Diels-Alder Click-Crosslinked Hydrogels with Increased Reactivity Enable 3D Cell Encapsulation Supporting Information Figure S1: Characteristic rheological time sweep for HAmF Hydrogel O O O N O O O N -OH O N - O OH O O HN OH Figure S2: Mechanism of maleimide hydrolysis
Figure S3 M06-2x/6-311+G** calculated donor-acceptor interaction and calculated topological properties by QTAIM. The key CH methyl O interaction discussed is highlighted. Figure S4: Zoomed in section of furanic peaks of 1 H NMR spectrum of unreacted HAmF (top) and hyaluronidase-digested HA-mF/PEG hydrogels (bottom) Selected DFT Calculated Transition state geometries, pre-complexes, products and the related reactants & Thermochemical Data for Diels-Alder reaction of Furan-modified Hyaluronan (HA-FA) and methyl Furan-modified Hyaluronan (HA-mF) with maleimide Furan-modified Hyaluronan (HA-FA)
# opt=calcfc freq=noraman rb3lyp/6-31g(d,p) scrf=(iefpcm,solvent=water) geom=connectivity temperature=311 Zero-point correction= 0.551030 (Hartree/Particle) Thermal correction to Energy= 0.589583 Thermal correction to Enthalpy= 0.590568 Thermal correction to Gibbs Free Energy= 0.475298 Sum of electronic and zero-point Energies= -1831.163058 Sum of electronic and thermal Energies= -1831.124504 Sum of electronic and thermal Enthalpies= -1831.123519 Sum of electronic and thermal Free Energies= -1831.238790 0 1 C 1.17902800-1.55975000-0.45154300 C 1.98840100-2.81342300-0.09525700 O 3.32864500-2.62240100-0.54495300 C 4.00993700-1.60126000 0.17701000 C 3.34615800-0.23733800-0.08167700 C 1.82164200-0.30269300 0.14789800 C 1.44154800-4.07588100-0.76951100 O 0.18440600-4.45700500-0.22826100 O 5.31926000-1.53290200-0.26988300 N 3.96469700 0.78742500 0.74727300 C 4.15911500 2.07121400 0.36076800 O 3.84185900 2.49007000-0.76258800 O -0.14569200-1.74558300 0.03678100 C 4.76162500 2.99199700 1.40205200 H 3.97295100-1.85265600 1.25487500 H 3.52468100 0.02875300-1.12660400 H 1.60759100-0.28276400 1.22517700 H 1.18323000-1.45235900-1.54663100 H 1.96529400-2.96465900 0.99590900 H 2.14191400-4.89878500-0.59597800
H 1.38756400-3.90663500-1.85659200 H 5.55255200 3.58244100 0.93461200 H -0.33629900-3.63637100-0.16376900 H -0.66771100-0.94876200-0.17937100 H 4.22882900 0.53113100 1.68896400 H 5.16397800 2.46816300 2.27133500 H 3.98284000 3.68488500 1.73606700 O -3.75756700 0.84555900-1.40041700 C -3.36024700 0.71206000-0.24398000 C -2.17144200 1.53261900 0.28675700 C -2.27974200 2.99403000-0.16998600 O -1.00208000 0.90457200-0.26256600 H -2.13391800 1.50303000 1.38521100 C -0.98146900 3.74299800 0.13568700 O -3.39052600 3.53684200 0.53063600 H -2.46073100 3.00003200-1.25220900 C 0.23217600 1.54303000 0.13211800 C 0.22959200 2.97756700-0.40004800 O -1.03686600 5.03897900-0.44475600 H -0.88110200 3.82048500 1.23111800 O 1.27749200 0.87065600-0.47610200 H 0.31706200 1.51864200 1.23022700 O 1.37975100 3.70180500-0.00584800 H 0.15379500 2.91154100-1.49556900 H -0.14279900 5.40350100-0.35160000 H 2.16340200 3.32477700-0.45451000 C -4.14894800 4.49315900-0.20712900 H -3.54799400 5.37122700-0.46340600 H -4.55316800 4.05101800-1.12762300 H -4.97929000 4.79501100 0.43529500 C 6.13045300-2.64337000 0.12475400 H 5.76886800-3.57698400-0.31654900 H 7.13811700-2.43490900-0.23704900 H 6.15085100-2.74426100 1.21753600 N -3.88451100-0.16620700 0.64308300 H -3.48412900-0.22829200 1.56902100 C -4.93072200-1.12401100 0.28517000 H -5.23739600-0.86902400-0.73256300 H -5.79485700-0.99559800 0.94340800 C -4.47411700-2.54230400 0.37414600 C -4.86777600-3.60253400 1.13650200 C -4.04285700-4.71231200 0.75264000 H -5.65024800-3.59373200 1.88194100 C -3.20531600-4.24549300-0.21272000 H -4.07016600-5.71747100 1.14792700 O -3.45443100-2.92336900-0.45981000
H -2.40127700-4.68751700-0.78085500 methyl Furan-modified Hyaluronan (HA-mF) # opt=calcfc freq=noraman b3lyp/6-31g(d,p) scrf=(iefpcm,solvent=water) geom=connectivity temperature=311 Zero-point correction= 0.578676 (Hartree/Particle) Thermal correction to Energy= 0.618972 Thermal correction to Enthalpy= 0.619957 Thermal correction to Gibbs Free Energy= 0.501791 Sum of electronic and zero-point Energies= -1870.462035 Sum of electronic and thermal Energies= -1870.421740 Sum of electronic and thermal Enthalpies= -1870.420755 Sum of electronic and thermal Free Energies= -1870.538920 0 1 C 0.97922000 1.44793600-0.07276700 C 1.80720500 2.69977300-0.42959900 O 3.10171700 2.57529800 0.18312000 C 3.90260300 1.48083200-0.32079300 C 3.21032000 0.11035200-0.09674100 C 1.70334000 0.13633700-0.44589900 C 1.22196600 3.98363200 0.18721100 O 0.12657600 4.44250900-0.60378600 O 5.01799700 1.45203100 0.54976700 N 3.89204300-0.92226700-0.90451600 C 4.27592300-2.14953300-0.34072700 O 3.96047900-2.44028900 0.80155900 O -0.19875600 1.57370300-0.88070600 C 5.05369500-3.04863000-1.25488000 H 4.18678900 1.70632900-1.36622300
H 3.30770800-0.16311900 1.00523100 H 1.50449100-0.13338700-1.50502900 H 0.69068800 1.42425700 1.00451500 H 1.90921000 2.80754700-1.53345400 H 1.95275400 4.81495500 0.14855600 H 0.88895700 3.83309000 1.22957100 H 4.49840200-3.31454500-2.16434900 H -0.51012600 3.69075500-0.77870000 H -0.82768000 0.82405500-0.68018200 H 4.16528700-0.66918300-1.84768700 H 5.28531100-3.99728500-0.73788400 H 6.01535200-2.61176100-1.55661000 O -4.32412800-1.19771500-1.07363100 C -3.32585600-1.06635800-0.38420400 C -2.08497500-1.95861100-0.59761700 C -2.23506000-3.30458800 0.15101300 O -0.98850900-1.15211200-0.13808300 H -1.95156900-2.15114100-1.69204100 C -0.94868100-3.91739300 0.74235900 O -2.60478100-4.27148100-0.85495400 H -3.00926100-3.24888800 0.95536400 C 0.29615700-1.83739200-0.10345200 C 0.24922700-2.96610400 0.94533800 O -1.36958000-4.35777500 2.04513300 H -0.63069700-4.80245100 0.13066100 O 1.14141700-0.85644400 0.45914600 H 0.58319500-2.14553400-1.12406700 O 1.38774700-3.80380300 0.73761000 H 0.25955300-2.54347400 1.97848800 H -0.73014300-5.01579400 2.39940700 H 2.22097200-3.34589200 1.06275100 C -4.02613100-4.38111300-1.09015900 H -4.53047700-4.74954100-0.19290300 H -4.44000800-3.41769400-1.41898000 H -4.07121500-5.12202200-1.89720700 C 5.84148500 2.64326900 0.52333700 H 5.24121500 3.52061900 0.78729800 H 6.58138200 2.42526100 1.30394100 H 6.31440500 2.75488400-0.45476000 N -3.24586300-0.17449300 0.67271400 H -2.36312000-0.03855700 1.17123000 C -4.28645600 0.86605200 0.85963200 H -4.45564200 1.00892000 1.95474700 H -5.25384900 0.50622600 0.41813600 C -3.87907100 2.13957500 0.21774800 C -3.89077700 2.63274700-1.06017700
C -3.31538600 3.95307200-1.00770100 H -4.25482300 2.14798400-1.94732300 C -2.98564400 4.19736300 0.30266000 H -3.18196700 4.60430600-1.84903500 O -3.31909100 3.08785300 1.10211900 C -2.36482200 5.30807700 1.03075600 H -1.34008200 5.50176100 0.64653600 H -2.93653800 6.24171600 0.91313500 H -2.28014200 5.10494800 2.10908900 Truncated maleimide # opt=calcfc freq=noraman b3lyp/6-31g(d,p) scrf=(iefpcm,solvent=water) geom=connectivity temperature=311 Zero-point correction= 0.157922 (Hartree/Particle) Thermal correction to Energy= 0.169621 Thermal correction to Enthalpy= 0.170606 Thermal correction to Gibbs Free Energy= 0.116433 Sum of electronic and zero-point Energies= -552.437181 Sum of electronic and thermal Energies= -552.425482 Sum of electronic and thermal Enthalpies= -552.424497 Sum of electronic and thermal Free Energies= -552.478670 0 1 C -2.77996700-0.66812700-0.46648400 C -2.77995100 0.66816900-0.46647900 C -1.44926700-1.14660100 0.03706200 C -1.44923900 1.14660800 0.03707100 H -3.56352800-1.35259400-0.76187200 H -3.56349700 1.35265700-0.76186200 O -1.06627500 2.29174300 0.18873300 O -1.06633100-2.29174700 0.18871900 N -0.70185500-0.00000600 0.31854100
C 0.65489500-0.00002400 0.84172500 C 1.70229400-0.00000200-0.27220200 H 0.77662000-0.88782300 1.46610000 H 0.77663000 0.88774600 1.46614100 H 1.57476000-0.88935200-0.90936900 H 1.57475100 0.88936400-0.90934300 O 2.97100500-0.00000500 0.35321800 C 4.03960700-0.00000300-0.57952800 H 4.01510600 0.89188600-1.22250400 H 4.96960300 0.00000000-0.00692700 H 4.01511000-0.89189500-1.22250000 Pre-complex of DA reaction between HA-FA and maleimide (Endo route) # opt=calcfc freq=noraman b3lyp/6-31g(d,p) scrf=(iefpcm,solvent=water) geom=connectivity temperature=311 Zero-point correction= 0.709615 (Hartree/Particle) Thermal correction to Energy= 0.762370 Thermal correction to Enthalpy= 0.763355 Thermal correction to Gibbs Free Energy= 0.608176 Sum of electronic and zero-point Energies= -2383.602634 Sum of electronic and thermal Energies= -2383.549879 Sum of electronic and thermal Enthalpies= -2383.548894 Sum of electronic and thermal Free Energies= -2383.704073 SCF (RM062X/ 6-311+g(d,p)) = -2384.05527321 0 1 C 3.45828800-1.62215600 0.02381800 C 4.23095400-2.85675200 0.50682900 O 5.52693800-2.83624800-0.08832800 C 6.33322400-1.76038600 0.38198900 C 5.72354800-0.41634900-0.05299100
C 4.22960900-0.33062200 0.32234800 C 3.55220200-4.16861600 0.09815400 O 2.32896300-4.37045800 0.79216100 O 7.59323300-1.86548700-0.18381400 N 6.47635400 0.68978300 0.52013900 C 6.70966300 1.86436000-0.11327700 O 6.32030100 2.09221300-1.26869400 O 2.19085100-1.62753900 0.67408100 C 7.45141100 2.91412300 0.68813600 H 6.39009900-1.82261000 1.48599000 H 5.81004000-0.34741500-1.14024000 H 4.12802900-0.10387200 1.39225400 H 3.34100000-1.69924800-1.06750400 H 4.30927900-2.83054600 1.60535300 H 4.21718400-5.00092700 0.34860700 H 3.41053800-4.17107600-0.99408000 H 8.24713200 3.33379000 0.06872700 H 1.86055000-3.51701000 0.76460800 H 1.69967300-0.83133500 0.39788300 H 6.80286300 0.58969000 1.47176600 H 7.87676800 2.53693600 1.62024800 H 6.75017800 3.72176800 0.92040000 O -1.87259000 1.24308500 1.11277400 C -0.91826400 1.03751400 0.36433700 C 0.39147900 1.82146400 0.52402000 C 0.32723400 3.19761200-0.19575700 O 1.45793500 1.02020800-0.00776800 H 0.53608800 1.99337800 1.59783400 C 1.70501400 3.86305900-0.18138700 O -0.59201200 4.03974600 0.47835400 H 0.02741000 3.04186600-1.24051700 C 2.77091400 1.61304900 0.11526300 C 2.79182600 2.91442900-0.68506900 O 1.65570500 5.02693400-0.99175600 H 1.94015400 4.13168300 0.86214600 O 3.68771000 0.74945000-0.45642100 H 2.98477700 1.78781600 1.18097000 O 4.02192700 3.60324600-0.56504900 H 2.58034500 2.65082500-1.73213000 H 2.57798800 5.31042000-1.09061400 H 4.72667900 3.08218600-1.00073400 C -1.78691300 4.33150800-0.24016200 H -1.56771900 4.81900000-1.19857000 H -2.38590100 3.43117200-0.41811900 H -2.36345800 5.01882900 0.38298300 C 8.37425300-2.94818900 0.33092400
H 7.91209000-3.91398400 0.10565400 H 9.34824800-2.88691500-0.15617600 H 8.50487200-2.85445600 1.41674100 N -0.93607700 0.17048100-0.67536400 H -0.08060000 0.04265500-1.19794500 C -2.06964500-0.71120300-0.95211200 H -2.13392700-0.83429600-2.03809100 H -2.98100700-0.22119900-0.60666500 C -1.96594000-2.03982300-0.27426400 C -2.73761400-2.68071400 0.65021700 C -2.09524700-3.93681000 0.91835400 H -3.64915300-2.29321500 1.08161800 C -0.97891700-3.96680600 0.14123200 H -2.42103000-4.70712700 1.60253500 O -0.88466200-2.81845900-0.59788600 C -7.17603200-2.21310000-2.07726000 C -6.06211500-2.05747400-1.35571700 C -8.14187100-1.12619800-1.70514000 C -6.23247700-0.86050000-0.46727100 H -7.41221800-2.96433500-2.81853300 H -5.15574200-2.64760200-1.35304000 O -5.43873200-0.39294700 0.33182300 O -9.25790900-0.92276100-2.14396500 N -7.50408900-0.35207300-0.72960100 C -8.08223000 0.82030900-0.09160600 C -8.88550200 0.45744700 1.15774300 H -8.72924100 1.31680400-0.81817300 H -7.26645400 1.49667100 0.17232800 H -9.69702800-0.23882600 0.89364100 H -8.23612800-0.04760900 1.89007500 H -0.17036300-4.67064600 0.01680100 O -9.40168700 1.66492000 1.68288500 C -10.17241700 1.46423300 2.85675700 H -9.57417000 1.01110000 3.66061800 H -10.52431000 2.44465900 3.18489600 H -11.04124300 0.81798700 2.66440700 Transition state of DA reaction between HA-FA and maleimide (Endo route)
# opt=(calcfc,ts,noeigen) freq=noraman b3lyp/6-31g(d,p) scrf=(iefpcm,solvent=water) geom=connectivity temperature=311 Zero-point correction= 0.710481 (Hartree/Particle) Thermal correction to Energy= 0.761079 Thermal correction to Enthalpy= 0.762064 Thermal correction to Gibbs Free Energy= 0.618243 Sum of electronic and zero-point Energies= -2383.568258 Sum of electronic and thermal Energies= -2383.517661 Sum of electronic and thermal Enthalpies= -2383.516676 Sum of electronic and thermal Free Energies= -2383.660496 SCF (RM062X/ 6-311+g(d,p)) = -2384.03618092 0 1 C 1.56394300-1.78250500-0.15724200 C 1.41528400-3.27351300 0.17499400 O 2.48690900-3.98108600-0.44645100 C 3.75706200-3.66148200 0.11273300 C 4.09644700-2.18630000-0.16269000 C 2.94153400-1.25908200 0.26800000 C 0.10292700-3.86650800-0.34934200 O -1.02447100-3.36847100 0.35610800 O 4.72365500-4.44673700-0.49350000 N 5.34178500-1.82307100 0.49726900 C 6.25812400-0.96783500-0.01643300 O 6.12422900-0.42701100-1.12464600 O 0.51701100-1.08531500 0.51095000 C 7.45405000-0.67247100 0.86483200 H 3.71783100-3.85457900 1.20247300 H 4.24601600-2.07314400-1.23938200 H 2.94722900-1.14207000 1.35993700 H 1.48098500-1.66659700-1.24843200 H 1.44630400-3.40701000 1.26796700
H 0.12862800-4.95143300-0.20841000 H 0.03035800-3.67180600-1.43097500 H 8.36119100-0.72654800 0.25916500 H -0.90499900-2.40373000 0.40337000 H 0.62544200-0.13078500 0.34099000 H 5.51142100-2.20242900 1.41900900 H 7.54599900-1.34591300 1.71932200 H 7.35981700 0.35418500 1.23260000 O -1.00515000 3.52234400 1.50330600 C -0.32319000 2.92185800 0.67506500 C 1.18211200 2.72150300 0.88618000 C 1.99979900 3.93841700 0.36971800 O 1.56974700 1.52140100 0.20259800 H 1.34421000 2.62243900 1.96646100 C 3.49687200 3.62265900 0.40441200 O 1.74698200 5.05639100 1.20344000 H 1.71522200 4.14833800-0.66975200 C 2.96570700 1.17517000 0.35267700 C 3.80620600 2.28748100-0.27284700 O 4.19519900 4.67558300-0.24118500 H 3.80351800 3.55023600 1.46127000 O 3.19601700 0.01081100-0.35633700 H 3.18890600 1.05058300 1.42357400 O 5.19561200 2.06669600-0.12329900 H 3.52179900 2.34825100-1.33394500 H 5.10586800 4.35746200-0.34203800 H 5.45675500 1.28936700-0.65748500 C 1.02955500 6.12232100 0.58837700 H 1.56351600 6.51051800-0.28802100 H 0.01923200 5.81719000 0.29203000 H 0.95112900 6.91516300 1.33550000 C 4.67510600-5.82583200-0.11553900 H 3.73523900-6.29076300-0.42792800 H 5.50979600-6.31496500-0.61924300 H 4.79028200-5.93778700 0.97027200 N -0.80120100 2.42385800-0.49285400 H -0.15445600 1.94604400-1.10637300 C -2.21057800 2.48457600-0.85721200 H -2.35371700 3.13384800-1.72699300 H -2.74043800 2.92536000-0.01072100 C -2.78185300 1.12811900-1.15636200 C -2.82299300-0.01406000-0.30127500 C -3.07282700-1.09710600-1.10929700 H -2.77842900 0.01673400 0.77832700 C -3.18737600-0.57919000-2.43044500 H -3.25397100-2.12099500-0.81542100
O -2.62738500 0.67431500-2.44983300 C -5.12911700 0.27606000-2.36286500 C -4.87775500 1.39996300-1.54469600 C -6.00752900-0.65012300-1.59149900 C -5.57867100 1.18690700-0.25080200 H -5.23380900 0.31319500-3.43955100 H -4.75481800 2.41087600-1.91176800 O -5.66558400 1.93566000 0.71060900 O -6.52625700-1.69573500-1.94778600 N -6.15627500-0.08939000-0.31391300 C -6.93312700-0.68839000 0.75765200 C -6.07140400-1.51665200 1.71074600 H -7.69626700-1.32370800 0.30262500 H -7.42404000 0.11593000 1.31063100 H -5.56628400-2.32483000 1.15862200 H -5.29253000-0.88260400 2.16294100 H -3.14640600-1.12156500-3.36472700 O -6.93501000-2.04211000 2.70102200 C -6.25208000-2.83843500 3.65513000 H -5.48708900-2.25929500 4.19281800 H -6.99531200-3.19574600 4.37129100 H -5.76370200-3.70439200 3.18465800 Product of DA reaction between HA-FA and maleimide (Endo route) # opt=calcfc freq=noraman b3lyp/6-31g(d,p) scrf=(iefpcm,solvent=water) geom=connectivity temperature=311 Zero-point correction= 0.714200 (Hartree/Particle) Thermal correction to Energy= 0.764046 Thermal correction to Enthalpy= 0.765031
Thermal correction to Gibbs Free Energy= 0.623652 Sum of electronic and zero-point Energies= -2383.605781 Sum of electronic and thermal Energies= -2383.555935 Sum of electronic and thermal Enthalpies= -2383.554950 Sum of electronic and thermal Free Energies= -2383.696329 SCF (RM062X/ 6-311+g(d,p)) = -2384.08393584 0 1 C 1.49920400-1.81957600 0.10928600 C 1.36447900-3.29851500 0.49475000 O 2.35647200-4.03857200-0.21407200 C 3.68101200-3.72697000 0.20500900 C 4.01549100-2.26647300-0.14430100 C 2.92166400-1.30642900 0.36719900 C -0.00142900-3.88166900 0.11796500 O -1.04953200-3.33559100 0.90721900 O 4.56982500-4.54563200-0.47174500 N 5.32414200-1.91382400 0.38658700 C 6.20990000-1.09945200-0.23509300 O 5.98349500-0.57904400-1.33804200 O 0.54506400-1.08544600 0.87154500 C 7.49644400-0.82506200 0.51618900 H 3.74855900-3.88909800 1.29839400 H 4.06558800-2.18499600-1.23294000 H 3.04222400-1.15134800 1.44758600 H 1.29603400-1.72846800-0.96817800 H 1.50496700-3.40539100 1.58222700 H 0.01747600-4.96180600 0.29269700 H -0.17191800-3.72000400-0.95798500 H 8.33730800-0.93891800-0.17146800 H -0.88553200-2.37627800 0.94303600 H 0.62007100-0.14304400 0.63105400 H 5.57523200-2.28257000 1.29384900 H 7.64531100-1.47240600 1.38274300 H 7.48009000 0.21671100 0.85149200 O -0.83513600 3.66669900 1.69341400 C -0.23793400 2.98925200 0.85786000 C 1.26828100 2.73198200 0.98577400 C 2.08407100 3.91434300 0.38862900 O 1.57525100 1.50246000 0.31242800 H 1.49471900 2.65489100 2.05618300 C 3.56874600 3.55533300 0.30871400 O 1.92860600 5.04902800 1.22389400 H 1.72354000 4.11967700-0.62780500 C 2.97180300 1.12857000 0.36094600 C 3.78358200 2.20083600-0.36395800
O 4.24183800 4.57724400-0.40969300 H 3.95751100 3.49034200 1.33874400 O 3.12246900-0.06287700-0.32494200 H 3.28011300 1.03281300 1.41360700 O 5.17448900 1.94502100-0.32750800 H 3.41064900 2.24646900-1.39800700 H 5.13131800 4.22979600-0.57951500 H 5.37030400 1.14846500-0.86125400 C 1.25239100 6.15231700 0.62887600 H 1.77886300 6.51030000-0.26460700 H 0.21813400 5.90135900 0.36533900 H 1.24051400 6.94880500 1.37623000 C 4.53542000-5.91388800-0.05488600 H 3.56424800-6.37013600-0.26883400 H 5.31356400-6.42949600-0.61907200 H 4.74701600-6.00091400 1.01866500 N -0.81400300 2.46195800-0.24859100 H -0.24126600 1.91816900-0.88053100 C -2.22154900 2.62914900-0.56483300 H -2.35211300 3.36046500-1.37193500 H -2.72328500 3.01659900 0.32431500 C -2.84758100 1.31470200-0.98024900 C -2.72312400 0.11352000-0.04556200 C -2.79634400-0.96904200-0.82636800 H -2.67612900 0.17083100 1.03452500 C -2.97142900-0.43671000-2.24069900 H -2.80282600-2.01168300-0.53463100 O -2.23611700 0.80207700-2.18871900 C -4.43617800 0.14207600-2.37608700 C -4.34756000 1.39020800-1.47447700 C -5.55883000-0.69228500-1.78517700 C -5.41375200 1.19403300-0.41277500 H -4.65121700 0.36736900-3.42222800 H -4.51788300 2.33032600-2.00426900 O -5.68020400 1.93087900 0.51950400 O -5.97669800-1.76673600-2.17506500 N -6.06587400-0.01057200-0.67571100 C -7.14496800-0.53109900 0.15436600 C -6.61981100-1.41210500 1.28839600 H -7.81243100-1.10831400-0.48826800 H -7.68945300 0.32068300 0.56635000 H -6.06611800-2.26928300 0.87488000 H -5.92571500-0.83785200 1.92161700 H -2.64192500-1.05743900-3.07104300 O -7.74540100-1.84326100 2.02843400 C -7.39362600-2.68086700 3.11805500
H -6.73578400-2.16236300 3.83061500 H -8.32003100-2.95750700 3.62593500 H -6.88517900-3.59477200 2.77801800 Pre-complex of DA reaction between HA-FA and maleimide (Exo route) # opt=calcfc freq=noraman b3lyp/6-31g(d,p) scrf=(iefpcm,solvent=water) geom=connectivity temperature=311 Zero-point correction= 0.709617 (Hartree/Particle) Thermal correction to Energy= 0.762231 Thermal correction to Enthalpy= 0.763216 Thermal correction to Gibbs Free Energy= 0.610266 Sum of electronic and zero-point Energies= -2383.602708 Sum of electronic and thermal Energies= -2383.550094 Sum of electronic and thermal Enthalpies= -2383.549109 Sum of electronic and thermal Free Energies= -2383.702059 SCF (RM062X/ 6-311+g(d,p)) = -2384.05958156 0 1 C -0.95242900-1.46428700-1.08235800 C -0.86225300-2.76312600-1.89421600 O -1.55248500-3.78708400-1.18073900 C -2.95703300-3.56072000-1.11169400 C -3.24584600-2.29522400-0.28529600 C -2.41109300-1.09704100-0.78349600 C 0.58399500-3.22820800-2.09393500 O 1.30035300-2.36519100-2.96674400 O -3.55317000-4.63615400-0.47419800 N -4.67000300-1.99443300-0.30321900 C -5.35783200-1.48337600 0.74593000 O -4.82866800-1.23952700 1.84094500 O -0.30640800-0.44158200-1.83441100 C -6.82208600-1.18626300 0.49572000
H -3.34358000-3.44908500-2.14336900 H -2.96432300-2.50240600 0.75020600 H -2.85959700-0.68410100-1.69698600 H -0.44173200-1.62799500-0.12160200 H -1.31832000-2.60652000-2.88485900 H 0.57376700-4.22456700-2.54645800 H 1.07093200-3.31303300-1.10969100 H -7.40565000-1.55305500 1.34278300 H 1.07394700-1.45838000-2.69249900 H -0.36282300 0.39291000-1.33232200 H -5.16847000-2.13989400-1.17077900 H -7.20714000-1.62329400-0.42778100 H -6.94694200-0.09964000 0.45140500 O 0.49791600 4.38201400-1.78303800 C 0.22635700 3.52134100-0.94992000 C -1.22850800 3.14427800-0.63321100 C -1.79546500 3.97899100 0.54313500 O -1.26065100 1.74459700-0.31580000 H -1.81729200 3.35116500-1.53540600 C -3.18242600 3.45216000 0.92883800 O -1.84123400 5.32353900 0.10190000 H -1.12417600 3.87558800 1.40805900 C -2.58344600 1.22243700-0.05204400 C -3.15472800 1.94257700 1.16808100 O -3.63062200 4.11801700 2.10074400 H -3.86567900 3.65671800 0.08794500 O -2.45985800-0.11743900 0.26676800 H -3.21095700 1.37476800-0.94368400 O -4.48407000 1.55089400 1.45417500 H -2.48303800 1.72758200 2.01250600 H -4.42018700 3.63207500 2.38687300 H -4.48711100 0.61957700 1.75558300 C -1.63366200 6.30043400 1.12087300 H -2.43388000 6.28223200 1.86672000 H -0.66936300 6.14868800 1.62488000 H -1.62156000 7.27119600 0.62049400 C -3.57200500-5.83771000-1.25070000 H -2.55833900-6.19822800-1.44957800 H -4.11426200-6.57864200-0.66191500 H -4.09297400-5.67938900-2.20374000 N 1.14930800 2.85773400-0.21147400 H 0.82875200 2.10465900 0.38149700 C 2.58718700 3.01054100-0.42626600 H 3.08368700 2.79861200 0.52544200 H 2.78553900 4.04860800-0.69777900 C 3.12314700 2.12492300-1.50679400
C 3.78184600 2.35922300-2.67783900 C 4.01677400 1.07863000-3.28095700 H 4.06107900 3.32809200-3.06666500 C 3.48121500 0.15556500-2.43637500 H 4.51055200 0.87763600-4.22079600 O 2.93362100 0.77498000-1.34513900 C 6.34283000-0.34886200-0.13975000 C 5.93992900 0.75093200 0.50440000 N 4.52332700-0.96305000 1.16209000 C 5.44697600-1.48736500 0.25266200 C 4.75384000 0.39928300 1.35213600 O 5.48145600-2.64293400-0.12669200 O 4.09289300 1.13176500 2.06817800 H 7.16176800-0.47392400-0.83486900 H 6.34604500 1.75256200 0.46868700 C 3.43634500-1.71429000 1.76897700 C 3.84124500-2.32990400 3.10840600 H 3.13912400-2.50144800 1.07231700 H 2.59332600-1.03462300 1.91164300 H 4.69734600-3.00839300 2.96726700 H 4.15372300-1.53794300 3.80725700 H 3.37417600-0.91782300-2.47013100 O 2.71401300-3.02758200 3.60138300 C 2.96064100-3.64862200 4.85259200 H 2.03996200-4.15517700 5.15010000 H 3.77049200-4.38946800 4.78375900 H 3.22898800-2.91181500 5.62367700 Transition state of DA reaction between HA-FA and maleimide (Exo route)
# opt=(calcfc,ts,noeigen) freq=noraman b3lyp/6-31g(d,p) scrf=(iefpcm,solvent=water) geom=connectivity temperature=311 Zero-point correction= 0.710426 (Hartree/Particle) Thermal correction to Energy= 0.761118 Thermal correction to Enthalpy= 0.762103 Thermal correction to Gibbs Free Energy= 0.615954 Sum of electronic and zero-point Energies= -2383.570281 Sum of electronic and thermal Energies= -2383.519589 Sum of electronic and thermal Enthalpies= -2383.518604 Sum of electronic and thermal Free Energies= -2383.664753 SCF (RM062X/ 6-311+g(d,p)) = -2384.03463854 0 1 C -1.52067900-1.71339800-0.63528900 C -1.58170600-3.11387400-1.25931900 O -2.32760200-3.96192700-0.38881400 C -3.70135500-3.59531800-0.30288600 C -3.83589600-2.20990500 0.35290200 C -2.92548700-1.17378300-0.33859000 C -0.19195600-3.73586000-1.43388400 O 0.56969300-3.05687200-2.42399200 O -4.36084600-4.51548900 0.49493300 N -5.22727600-1.78168200 0.34670400 C -5.81178500-1.06209200 1.33465200 O -5.20774500-0.71543900 2.36094800 O -0.82415900-0.86762000-1.54676100 C -7.25527600-0.66726300 1.09982100 H -4.12481500-3.58398300-1.32598100 H -3.52143600-2.30193700 1.39567800 H -3.38219900-0.85011100-1.28340500 H -0.98104700-1.78963500 0.32041600 H -2.06509900-3.05187700-2.24748500 H -0.30913800-4.77469400-1.75762000 H 0.31870900-3.74517100-0.45834400 H -7.82687400-0.86490500 2.00920000 H 0.41800900-2.10652800-2.27085900 H -0.77651100 0.02675700-1.15964600 H -5.78152200-2.00317000-0.46935400 H -7.72041700-1.18424700 0.25819100 H -7.28845700 0.41099400 0.91424400 O 0.54084200 3.76820900-2.09694400 C 0.18044500 3.06126500-1.16000600 C -1.30256200 2.89935200-0.79359500 C -1.75292100 3.94544000 0.25799600 O -1.47700300 1.56663100-0.29096800 H -1.87992000 3.04681600-1.71459700
C -3.17097700 3.62005900 0.74319700 O -1.68548100 5.20868200-0.37768000 H -1.06872900 3.90532200 1.11810500 C -2.83688200 1.22870300 0.06912700 C -3.28396500 2.16295200 1.19164100 O -3.50762000 4.48430100 1.81870200 H -3.86045800 3.77549700-0.10308300 O -2.83901000-0.06108200 0.56608600 H -3.47677700 1.32628300-0.82117800 O -4.63258900 1.95270800 1.56434000 H -2.60307500 1.99525900 2.03937200 H -4.33045100 4.12720600 2.18870900 H -4.71256100 1.07777300 1.99612200 C -1.36248500 6.30130100 0.48140500 H -2.14400600 6.47286400 1.22747800 H -0.40641500 6.13209600 0.99524500 H -1.26843100 7.18062000-0.15952400 C -4.52629600-5.80061600-0.11210300 H -3.56006500-6.27603000-0.30549800 H -5.09651800-6.40569300 0.59384100 H -5.08413900-5.71926400-1.05391000 N 1.03224700 2.38805700-0.34497800 H 0.63536300 1.75648700 0.33745400 C 2.47100800 2.34735700-0.58214300 H 2.97896200 2.21679100 0.37488400 H 2.77712800 3.30595800-1.00398500 C 2.85954800 1.25952700-1.54480300 C 2.89695400 1.30726800-2.96551800 C 2.98128100 0.00741400-3.39938900 H 2.94001100 2.21521900-3.54985300 C 3.05630800-0.79692600-2.21969100 H 3.12910300-0.35150300-4.40826300 O 2.60365900-0.02752700-1.16275300 C 5.00686800-0.58609700-1.76678900 C 5.11411100 0.75846000-1.33546800 N 5.13344200-0.58056300 0.55607000 C 5.08753600-1.44587100-0.53322800 C 5.21796100 0.76006200 0.13443900 O 5.08393300-2.66411300-0.45685300 O 5.33654900 1.70295900 0.90810200 H 5.46199900-0.97324800-2.66983500 H 5.51837000 1.58131700-1.90656900 C 5.09514800-1.00089000 1.94613800 C 6.49591800-1.22888200 2.51480100 H 4.51678400-1.92556800 2.00661500 H 4.58520400-0.22516100 2.52191600
H 7.01671800-2.00389700 1.93076600 H 7.08491100-0.30125200 2.44290500 H 2.83165800-1.85296400-2.13535200 O 6.33920200-1.62882000 3.86339400 C 7.57825300-1.87583400 4.50709900 H 7.35663100-2.17916900 5.53271900 H 8.13942200-2.68039200 4.00961300 H 8.20991900-0.97567000 4.52929300 Product of DA reaction between HA-FA and maleimide (Exo route) # opt=calcfc freq=noraman b3lyp/6-31g(d,p) scrf=(iefpcm,solvent=water) geom=connectivity temperature=311 Zero-point correction= 0.714060 (Hartree/Particle) Thermal correction to Energy= 0.763962 Thermal correction to Enthalpy= 0.764947 Thermal correction to Gibbs Free Energy= 0.623066 Sum of electronic and zero-point Energies= -2383.609687 Sum of electronic and thermal Energies= -2383.559784 Sum of electronic and thermal Enthalpies= -2383.558800 Sum of electronic and thermal Free Energies= -2383.700680 SCF (RM062X/ 6-311+g(d,p)) = -2384.08710921 0 1 C -1.89909500-1.81132100-0.25600100 C -2.07221700-3.25891200-0.73414100 O -2.99623800-3.91351400 0.13277300 C -4.31591100-3.38553200 0.03720000 C -4.33613900-1.93040400 0.53716800 C -3.24716400-1.08824700-0.15692600
C -0.75827400-4.04715200-0.68708800 O 0.18694700-3.56372400-1.63146200 O -5.15561100-4.13149600 0.84768600 N -5.65529900-1.34517800 0.34893300 C -6.23468200-0.47503000 1.21066600 O -5.69292900-0.11595000 2.26703600 O -1.03342700-1.15737700-1.17896900 C -7.58373900 0.07249500 0.79226000 H -4.63786400-3.43960200-1.02066500 H -4.13062100-1.94444300 1.61039700 H -3.57491800-0.82119500-1.17051200 H -1.45598000-1.83580700 0.75087700 H -2.44700400-3.25632800-1.77002500 H -0.96637200-5.09401800-0.92939200 H -0.36473000-4.01454000 0.34125500 H -8.26283500 0.02734400 1.64640900 H 0.14575800-2.59159700-1.57867800 H -0.92691300-0.22910800-0.89941300 H -6.14665300-1.56314400-0.50736000 H -8.02884500-0.45426200-0.05425000 H -7.45500400 1.12624200 0.52536100 O 0.73356100 3.34726800-2.23147700 C 0.29064800 2.73047600-1.26449700 C -1.20996800 2.73264600-0.94009300 C -1.58889100 3.92258600-0.02062300 O -1.53230000 1.48731000-0.30427100 H -1.74426800 2.83214600-1.89303900 C -3.05171300 3.79548000 0.41948900 O -1.36876000 5.10661200-0.76466100 H -0.94741600 3.89746800 0.87204800 C -2.93508000 1.32435500 0.00989000 C -3.34103700 2.41272800 1.00270200 O -3.33606900 4.79948700 1.38310300 H -3.68449200 3.93254200-0.47305800 O -3.09685600 0.10179100 0.63517600 H -3.51844200 1.38745900-0.92154200 O -4.72287800 2.37888100 1.30545600 H -2.72862900 2.26943400 1.90535500 H -4.21320700 4.58067800 1.73488100 H -4.92416400 1.56107800 1.80368800 C -0.90674100 6.22002200-0.00222400 H -1.65008700 6.54195200 0.73347300 H 0.03293200 5.98395100 0.51559300 H -0.72410200 7.02806400-0.71399800 C -5.42235700-5.44810600 0.35531800 H -4.51034500-6.05147000 0.31945100
H -6.13258200-5.90048100 1.04858800 H -5.86841700-5.40767600-0.64680600 N 1.05610600 2.03889800-0.38543300 H 0.58837500 1.50877100 0.33668800 C 2.49965300 1.92410600-0.51251000 H 2.94689300 1.97351400 0.48178900 H 2.85676400 2.78079900-1.08762500 C 2.92430100 0.64214300-1.21374300 C 2.33676600 0.36037300-2.59742500 C 2.34830700-0.96700700-2.73758500 H 2.05992400 1.12774300-3.30832700 C 2.95442700-1.50526600-1.44946000 H 2.09586900-1.56377600-3.60480300 O 2.52064800-0.53342100-0.47635500 C 4.48839900-1.18008600-1.51205600 C 4.47939200 0.36070800-1.34919300 N 5.63632200-0.61049800 0.47576600 C 5.22885000-1.70076000-0.29025200 C 5.25396200 0.61430300-0.06329400 O 5.43344800-2.86296900 0.00712200 O 5.50714300 1.69220300 0.44600700 H 4.96305200-1.55570900-2.42005700 H 4.93123800 0.92637400-2.16536500 C 6.35528400-0.73910800 1.73748800 C 7.86989600-0.68467800 1.53678300 H 6.07154600-1.69294100 2.18594100 H 6.03755100 0.07584100 2.39083900 H 8.19183400-1.49972400 0.86977600 H 8.15320000 0.26845900 1.06379100 H 2.69424200-2.51656500-1.14210000 O 8.45829900-0.81164300 2.81669100 C 9.87568400-0.77117500 2.77197300 H 10.23489300-0.87079900 3.79848700 H 10.28485500-1.59405300 2.16797100 H 10.23986900 0.17932600 2.35570100 Pre-complex of DA reaction between HA-mF and maleimide (Endo route)
# opt=calcfc freq=noraman b3lyp/6-31g(d,p) scrf=(iefpcm,solvent=water) geom=connectivity temperature=311 Zero-point correction= 0.737586 (Hartree/Particle) Thermal correction to Energy= 0.791912 Thermal correction to Enthalpy= 0.792897 Thermal correction to Gibbs Free Energy= 0.636933 Sum of electronic and zero-point Energies= -2422.899630 Sum of electronic and thermal Energies= -2422.845304 Sum of electronic and thermal Enthalpies= -2422.844319 Sum of electronic and thermal Free Energies= -2423.000283 SCF (RM062X/ 6-311+g(d,p)) = -2423.36661191 0 1 C 2.30842100-1.77525800 0.38883500 C 2.56707100-3.18947200 0.92535400 O 3.56375300-3.80127400 0.10901000 C 4.84047900-3.18395300 0.23957000 C 4.78314700-1.73781800-0.28411700 C 3.60607800-0.96033100 0.34068100 C 1.31774900-4.07393700 0.87567000 O 0.33794500-3.65159400 1.81476900 O 5.75613700-3.88334600-0.52924100 N 6.05037500-1.06338100-0.04397900 C 6.61539100-0.17249700-0.89377400 O 6.10162300 0.13817500-1.97905900 O 1.34076900-1.16044100 1.23428200 C 7.90914700 0.46122100-0.42554600 H 5.12905300-3.20040000 1.30847300 H 4.63077600-1.78056200-1.36544600 H 3.86499500-0.65354300 1.36310000 H 1.92993900-1.86648800-0.64038100 H 2.90762200-3.12688600 1.97126300 H 1.60195300-5.09894300 1.13247400 H 0.92449800-4.08284100-0.15262000 H 7.70769900 1.51069600-0.18875400
H 0.27394100-2.68442200 1.71807000 H 1.19885700-0.24519600 0.92643000 H 6.51556000-1.24067900 0.83586500 H 8.62955800 0.43874600-1.24614900 H 8.34303200-0.02165000 0.45237600 O -0.81453300 3.21665500 2.05854000 C -0.26019500 2.62574500 1.13414300 C 1.25983400 2.71444300 0.93370800 C 1.63604000 3.93003000 0.04611300 O 1.70472500 1.49172600 0.32819200 H 1.71041500 2.84322900 1.92556000 C 3.12781100 3.88758700-0.30361400 O 1.30692900 5.09338900 0.78334800 H 1.05424000 3.88117100-0.88562900 C 3.13303200 1.41865100 0.11355700 C 3.53362500 2.52418100-0.86144700 O 3.41076300 4.90635700-1.25236900 H 3.69605400 4.06213400 0.62514500 O 3.41668100 0.20314900-0.48159900 H 3.64585000 1.52782300 1.08164100 O 4.93091500 2.57192300-1.07970900 H 2.98756700 2.34147200-1.79895200 H 4.31971800 4.74066800-1.54793000 H 5.20872600 1.76670800-1.56118200 C 0.84383900 6.19262300 0.00162500 H 1.62220400 6.56722300-0.67026200 H -0.03870600 5.91466100-0.59052600 H 0.56228900 6.97735700 0.70726100 C 6.09334000-5.17165500-0.00624600 H 5.22371000-5.83551800 0.00663100 H 6.85770100-5.58378700-0.66622400 H 6.49850100-5.08726900 1.01038500 N -0.91519100 1.90412200 0.19425900 H -0.36972500 1.40854700-0.49706400 C -2.37139300 1.74593400 0.20719600 H -2.70284400 1.60888600-0.82529600 H -2.80265000 2.67461800 0.58576200 C -2.86626200 0.61981000 1.05484100 C -3.50848700 0.56530200 2.25552800 C -3.72752200-0.82407100 2.54156100 H -3.78846400 1.41409900 2.86325100 C -3.20035300-1.52917500 1.49944400 H -4.21409200-1.24550700 3.40978800 O -2.66985000-0.65613200 0.57998300 C -3.09405900-2.98130200 1.18980300 H -2.05304000-3.32491700 1.20544600
H -3.65203500-3.55467200 1.93367000 H -3.50816700-3.20635300 0.20080100 C -5.12524600-2.51547600-2.54479600 C -4.33600200-1.44088700-2.63985100 C -6.44041900-2.09202500-1.95706200 C -5.08925900-0.24913900-2.12525200 H -4.92289600-3.54043500-2.82458200 H -3.32510200-1.36504700-3.01643000 O -4.71898700 0.90996300-2.05963300 O -7.41662900-2.77769100-1.71849100 N -6.34333200-0.71560000-1.73114600 C -7.39471000 0.11250000-1.15774300 C -7.21883400 0.28951000 0.36005300 H -8.34672300-0.36839700-1.39118200 H -7.36590400 1.08908700-1.64652300 H -7.23425100-0.69280900 0.85493900 H -6.24753400 0.75321500 0.55834700 O -8.20159900 1.15272000 0.90599500 C -9.44914400 0.52188600 1.16675400 H -10.08767500 1.26723500 1.64602800 H -9.94639700 0.17436600 0.25147700 H -9.32906700-0.33480900 1.84495500 Transition state of DA reaction between HA-mF and maleimide (Endo route) # opt=(calcfc,ts,noeigen) freq=noraman b3lyp/6-31g(d,p) scrf=(iefpcm,solvent=water) geom=connectivity temperature=311 Zero-point correction= 0.738077 (Hartree/Particle) Thermal correction to Energy= 0.790318 Thermal correction to Enthalpy= 0.791303 Thermal correction to Gibbs Free Energy= 0.644717
Sum of electronic and zero-point Energies= -2422.867344 Sum of electronic and thermal Energies= -2422.815103 Sum of electronic and thermal Enthalpies= -2422.814118 Sum of electronic and thermal Free Energies= -2422.960704 SCF (RM062X/ 6-311+g(d,p)) = -2423.34870289 0 1 C 2.32452300-1.80851000-0.12988800 C 2.47768100-3.27213200 0.30448800 O 3.73964700-3.74728800-0.16002900 C 4.83989800-3.11576000 0.48751700 C 4.86761700-1.61700600 0.13833100 C 3.49383800-0.95892900 0.38126300 C 1.39387700-4.17726000-0.28928500 O 0.11516600-3.90368800 0.26894500 O 6.01610200-3.68568500 0.02951000 N 5.91745700-0.94355300 0.88852200 C 6.67544400 0.06819400 0.40155700 O 6.55406600 0.50077100-0.75454600 O 1.08000300-1.33513400 0.37635900 C 7.66892600 0.67626900 1.36978600 H 4.73085300-3.25879900 1.58002300 H 5.10956600-1.52585600-0.92357300 H 3.35256800-0.77962800 1.45528900 H 2.33939700-1.77640000-1.22971100 H 2.42079300-3.33396400 1.40301400 H 1.63953600-5.21824700-0.05847000 H 1.39567800-4.06745000-1.38470000 H 7.32115000 1.68170900 1.62695300 H 0.02375200-2.93377200 0.26728100 H 0.99295600-0.39063400 0.14733000 H 6.05768000-1.22073000 1.85069500 H 8.63405700 0.77701200 0.86849900 H 7.79466400 0.10044500 2.28878100 O -1.53449900 2.82138200 0.86244300 C -0.64454100 2.38285200 0.13743600 C 0.83713000 2.54713100 0.50160300 C 1.40991200 3.87489400-0.05963800 O 1.55144200 1.42358200-0.03240200 H 0.90011300 2.56400100 1.59653500 C 2.92866100 3.91931200 0.14564000 O 0.75570400 4.92335700 0.63043400 H 1.19763500 3.92470100-1.13756100 C 2.96719300 1.41744500 0.26745900 C 3.60174100 2.64956400-0.37475100 O 3.45474200 5.05670100-0.52289800
H 3.11952800 3.99048700 1.22931500 O 3.52397300 0.29615000-0.31901300 H 3.09991400 1.41603000 1.36035700 O 4.97935300 2.76710000-0.07453500 H 3.43232000 2.57126800-1.45892900 H 4.41876500 4.95223900-0.49251400 H 5.46741800 2.03888700-0.50959000 C 0.54336700 6.10968200-0.13308800 H 1.48871700 6.58285800-0.41497600 H -0.03757800 5.89825400-1.04116700 H -0.02989200 6.78781500 0.50281700 C 6.23501800-5.02264200 0.48970000 H 5.46792500-5.70418000 0.11003400 H 7.21203600-5.32465300 0.11034500 H 6.24328900-5.06258100 1.58659400 N -0.87068600 1.76485200-1.04848300 H -0.08228100 1.36977200-1.54266800 C -2.21604000 1.54167500-1.56245200 H -2.17258000 1.55390100-2.65350100 H -2.84929400 2.36742600-1.23123000 C -2.84540600 0.25534000-1.09518200 C -3.15369700-0.10965900 0.25384200 C -3.32997500-1.46955200 0.25295600 H -3.33014100 0.59328500 1.05507400 C -3.08603700-1.91575300-1.08137100 H -3.68847000-2.09718000 1.05724700 O -2.44630500-0.89932500-1.74899700 C -2.83745000-3.30716600-1.56231200 H -1.88579200-3.68488600-1.17034700 H -3.63772500-3.96341800-1.21156600 H -2.80878500-3.34091300-2.65363800 C -4.96883200-1.23014600-1.98585300 C -4.72070700 0.16205800-1.97858900 C -6.06430400-1.50159900-1.02827900 C -5.68284300 0.78115300-1.01777200 H -4.84412700-1.87755500-2.84333200 H -4.44653000 0.72954600-2.86006100 O -5.85383900 1.96339200-0.75856200 O -6.62731600-2.55530000-0.76898100 N -6.38583100-0.27016900-0.42381000 C -7.41015800-0.10019200 0.59377800 C -6.81384400-0.00519600 2.00805200 H -8.08509300-0.95453900 0.51030300 H -7.96743600 0.81408900 0.37403500 H -6.23879700-0.91523400 2.23458200 H -6.13171500 0.84940900 2.05229600
O -7.81082600 0.22396500 2.99031400 C -8.51042500-0.94715600 3.39050200 H -9.18705500-0.65353200 4.19617500 H -9.10598300-1.38216000 2.57695000 H -7.82033400-1.71604800 3.76634800 Product of DA reaction between HA-mF and maleimide (Endo route) # opt=calcfc freq=noraman b3lyp/6-31g(d,p) scrf=(iefpcm,solvent=water) geom=connectivity temperature=311 Zero-point correction= 0.741732 (Hartree/Particle) Thermal correction to Energy= 0.793183 Thermal correction to Enthalpy= 0.794167 Thermal correction to Gibbs Free Energy= 0.650217 Sum of electronic and zero-point Energies= -2422.902292 Sum of electronic and thermal Energies= -2422.850842 Sum of electronic and thermal Enthalpies= -2422.849857 Sum of electronic and thermal Free Energies= -2422.993807 SCF (RM062X/ 6-311+g(d,p)) = -2423.39525759 0 1 C 2.16054600-1.82702300-0.16602900 C 2.22775300-3.30022100 0.25690500 O 3.46935800-3.83976700-0.19243000 C 4.59302200-3.27372000 0.47492100 C 4.70633400-1.77673200 0.13617400 C 3.36721500-1.04709300 0.36771000 C 1.10857900-4.14052400-0.36477700 O -0.16633000-3.79953800 0.16344500
O 5.74305700-3.90351500 0.02857000 N 5.78245100-1.16444500 0.90084700 C 6.60436200-0.19955800 0.42210400 O 6.52100000 0.23818900-0.73536100 O 0.93693900-1.29143700 0.32902100 C 7.62191200 0.34962400 1.40038500 H 4.46136700-3.41846900 1.56480700 H 4.96520100-1.69256000-0.92226100 H 3.22155800-0.87022600 1.44156100 H 2.19148400-1.78642000-1.26523900 H 2.15000000-3.36750300 1.35379900 H 1.29095000-5.19467200-0.13462800 H 1.14289700-4.02620200-1.45928200 H 7.32520900 1.36990300 1.66322400 H -0.20244800-2.82602800 0.17490100 H 0.90308700-0.34080900 0.11255300 H 5.89240000-1.44713100 1.86536400 H 8.59363300 0.40385800 0.90478300 H 7.71276400-0.23886900 2.31545100 O -1.39412200 3.01246200 1.03020900 C -0.56199400 2.53707100 0.26035300 C 0.93797400 2.60289700 0.57538600 C 1.57395500 3.90137300 0.01314600 O 1.57056300 1.45030400 0.00260300 H 1.03793900 2.59873800 1.66781500 C 3.09548300 3.85768100 0.19603400 O 0.99230300 4.98284900 0.71730600 H 1.34845500 3.96804400-1.06118100 C 2.98614800 1.35528600 0.28563400 C 3.68778500 2.55671500-0.34557100 O 3.67644400 4.97015400-0.46900600 H 3.30499500 3.90685000 1.27746600 O 3.47078300 0.21080200-0.31992300 H 3.12863800 1.33022200 1.37696300 O 5.07209800 2.58948800-0.05443600 H 3.50637700 2.50355800-1.42932900 H 4.63360400 4.81373800-0.44894500 H 5.51364700 1.83699200-0.49713900 C 0.82837300 6.17949500-0.04188600 H 1.79175100 6.59889000-0.34712300 H 0.21430100 6.00162800-0.93523100 H 0.30991000 6.88861000 0.60715100 C 5.88227300-5.25379500 0.48055600 H 5.08616500-5.89021200 0.08272900 H 6.84785700-5.60495800 0.11442000 H 5.87024100-5.30289300 1.57705900
N -0.86936200 1.96390900-0.92973900 H -0.12196800 1.55275400-1.47162100 C -2.23068800 1.89696800-1.43267100 H -2.22112000 2.09235300-2.50894100 H -2.80689400 2.68641700-0.94457300 C -2.92928500 0.57323600-1.17657400 C -2.91955200-0.00973000 0.23384500 C -3.10708300-1.32361200 0.08191100 H -2.86188100 0.57612500 1.14216400 C -3.22233800-1.56868100-1.42243400 H -3.24710100-2.08062800 0.84406000 O -2.37315000-0.51422100-1.94407900 C -2.86124800-2.93101800-1.96334300 H -1.89619900-3.26349900-1.57269400 H -3.62368600-3.65479300-1.66007600 H -2.82552000-2.90922200-3.05632600 C -4.62737700-0.99225800-1.88599400 C -4.42220400 0.51995600-1.70613900 C -5.82008700-1.33711300-1.01502900 C -5.49599100 0.95743900-0.72842900 H -4.81938200-1.29584500-2.91740000 H -4.50698600 1.09289400-2.63277500 O -5.68823100 2.07510200-0.28294200 O -6.33345800-2.42914900-0.84879200 N -6.25878100-0.16303100-0.39758000 C -7.37005500-0.12332900 0.54653200 C -6.89422400-0.32497000 1.99590700 H -8.07135500-0.90575200 0.25114300 H -7.85597100 0.84963900 0.45099600 H -6.37096000-1.28784400 2.08717700 H -6.19161200 0.47221100 2.25685700 O -7.96723600-0.23807800 2.91733900 C -8.72527300-1.43516700 3.04059400 H -9.46396100-1.26306400 3.82646100 H -9.25548800-1.69595300 2.11515700 H -8.08808900-2.28327600 3.32848800 Pre-complex of DA reaction between HA-mF and maleimide (Exo route)
# opt=calcfc freq=noraman b3lyp/6-31g(d,p) scrf=(iefpcm,solvent=water) geom=connectivity temperature=311 Zero-point correction= 0.737278 (Hartree/Particle) Thermal correction to Energy= 0.791656 Thermal correction to Enthalpy= 0.792641 Thermal correction to Gibbs Free Energy= 0.635425 Sum of electronic and zero-point Energies= -2422.901346 Sum of electronic and thermal Energies= -2422.846968 Sum of electronic and thermal Enthalpies= -2422.845984 Sum of electronic and thermal Free Energies= -2423.003199 SCF (RM062X/ 6-311+g(d,p)) = -2423.37014148 0 1 C -1.89282500-1.70606700-0.75672100 C -2.12617000-3.06948100-1.42163400 O -2.92208500-3.86395700-0.54423100 C -4.24698100-3.36317000-0.39491000 C -4.21653600-1.98505200 0.28929500 C -3.22476100-1.03184200-0.40922700 C -0.82126100-3.82831200-1.67942500 O -0.04367700-3.20755800-2.69453700 O -4.96444600-4.22837100 0.41452700 N -5.55555000-1.41628800 0.33612400 C -6.03729400-0.68167100 1.36720100 O -5.37262500-0.43911900 2.38604800 O -1.12781200-0.90937500-1.65650900 C -7.43684500-0.13039100 1.18999000 H -4.70714300-3.28987600-1.39932600 H -3.88367200-2.13152200 1.31992900 H -3.67116900-0.64327800-1.33447600 H -1.34439900-1.87551100 0.18195700 H -2.64032000-2.92191700-2.38485800
H -1.06343400-4.83965300-2.01986100 H -0.26542300-3.91748200-0.73319000 H -7.35895300 0.94894400 1.02483000 H -0.04442900-2.25564800-2.48759600 H -1.00662800-0.02537200-1.26113000 H -6.15029200-1.54948000-0.47068000 H -7.99674400-0.28562400 2.11461300 H -7.98099900-0.57641800 0.35513800 O 0.53804700 3.74089600-2.20592800 C 0.17835700 2.98510500-1.30594200 C -1.29585200 2.89988700-0.88425100 C -1.62904300 3.96752600 0.19204600 O -1.54375100 1.57982200-0.37873100 H -1.90125700 3.09245600-1.77858900 C -3.04254700 3.74026900 0.73943800 O -1.50877300 5.23295400-0.43149500 H -0.91132400 3.87032300 1.01951100 C -2.91029200 1.34336100 0.03270300 C -3.24050000 2.29204700 1.18335500 O -3.26599800 4.61933300 1.83267800 H -3.75701100 3.95247100-0.07317700 O -2.99667900 0.04855600 0.51020300 H -3.57541000 1.50571900-0.82952200 O -4.58404600 2.17664700 1.61169200 H -2.53825600 2.06673100 1.99971100 H -4.09689700 4.32313700 2.23649600 H -4.71300800 1.30317700 2.03374200 C -1.02330700 6.27539400 0.41225200 H -1.71267200 6.48094100 1.23676900 H -0.03556800 6.02559100 0.82319600 H -0.92972800 7.16394800-0.21597900 C -5.28554500-5.47717400-0.20549300 H -4.38290700-6.05193500-0.43359700 H -5.89883000-6.02883000 0.50813500 H -5.85677600-5.31939600-1.12937000 N 1.02278500 2.21609100-0.57775600 H 0.62994300 1.59224700 0.11324200 C 2.46969400 2.21975400-0.80033800 H 2.95402300 2.05039600 0.16561400 H 2.74723100 3.21654500-1.14814500 C 2.94799300 1.22821200-1.81080700 C 3.45616900 1.35607800-3.06942100 C 3.73126100 0.03031400-3.53807900 H 3.61346200 2.28597600-3.59743000 C 3.36942400-0.82645900-2.53831800 H 4.14208400-0.25401700-4.49646600
O 2.88912700-0.10417400-1.47138500 C 3.37771300-2.30979200-2.41092900 H 3.83293300-2.74406900-3.30420700 H 3.95791600-2.63771900-1.54173400 H 2.36306000-2.71376900-2.31723000 C 6.72250600-0.18962200-0.98757500 C 6.39569800 1.01687100-0.51281500 N 5.52686600-0.54163800 0.96882900 C 6.16904100-1.23170500-0.06220900 C 5.60917500 0.83480500 0.75098800 O 6.23136400-2.44412500-0.16272700 O 5.11072000 1.69070800 1.46122600 H 7.28188200-0.44715600-1.87637500 H 6.62094800 1.99497600-0.91493200 C 4.81449400-1.16882700 2.07066500 C 5.74064100-1.49270200 3.24313500 H 4.34943500-2.08563300 1.70121200 H 4.02942500-0.48231600 2.39433500 H 6.54260500-2.17124600 2.91248600 H 6.21447000-0.57059400 3.61534700 O 4.94451600-2.09640300 4.24424100 C 5.69297300-2.45668200 5.39406500 H 4.99845400-2.91216400 6.10324400 H 6.48324800-3.18184100 5.15105500 H 6.16004700-1.57899700 5.86411500 Transition state of DA reaction between HA-mF and maleimide (Exo route)
# opt=(calcfc,ts,noeigen) freq=noraman b3lyp/6-31g(d,p) scrf=(iefpcm,solvent=water) geom=connectivity temperature=311 Zero-point correction= 0.738275 (Hartree/Particle) Thermal correction to Energy= 0.790558 Thermal correction to Enthalpy= 0.791542 Thermal correction to Gibbs Free Energy= 0.644936 Sum of electronic and zero-point Energies= -2422.868413 Sum of electronic and thermal Energies= -2422.816130 Sum of electronic and thermal Enthalpies= -2422.815145 Sum of electronic and thermal Free Energies= -2422.961752 SCF (RM062X/ 6-311+g(d,p)) = -2423.34859560 0 1 C -2.21357300-1.81877400-0.17488500 C -2.50723900-3.25830100-0.61902600 O -3.46542600-3.81937400 0.27575400 C -4.74187000-3.19339100 0.18487500 C -4.64062100-1.72848600 0.64417900 C -3.50211100-0.99294100-0.09143200 C -1.26081600-4.14754100-0.57977800 O -0.31962500-3.77922800-1.57975300 O -5.62319700-3.85047700 1.02723600 N -5.91422600-1.04878100 0.46132500 C -6.40860900-0.11512500 1.30937200 O -5.81778900 0.23110200 2.34351400 O -1.29780300-1.25777600-1.11093900 C -7.72215100 0.52017600 0.90296700 H -5.08491000-3.24874500-0.86645900 H -4.41667300-1.72890500 1.71379900 H -3.82209400-0.73847700-1.11068700 H -1.77267600-1.85574100 0.83267900 H -2.89771600-3.24873700-1.64912700 H -1.55999000-5.18247300-0.77161000 H -0.82379100-4.10667800 0.42986200 H -7.52159600 1.55436600 0.60580200 H -0.26386600-2.80699300-1.55120600 H -1.13988500-0.32575000-0.86909100 H -6.43957900-1.25531500-0.37739700 H -8.38464200 0.54669100 1.77084400 H -8.22221500 0.00683200 0.07918500 O 0.73652200 3.04684100-2.40133800 C 0.26997600 2.52962200-1.38861200 C -1.22358500 2.63834900-1.05425800 C -1.51724800 3.89590700-0.19503700 O -1.61258700 1.44973200-0.35126100
H -1.76214800 2.72029200-2.00640500 C -2.97774900 3.88095700 0.26995100 O -1.23669000 5.02296300-1.00443900 H -0.86509100 3.87960300 0.69011200 C -3.02050500 1.39318700-0.02040700 C -3.34101200 2.54888000 0.92598000 O -3.18529600 4.94690000 1.18509700 H -3.61551900 4.01151700-0.61998100 O -3.25597900 0.21044200 0.65481500 H -3.60705700 1.45671400-0.94979100 O -4.71654000 2.61715900 1.25102300 H -2.72271400 2.41054500 1.82525900 H -4.06788300 4.79908700 1.55970700 H -4.95860900 1.84063500 1.79496000 C -0.70741500 6.14904500-0.30657800 H -1.42786700 6.55570600 0.40967600 H 0.21821600 5.88743000 0.22402700 H -0.47948200 6.90277600-1.06342800 C -5.99880100-5.15471700 0.57447800 H -5.13628900-5.82699700 0.53998300 H -6.72879100-5.53332300 1.29102600 H -6.45875000-5.10559600-0.42096500 N 1.01215800 1.86993000-0.46548600 H 0.53627400 1.42703900 0.30834600 C 2.45871300 1.73006200-0.58931800 H 2.89522900 1.72492400 0.40938900 H 2.83480700 2.60775000-1.11823400 C 2.88719000 0.50228600-1.35130200 C 2.59928600 0.21527800-2.72546600 C 2.77263600-1.13332000-2.88229500 H 2.41681000 0.96556600-3.48130400 C 3.12631600-1.65746400-1.59960600 H 2.76474900-1.70698500-3.79899400 O 2.83327200-0.69802500-0.66387400 C 3.09950200-3.08075200-1.15204300 H 3.58243400-3.70766100-1.90527400 H 3.62727100-3.21217600-0.20621800 H 2.06407900-3.42317500-1.04008500 C 5.22287700-0.91918300-1.71353800 C 4.97552900 0.45914000-1.48901500 N 5.76748500-0.46211700 0.49323100 C 5.77404500-1.49029400-0.46538600 C 5.39703600 0.75188700-0.08195500 O 6.16516000-2.62689700-0.23615500 O 5.41410200 1.82607700 0.50361200 H 5.50624700-1.35964600-2.65889000
H 5.12567100 1.23708000-2.22640600 C 6.16099800-0.63031500 1.88137900 C 7.65888100-0.39949800 2.08353000 H 5.89950500-1.64563500 2.18776300 H 5.59282000 0.07993300 2.48648600 H 8.23330700-1.10921700 1.46780400 H 7.92731300 0.61900400 1.76207900 O 7.93049400-0.58597800 3.46011900 C 9.30023000-0.39946400 3.77546700 H 9.41183600-0.56408900 4.84946800 H 9.94051500-1.11272500 3.23597900 H 9.63642300 0.61938000 3.53309100 Product of DA reaction between HA-mF and maleimide (Exo route) # opt=calcfc freq=noraman b3lyp/6-31g(d,p) scrf=(iefpcm,solvent=water) geom=connectivity temperature=311 Zero-point correction= 0.741837 (Hartree/Particle) Thermal correction to Energy= 0.793335 Thermal correction to Enthalpy= 0.794320 Thermal correction to Gibbs Free Energy= 0.650084 Sum of electronic and zero-point Energies= -2422.905480 Sum of electronic and thermal Energies= -2422.853982 Sum of electronic and thermal Enthalpies= -2422.852997 Sum of electronic and thermal Free Energies= -2422.997233 SCF (RM062X/ 6-311+g(d,p)) = -2423.39795624 0 1 C -2.29799400-1.80465800-0.19629400 C -2.63245800-3.23504000-0.64077300 O -3.60057600-3.77177300 0.25853300