 --> 00:28:15,230 couple of our favorite systems the iron 558 00:28:22,360 --> 00:28:19,190 iron hydrogenase so this is an enzyme 559 00:28:27,029 --> 00:28:22,370 that has a number of different metal 560 00:28:29,769 --> 00:28:27,039 clusters one of these complex 561 00:28:32,560 --> 00:28:29,779 iron-sulfur clusters there's a 4-iron 562 00:28:35,500 --> 00:28:32,570 for sulfur cluster that's bridge to this 563 00:28:38,740 --> 00:28:35,510 really organometallic e to iron unit 564 00:28:41,529 --> 00:28:38,750 that has carbon monoxide and cyanides as 565 00:28:44,460 --> 00:28:41,539 ligands I'm these hydrogenation systems 566 00:28:48,909 --> 00:28:44,470 are the only known systems that have 567 00:28:53,470 --> 00:28:48,919 this variation of modification to an 568 00:28:57,930 --> 00:28:53,480 iron-sulfur cluster these diatomics and 569 00:29:02,379 --> 00:28:57,940 then my charge note and this is the 570 00:29:05,080 --> 00:29:02,389 protein that harbors the active site for 571 00:29:08,139 --> 00:29:05,090 nitrogen reduction to a milling at the 572 00:29:10,000 --> 00:29:08,149 iron molybdenum cofactor so this shows 573 00:29:12,549 --> 00:29:10,010 the protein environment here this is a 574 00:29:14,680 --> 00:29:12,559 mono merrick protein as these five 575 00:29:16,930 --> 00:29:14,690 different metal clusters that has these 576 00:29:20,049 --> 00:29:16,940 accessory clusters that were presumably 577 00:29:22,779 --> 00:29:20,059 involved in shuttling electrons to or 578 00:29:25,870 --> 00:29:22,789 from that active site in reversible 579 00:29:28,299 --> 00:29:25,880 hydrogen oxidation and nitrogenase which 580 00:29:32,200 --> 00:29:28,309 is a hetero tetra mer two types of 581 00:29:34,690 --> 00:29:32,210 subunit two types of metal clusters 12 p 582 00:29:37,360 --> 00:29:34,700 clusters which are again intermediates 583 00:29:38,150 --> 00:29:37,370 and electron transfer to the business 584 00:29:42,270 --> 00:29:38,160 sizes 585 00:29:44,340 --> 00:29:42,280 co-factors which I it's a complex 586 00:29:48,210 --> 00:29:44,350 iron-sulfur cluster but it's hetero 587 00:29:52,310 --> 00:29:48,220 metallic it has molybdenum in addition 588 00:29:55,830 --> 00:29:52,320 to iron and sulfur and again some 589 00:30:00,060 --> 00:29:55,840 organic groups that are present to tune 590 00:30:03,510 --> 00:30:00,070 the reactivity of that system okay so 591 00:30:05,280 --> 00:30:03,520 now we're in this threat moving through 592 00:30:07,500 --> 00:30:05,290 this continuum what are the structural 593 00:30:11,040 --> 00:30:07,510 determinants of catalysis and how they 594 00:30:14,280 --> 00:30:11,050 derive really what are the structure and 595 00:30:17,090 --> 00:30:14,290 reactivity of these ends on how is 596 00:30:21,570 --> 00:30:17,100 modifications confer that's the bottom 597 00:30:26,520 --> 00:30:21,580 and then what's the evolutionary history 598 00:30:28,530 --> 00:30:26,530 of the origin of iron sisters okay so in 599 00:30:31,410 --> 00:30:28,540 this far i'm just showing what kind of 600 00:30:33,150 --> 00:30:31,420 known about the biosynthesis of the iron 601 00:30:37,710 --> 00:30:33,160 molybdenum cofactor in nitrogen 602 00:30:40,170 --> 00:30:37,720 interestingly you know that making a 603 00:30:43,310 --> 00:30:40,180 complex iron-sulfur cluster these unique 604 00:30:45,750 --> 00:30:43,320 modifications to the variations on the 605 00:30:49,200 --> 00:30:45,760 conflict or this iron sulfur 606 00:30:52,440 --> 00:30:49,210 coastertheme requires an enzymatic 607 00:30:54,990 --> 00:30:52,450 pathway requires a lot of biochemical 608 00:30:58,350 --> 00:30:55,000 machinery requires scaffolds and 609 00:30:59,970 --> 00:30:58,360 carriers and enzymes and a bunch of 610 00:31:02,460 --> 00:30:59,980 things that are thus far it might know 611 00:31:05,760 --> 00:31:02,470 this side really isn't from our work 612 00:31:07,200 --> 00:31:05,770 here this represents about 30 years of 613 00:31:09,870 --> 00:31:07,210 work from a number of different 614 00:31:13,860 --> 00:31:09,880 investigators to really at least at this 615 00:31:16,500 --> 00:31:13,870 level of insight on ironwood them 616 00:31:20,400 --> 00:31:16,510 cofactor bio synthesis and so what this 617 00:31:24,330 --> 00:31:20,410 slide is showing us just to simplify the 618 00:31:26,490 --> 00:31:24,340 if you have a scaffold and a scaffold 619 00:31:30,210 --> 00:31:26,500 that structurally similar to the 620 00:31:32,310 --> 00:31:30,220 molybdenum iron protein where a bunch of 621 00:31:36,620 --> 00:31:32,320 different enzymes and carriers at to 622 00:31:39,210 --> 00:31:36,630 build an iron molybdenum cofactor and 623 00:31:44,250 --> 00:31:39,220 after that i erm live in and cofactors 624 00:31:47,700 --> 00:31:44,260 built that's inserted into an organic 625 00:31:50,519 --> 00:31:47,710 mass or an 80 protein 626 00:31:52,289 --> 00:31:50,529 to give it its reactivity so this is 627 00:31:54,090 --> 00:31:52,299 really interesting in terms of the 628 00:31:55,980 --> 00:31:54,100 prebiotic chemistry the way we're 629 00:31:58,440 --> 00:31:55,990 thinking about things because you have 630 00:32:01,380 --> 00:31:58,450 the apparatus for the cluster is really 631 00:32:04,320 --> 00:32:01,390 separate to building the mess and in the 632 00:32:06,960 --> 00:32:04,330 final step to make the cluster reactive 633 00:32:13,560 --> 00:32:06,970 you insert the cluster in the nest to 634 00:32:16,909 --> 00:32:13,570 make an active India okay so there's 635 00:32:20,549 --> 00:32:16,919 some really interesting ties between the 636 00:32:23,669 --> 00:32:20,559 biosynthesis of the cluster I just 637 00:32:26,539 --> 00:32:23,679 showed you that the iron ilysm cofactor 638 00:32:30,659 --> 00:32:26,549 and our hydrogenation system and that 639 00:32:34,100 --> 00:32:30,669 link is in iron sulfur face radical 640 00:32:36,990 --> 00:32:34,110 chemistry so there's two enzymes in the 641 00:32:40,350 --> 00:32:37,000 biosynthesis of this cluster the H 642 00:32:43,760 --> 00:32:40,360 cluster and one enzyme involved in the 643 00:32:47,909 --> 00:32:43,770 synthesis of the iron ilysm cofactor 644 00:32:52,470 --> 00:32:47,919 that are radical Salmons iron sulfur 645 00:32:54,870 --> 00:32:52,480 based radical generating in zones so 646 00:32:57,720 --> 00:32:54,880 this is the active side of that in front 647 00:33:01,769 --> 00:32:57,730 of this whole class of radical fanzines 648 00:33:06,060 --> 00:33:01,779 on which hi-de-hi g and myth be our 649 00:33:08,940 --> 00:33:06,070 members where you have an iron-sulfur 650 00:33:11,430 --> 00:33:08,950 cluster and epidemic feel defining and 651 00:33:14,580 --> 00:33:11,440 that iron-sulfur clusters please 652 00:33:17,610 --> 00:33:14,590 epidemic feel defining form of dining 653 00:33:19,889 --> 00:33:17,620 and and erratic and that radical is 654 00:33:25,139 --> 00:33:19,899 coupled to a lot of different chemistry 655 00:33:29,399 --> 00:33:25,149 in nature generating radicals of amino 656 00:33:31,590 --> 00:33:29,409 acids it can be intermediate a radical 657 00:33:34,139 --> 00:33:31,600 of a minute and maybe a radical 658 00:33:36,360 --> 00:33:34,149 intermediate of an amino acid is 659 00:33:43,049 --> 00:33:36,370 involved in amino acid isomerization 660 00:33:44,909 --> 00:33:43,059 reaction is the reaction who the radical 661 00:33:47,669 --> 00:33:44,919 generation is important for sulfur 662 00:33:50,909 --> 00:33:47,679 insertion like the filter insertion to 5 663 00:33:54,659 --> 00:33:50,919 10 and shown here and this five consent 664 00:33:59,410 --> 00:33:54,669 brave soul for insertion for generating 665 00:34:04,690 --> 00:33:59,420 lopaka those 666 00:34:06,940 --> 00:34:04,700 so the known radical Sam chemistry 667 00:34:09,130 --> 00:34:06,950 really sparked us to kind of generate a 668 00:34:12,640 --> 00:34:09,140 hypothesis how that type of chemistry 669 00:34:14,409 --> 00:34:12,650 could be involved in hydrogenase H 670 00:34:16,600 --> 00:34:14,419 cluster biosynthesis and as I mentioned 671 00:34:18,430 --> 00:34:16,610 that's a really interesting variation on 672 00:34:21,100 --> 00:34:18,440 the iron sort of thing that has very 673 00:34:25,300 --> 00:34:21,110 unique ligands and that we can see this 674 00:34:28,510 --> 00:34:25,310 up here we have a bye byways ligand only 675 00:34:31,419 --> 00:34:28,520 place in nature that scene it's a non 676 00:34:33,760 --> 00:34:31,429 protein-dye pilot this isn't 15 this is 677 00:34:36,430 --> 00:34:33,770 a thigh late ligand that's not 678 00:34:38,950 --> 00:34:36,440 associated with approaching and these 679 00:34:42,940 --> 00:34:38,960 carbon monoxide and cyanide ligands 680 00:34:45,159 --> 00:34:42,950 again a unique feature to hydrogenate so 681 00:34:48,300 --> 00:34:45,169 we started to ask question you know how 682 00:34:50,950 --> 00:34:48,310 could those ligands be generated by 683 00:34:53,350 --> 00:34:50,960 radical same chemistry and we thought 684 00:34:55,480 --> 00:34:53,360 about that in the context of known 685 00:34:58,420 --> 00:34:55,490 radical Sam chemistry and came up with 686 00:35:01,200 --> 00:34:58,430 the hypothesis a hypothesis that if we 687 00:35:05,470 --> 00:35:01,210 started with a simple iron-sulfur 688 00:35:09,880 --> 00:35:05,480 cluster precursor we could introduce a 689 00:35:12,160 --> 00:35:09,890 dive bar leg leg in from a central 690 00:35:15,070 --> 00:35:12,170 metabolite amino acid or glycolytic 691 00:35:19,630 --> 00:35:15,080 intermediate we don't know the substrate 692 00:35:23,980 --> 00:35:19,640 for that yet by chemistry that's very 693 00:35:25,870 --> 00:35:23,990 similar to known sulfur insertion 694 00:35:29,760 --> 00:35:25,880 chemistry chemistry that we know that 695 00:35:33,130 --> 00:35:29,770 these radical salmon's on will catalyze 696 00:35:35,530 --> 00:35:33,140 and we could generate an intermediate 697 00:35:38,140 --> 00:35:35,540 that actually shifts the reactivity in 698 00:35:39,810 --> 00:35:38,150 this small iron-sulfur cluster to the 699 00:35:42,490 --> 00:35:39,820 iron atoms and we can think about 700 00:35:46,270 --> 00:35:42,500 reactivity occurring at the iron atom 701 00:35:49,090 --> 00:35:46,280 and the generation of these diatomic 702 00:35:51,460 --> 00:35:49,100 allegiances unique diatomic physics and 703 00:35:53,830 --> 00:35:51,470 then again we go back to this known 704 00:35:56,620 --> 00:35:53,840 reactivity for the radical salmon runs 705 00:35:58,300 --> 00:35:56,630 and we've proposed that if we formed an 706 00:36:02,950 --> 00:35:58,310 amino acid radical through this 707 00:36:06,280 --> 00:36:02,960 chemistry that that access iron die 708 00:36:08,660 --> 00:36:06,290 violently or iron violates sites that we 709 00:36:12,319 --> 00:36:08,670 could get decomposition of an 710 00:36:15,079 --> 00:36:12,329 mastered radical to form carbon monoxide 711 00:36:18,589 --> 00:36:15,089 and cyanide if you think about that you 712 00:36:22,099 --> 00:36:18,599 think about glycine well I've seen if 713 00:36:24,559 --> 00:36:22,109 you take glycine you bind it at an iron 714 00:36:27,890 --> 00:36:24,569 thiolate side a glycine radical if you 715 00:36:30,799 --> 00:36:27,900 shuffle around the electrons you can 716 00:36:33,170 --> 00:36:30,809 generate carbon monoxide cyanide and 717 00:36:37,789 --> 00:36:33,180 water very similar to the legand 718 00:36:41,349 --> 00:36:37,799 arrangement received in the iron ion 719 00:36:45,920 --> 00:36:41,359 hydrogen so this is our really this is a 720 00:36:48,740 --> 00:36:45,930 hypothesis and it's very intriguing and 721 00:36:51,770 --> 00:36:48,750 very intriguing in terms of astrobiology 722 00:36:53,630 --> 00:36:51,780 and Robert szilagyi generated a 723 00:36:57,470 --> 00:36:53,640 potential energy surface to map this 724 00:37:01,819 --> 00:36:57,480 reaction and if we have an iron one file 725 00:37:04,700 --> 00:37:01,829 a and this is an in silico experiment 726 00:37:07,250 --> 00:37:04,710 here we can generate a potential energy 727 00:37:09,859 --> 00:37:07,260 surface or a reaction coordinate that 728 00:37:12,770 --> 00:37:09,869 describes a favorable reaction of the 729 00:37:15,140 --> 00:37:12,780 decomposition of glycine the carbon 730 00:37:17,450 --> 00:37:15,150 monoxide cyanide and water that is iron 731 00:37:19,370 --> 00:37:17,460 thigh wavelength we have a favorable 732 00:37:22,130 --> 00:37:19,380 reaction we have an activation barrier 733 00:37:26,750 --> 00:37:22,140 that the activation barrier in this 734 00:37:29,450 --> 00:37:26,760 reaction is generating that amino acid 735 00:37:31,700 --> 00:37:29,460 radical and we know that we can overcome 736 00:37:33,859 --> 00:37:31,710 those barriers with radical same enzyme 737 00:37:37,160 --> 00:37:33,869 so this is you know if you think about 738 00:37:38,900 --> 00:37:37,170 this reaction you have the decomposition 739 00:37:41,990 --> 00:37:38,910 going in this direction to decomposition 740 00:37:44,900 --> 00:37:42,000 of an amino acid to form carbon monoxide 741 00:37:46,760 --> 00:37:44,910 cyanide and water if we think about the 742 00:37:49,339 --> 00:37:46,770 reaction in the reverse which we can get 743 00:37:52,160 --> 00:37:49,349 a favorable reaction immersively monkey 744 00:37:54,589 --> 00:37:52,170 with the oxidation of the metal side of 745 00:37:56,990 --> 00:37:54,599 the iron filings then we're talking 746 00:38:01,220 --> 00:37:57,000 about a condensation reaction where we 747 00:38:04,190 --> 00:38:01,230 have co and cyanide and water to form an 748 00:38:07,609 --> 00:38:04,200 immense and so really this represents in 749 00:38:10,430 --> 00:38:07,619 another potential leg involving iron 750 00:38:12,740 --> 00:38:10,440 sulfur motives linking hating chemistry 751 00:38:15,160 --> 00:38:12,750 and abiotic chemistry or inter 752 00:38:24,990 --> 00:38:15,170 conversion between small molecules and 753 00:38:29,049 --> 00:38:27,730 again you know in these studies and I'm 754 00:38:32,170 --> 00:38:29,059 just going to talk about a few examples 755 00:38:35,829 --> 00:38:32,180 of what we're doing instruction function 756 00:38:37,809 --> 00:38:35,839 of nitrogenase and hydrogenation you 757 00:38:40,359 --> 00:38:37,819 know an interesting and I've already 758 00:38:42,270 --> 00:38:40,369 drawn your attention to this is an 759 00:38:46,960 --> 00:38:42,280 interesting observation deck for 760 00:38:49,059 --> 00:38:46,970 nitrogenase has the synthesis of the 761 00:38:54,250 --> 00:38:49,069 iron molybdenum cofactor occurs on a 762 00:38:57,490 --> 00:38:54,260 scaffold and we've been examining this 763 00:39:00,160 --> 00:38:57,500 process or the synthesis just showing 764 00:39:02,440 --> 00:39:00,170 you that hypothesis for iron iron 765 00:39:04,809 --> 00:39:02,450 hydrogen's clusters and a lot of the 766 00:39:07,299 --> 00:39:04,819 ideas that we generated in terms of 767 00:39:09,609 --> 00:39:07,309 developing its experimental line to 768 00:39:12,599 --> 00:39:09,619 probe H poster biosynthesis was really 769 00:39:15,010 --> 00:39:12,609 based on some of the observations in 770 00:39:17,049 --> 00:39:15,020 nitrogenated device and system one of 771 00:39:21,279 --> 00:39:17,059 the questions that we've been asking is 772 00:39:24,430 --> 00:39:21,289 that theme carry over to hydrogenous do 773 00:39:28,390 --> 00:39:24,440 you make a cluster independent of the 774 00:39:30,910 --> 00:39:28,400 protein on a scaffold and then insert 775 00:39:33,549 --> 00:39:30,920 the cluster into the organic nest to 776 00:39:36,910 --> 00:39:33,559 define its reactivity and we have some 777 00:39:40,660 --> 00:39:36,920 new results that we're we're looking at 778 00:39:44,799 --> 00:39:40,670 the structure of that a PO end zone for 779 00:39:48,490 --> 00:39:44,809 the hydrogenase before it's been acted 780 00:39:51,490 --> 00:39:48,500 on by those biosynthetic genes and what 781 00:39:54,789 --> 00:39:51,500 we've been able to show is that a PO 782 00:39:57,339 --> 00:39:54,799 enzyme is devoid of not the whole 783 00:39:58,990 --> 00:39:57,349 cluster but just that to iron Union and 784 00:40:02,230 --> 00:39:59,000 from that we can get the insight that 785 00:40:04,740 --> 00:40:02,240 all this machinery is directed at just 786 00:40:06,849 --> 00:40:04,750 that to iron unit just that 787 00:40:09,970 --> 00:40:06,859 organometallic key thing with co and 788 00:40:12,579 --> 00:40:09,980 cyanide and dilate and that's kind of 789 00:40:15,130 --> 00:40:12,589 what we have proposed in this hypothesis 790 00:40:17,470 --> 00:40:15,140 because these iron-sulfur clusters these 791 00:40:19,390 --> 00:40:17,480 who are for sulfur clusters which is the 792 00:40:22,599 --> 00:40:19,400 other component of that cluster are 793 00:40:26,019 --> 00:40:22,609 typically made by host you know 794 00:40:30,190 --> 00:40:26,029 housekeeping cell machine but what we've 795 00:40:32,160 --> 00:40:30,200 been also able to show is in showing the 796 00:40:35,910 --> 00:40:32,170 AVO protein 797 00:40:37,190 --> 00:40:35,920 ways to accept this to iron unit that 798 00:40:40,079 --> 00:40:37,200 there are really just amazing 799 00:40:45,960 --> 00:40:40,089 similarities between this hydrogen egg 800 00:40:48,569 --> 00:40:45,970 and the nitrogenous into in the 80 801 00:40:51,720 --> 00:40:48,579 proteins of both of those systems you 802 00:40:54,510 --> 00:40:51,730 have a channel leading to the active 803 00:40:57,359 --> 00:40:54,520 site ready to be the recipient of this 804 00:41:00,450 --> 00:40:57,369 cluster it's a positively charged 805 00:41:05,089 --> 00:41:00,460 channel here we have the hydrogenase in 806 00:41:07,829 --> 00:41:05,099 the positively charged channel and the 807 00:41:10,849 --> 00:41:07,839 nitrogenous it's positively charged 808 00:41:13,680 --> 00:41:10,859 general in both of these metal clusters 809 00:41:16,170 --> 00:41:13,690 without the influence of their protein 810 00:41:21,299 --> 00:41:16,180 environment are negatively charged 811 00:41:24,450 --> 00:41:21,309 clusters so amazing of parallels between 812 00:41:28,950 --> 00:41:24,460 the two systems and a general theme of 813 00:41:35,420 --> 00:41:28,960 in terms of the final step the organic 814 00:41:43,069 --> 00:41:35,430 nesting these catalytic clusters okay 815 00:41:46,859 --> 00:41:43,079 another nor study or this team for 816 00:41:48,690 --> 00:41:46,869 nitrogenase see moco biosynthesis is 817 00:41:50,870 --> 00:41:48,700 really kind of inspiration for our 818 00:41:53,370 --> 00:41:50,880 studies aimed at looking at the 819 00:41:58,530 --> 00:41:53,380 evolutionary origins of nitrogen 820 00:42:01,230 --> 00:41:58,540 fixation as I mentioned this nifty n or 821 00:42:06,390 --> 00:42:01,240 this scaffold protein is structurally 822 00:42:12,420 --> 00:42:06,400 similar to nifty k for the hydrogen's 823 00:42:15,690 --> 00:42:12,430 and so this was generated this scaffold 824 00:42:18,569 --> 00:42:15,700 in defining the entire process were 825 00:42:21,000 --> 00:42:18,579 getting an active nitrogenase this was 826 00:42:25,260 --> 00:42:21,010 generated from gene duplication event 827 00:42:28,190 --> 00:42:25,270 where DK was duplicated as a unit to 828 00:42:32,190 --> 00:42:28,200 form en and so we've been using that 829 00:42:35,700 --> 00:42:32,200 gene duplication event as well as gene 830 00:42:38,280 --> 00:42:35,710 fusions of events or the traits of seven 831 00:42:40,190 --> 00:42:38,290 different genetic loci to trace the 832 00:42:43,770 --> 00:42:40,200 evolutionary or 833 00:42:45,930 --> 00:42:43,780 nitrogen fixation in extant organisms 834 00:42:48,690 --> 00:42:45,940 and this work was just submitted for 835 00:42:51,930 --> 00:42:48,700 publication and I don't have time to go 836 00:42:53,790 --> 00:42:51,940 through and describe all the facets of 837 00:42:57,720 --> 00:42:53,800 the work but basically the bottom line 838 00:43:01,470 --> 00:42:57,730 is that we can we can say from the 839 00:43:03,840 --> 00:43:01,480 occurrence that nitrogen fixation was 840 00:43:06,960 --> 00:43:03,850 not likely to be present in the last 841 00:43:10,220 --> 00:43:06,970 Universal common ancestor and that 842 00:43:12,780 --> 00:43:10,230 nitrogen fixation or at least molybdenum 843 00:43:15,540 --> 00:43:12,790 nitrogenase catalyzed biological 844 00:43:18,480 --> 00:43:15,550 nitrogen fixation original in 845 00:43:22,560 --> 00:43:18,490 methanogenic archaea and I think you 846 00:43:25,770 --> 00:43:22,570 know this line has been of interest to 847 00:43:28,290 --> 00:43:25,780 the Arizona group and the work of Bob 848 00:43:31,500 --> 00:43:28,300 Blankenship in Jason Raymond who's a 849 00:43:33,060 --> 00:43:31,510 part of their in 18 and but also you 850 00:43:36,330 --> 00:43:33,070 know where do we find nitrogen fixation 851 00:43:39,120 --> 00:43:36,340 or where do we find hydrogen metabolism 852 00:43:42,240 --> 00:43:39,130 where were these processes likely to 853 00:43:45,180 --> 00:43:42,250 emerge on earth our topics that really 854 00:43:50,010 --> 00:43:45,190 bridge the interests of our teams and 855 00:43:52,830 --> 00:43:50,020 Arizona team aims Penn State with Greg 856 00:43:55,860 --> 00:43:52,840 ferry the carnegie team at which john 857 00:43:59,460 --> 00:43:55,870 Barris is is a member so there are some 858 00:44:07,940 --> 00:43:59,470 a lot of good connections to make in 859 00:44:12,150 --> 00:44:07,950 these areas okay so to pour the our 860 00:44:14,670 --> 00:44:12,160 experimental to kind of come to a 861 00:44:17,760 --> 00:44:14,680 conclusion with our experimental line in 862 00:44:21,420 --> 00:44:17,770 terms of our project really robert 863 00:44:24,180 --> 00:44:21,430 szilagyi is he's a computational chemist 864 00:44:27,240 --> 00:44:24,190 theoretical chemist physical chemist 865 00:44:31,500 --> 00:44:27,250 that is really using theoretical 866 00:44:35,340 --> 00:44:31,510 chemistry and x-ray absorption 867 00:44:38,700 --> 00:44:35,350 spectroscopy to bridge all our three 868 00:44:40,830 --> 00:44:38,710 thrusts together so Robert is able to 869 00:44:42,780 --> 00:44:40,840 use one approach or these two approaches 870 00:44:45,390 --> 00:44:42,790 theoretical chemistry and x-ray 871 00:44:48,420 --> 00:44:45,400 absorption spectroscopy to analyze all 872 00:44:50,130 --> 00:44:48,430 materials across the continuum so he can 873 00:44:52,920 --> 00:44:50,140 use one approach to look at all these 874 00:44:53,339 --> 00:44:52,930 different things that are we're 875 00:44:54,870 --> 00:44:53,349 listening 876 00:45:00,779 --> 00:44:54,880 in the mineral thrust the pneumatic 877 00:45:03,120 --> 00:45:00,789 thrust and iron sulfur enzyme thrust we 878 00:45:04,799 --> 00:45:03,130 have a very strong philosophy component 879 00:45:07,109 --> 00:45:04,809 and have been developing a strong 880 00:45:08,999 --> 00:45:07,119 philosophy components and in these 881 00:45:12,180 --> 00:45:09,009 origin alive studies and war Jenna 882 00:45:14,779 --> 00:45:12,190 catalysis there's some number of 883 00:45:17,160 --> 00:45:14,789 interesting questions that can be posed 884 00:45:20,039 --> 00:45:17,170 philosophically the traditional 885 00:45:22,999 --> 00:45:20,049 questions the analysis of RNA versus 886 00:45:26,460 --> 00:45:23,009 metabolism debate the analysis of that 887 00:45:29,160 --> 00:45:26,470 those questions whether we're asking the 888 00:45:32,940 --> 00:45:29,170 right questions whether we can use 889 00:45:35,039 --> 00:45:32,950 traditional philosophical approaches to 890 00:45:38,059 --> 00:45:35,049 analyze that question and that really 891 00:45:40,920 --> 00:45:38,069 brings in can you use traditional 892 00:45:46,499 --> 00:45:40,930 philosophical approach to take a look at 893 00:45:48,390 --> 00:45:46,509 emerging sciences and and review them 894 00:45:51,420 --> 00:45:48,400 and theories about the definitions was 895 00:45:53,549 --> 00:45:51,430 really creating framework to pursue 896 00:45:57,289 --> 00:45:53,559 philosophical questions related to the 897 00:46:01,229 --> 00:45:57,299 nature of living things in this group 898 00:46:04,559 --> 00:46:01,239 from shortly after our project started 899 00:46:06,180 --> 00:46:04,569 we had a weekly working grid for the 900 00:46:09,779 --> 00:46:06,190 philosophy component of this in this 901 00:46:12,380 --> 00:46:09,789 group consists of students in philosophy 902 00:46:14,579 --> 00:46:12,390 and students in our science programs 903 00:46:18,150 --> 00:46:14,589 graduate students and undergraduate 904 00:46:22,559 --> 00:46:18,160 students students and faculty and this 905 00:46:25,079 --> 00:46:22,569 has really been a powerful tool for 906 00:46:27,539 --> 00:46:25,089 actually for all of us in the center of 907 00:46:31,950 --> 00:46:27,549 thinking about how we think about our 908 00:46:35,690 --> 00:46:31,960 problems we've traditionally at MSU had 909 00:46:39,420 --> 00:46:35,700 a strong outreach program in 910 00:46:42,450 --> 00:46:39,430 astrobiology relevant areas with our 911 00:46:45,469 --> 00:46:42,460 thermo biology Institute and we're 912 00:46:49,259 --> 00:46:45,479 continuing that tradition in our 913 00:46:51,559 --> 00:46:49,269 outreach program really now kind of 914 00:46:55,469 --> 00:46:51,569 catering that to this new thrust of 915 00:46:57,479 --> 00:46:55,479 prebiotic chemistry and we have a lot of 916 00:47:00,870 --> 00:46:57,489 successes in this train the trainer 917 00:47:03,200 --> 00:47:00,880 molecule and just their model stuck on 918 00:47:05,200 --> 00:47:03,210 molecules it's a train-the-trainer model 919 00:47:08,400 --> 00:47:05,210 where we're 920 00:47:10,960 --> 00:47:08,410 we have a number of classes aimed at 921 00:47:12,850 --> 00:47:10,970 science teachers and mainly science 922 00:47:15,910 --> 00:47:12,860 teachers at the middle school level and 923 00:47:18,400 --> 00:47:15,920 so this is part of their curriculum and 924 00:47:21,100 --> 00:47:18,410 professional advancement their masters 925 00:47:23,770 --> 00:47:21,110 in signs in science education courses 926 00:47:26,200 --> 00:47:23,780 most of them are classes that are held 927 00:47:29,500 --> 00:47:26,210 here at MSU but we're having we're 928 00:47:35,440 --> 00:47:29,510 developing distance learning components 929 00:47:37,360 --> 00:47:35,450 for these classes we have a firm of this 930 00:47:39,280 --> 00:47:37,370 class that's really more traditionally 931 00:47:42,100 --> 00:47:39,290 the thermal biology Institute's threat 932 00:47:46,540 --> 00:47:42,110 that's on more microbiology and more the 933 00:47:48,790 --> 00:47:46,550 abrc stress which is on chemistry so for 934 00:47:52,930 --> 00:47:48,800 chemistry teachers and formal biology 935 00:47:56,440 --> 00:47:52,940 teachers we have developed online 936 00:47:59,830 --> 00:47:56,450 learning tools we have this year a 937 00:48:03,880 --> 00:47:59,840 couple of very successful community 938 00:48:06,220 --> 00:48:03,890 lectures and a lot of programs there and 939 00:48:08,560 --> 00:48:06,230 a lot of those programs they can be you 940 00:48:11,800 --> 00:48:08,570 can take a look at our website and we'll 941 00:48:13,300 --> 00:48:11,810 be highlighting what's going on with the 942 00:48:16,510 --> 00:48:13,310 outreach program as well as the 943 00:48:19,090 --> 00:48:16,520 scientific program at thanks to rest on 944 00:48:20,920 --> 00:48:19,100 our website so i encourage you to take a 945 00:48:24,100 --> 00:48:20,930 look at what's going on at the website 946 00:48:26,230 --> 00:48:24,110 so i'll just close here and they can't 947 00:48:29,740 --> 00:48:26,240 believe it's like almost exactly 50 948 00:48:34,090 --> 00:48:29,750 minutes close here with the slide that 949 00:48:38,020 --> 00:48:34,100 is really just some cover art that we've 950 00:48:40,390 --> 00:48:38,030 made for a research that just come out 951 00:48:42,880 --> 00:48:40,400 in dalton transactions which is a 952 00:48:47,400 --> 00:48:42,890 chemical journal where we're kind of 953 00:49:00,260 --> 00:48:47,410 showing this continuum from minerals to 954 00:49:07,410 --> 00:49:05,340 John thank you very much we are going to 955 00:49:09,420 --> 00:49:07,420 open up for questions in just a second 956 00:49:11,760 --> 00:49:09,430 so if you have a question either raise 957 00:49:13,440 --> 00:49:11,770 your hand in Adobe Connect or if no one 958 00:49:16,320 --> 00:49:13,450 raises their hand you can just jump in I 959 00:49:18,270 --> 00:49:16,330 just wanted to make an observation and 960 00:49:21,840 --> 00:49:18,280 that is that one other connection 961 00:49:24,870 --> 00:49:21,850 between your work and work of the other 962 00:49:28,470 --> 00:49:24,880 teams that struck me thinking back to 963 00:49:30,450 --> 00:49:28,480 the Wisconsin seminar and Nita saw highs 964 00:49:33,080 --> 00:49:30,460 description of that very nice work 965 00:49:35,910 --> 00:49:33,090 looking at the very detailed 966 00:49:39,180 --> 00:49:35,920 interactions between mineral surfaces 967 00:49:41,400 --> 00:49:39,190 and small molecules seems that your the 968 00:49:43,710 --> 00:49:41,410 techniques that she's applying probably 969 00:49:45,780 --> 00:49:43,720 are applicable to the work that you're 970 00:49:49,820 --> 00:49:45,790 doing as well so just drop me as one 971 00:49:52,170 --> 00:49:49,830 additional connection and I suspect 972 00:49:54,300 --> 00:49:52,180 something that could have to mention 973 00:49:58,620 --> 00:49:54,310 I've met to mention that and that really 974 00:50:00,840 --> 00:49:58,630 also is Todd to radical chemistry and 975 00:50:03,480 --> 00:50:00,850 some other things so I think that you 976 00:50:07,830 --> 00:50:03,490 know thanks very much for making that 977 00:50:11,370 --> 00:50:07,840 point okay I John chalk is open for 978 00:50:13,380 --> 00:50:11,380 questions please including questions 979 00:50:15,330 --> 00:50:13,390 from right there at Montana State I 980 00:50:16,440 --> 00:50:15,340 could imagine with all those folks in 981 00:50:18,510 --> 00:50:16,450 the room there might be a question or 982 00:50:20,880 --> 00:50:18,520 two for you John I think we have went 983 00:50:28,440 --> 00:50:20,890 from Lauren William okay Lauren please 984 00:50:30,360 --> 00:50:28,450 go ahead oh that's hot me bout the part 985 00:50:33,570 --> 00:50:30,370 because I I didn't really have a 986 00:50:40,290 --> 00:50:33,580 question formulated oh okay I saw your 987 00:50:41,970 --> 00:50:40,300 hand raised my top five it's like George 988 00:50:45,570 --> 00:50:41,980 looks like George cody has a question 989 00:50:48,120 --> 00:50:45,580 okay John there was a wonderful talk 990 00:50:50,100 --> 00:50:48,130 thank you very much this radical Sam 991 00:50:51,870 --> 00:50:50,110 chemistry is really something that's 992 00:50:53,250 --> 00:50:51,880 intriguing and not something that I know 993 00:50:54,780 --> 00:50:53,260 a lot about side like two talked about 994 00:50:57,600 --> 00:50:54,790 in the future but I just had two 995 00:50:59,190 --> 00:50:57,610 questions the enzymes associated with 996 00:51:00,600 --> 00:50:59,200 this radical Sam chemistry do you find 997 00:51:02,520 --> 00:51:00,610 that these tend to be a conservative 998 00:51:04,320 --> 00:51:02,530 group of enzymes and the other is are 999 00:51:05,880 --> 00:51:04,330 there any metallo centers associated 1000 00:51:07,680 --> 00:51:05,890 with these enzymes so sir transition 1001 00:51:09,750 --> 00:51:07,690 metal chemistry associated with the 1002 00:51:12,339 --> 00:51:09,760 radical Sam chemistry for the Assembly 1003 00:51:15,789 --> 00:51:12,349 of the H Center for example in hydrology 1004 00:51:19,329 --> 00:51:15,799 that's my question Joan do you want me 1005 00:51:23,200 --> 00:51:19,339 okay so they have a four-on-four sulfur 1006 00:51:26,079 --> 00:51:23,210 cluster is the inorganic part of those 1007 00:51:29,920 --> 00:51:26,089 guns they all have a foreign force 1008 00:51:32,200 --> 00:51:29,930 officer and it's a differentiated forum 1009 00:51:34,589 --> 00:51:32,210 for such a cluster we have three of the 1010 00:51:37,229 --> 00:51:34,599 irons have 15 ligands and the other 1011 00:51:39,940 --> 00:51:37,239 ligation is provided by the 1012 00:51:42,249 --> 00:51:39,950 s-adenosylmethionine and then has a 1013 00:51:45,849 --> 00:51:42,259 group evolutionarily they're you know 1014 00:51:48,729 --> 00:51:45,859 they're not all that conserved there's 1015 00:51:54,099 --> 00:51:48,739 enough conservation to actually identify 1016 00:51:57,430 --> 00:51:54,109 them and annotate them as a class if you 1017 00:51:59,019 --> 00:51:57,440 look at the end zones and the way 1018 00:52:02,920 --> 00:51:59,029 they're annotated in terms of their 1019 00:52:05,380 --> 00:52:02,930 function most of them now I won't say 1020 00:52:10,059 --> 00:52:05,390 most of the many of them are incorrect 1021 00:52:11,710 --> 00:52:10,069 so they're hard to put into their 1022 00:52:14,380 --> 00:52:11,720 different functional classes but we're 1023 00:52:17,099 --> 00:52:14,390 looking at that and we're trying to look 1024 00:52:19,989 --> 00:52:17,109 at the evolutionary trajectory of those 1025 00:52:23,440 --> 00:52:19,999 those radical sammons ons and you know 1026 00:52:25,599 --> 00:52:23,450 like in the context of a whip a or by OB 1027 00:52:29,319 --> 00:52:25,609 or some of these other enzymes involved 1028 00:52:32,259 --> 00:52:29,329 in isomerization of amino acids and our 1029 00:52:33,819 --> 00:52:32,269 enzymes involved in cluster biosynthesis 1030 00:52:35,529 --> 00:52:33,829 we're trying to look at the evolutionary 1031 00:52:42,279 --> 00:52:35,539 relationships there which I think will 1032 00:52:51,039 --> 00:52:44,349 and we have a question from jen maca 1033 00:52:53,979 --> 00:52:51,049 lady hi John thanks for your nice 1034 00:52:55,989 --> 00:52:53,989 overview I have a question you may or 1035 00:52:57,789 --> 00:52:55,999 may not want to speculate about but I 1036 00:53:01,359 --> 00:52:57,799 was just reminded this weekend about 1037 00:53:05,529 --> 00:53:01,369 Paul Davies ideas about weird life and 1038 00:53:08,469 --> 00:53:05,539 it strikes me that if iron-sulfur 1039 00:53:11,589 --> 00:53:08,479 chemistry was a feature of Hadean of 1040 00:53:14,079 --> 00:53:11,599 Haiti in the 80 in the world you might 1041 00:53:16,419 --> 00:53:14,089 expect both normal life in weird life to 1042 00:53:22,329 --> 00:53:16,429 have iron sulfur catalysis have you 1043 00:53:24,939 --> 00:53:22,339 thought about that at all um no I 1044 00:53:28,329 --> 00:53:24,949 haven't that interesting i'll think 1045 00:53:32,499 --> 00:53:28,339 about that i'm not sure what to say 1046 00:53:34,839 --> 00:53:32,509 about that we have a question from barry 1047 00:53:38,549 --> 00:53:34,849 bloomberg carried in any I central ferry 1048 00:53:42,009 --> 00:53:38,559 you can just go right ahead it does it 1049 00:53:46,539 --> 00:53:42,019 thanks for that talk how does this 1050 00:53:49,839 --> 00:53:46,549 relate to the formation of big neither 1051 00:53:55,439 --> 00:53:49,849 somes that occur in bacteria arcade 1052 00:53:59,309 --> 00:53:55,449 other organization or organisms is there 1053 00:54:01,569 --> 00:53:59,319 someone standing of that connection 1054 00:54:03,749 --> 00:54:01,579 terminal yes there is there definitely 1055 00:54:07,719 --> 00:54:03,759 is on a mechanistic level there's a 1056 00:54:09,009 --> 00:54:07,729 similarity those are deposited what we 1057 00:54:12,939 --> 00:54:09,019 know about them is that there are metal 1058 00:54:15,399 --> 00:54:12,949 transporters that pump metals across a 1059 00:54:17,349 --> 00:54:15,409 membrane into a vesicle and those things 1060 00:54:19,209 --> 00:54:17,359 have grown from very very small 1061 00:54:23,019 --> 00:54:19,219 particles into their final state and are 1062 00:54:25,029 --> 00:54:23,029 confined by the vesicle and they make 1063 00:54:27,159 --> 00:54:25,039 both an iron oxide in and iron sulfide 1064 00:54:33,189 --> 00:54:27,169 and sometimes a mixed oxide sulphide 1065 00:54:37,079 --> 00:54:33,199 phase and how high up at the 1066 00:54:43,120 --> 00:54:37,089 evolutionary scheme do you find the 1067 00:54:45,899 --> 00:54:43,130 formed begged in zones Oh John I don't 1068 00:54:49,040 --> 00:54:45,909 know the answer yet I don't know that 1069 00:54:56,810 --> 00:54:54,320 and we have a question from Goddard yeah 1070 00:55:00,200 --> 00:54:56,820 hi it was very interesting talk and I 1071 00:55:03,170 --> 00:55:00,210 wanted to ask you a question which isn't 1072 00:55:07,130 --> 00:55:03,180 directly related to the mineralogy are 1073 00:55:10,400 --> 00:55:07,140 doing but no related to the piece of the 1074 00:55:12,680 --> 00:55:10,410 phrase which will my question will 1075 00:55:16,490 --> 00:55:12,690 reveal my own ignorance and so I hope to 1076 00:55:19,550 --> 00:55:16,500 be educated and the question is what do 1077 00:55:24,710 --> 00:55:19,560 you mean by evaluative methods of the 1078 00:55:28,280 --> 00:55:24,720 philosophy of science yeah well I 1079 00:55:29,810 --> 00:55:28,290 prashanta birthday well what we do in 1080 00:55:32,120 --> 00:55:29,820 philosophy of science we have some 1081 00:55:34,160 --> 00:55:32,130 standard criteria to evaluate two 1082 00:55:36,320 --> 00:55:34,170 competing theories for example the skull 1083 00:55:38,450 --> 00:55:36,330 of a theory the fruitfulness of theory 1084 00:55:40,430 --> 00:55:38,460 theory and the predicate part of a 1085 00:55:42,110 --> 00:55:40,440 theory but when you look at it finished 1086 00:55:44,750 --> 00:55:42,120 theory for example general theory of 1087 00:55:46,940 --> 00:55:44,760 relativity so we have a very specific 1088 00:55:49,790 --> 00:55:46,950 way to evaluate that theory whether the 1089 00:55:51,500 --> 00:55:49,800 cure is better than the Newtonian theory 1090 00:55:53,270 --> 00:55:51,510 of gravitation but in the case of 1091 00:55:55,400 --> 00:55:53,280 emerging science like you know when you 1092 00:55:57,440 --> 00:55:55,410 are concerned with the metabolism first 1093 00:55:59,930 --> 00:55:57,450 theory versus the ordinal world 1094 00:56:03,170 --> 00:55:59,940 hypothesis so it's very difficult to 1095 00:56:04,910 --> 00:56:03,180 apply those criteria in you know in 1096 00:56:06,800 --> 00:56:04,920 knowing whether which one is a better 1097 00:56:10,130 --> 00:56:06,810 fuel than the other so we are hoping 1098 00:56:12,110 --> 00:56:10,140 that by analyzing our by looking at 1099 00:56:14,810 --> 00:56:12,120 those different hypotheses like the 1100 00:56:17,240 --> 00:56:14,820 ordinary world all the metabolism first 1101 00:56:19,370 --> 00:56:17,250 hypothesis we as a philosopher of 1102 00:56:21,530 --> 00:56:19,380 science we'd like to know what 1103 00:56:24,020 --> 00:56:21,540 philosophy of science can learn from 1104 00:56:28,250 --> 00:56:24,030 also astrobiology not also the other way 1105 00:56:32,290 --> 00:56:28,260 around well of course I'm very familiar 1106 00:56:35,060 --> 00:56:32,300 with the standard scientific method for 1107 00:56:37,670 --> 00:56:35,070 drawing predictions from a hypothesis 1108 00:56:39,740 --> 00:56:37,680 and then testing those by going into the 1109 00:56:42,260 --> 00:56:39,750 experimental world and making 1110 00:56:46,370 --> 00:56:42,270 measurements that can affect quantify 1111 00:56:49,940 --> 00:56:46,380 those predictions and ever i iterate the 1112 00:56:52,250 --> 00:56:49,950 theory when hypothesis unless clear on 1113 00:56:56,309 --> 00:56:52,260 how one does this in the philosophical 1114 00:57:00,460 --> 00:56:56,319 world other than through this course 1115 00:57:02,140 --> 00:57:00,470 how do you do it well you know the 1116 00:57:04,450 --> 00:57:02,150 standard philosophers of science you 1117 00:57:06,730 --> 00:57:04,460 know the way scientists evaluate why 1118 00:57:08,290 --> 00:57:06,740 general serial to exhibit is better than 1119 00:57:12,370 --> 00:57:08,300 the other so there are like three 1120 00:57:15,490 --> 00:57:12,380 classical tests like one is you know the 1121 00:57:16,990 --> 00:57:15,500 painting of light case then we have in 1122 00:57:19,720 --> 00:57:17,000 the mercury spill is very hidden 1123 00:57:21,819 --> 00:57:19,730 precision explanation so those are so 1124 00:57:24,880 --> 00:57:21,829 the classical test you know scientists 1125 00:57:26,500 --> 00:57:24,890 use you know to explain whether general 1126 00:57:29,200 --> 00:57:26,510 relativity successfully explaining the 1127 00:57:31,870 --> 00:57:29,210 theory so similarly question is whether 1128 00:57:34,180 --> 00:57:31,880 we can apply those criterion you know 1129 00:57:37,510 --> 00:57:34,190 better explanation better confirmation 1130 00:57:39,849 --> 00:57:37,520 in evaluating two competing hypotheses 1131 00:57:41,680 --> 00:57:39,859 like that metabolism products versus the 1132 00:57:43,599 --> 00:57:41,690 oar in the water hypothesis it's very 1133 00:57:46,240 --> 00:57:43,609 difficult to you know clean point their 1134 00:57:47,380 --> 00:57:46,250 predictions and you know because we are 1135 00:57:59,669 --> 00:57:47,390 mostly doing the speculative 1136 00:58:07,929 --> 00:58:04,359 mm I a question I could get in please go 1137 00:58:09,489 --> 00:58:07,939 ahead oh hey John I judge yourself 1138 00:58:12,999 --> 00:58:09,499 something I'm not ready to ask a 1139 00:58:15,459 --> 00:58:13,009 question and I think maybe this was a 1140 00:58:20,409 --> 00:58:15,469 mass before but I just so clarify it for 1141 00:58:23,349 --> 00:58:20,419 me if you would if if these helicopters 1142 00:58:25,089 --> 00:58:23,359 are so ancient and I would assume that 1143 00:58:28,569 --> 00:58:25,099 would mean the proteins that bind them 1144 00:58:30,789 --> 00:58:28,579 should be ancient so what kind of 1145 00:58:32,529 --> 00:58:30,799 sequence conservation do you anticipate 1146 00:58:35,679 --> 00:58:32,539 what's predicted by them and what's 1147 00:58:38,049 --> 00:58:35,689 observe you know I'm just thinking of 1148 00:58:42,999 --> 00:58:38,059 course always in terms of ribosomal RNA 1149 00:58:45,509 --> 00:58:43,009 genes and which are ancient and you can 1150 00:58:49,929 --> 00:58:45,519 see that and so how would you compare 1151 00:58:51,309 --> 00:58:49,939 that Pacific Ocean society well i think 1152 00:58:53,169 --> 00:58:51,319 you know that's the interesting question 1153 00:58:55,239 --> 00:58:53,179 because I kind of just close with an 1154 00:58:58,120 --> 00:58:55,249 example saying that they're not ancient 1155 00:59:00,579 --> 00:58:58,130 or at least that you know there's one 1156 00:59:03,099 --> 00:59:00,589 example for nitrogenase our results 1157 00:59:05,199 --> 00:59:03,109 indicate that they're not present that 1158 00:59:07,629 --> 00:59:05,209 they're not likely to be present in the 1159 00:59:09,579 --> 00:59:07,639 last common ancestor and interpolated 1160 00:59:11,739 --> 00:59:09,589 you know what talking about is you've 1161 00:59:14,949 --> 00:59:11,749 got a number of different mineral 1162 00:59:18,249 --> 00:59:14,959 catalysis going on some of that mineral 1163 00:59:20,799 --> 00:59:18,259 catalysis is providing the raw materials 1164 00:59:24,909 --> 00:59:20,809 maybe the raw materials for life-forms 1165 00:59:27,939 --> 00:59:24,919 and you know eventually those are taken 1166 00:59:30,069 --> 00:59:27,949 up and made up into biological processes 1167 00:59:31,449 --> 00:59:30,079 of course I'm you know speculating and 1168 00:59:33,909 --> 00:59:31,459 kind of represent in our point of view 1169 00:59:36,639 --> 00:59:33,919 or maybe hydrogen metabolism that 1170 00:59:38,319 --> 00:59:36,649 happened earlier and maybe it is present 1171 00:59:40,269 --> 00:59:38,329 in the first life forms and we'll have 1172 00:59:42,609 --> 00:59:40,279 to figure out an approach that we've 1173 00:59:45,069 --> 00:59:42,619 used that's similar to what we use for 1174 00:59:47,589 --> 00:59:45,079 nitrogenase to ask those questions or a 1175 00:59:52,959 --> 00:59:47,599 fourth you know acetyl co a synthase or 1176 00:59:54,939 --> 00:59:52,969 for co dehydrogenase etc so i don't 1177 00:59:57,069 --> 00:59:54,949 think you know they don't necessarily is 1178 01:00:00,519 --> 00:59:57,079 that we see relationships between 1179 01:00:03,039 --> 01:00:00,529 mineral catalysis and iron sulfur enzyme 1180 01:00:06,099 --> 01:00:03,049 catalysis doesn't mean to say that those 1181 01:00:08,349 --> 01:00:06,109 were the first enzymes necessarily i 1182 01:00:09,560 --> 01:00:08,359 think that probably find a subset of 1183 01:00:12,860 --> 01:00:09,570 those or 1184 01:00:17,720 --> 01:00:12,870 maybe product testers for those perhaps 1185 01:00:20,480 --> 01:00:17,730 work but they don't have to do that make 1186 01:00:23,870 --> 01:00:20,490 them yeah yeah I got that very good 1187 01:00:28,820 --> 01:00:23,880 thank you we have a question at Penn 1188 01:00:32,540 --> 01:00:28,830 State John this chris house I was just 1189 01:00:38,420 --> 01:00:32,550 curious how if any iron-sulfur clusters 1190 01:00:44,960 --> 01:00:38,430 are known from viruses from what I know 1191 01:00:48,080 --> 01:00:44,970 no and I'm getting for my virus 1192 01:00:51,400 --> 01:00:48,090 colleagues they say now as well so John 1193 01:00:53,900 --> 01:00:51,410 that's not totally true that's there 1194 01:00:55,670 --> 01:00:53,910 that that people that we don't actually 1195 01:00:59,360 --> 01:00:55,680 know there are lots of viruses that 1196 01:01:02,000 --> 01:00:59,370 carry disease algo viruses Prince's 1197 01:01:04,280 --> 01:01:02,010 carry photosynthetic jeans I don't know 1198 01:01:06,560 --> 01:01:04,290 that anybody's actually looked well so I 1199 01:01:08,750 --> 01:01:06,570 think that the answer the question is no 1200 01:01:11,690 --> 01:01:08,760 nobody's made that connection and 1201 01:01:15,020 --> 01:01:11,700 nobody's found an iron-sulfur cluster 1202 01:01:17,660 --> 01:01:15,030 containing protein in the virus you know 1203 01:01:19,070 --> 01:01:17,670 for standard like ferredoxin like motifs 1204 01:01:21,350 --> 01:01:19,080 and stuff which people have looked at 1205 01:01:24,710 --> 01:01:21,360 fairly extensively nobody found that 1206 01:01:33,210 --> 01:01:24,720 either so I think that there maybe 1207 01:01:39,430 --> 01:01:35,500 okay are there any other questions for 1208 01:01:43,030 --> 01:01:39,440 John John I would just make the 1209 01:01:45,970 --> 01:01:43,040 observation that in response to your 1210 01:01:48,850 --> 01:01:45,980 last comment about the the enzymes may 1211 01:01:49,930 --> 01:01:48,860 not be ancient by which I think you 1212 01:01:52,020 --> 01:01:49,940 meant that they may not have been 1213 01:01:55,840 --> 01:01:52,030 present in the very first life-forms 1214 01:01:57,970 --> 01:01:55,850 methanogenesis where you suggested they 1215 01:02:00,850 --> 01:01:57,980 may have originated may very well be an 1216 01:02:02,860 --> 01:02:00,860 extremely ancient metabolism so it could 1217 01:02:07,210 --> 01:02:02,870 have been not all that long after Luca 1218 01:02:09,700 --> 01:02:07,220 conceivably absolutely and I think that 1219 01:02:11,710 --> 01:02:09,710 you know that's what something that our 1220 01:02:13,180 --> 01:02:11,720 study says you know we haven't put any 1221 01:02:16,450 --> 01:02:13,190 sort of clock on these and that's 1222 01:02:21,010 --> 01:02:16,460 something that we we can do we can do 1223 01:02:24,970 --> 01:02:21,020 and we're trying to learn to do any 1224 01:02:32,740 --> 01:02:24,980 other questions for John ok well let's 1225 01:02:35,020 --> 01:02:32,750 thank him again as I think you all know 1226 01:02:37,090 --> 01:02:35,030 we'll continue this series on Wednesday 1227 01:02:39,850 --> 01:02:37,100 this week with Lauren Williams also 1228 01:02:42,300 --> 01:02:39,860 talking about the origin of the earliest 1229 01:02:45,010 --> 01:02:42,310 proteins particularly how the ribosome 1230 01:02:47,410 --> 01:02:45,020 came to be and how RNA learned to make