Supporting Information Kβ Valence to Core X-ray Emission Studies of Cu(I) binding proteins with mixed Methionine Histidine Coordination. Relevance to the Reactivity of the M- and H-sites of Peptidylglycine Monooxygenase. Vlad Martin-Diaconescu, Kelly N. Chacón, Mario Delgado, Dimosthenis Sokaras, Tsu-Chien Weng, Serena DeBeer $* and Ninian J. Blackburn * Max Planck Institute for Chemical Energy Conversion, Stiftstr. 34 36, D- 4547 Mülheim an der Ruhr, Mülheim an der Ruhr, Germany Institute of Environmental Health, Oregon Health & Sciences University, Mail Code HRC3, 3181 SW Sam Jackson Park Road, Portland, OR 97239 Stanford Synchrotron Radiation Lightsource, 2575 Sand Hill Road, Menlo Park, CA 9725 $ Cornell University, Department of Chemistry and Chemical Biology, Ithaca, New York, 14853, United States (Current affiliation) Group de Química Bioinorgànica, Supramolecular i Catàlisi (QBIS-CAT), Institut de Química Computacional i Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus Montilivi, 1771 Girona (Spain) (Current affiliation) Reed College - Department of Chemistry, 323 SE Woodstock Blvd., Portland OR 9722 (Current affiliation) Inorganic Chemistry and Catalysis Group, Debye Institute for Nanomaterials Science, Utrecht University, 3584 CG, Utrecht, the Netherlands (Current affiliation) Center for High Pressure Science & Technology Advanced Research #6-48, 169 Cailun Rd., Pudong, Shanghai 2123, P. R. China * Corresponding Authors serena.debeer@cec.mpg.de; blackbni@ohsu.edu Tel.: 53-346-3428; Fax: 53-346-3427 Received: Running Title: XES of His-Met-containing Copper Proteins S1
Table of Contents Section S1 - Representative fits of the Experimental XES Spectra S3 Section S2 - XYZ of geometry optimized protein metal site S6 Section S3 - XYZ of Truncated Models S11 Section S4 - XYZ of CusB Geometry Study S13 Section S5 - XYZ of PHM CuH Geometry Study S14 Section S6 - Overlays of calculated VtC XES from truncated and full models S15 Section S7 - Overlays of additionally calculated VtC XES for CusF S15 S2
Section S1 - Representative fits of the Experimental XES Spectra 45 a) 1.5 b) 4 35 Experimental data Average of good fits 3 1 25 2 15.5 1 5 888 889 89 891 892 892 894 896 898 9 Fig. S1.1- Average of good fits a) in the Kβ mainline region; and b) in the VtC region for CusF. Colored features in b) correspond to peak features in the VtC region contributing to the total area. In gray dotted lines are shown, the offset, the tails from the Kβ mainline peak features (shown in a), and the two features above 898 ev corresponding to K+L excitations..12.1 a) Experimental data Average of good fits 4 x 1 3 b) 3.5 3.8 2.5.6 2 1.5.4 1.5.2.5 888 889 89 891 892 892 894 896 898 9 Fig. S1.2- Average of good fits a) in the Kβ mainline region; and b) in the VtC region for CusB. Colored features in b) correspond to peak features in the VtC region contributing to the total area. In gray dotted lines are shown, the offset, the tails from the Kβ mainline peak features (shown in a), and the two features above 898 ev corresponding to K+L excitations. S3
.14 a) 5 x 1 3 b).12.1 Experimental data Average of good fits 4 3.8.6 2.4 1.2 888 889 89 891 892 1 892 894 896 898 9 Fig. S1.3- Average of good fits a) in the Kβ mainline region; and b) in the VtC region for PHMCu M. Colored features in b) correspond to peak features in the VtC region contributing to the total area. In gray dotted lines are shown, the offset, the tails from the Kβ mainline peak features (shown in a), and the two features above 898 ev corresponding to K+L excitations..12.1 a) Experimental data Average of good fits 5 x 1 3 4 b).8 3.6 2.4 1.2 888 889 89 891 892 1 892 894 896 898 9 Fig. S1.4- Average of good fits a) in the Kβ mainline region; and b) in the VtC region for PHM- CO. Colored features in b) correspond to peak features in the VtC region contributing to the total area. In gray dotted lines are shown, the offset, the tails from the Kβ mainline peak features (shown in a), and the two features above 898 ev corresponding to K+L excitations. S4
.7.6.5 a) Experimental data Average of good fits 3 x 1 3 b) 2.5 2.4.3 1.5 1.2.5.1.5 888 889 89 891 892 892 894 896 898 9 Fig. S1.5- Average of good fits a) in the Kβ mainline region; and b) in the VtC region for PHMCu H. Colored features in b) correspond to peak features in the VtC region contributing to the total area. In gray dotted lines are shown, the offset, the tails from the Kβ mainline peak features (shown in a), and the two features above 898 ev corresponding to K+L excitations. Fig. S1.6- Normalized VtC XES reflecting the results from the fits for CuB and CusF Fig. S1.7- Normalized VtC XES reflecting the results from the fits for PHMCu H, PHM-CO and PHMCu M. S5
Section S2 - XYZ of geometry optimized protein metal site: CusB (CuMet 3), CusF (CuMet 2His 1), PHM Cu M site (CuMet 1His 2), and PHM CuH site (CuHis 3). CusB-CuMet3 Cu 6.9968991398254-6.122818894293-2.85763467118 N 1.4889241577875-6.6223128512583-7.85359674437 C 1.3348138645931-5.48616956392488-6.9289726294799 C 11.6467769342574-4.65612449843542-6.9379647572943 O 11.89156521694472-3.78491173744555-6.12639242369 C 9.89569682924345-5.8913583257654-5.5163664732 C 9.528222968799-4.72593381732-4.612966488143 S 9.1957167633478-5.274458268155-2.91468997623974 C 9.146393531638-3.6992144324511-2.1146153936261 H 9.5687585535356-4.81237323869526-7.35747824898 H 1.719867974512-6.46347755485738-5.2834153714653 H 9.321848395998-6.5753467221735-5.59852221453877 H 8.678425196896-4.13931791415874-5.244863466329 H 1.38927747147675-4.284621432622-4.51522729482 H 1.1525251876723-3.26472222851293-2.1682394422 H 8.943239266323-3.914499747177 -.9571452365248 H 8.39178943324623-2.99245466696177-2.3895755581422 H 1.78286664528575-7.4716634868752-7.37152221647361 H 9.624557569184-6.8336239649898-8.3638481131298 O 12.465358884562-4.9719651441716-7.947313254491 H 11.99666321787427-5.728445594617-8.41192451817998 N 5.98976725881 -.852829341365-4.27767382869238 C 4.5447131462292-2.14751223815798-3.91635379846632 C 4.6369736435634-2.3687535465721-2.479388777737 O 3.74749368191722-2.88866182524198-1.7479559252366 C 5.2127759722288-3.37987499287141-4.6129666538511 C 4.4597184373469-4.6924413963734-4.3658837613574 S 5.56519273336945-6.14624321199436-4.5978586257533 C 4.378731688463-7.5927173659154-4.35257828472595 H 3.47141423997398-2.14369385427933-4.1577547596993 H 6.24892513596-3.45128825833818-4.2441775468679 H 5.269696624825-3.17261778351289-5.69179131389 H 3.63197687535453-4.817315726996-5.781997948897 H 4.4646952324247-4.7357634288773-3.34928856571 H 3.8917953768229-7.4366483896572-3.37351363693954 H 4.9449118926622-8.4463481161441-4.41494643481129 H 3.6341376544499-7.4855919829459-5.1581579327658 H 6.853328923289 -.77559452251874-4.271955427874 H 4.9955984184412 -.6656214642182-5.2754881811 O 5.8365959353218-2.254127899298-1.9147675555689 H 5.89872289-2.2628559548176 -.93897111513841 N 3.5395656729778-3.535585376951 1.35624928131973 C 4.74678168942771-4.338642181286 1.49163669366553 C 5.886791996197-3.31614649229414 1.59669212321318 O 6.364389836132-2.69342555926931.6528615413159 C 4.98573859826317-5.3436869881638.3412257436864 C 6.2424617518514-6.1958856559375.577867116399 S 6.4255521599586-7.34262994995 -.91927396639154 C 7.9313593441364-8.25418924791154 -.4443966179753 H 4.69851137182941-4.8719955213184 2.4531972923995 H 5.32734366732-4.77167695384463 -.598446462169 H 4.9736114136735-5.999181531946.28298432637626 H 6.184718583395-6.8317873947854 1.4362375111345 H 7.156341885729-5.58694324148.5764963799527 H 8.78369889533325-7.577399294194 -.316881376444 H 8.1442951411-8.96316117328277-1.2538663389 H 7.73571485925795-8.8128294257274.47918596636682 H 3.42138413835-3.227271326365.3875969496813 H 2.7115245814227-4.2225722515657 1.6875945523228 O 6.29518633697488-3.12798252669 2.8572762651863 H 6.942168525692-2.3881797782948 2.8551598481115 S6
CusF-CuMet 2His 1 N 13.7318692269943 6.689397488689 15.599839378327 C 12.4938294895579 7.9386186788826 15.1789322739855 C 12.89392375431 9.695824774673 16.118244217432 O 13.382228982861 8.91453297395647 17.211878186598 C 1.92143285631984 7.99543249378869 15.3929888431615 C 1.1871162399946 7.45422341665722 16.22164754175255 C 9.296225757381 6.3958489126468 16.32637359981182 N 1.28659245831 7.9637889141129 17.59413192619 C 9.481424349961 7.234797338462 18.33428836775148 N 8.8678694863853 6.2746132273712 17.6424626134 N 5.451567493811 9.98873871414 18.64211163964 C 6.14277775574 1.938427745114 19.973984496476 C 7.17199999881753 11.69169815 19.98799999738743 O 7.7374596453926 11.4644371964969 18.979842714979 C 6.54714478974432 8.7589839573965 2.61493542231 C 5.5295794949125 7.66836746463522 2.629918747412 C 4.633333563369 7.3398983566644 21.6411699238543 C 5.2463431191628 6.76367149658 19.5383574463371 C 4.199381316211 5.8884919556348 19.963882138732 C 5.786246777852 6.6384392948 18.2417219992514 N 3.84691929568358 6.2673781181255 21.23881313762724 C 3.7135655448293 4.8514817775494 19.1541515794515 C 5.2962486644759 5.569228441641 17.427455512631 C 4.27613333242724 4.69758752977754 17.89223445271468 N 11.5152613264633 6.436396237712 2.6625649645262 C 11.7463423145778 5.11715825633 2.4282772963744 C 12.68747662984336 4.7823389496 19.236269374894 O 12.876785381675 5.65889114451 18.3587365356674 C 1.43522252926 4.2695744847569 2.247523656535 C 9.28476523252793 4.526717933815 2.9938383159343 S 7.7533911779 3.826337248245 2.25969366267623 C 6.5573882639248 4.28375661283668 21.537292294464 N 13.263339531796 3.552826274565 19.15915873831451 C 13.687136878952 2.9842834652567 17.8913579349795 C 12.54199999938 2.724938 17.4169999976783 O 11.9611893261154 1.32888261717822 18.2212595464795 C 15.2154461552588 2.2198623538 18.2663348796971 C 15.51882527882391 1.744239471611 16.66864875376326 O 15.9974321487586 2.9828479737721 18.748831435158 N 12.25925682277 2.16168535481276 16.14139786696 C 11.18812693823456 1.3684217457729 15.5177337582196 C 11.65441291257271.8297919836314 14.15423686195334 O 12.69458837598828 1.2472298475255 13.6384573393957 C 9.7994149478453 1.991628185672 15.3853124529789 C 9.359929629637 2.662382183168 16.6888939351743 S 7.6537768324278 3.381712434 16.598484537215 C 6.716853793138 1.85197241641 17.148119696681 Cu 7.5277689321436 4.914559743 18.286322771758 C 12.68893567864267 5.51834263135195 14.83415235536762 H 12.9511686169 6.53317562786898 16.6117792795452 H 12.8764566466 8.222364474894 14.16751476779984 H 12.6517924952727 1.99295342376 15.78667883769 H 1.62346664181558 7.4148988853231 14.15478876811 H 1.6119923519417 9.417782331291 14.82495676455964 H 8.92711512135762 5.7355839243237 15.5353719464742 H 9.4368455219237 7.3865138649334 19.4165464491391 H 4.8367673929617 9.17128121483128 18.582484462246 H 6.21117921693617 9.844586994767 17.96231728954 H 5.24551593435 1.492537265336 2.6788252964147 H 7.526533657636 11.371329459642 21.147877731263 H 7.42978398749295 8.426852614261 2.273378531729 H 6.912957211671 8.964936265939 21.646171338133 H 4.51613115438 7.767723414922 22.63862352426792 H 6.495386474727 7.3269618937499 17.8399842123324 H 3.13155527351546 5.81824739198296 21.81164869269 H 2.91913529566 4.18849332495245 19.512575255331 H 5.6266123999344 5.496921346142 16.3913156589699 H 3.971675653859 3.91167786177493 17.23193269767595 H 11.79274559751879 6.9161635936384 19.789968684545 H 12.1798927988792 6.77212441298884 21.3797244195236 H 12.15319477571128 4.53733333251858 21.3433135354141 H 1.6393582454896 3.18487629135696 19.915751114218 H 1.13492943138752 4.638335179712 19.264677581357 H 9.1521643122376 5.58288532229 21.18477818147 H 9.452261563395 3.9837222362565 21.96744566985 H 5.5736512644929 3.91533735191448 21.1998463785696 H 6.5246736522632 5.38119713227352 21.668538613512 H 6.83471433155942 3.7893936113772 22.4879577838 H 13.791986372897 2.8659674892125 19.8778172297312 S7
H 13.83812242845 3.8342489986353 17.1931356136772 H 14.82524546346853 1.333949374 18.6913815931295 H 15.7312542516187 2.56155419252599 15.985766341284 H 14.793227967387 1.292598375793 16.17748215666612 H 16.476553856546 1.15311281136331 16.79456225363614 H 16.2587826763468 3.7837889259157 18.155965328984 H 12.79575936955946 2.6836371375632 15.45254951848 H 11.72268495634.4185462276998 16.1782667427946 H 1.958119492247.1252591697199 13.631895927731 H 9.6512415424 1.21766815782325 15.7675135366571 H 9.82859587175127 2.749875598477 14.57574285796663 H 9.996832428862 3.5413748689964 16.976879887794 H 9.43173681527 1.9813251566935 17.5589885998423 H 5.659322179623 2.14423499494122 17.1385145555445 H 7.1381243214887 1.575171286967 18.1773423282514 H 6.87645426343 1.583629516374 16.45286456333 H 12.8792434513898 5.6817435518827 13.75221699357263 H 11.6212114823456 5.215795619253 14.9413268121128 H 13.32347491781154 4.6643327783828 15.14269793764 H 1.87286943527253 8.7433231651726 17.8714933754472 PHMCu M-CuMet 1His 2 N 39.33682326415199 22.7892353924481 36.73832997145459 C 39.98629482951322 24.12333113999 36.925448422593 C 41.185925379718 24.77196379417 35.9591445217146 O 42.24644588121 23.4761412419735 36.17654944559288 C 4.47461914182973 24.14397126169568 38.3853725223973 C 41.2797141277572 25.38325384494668 38.59486713746 C 42.6523727116664 25.5684361926293 38.6134937463 N 4.754257211342 26.66825779972562 38.64485236682 C 41.7748816673783 27.5656211979373 38.61856839327834 N 42.947148393494 26.9188574994898 38.61942986988637 N 4.9527651529416 24.8339255484282 34.8592136239 C 41.82115442962618 24.798457141486 33.692486956167 C 41.899582 26.19399999887372 33.5756287 O 4.88478914428221 26.8774421672645 32.83983151848 C 41.34597576695677 23.71176654793264 32.67794421827 C 42.269621582858 23.68651228129 31.46364974587365 O 41.19885226697545 22.465519193124 33.345352147732 N 43.1695844865135 26.577485192658 32.78856848591825 C 43.4725868349 27.83596337151956 32.147189616911 C 43.3869181521289 27.747614977541 3.621177627299 O 43.195382167216 26.76493492813 3.724451169511 C 44.8348223677348 28.431693161483 32.5818281811425 C 44.9247948532717 28.68673193916871 34.53755374883 C 44.31646939211 28.1957886631417 35.1567358918554 N 45.785712713986 29.636883254658 34.5733227233934 C 45.69759411238972 29.61864812953682 35.93254393924532 N 44.8127323493351 28.697374413945 36.3172693562954 N 45.24799743328137 24.3849226157667 33.727578715975 C 45.538444949511 23.628916843476 34.938733924762 C 44.75153892 22.3349999995465 35.51525 O 44.391238673711 21.92429758637453 34.631633296697 C 45.42466764874236 24.42543674829 36.236689933872 C 46.515617716413 25.49163158861612 36.327893727574 S 46.556291798298 26.265334864792 37.9871547932531 C 47.91183524784 27.4384696595429 37.7328398654331 Cu 44.6525694688111 27.515688196743 37.9187111577251 H 39.8414195599571 22.669262551278 35.74547117124816 H 38.4384763763756 22.713612789936 37.2425442618573 H 39.3193159891431 24.881935856399 36.69796629268855 H 41.1129898961597 23.2659227111376 38.65949733386 H 39.59832439243475 24.1511333366666 39.6562277466764 H 43.4356543584754 24.79914216346361 38.5932486621181 H 41.6352832972631 28.65663449225 38.6268123678557 H 4.3574694527515 25.27349396947 34.72954477165557 H 42.827671896782 24.5175421716476 34.4953662869512 H 4.3233228869721 23.99814892568592 32.34547666434533 H 43.285556351362 23.2846931987443 31.784946329412 H 42.3772824789686 24.57443177626814 3.929839764533 H 41.8766828655532 22.848641737715 3.75969495441641 H 42.951623139836 22.1931861763328 33.64852666231924 H 43.9318821134295 25.9227964799494 33.5779229892184 H 42.6717378772 28.56161755952 32.42697394147414 H 43.674563154917 28.69976893694795 3.899362328111 H 45.321296778312 29.333664328682 32.115176524817 H 45.63683357896461 27.68935178279 32.28622823754581 H 43.5688287714531 27.3146719439136 35.1985833679968 H 46.2664879329541 3.2852489487417 36.5874112638462 S8
H 45.3916738854411 23.774375266693 32.97312577128 H 46.124525857926 24.8649961148585 33.4227775441319 H 46.586756477531 23.18682734533 34.92339365388334 H 44.7796467766525 21.76623883274292 35.9751497689983 H 45.5161846575751 23.7296294241424 37.98931987614 H 44.4197486973166 24.87378727761558 36.28683641164429 H 46.3664844516925 26.29669973629422 35.5791824697466 H 47.5183376616134 25.4388443745211 36.179626442288 H 47.99689822932186 28.42972617222 38.65597934761648 H 47.68793883297555 28.998396777245 36.87381737947 H 48.85143566163136 26.8839664524229 37.559191745959 H 39.7597933998691 26.9989551648529 38.61626613872142 H 46.3822758561783 3.2656937991292 34.28437792612 PHMCu H-CuHis 3 N 34.761859355878 39.5851521317971 38.6982642674576 C 34.658292197752 38.688274275322 37.76952336291721 C 33.7325722181232 37.3566928472434 38.4633974652556 O 32.74999999952483 36.6799999984423 38.1499999719416 C 34.953979698687 38.477976728317 36.511553567364 C 34.621442659265 37.2818541772466 35.69266549286 N 35.9639176838 36.2179847513343 36.4354989819159 C 33.76829161826815 37.136821293438 34.5964453988777 C 34.565217158582 35.143834664735 35.1844752269366 N 33.764253917719 35.7879672414334 34.2954771927926 N 34.642723938574 36.97969119264435 39.44979984696459 C 34.2184472538275 35.95744619854689 4.45938918138 C 34.882916629995 36.2161685414984 41.73619461545553 O 35.6135487311489 37.1674191175291 41.959916314557 C 34.473371998727 34.4936782335153 39.94443812624663 C 35.912754384 34.892891981891 39.926978943912 N 36.774627582569 34.48615194985 38.973264173774 C 36.6419587848851 33.3549159925192 4.85271625729637 C 37.9855724816797 34.157241925745 39.24267537522 N 37.93472689732435 33.3123812673479 4.3736834589578 C 37.9223841928582 38.8735342147 4.2266453891884 C 38.41331633 37.4938515 39.744256416 C 38.81812132567 37.47694427183276 38.35726416712 N 37.986364574615 36.9653614923473 37.332719223937 C 39.952999411879 37.98917851133935 37.6983982927114 C 38.688494972411 37.1633596921614 36.1343538798575 N 39.8178145417937 37.779713154958 36.345892156712 Cu 36.3518218647246 35.7491759386854 37.49348935263775 H 34.9939258832982 4.57476915361 39.355734297963 H 35.1886446319848 4.374389169884 38.17622724915448 H 33.7368689241117 39.6152167434628 37.4229374316226 H 34.98672874242 39.3976747246658 35.8949973825727 H 36.1129715342 38.35931127844876 36.8635575122349 H 33.188542925949 37.86317845153695 34.23455417714 H 34.7434666721657 34.646871729492 35.17467922859895 H 35.24386239895392 37.72232543412139 39.7776425489174 H 33.1172413487394 36.284618321261 4.57475549569259 H 34.65626475984 35.451644362184 42.528519274464 H 33.9116684935377 33.818672518969 4.623192141352 H 34.2954687215824 34.38952515479 38.93346139457374 H 36.3537586397755 32.8637388563678 41.78634963668958 H 38.895464223729 34.13721715257 38.61232855375914 H 37.6187655231598 38.8261531383179 41.2988613685943 H 37.41578394552 39.292227725616 39.646497871558 H 38.7236999428259 39.63354489625541 4.123471956662 H 39.24874417893565 37.1475382651 4.37276826766313 H 37.58962173545 36.75127575863 39.874587582996 H 4.847864638758 38.4775671971878 38.1125184856662 H 38.2324951179812 36.87716126172415 35.1471567892379 H 38.7225366561213 32.83276566831 4.81548362775759 H 4.474244166275 38.373619198881 35.6139892681165 H 33.253925694182 35.3463922163 33.5271894371959 S9
PHMCu MCO-CuMet 1His 2CO N 39.323453437979 22.697789874744 36.93991731422896 C 39.9311237178223 24.3839293989481 36.85365828688968 C 41.83625624271 24.84879959457 35.86775638211 O 42.12447864623 23.37536495623795 36.898631684457 C 4.4328311128151 24.4594746434584 38.2431858164783 C 41.24426297346386 25.71264543318 38.19122167184 C 42.5993197688743 25.927273488882 38.39575511963579 N 4.753611464371 26.9396274729776 37.7717127872468 C 41.77811189118256 27.8341524468254 37.7328648754595 N 42.91411567641279 27.2381655631 38.187715164 N 4.8785771123798 24.762282891772 34.74638635835787 C 41.872732639138 24.7748326533253 33.637735291934 C 41.8913967 26.19399999881361 33.5759321 O 4.8967187371889 26.87274386667 32.7921232384277 C 41.41541453791 23.71321285385115 32.5629426433626 C 42.39464516294817 23.6843748418939 31.389519187458 O 41.2812421867356 22.439377845587 33.1797676944687 N 43.1779895221462 26.621241168967 32.8823155732258 C 43.52385272645 27.8698448451459 32.2697774399651 C 43.34678755297 27.8462368518664 3.746633749349 O 42.96918899168851 26.8846887876866 3.125121514835 C 44.9163626493828 28.3444951495842 32.64148191493967 C 45.88577521263 28.6434611874286 34.993928894118 C 44.4778388759995 28.14588661538554 35.245458473463 N 46.392143223962 29.53725973939992 34.563461743573 C 45.9916751235114 29.5741158774458 35.9186791817385 N 45.47361642385 28.738478882423 36.36161283483 N 45.2411682484925 24.4448671397134 33.82981261259864 C 45.4872491758742 23.63571889391935 35.3537392616 C 44.7514957 22.33499999956477 35.512171 O 44.111833114213 21.93598539779478 34.1755481924622 C 45.2594311249913 24.44963647881 36.34634256895632 C 46.3538765472357 25.561624688613 36.53625242281591 S 46.24543588615529 26.236345614836 38.23491246619112 C 47.8124179793894 27.13863957696964 38.2155518848437 Cu 44.73421912512816 28.9224458384823 38.24431876142 H 38.94375786665247 22.43537878877 36.1793963648142 H 38.4974148948832 22.737226421184 37.55868786567785 H 39.17955165134669 24.81787344596446 36.5385318961999 H 41.7657223131 23.64215219656 38.6169418473213 H 39.5735636924563 24.56386945489 38.943163818149 H 43.3528121181848 25.1983865935 38.72591128248472 H 41.6595925972125 28.8827449883213 37.438664619275 H 39.97835925214 25.2381422718 34.684754719631 H 42.79685544451351 24.48215888176253 34.41167597911 H 4.399549971976 23.9784499632456 32.194594146523 H 43.442266939 23.39271951331 31.7457876694539 H 42.476515913214 24.6694261428138 3.8892921488523 H 42.6514758519553 22.9295333497623 3.6487247474217 H 42.1776479531688 22.18959623593153 33.518573459291 H 43.9399489743135 25.94597973944288 33.1786412883411 H 42.76221534665 28.6376685266217 32.6137384237956 H 43.58389339762125 28.8292936924756 3.24951859676456 H 45.1578364264 29.25589438239871 32.5435743682667 H 45.6536458563553 27.576275437467 32.315591923542 H 43.67854895627 27.45518477518 35.3356976997994 H 46.633362678572 3.2172238825173 36.5312616536131 H 45.969416623139 23.793834282578 33.421131516475 H 46.9583317296222 24.96494132265815 33.5919959873636 H 46.545364478893 23.2567341252214 35.66354882861 H 44.75557272621682 21.732777648762 35.9517972467916 H 45.32675895359 23.6817395852385 37.18765573844561 H 44.227794853299 24.81119351969426 36.356946839776 H 46.174256227296 26.325533928972 35.8644692962143 H 47.32756149564618 25.8489338223 36.41835661675422 H 47.8952966829456 27.6551743275695 39.1897636478684 H 47.8212815544697 27.884275772741 37.3973722992765 H 48.662678464499 26.44197327486 38.999675782597 H 39.779355985466 27.152217381156 37.542278198355 H 46.6683786946 3.939948472923 33.9751379768236 C 45.1797867225223 29.124986925666 39.681955235137 O 45.4841383449386 29.75355481711188 4.59823323148267 S1
Section S3 - XYZ of truncated metal site models: CusB (CuS 3), CusF (CuS 2I 1), PHM Cu M site (CuS 1I 2), PHM Cu H site (CuI 3) and PHM Cu M-CO (CuS 1I 2CO). Where S = S(CH 3) 2; I = imidazole. CuS3 Cu 6.997-6.123-2.86 C 9.528-4.73-4.613 S 9.11-5.274-2.915 C 9.146-3.691-2.11 H 8.678-4.139-5.24 H 1.389-4.28-4.515 H 1.153-3.265-2.17 H 8.943-3.91 -.957 H 8.392-2.992-2.39 C 4.46-4.692-4.366 S 5.565-6.146-4.598 C 4.379-7.59-4.353 H 3.632-4.817-5.78 H 4.46-4.736-3.349 H 3.891-7.437-3.374 H 4.945-8.446-4.415 H 3.634-7.485-5.158 C 6.242-6.196.58 S 6.426-7.343 -.919 C 7.931-8.254 -.444 H 6.18-6.832 1.44 H 7.151-5.58.576 H 8.784-7.577 -.316 H 8.144-8.963-1.253 H 7.736-8.813.479 H 9.774-5.549-5.254 H 4.993-3.757-4.538 H 5.353-5.575.43 CuS2I1 H 1.773144 7.795767 15.35938 C 1.218754 7.386335 16.2975 C 9.319381 6.336465 16.326278 N 1.315515 7.911112 17.4947 C 9.59575 7.198837 18.32375 N 8.889225 6.234999 17.641192 H 6.28538 8.59627 2.614958 C 5.551591 7.692324 2.61916 C 4.66637 7.374736 21.625546 C 5.27429 6.775844 19.53419 C 4.215956 5.914987 19.965925 C 5.89936 6.59625 18.236264 N 3.86638 6.312497 21.235852 C 3.722764 4.871814 19.168858 C 5.312234 5.555271 17.434566 C 4.2849 4.697837 17.9937 H 1.94236 4.357938 2.271328 C 9.289792 4.499247 21.16944 S 7.753568 3.828449 2.2982 C 6.56421 4.31123 21.5611 C 9.35399 2.6764 16.735238 S 7.652153 3.25823 16.635545 C 6.7335 1.823843 17.22524 Cu 7.53799 4.893791 18.33147 H 8.941449 5.67193 15.54941 H 9.398817 7.416472 19.39129 H 4.5248 7.844119 22.66457 H 6.5743 7.336425 17.819798 H 3.117741 5.96644 21.79821 H 2.91578 4.225496 19.515158 H 5.63288 5.475819 16.38465 H 3.885252 3.917358 17.2444 H 9.18175 5.576368 21.24887 H 9.546435 3.94228 21.939888 H 5.578158 3.92747 21.233272 H 6.511477 5.411236 21.67781 H 6.835546 3.831687 22.521367 H 1.38187 3.439915 16.489117 H 9.57533 2.23517 17.754659 H 5.64228 2.133854 17.232452 H 7.2611 1.516183 18.218522 H 6.814386.98227 16.491293 H 1.9141 8.74947 17.76365 H 9.493994 1.792866 15.997291 CuS 1I 2 H 4.63269 24.458614 38.548494 C 41.26129 25.353856 38.54811 C 42.633388 25.532836 38.574934 N 4.734196 26.638318 38.56274 C 41.75381 27.536711 38.58161 N 42.926724 26.8911 38.586488 H 44.81678 28.5293 32.95253 C 44.925637 28.66434 34.28771 C 44.31232 28.8577 35.131625 N 45.782924 29.614993 34.556741 C 45.687948 29.595691 35.915484 N 44.799639 28.673227 36.2956 H 45.699118 24.714418 36.311145 C 46.5824 25.469226 36.3121 S 46.53425 26.241763 37.97198 C 47.893639 27.416477 37.725393 Cu 44.635139 27.49162 37.877994 H 43.41928 24.77476 38.65434 H 41.61231 28.623175 38.58142 H 43.547597 27.31457 35.151639 H 46.244641 3.272646 36.573233 H 46.314825 26.221934 35.52293 H 47.473689 24.956892 36.132581 H 47.992493 28.6255 38.656916 H 47.687124 28.95335 36.874644 H 48.839726 26.866548 37.552831 H 39.738423 26.872635 38.57652 H 46.369515 3.252551 34.1233 CuI 3 H 34.879538 38.215425 36.262621 C 34.69 37.311924 35.711695 N 35.817 36.48889 36.6444 C 33.769921 37.172868 34.611754 C 34.556872 35.175664 35.196513 N 33.761665 35.825751 34.36449 H 34.818876 34.364545 39.94228 C 35.88112 34.1844 39.94781 N 36.74983 34.497627 38.925868 C 36.63558 33.36719 4.86783 S11
C 37.956975 34.7437 39.225997 N 37.898889 33.31472 4.392983 H 38.517359 37.453691 39.394374 C 38.79911 37.482465 38.336684 N 37.97632 36.977263 37.331584 C 39.945619 37.992217 37.74641 C 38.64456 37.17658 36.168695 N 39.798935 37.787665 36.381575 Cu 36.336692 35.766782 37.514437 H 33.19661 37.94884 34.346 H 34.71893 34.92131 35.193645 H 36.35383 32.86836 41.79819 H 38.871538 34.1468 38.63865 H 4.83293 38.48218 38.1678 H 38.226457 36.92858 35.176941 H 38.679725 32.827694 4.83817 H 4.473734 38.5877 35.66236 H 33.24918 35.3915 33.54298 CuS1I2CO H 4.6765 24.785935 38.289715 C 41.24245 25.67788 38.1728 C 42.5947 25.888117 38.377543 N 4.743985 26.897224 37.7554 C 41.764139 27.79671 37.711543 N 42.92697 27.26679 38.89232 H 44.92949 28.413922 33.15312 C 45.741 28.614638 34.8151 C 44.464587 28.118597 35.22626 N 46.19818 29.516744 34.54882 C 45.97844 29.55528 35.899121 N 45.326 28.715324 36.34221 H 45.37134 24.9829 36.37119 C 46.33877 25.483865 36.521976 S 46.238912 26.188645 38.219718 C 47.81323 27.131277 38.2623 Cu 44.718475 28.69857 38.22541 H 43.351714 25.18619 38.732646 H 41.641969 28.845983 37.41994 H 43.6617 27.37959 35.31218 H 46.59995 3.29687 36.512895 H 46.374269 26.283125 35.76231 H 47.168718 24.796473 36.448587 H 47.896863 27.632431 39.182457 H 47.79515 27.888799 37.392793 H 48.65727 26.44779 38.67887 H 39.7677 27.98283 37.522998 H 46.639364 3.8669 33.953218 C 45.148846 29.16482 39.662198 O 45.45869 29.737681 4.577987 S12
Section S4 - XYZ of truncated metal site models for CusF (CuI 1S 2; where I = imidazole; S= S(CH 3) 2) with S-Cu-S bond angles at 75 o and 95 o. 116 o Cu 1.9331 3.13815-3.9666 C.8756 2.97672.13226 N 1.21197 1.65341 -.11427 C 1.6284 1.5224-1.4618 H 1.922.5764-1.83837 N 1.53939 2.7548-2.1863 C 1.9132 3.61472-1.6877 H.96744 4.66865-1.2985 H 1.15566.88985.55291 C.5174 4.41486-6.74135 S.6528 4.7131-4.9284 C -1.7743 4.42163-4.42322 H.43972 3.3343-6.93165 H -.4399 4.88517-7.5276 H -1.7162 5.18281-4.89444 H -1.11854 4.53292-3.33347 H -1.4141 3.417-4.7342 C 4.22393.6827-4.48542 S 3.6961 2.32616-5.11297 C 5.1622 3.34965-4.58594 H 5.19272.46739-4.96177 H 4.37283.7597-3.39928 H 5.24169 3.3272-3.49913 H 4.88979 4.3829-4.8846 H 6.196 3.512-5.1139 H.53955 3.38967 1.1632 H 1.33939 4.81655-7.2723 75 o Cu.559.751 -.248 C -1.11 -.859 3.791 N -.6651-1.499 3.545 C -.2741-1.549 2.253 H.429-2.4869 1.821 N -.3381 -.3579 1.64 C -.7861.5521 2.59 H -.911 1.661 2.368 H -.7211-2.1729 4.212 C -.4325.8256-3.557 S -.6788 1.4931-1.8521 C -2.511 1.514-1.7863 H -.616 -.2583-3.5428 H -1.1848 1.382-4.187 H -2.8755 2.2113-2.5455 H -2.786 1.8698 -.7891 H -2.9147.512-1.955 C 2.3481-1.8352-1.8945 S 1.4998 -.266-1.9915 C 2.8911.984-1.647 H 3.175-1.87-2.6262 H 2.7742-1.9431 -.8874 H 3.3178.6782 -.6213 H 2.498 1.9312-1.633 H 3.6554.8141-2.386 H -1.3371.3271 4.675 H.561 1.13-3.94 H 1.6799-2.6475-2.934 95 o Cu.559.751 -.248 C -1.5586.4968 3.5825 N -1.2827 -.8632 3.552 C -.7265-1.1814 2.3567 H -.4179-2.194 2.946 N -.6243 -.87 1.69 C -1.1364.966 2.3568 H -1.1564 1.9814 1.9918 H -1.4824-1.5286 4.2919 C -1.8355 1.5887-2.665 S -1.4359 1.664 -.8687 C -3.575 1.245 -.1699 H -1.876.5375-2.9853 H -2.8342 2.281-2.7795 H -3.797 1.9725 -.445 H -2.9455 1.1783.925 H -3.3812.227 -.5296 C 2.3469-2.389 -.826 S 1.8139 -.7369-1.454 C 3.2289.2871 -.927 H 3.3159-2.5959-1.33 H 2.4959-2.339.26 H 3.3649.241.16 H 3.129 1.3191-1.225 H 4.1339 -.579-1.442 H -1.9848 1.381 4.357 H -1.161 2.187-3.2496 H 1.6269-3.1439-1.39 S13
Section S5 - XYZ of truncated metal site models for PHM Cu H (CuI 3; where I - imidazole) with different coordination geometries. T-Shaped Cu -.737 -.116.3787 N 1.6216-1.176.3294 C 1.759-2.4173 -.1721 C 2.9257 -.7317.8337 N 3.377-2.8144 -.361 C 3.7931-1.7352.699 N -1.769.9439.428 C -2.717 1.9815 -.3739 C -2.8929.7217 1.3445 N -3.2928 2.4495 -.56 C -3.8263 1.6439 1.48 N -1.1232-1.786.214 C -1.6975-2.1123-1.1497 C -1.3972-2.8465.9916 N -2.3187-3.2993-1.215 C -2.1295-3.7767.3528 H.9742-2.9978 -.614 H 3.1449.212 1.2918 H 3.41-3.6959 -.3263 H -1.442 2.3731-1.1438 H -2.9577 -.298 2.134 H -3.758 3.2167 -.4977 H -1.6652-1.5243-2.431 H -1.761-2.8778 2.118 H -2.8239-3.7754-1.7413 H 4.8344-1.7446.8558 H -4.7758 1.7665 1.5258 H -2.525-4.6898.7676 Trigonal pyramidal Cu -.725 -.182 -.2261 N 1.7796 -.6113.3935 C 2.377-1.8185.3257 C 2.7234.3349.9986 N 3.6141-1.7354.8341 C 3.8471 -.3536 1.2685 N -.6345 1.5843.5295 C -.291 2.796.111 C -1.58 1.7823 1.6336 N -.7969 3.7511.848 C -1.6795 3.196 1.8287 H 1.9223-2.756 -.74 H 2.551 1.3737 1.1888 H 4.2685-2.4883.939 H.4875 2.9596 -.6834 H -2.923 1.176 2.1792 H -.6559 4.7357.7446 H 4.7398.325 1.7145 H -2.2861 3.629 2.5592 H -1.126-2.281-2.8289 C -.6629-1.184-3.1196 C -.4822 -.6641-4.3764 H -.7741-1.1627-5.277 C.3861.9147-2.9736 H.8562 1.7977-2.5938 N -.132 -.92-2.2238 N.1917.6352-4.2756 H.4612 1.2151-5.445 Trigonal planar Cu -.737 -.116.3787 N 1.9167 -.289.5514 C 2.6937-1.2337.1548 C 2.7764.8285 1.1318 N 3.985 -.9495.4281 C 4.46.3749 1.563 N -1.199 1.627.6369 C -.842 2.736 -.146 C -2.252 1.9127 1.6665 N -1.6443 3.7136.3556 C -2.476 3.199 1.4942 N -1.1232-1.786.214 C -1.6975-2.1123-1.1497 C -1.3972-2.8465.9916 N -2.3187-3.2993-1.215 C -2.1295-3.7767.3528 H 2.3432-2.1337 -.358 H 2.4588 1.7663 1.5375 H 4.7634-1.5411.2354 H -.168 2.8263 -.937 H -2.3851 1.2345 2.4117 H -1.791 4.6399 -.157 H -1.6652-1.5243-2.431 H -1.761-2.8778 2.118 H -2.8239-3.7754-1.7413 H 4.9212.8827 1.393 H -3.131 3.7241 2.761 H -2.525-4.6898.7676 S14
Section S6 - Overlays of calculated VtC XES from truncated and full models Section S7 - Overlays of additionally calculated VtC XES for CusF (S 2I 1; where S = S(CH 3) 2, I = imidazole). (1) The imidazole - Cu bond was set to 2.1 Å ( +.1 Å; longer Cu-N bond); (2) The imidazole -Cu bond was set to 1.87 Å (-.1 Å; shorter Cu-N bond) resulting in Cu-S bonds at 2.35 Å and 2.32 Å (+.7 Å; longer Cu-S bonds); (3) the Cu center was moved out of plane of to yield a C 3v pyramidal geometry. 116 o D3h model of CusF with S-Cu-S angle of 116 o lacking tryptophan residue (section S4); CusF truncated CusF model (with tryptophan residue). S15