Reprinted from the Jourmal of the Arnerican Chemical Society, 1993,115.Copyright O 1993 by the American Chemical Society and reprinted by permission of the copyright nding:Aggregationof Five MoleculesTo Form a DiscreteSupramolecularStructureChristopher T. Seto, John P. Mathias, and George M. tilhitesidesfContributionfrom the Departmentof Chemistry,Hansard Uniaersity,Cambridge,Massachusetts02 38. ReceiuedAugust7, /,992Abstract: This article describesreactionsof the trivalent 5-Brl,(hubM3)and NH2)(NH(CH2)2C(CH3)r)1,(trisMr) with the bivalentisocyanuratederivativesCuHz-l,5.[CH(CH)2 3'4-[cH,ffi6[NHC(O)12 (furanCA2) in CHCI3 to afford a seriesof supramolecularaggregatescontaining2 equivof the tris melamineand3 equivof the bis cyanurate(2 3 complexes).Thesecornplexesconsistof two parallel hydrogen-bondedlatticesthat incorporate36 hydrogenbonds. The structureshavebeencharacterizedby 'H NMR, r3CNMR, and UV spectroscopies,gel permeationchromatography,and vapor pressureosmometry.Thesetechniquesdemonstratethat the 2 * 3 aggregatesin CHCI3 solutionare stableand structurallywell-defined.hubM3 is more rigid than trisM3. This differencein rigidity is usedto probetherelationshipbetweenthe molecularstructureof the trivalentmelaminederivativeand the geometryand stabilityof the resultingaggregate.(hubMr):(benzCA2)3and (hubM3)2(furanCA2)3eachseemto exist in one isomericform; (trisM3)2(benzCA2),and (trisM3)2(furanCA2)3are both mixturesof isomers(due, probably,to the relativeflexibility of the arms of trisMr).IntroductionWe are devclopingmolecularself-assemblyas the basisof aprogramto pramolecularaggregates.r-3One impetusfor this programisthe precedentin biologyfor self-assemblyand structural stabilizationthroughnetworksof e illustratedby the foldingof RNA chainsinto functioningIRNA moleculesaand the stabilizationof telomcresby stackedcyclicarraysof hydrogenbonds,samongmanyotherexamples.6A secondimpetusis the developmentof molecularself-assemblyas a syntheticstrategyfor makingnanostructures.TTo define rules for designingaggregatesthat are basedonmolecularself-assembly,we are preparinga seriesof hydrogenbondedsupramolecularaggregates.This serieswill (i) sharpenthe criteria for designof self-assembledstructures;(ii) explorethe thermodynamicaspectsof self-assembly,especiallythe interplayof enthalpicand entropiceffects;and (iii) developtechniquesfor characterizingnoncovalentlyboundspeciesin organicsolution.The strategythat we haveemployedto build self-assemblingaggregateshas beento usefragmentsof the hydrogen-bondedlatticctbat existsin the 1:l complexof cyanuricacidandmelamine(CA.M) as thc foundationfor solublestructures.s We havedescribedthe preorganizationof threemelamine(M) units bycovalentlylinking them togetherthrougha 'hub" and'spoke"architectureto form the trivalentmelaminederivativehubM3.2'eThis moleculecomplexeswith 3 equivof monomericisocyanurates(CA) and formshighlystructuredI 3 supramolecularaggre( I ) For a preliminaryreport of this work, sec: Seto,C. T.; Whitcsides,G.M . J . A m . C h e m .S o c . 1 9 9 1 .I 1 3 . 7 1 2 .(2) Seto, C. T.; Whitcsides,G. M. J. Am. Chem. Soc., in press.(3) For further examplesof sclf-asscmbly,see: Lehn, J. M. Angav. Chem.,Int, Ed. Engl.1990, 29,1304. Tccilla, P.; Dixon, R. P.; Slobodkin,G.; Alavi,D. S.; Waldbcck,D. H.; Hamilton,A. D. J. Am. Chem.Soc. 190. I I2.94flE.Stoddart,J. F.; .t al.J. Am. Chem.Soc.1992,I14,193. Zimmerman.S. C.:Duerr, B. F. J. Org. Chem. 1992,57,2215.(4) Draper,D. E. Acc. Chem,Res. 1992, 25,20t.(5) Kang, C.; Zhang, X.; Ratliff, R.; Moyzis, R.; Rich, A. Nature 1992,350,126. Srnith, F. W.; Fcigon,J. Nature 1992, 350, t64.( 6 ) L i n d s c y ,J . S . N e w J . C h e m . l 9 9 l , / J , 1 5 3 .(7) Whilesides,G. M.; Mathias,J. P.; Seto,C.T. Science1991,254.t3t2.(8) The CA.M lattice is the putative two-dimensionalhydrogen-bondcdsheetstructurethat forms on mixing cyanuric acid and melamine.(9) Seto,C. T.; Whitesides,G. M. J. Am. Chem.Soc.1990.I12.6409.Scheme I. Schematic Representation of the I * 3 and 2 * 3Supramolecular Aggregates1 32 3gates(onehubM, * threeCA) (SchemeI). In this articlewedescribereactionsof the trivalentmelaminederivativeshubM3and trisM3with the bivalentisocyanuratesberuCA, and furanCA2(SchemeII). Thesethat give2 3 supramolecularaggregatessystemsare composedof two parallel,planarhydrogen-bondedlattices. Our objectivesin the progressionfrom single-layerstructures(l 3) to double-layerstructures(2 * 3) havebeen(i) to increasesubstantiallythe numbcrof hydrogenbonds(from18 to 36) that stabilizetheseaggregateswhile increasingthenumberof moleculesinvolved(and thus the unfavorableentropyof association)relativelyless;(ii) to generatea more stablestructuralmotif; (iii) to increasethe sizeand complexityof thesestructures;and (iv) to assess(rigidthe role of preorganizationhubM3vs flexibletrisM3)in the self-assemblyof thesecomplexes.Designof ConstituentMolecules. A. hubM3. The molecularstructureof the trivalent melaminederivativehubM3preorganizcsthis compoundfor complexationwith isocyanuratederivatives.The crucial aspectof this organizationseernsto bc a conformationdeterminedby the aanthranilategroupsthat facilitatesthe l80oturn neccssaryin the attachmentof the melaminerings to thecentral 'hub' to form aggregatesbasedon the cyclic CA3M3motif.2B. trisM3. trisM3 is an analogof hubM, with moreflexiblespokesthan hubMl. We are interestedin the interplaybetweenthe rigidity/flexibility of constituentmolecules,their easeofsynthesis,and their successfulincorporationinto self-assembledstructures.trisM3 hasretainedthe ortho-substitutedaromaticring. The aminogroupof the centralhub of trisM3 will allowu wentually to link thce self-assemblings)6temstogetherto formlarge supramoleculararrays. Flexibleanalogsof hubM3leadtoI * 3 aggregatcwith monomericisocyanuratesthat are lessstablethan aggregatesformedby hubM3.2We wantedto determinewhetherthe enthalpyof formationof the 2 3 complexes,which0002-7863@ 1993AmericanChemicalSocietv193I rsls-1321 04.00/0
1322 J. Am. Chem. Soc.,Yol. ll5, No.4, 1993Seto et al.SchemeIII. Synthesisof benzCA2'and furanCA2tScbemeII. Self-Assemblyof 2 equivof hubM3or trisM3with 3equivof benzCA2or furanCA2To Give a 2 t 3 SupramolecularAggregate o iH'*'l-BocI. f.Q 6o{prn\J(po):.H. ,Jor.vv\H- J/:\["-X;5il l--2ts''[ru- l;{i.,''\-/d -ill\ .)\?\TH2N NH',''\ ]H''t-\- -iltrisM3hubM3NHzNHzn'*'o.A.'N'H -r-b- ,YT rn ."- .U\Hl,N.*ll"lill AAv4vvbenzCA2N -ta N*t*.N.-.D "- .)-(- b.-ty'o\1 At: 5i #"*"or -cFt"]{Ft" {F*"benzCA2N-/ttlH.-A.:-" N-tl--a*\ -zmelamrne""'*'"o/t"I \"r"*,0his twicethe enthalpyof formationof the I * 3 complexes,is largeenoughto offset the unfavorableentropyof conformationassociatedwith flexiblespokes.C. benzcA2ed frnanCAl For two hubM3or trisM3 moleculesto assembleface-to-face,the CA rings of the bis isocyanuratederivativesmust be approximatelyparallel. Molecularmodelssuggestthat the CA rings in furanCA2arealmostexactlyparallel.In benzCA2,they are tilted towardeachother by approximately20o whenthe phenylring and the CA groupsare perpendicular(SchemeII); by skewingthe phcnylring it is possibleto makethe CA ringsparallel. The similarstabilityof complexesbasedon benzCA2andfuranCAr suggeststhat the differencein goometrybctwecnthesemoleculesis not important. The isopropylgroupsrestrict the CA moietiesto a conformationin which the CA ringsare approximatelyparallelandpointedin the samedirection. Thispreorganizationminimizesthe conformationalentropy lost onformingthe 2 * 3 aggregates.ResultsSef-Assemblyof 2 3 SupremolecularAggregates.SchemeII outlincsthe self-assemblyof the 2 * 3 complexes.The followingdiscussionswill focuson (hubMr)z(benzCA2)3and (trisMr)2(benzCAz)r;the resultsobtainedfor (hubM3)2(furanCA2)3and(trisMr)z(furanCA2)3are analogousandarenot outlinedin dctail.Synthesisof Components.The synthesisof hubM3 hasbeendccribcd previorsly.2The synthesesof benzCA2,furanCA2,srdtrisM3are outlinedin SchemesIII and IV.Prepentioo of SupramolecularAggegates. hubM3and trisM,are readilysolublein CHCI3 ( 15 mM), but the solubilitiesofbenzCA2and furanCA2in this solventare low ( 0.1 mM).Simply mixing 2 equivof hubM3with 3 equivof benzCA,inCHCI3at roomtcrnpcraturedoesnot afford(hubM3)2@enzCAr)r,becausethe benzCA2docsnot dissolve.To prepare2 * 3 complexes,we usedthreesimilar strategies(whichwe outlinefor thepreparation(l) hubM3andbcnzCA,of (hubM3)2(benzCAz):):weredissolvedin a l:l mixtureof MoOH and CHCI3to afforda homogeneoussolution;(2) hubM3andbcnzCA2weresuspcndedin CHCI3containingSVoMeOHandheatedbriefly (-10 s) until1.::a CA'INH.N-rrtt*!IfuranCA2iTx'Nl./, u8CoReagents:(a) paraformaldchyde,CH,C\. ACOH.HSO. 90 oC.4 0 V o( ;b ) 3 N a q u e o uHs C l , r e f l u x9, 4 % :( c ) H : \ C ( O ) \ H C r O t \ - H (d) (EtO)rCO,NaOEt,EIOH. rellux.1t?.NO2,H2O,reflux,85Vo;DReagents:(a) ptoluenesulfonicacid. toiuene.reflux. -(tct. (b) .\'CCla, reflux; (c) NaN3, DMF. 60 oC. ,104 (lbromosuccinimide,(2(d) Pd(OH)2,H2,MeOH;(e) nitrobiuret.H.O. refiur.69d steps);steps);(0 (EtO)zCO,NaOEt, EIOH, reflux,50%.SchemeIV. Synthesisof trisMroHTo*naNlonr-eo. f[[10\-oH9H.Not'\.r-e&31- - 6OHa-.'JF.coruesg'\-z s 3c".I- AN12 ORORr-a6cr?HH'N-"'*fi\./4*l*NH2HT",t'e ,nro"'i-rAVeT ".*A*\",r-Boc'N15H 'HN 'H 'HN 'IlNIHrlln------- , . ' ," ' * A - * * ' nLlr.aoc'N*rr\7717 N4Ntll,H.N,\-N\lH.N-,A.ill\vt8.N''\l--4 triSM3oReagents:(BOC-ON)'DMF,(a) (CH:)TCOCO2N:C(C6H5)CN(b\ allyl bromide,KOH, DMSO, 16 oC, a0%;(c) methyl50 oC, 78Vo;(d) NaOH, THF'SSVo;THF, ltu, room temperaturc,2-thioacctate,90Vo:(e) BOC'ON, DMF, 55 oC' (66%);McOH, roomtempcrature,(f) cyanuricchloride,THF, 0 oC; (g) NH3, THF, 0 "C, 947o(twoCH2CI2,THF, reflux,83Vo;(i) F3CCO2H,stcps);(h) neohexylamine,THF,25 oC, 94Va;(i 0.33equivof 13,DCC, l'hydroxybenzotriazole,25oC.88Vo.
I 3 and 2 * 3 SupramolecularAggregatesJ. Am. Chem.Soc.,Vol. II5, No.4, 1993 1323bN'Ho'888***6o 55nmIo(,6tll-o 319"'255m270nmIlltfooltEquiv of BenzCA2300nmngurc t. Titrationof hubM3with benzCA2monitoredby UV spectrcopy (0.1mM in CH2CI).Theinsctgraphshowsplosof ahorbancevscquivalensof benzCA2for twoseparateruns(A andB). Bcyondthe(1.5equivof bcnzCA2)2:3stoichiometrythe UV sp ctrumdocsnotchangc.thc solutionbccamehomogencous;(3) hubM3and benzCA2weresrspcndodin CHCI3and hcatodat reflux until the solutionbecame(-5 min). In each qre, concentrationof thehomogcneoussolutionin vacuoto drynessaffordedthe 2 * 3 aggregateas awhitesolidthat wasrcadily solublein CHCI3. Analyscsof complexcsformedby cachof thesemethodswereindistinguishable.Qurfitrdve Evidmoefq tte Forntioo oI 2 * 3 SrpnmoleorhrAgrtgrtes. If morethan 1.5equivof benzCA2waspresent,theexccssbcnzCA2did not dissolvein CHCI3. This resultsuggestsa 2:3stoichiomAryfor the conrplexbetwecnhubM3and benzCAr.ExperimentsusingtrisM3 and benzCA2or furanCA2in CHCI3also indicatcdstoichiometriesof 2:3.(hubM3)2(beuzCAJ3end (hubM3)2(fimrcAJr. A. Cheracterizetion of (hubM3)2(benzCAJrby W Spectrccopy. Thechangein trftom 270 nm in free hubM3 to 255 nm in",(hubMr)dbcnzCAJron titration of hubM3with benzcAz(Figurel) is consistentwith a 2:3 stoichiometry. Beyondthis stoichiometry,no further changesoccurbccauscthe addedbenzCA2docsnot dissolve.B. Ctrncterizrtion of (hubM3)2QenzCAr)sby rH I{MRSpectrccopy. Tltrdotr of bubM3with beozCA2.Figure 2 showsthe titration of hubM3with benzCA2in CDCI3as monitoredbyrH NMR spectrcopy. Thc rcsonanccsin the spectrumof hubM3in CDCI3 are broad bccauseof self-associationand hinderedrotationaroundthe amideand RNH triazine bonds. In the 2:lmixturc betwecnhubM3and bcnzCA2,sharpresonanc sappeartbat corrcspondto (hubMr)z(bcnzCA)3 againsta backgroundof uncomplcxedhubM3. The hydrogen-bondedimide protons(y,for free (broad)and/) at d 14.8and 15.5ppm and resonanc sbound(sharp) ncohexylgroupsand 4-tert-butylbenzylgroup inthe rcgion 2.H.8 ppm are clearly visible. In this mixture,one-third of the hubM3 is presentas fully formed (hubM3)2(bcnzCAtr, 8nd two-thirdsof the hubM3remainsuncomplexed.Exchangcbetwccnfrce and boundspeciesis slowon the NMRtime scale.A solutionof hubM3that haslessthat 1.5equivofbcnzCA2 (i.c., bclow thc 2:3 stoichiometry required forhubM3/bcnzCA) containsonly free hubM3 and (hubM3)2GcnrcAr3 and dm not containpartialb forrred complexeswithstoichiomctricsother than 2:3. Theseobservationssuggestthatformationof (hubM3)r(bcnzCA2)3is a coopcrativeprocess.Atthe 2:3ratio of hubM3to benzCA2,the hubM3is fully complexed;furthcr additionof bcnzCA,ds not changethe spectrumbecauseit docsnot dissolve.The top spectrumof Figure2 showshubM3and bcnzCA2in a ratio of 2:*6'; the 3 equivof benzCA2beyondthat rcquircdfor formationof the 2 * 3 complcxrcmaininsoluble.We bclievc that thc minor resonancesin the spcctrum of(hubM3)2(bcnzCA2)3are associatcdwith geometricalisomersof(hubM3)2(benzCA)3(sccthe Discussionsection).The spcctraof hubM3 and benzCA2in DMSO-d6 illustrate thc effcct ofr-l15.010.08.06.0PPM4.02.0O.OFigure2. rH NMR spectraof mixturesof hubM3with benzCA2(500MHa CDCI3). The pcakassignmenrsare shownat the top of the figure.The bottomtwo spectrashowhubM3and benzCA,alonein DMSO-d6for reference.Severalof the minor resonancesthat we believeconespondto othergeometricalisomersof the complexhavebeenmarkedbelowthebaseline of the top spectrum.(hubM3)2fiienfAdg-*/Figure3. IntermolecularNOEs (7o)amongthe protonsin (hubMr)2(benzCA2)3.The NOEs amongthe hydrogen-bondedprotonsare shownin the upperstructure,and the NOEs amongother protonsare shownin the lowcr structure. The NOEs that are not shownare eitherwcakor the NOE signalis obscurcdby incompletcsubtractionof othcr resonancesin thc diffcrencespectrum.breaking up self-association due to hydrogen bonding in thesecompounds.C. Charecteristic Feetures of the tH NMR Spectnrm of(hubMr)r(benzcA2)3. l. Assignment of hotom.(hubM3)1
r324 J. Am. Chem.Soc.,Yol. ll5, No.4, 1 9 9 3free hubM3Seto et al.prylene6000( h u b M 3 ) 2( b e n z C A 2 ) 3E)o sf(hubM3)2(furanCAz)s()( h u b M 3 ) 2( b e n z C A 2 ) 3s 5519-i-5000IIIgoEYII-rfree lystyrene(hubMs)z(benzCAz)s/CHClghubM3 (neohexylCA)3/CHCl3AA\ /PSSOStandardsPCFigrrre5. Estimation of the molecular weights of (hubM3)2(benzCAz):(o) and (trisMr)r(benzCA2)3 (o) by vapor pressureosmometry,usingfour different molecular weight standards. The solid and dashed horizontal lines correspondto the calculatedMWs of (hubM:):(bcnzCA2)3and (trisM3)2(benzCA2)3, respectively. Thc four MW standards wcreGS ffNrbis(t-Boc)gramicidin S (MW 1342). SO sucroseoctaacetate (MW 679), PS polystyrene(averageMW 5050, polydispersity 1.05), and PC perbenzoylB-cyclodextrin(MW 3321). The errorbars correspond to the sum of the standard deviations of the VPO measurements of the standard and unknown. These expcriments were pcrformed at 37 oC in CHCI, over the conccntrationrange 2-16 mM complex. No special precautions were taken to ensure thc dryness of thesolvent.of theaggregatesunderthe times(10-15 min) and conditionsrun.l0 We used3 mM solutionsof pxylene as an internalstandardand CH2Clror CHCI3astheeluent.The GPC column0.04.02.01006.08.012.014.0wasmadefrom cross-linkedstyrene/divinylbenzeneand had aRetention time (min)molecularweight cutoff of 30 kDa.hubM3chromatogramsof freeandcomplexedFigure4. Gelpcrmeationl. GPC oI2 * 3 Adductswith CHzCl2es tbe Eluenl FigureusedasaninternalandtrisM3.Thcsmallpeakat I 1.5minisp-xylene4 showsthe GPC tracesof freeand complexedhubM3. heelutionsolvcntThe pcakalonein methylenechloridesolutionis self-associated.(avMW am 1.05)for referencc. (hubMr)z(benzCA2)3intodueto hubM3is not detectedbecausethis peakis broadenedpolydispcrsityand(a lessstablecomplexthat showssubstantial the baseline and becausefree hubMshasa weakerabsorbancehubM3(neohcxylCA)3In chloroformat254 nm (the wavelengthto which tbe LY detectoris set) thanor (trisMr)2(furanCA2)3. doescomplexedhubM3. The uncomplexcdnopcaksaredetectablefor (trisM3)2(bcnzCA2)3moleculeexistsin abred distributionof self-assaiatedspccieswith dilferent apparentmolecularweightsin solution.In contrast,(hubM3)2(benzCA)3(benzCA)3 has bcen characterizedusing fl D exchange,givesharppcaksin their GPC tracesand (hubMr)r(furanCA2)3of resonancesCOSY, and NOE exp riments.The assignmentsat 8.7-E.8min. Theseobservationssuggestthat the complexcsare shownin Figure2; the NOEs are summarizedin Figure3.existin Effects. The proximity 1-2.5 A) of2. NucleerOverheuserweights. Comparisonof theseretentiontimes to that of theresultsNH protonsin (hubM3)2(benzCA)3the hydrogen-bondedpolystyrenestandard(averageMW 5050,polydispcrsity1.05)in strongintermolecularNOEs amongtheseprotons(Figure 3).confirmsthe similar sizesof theseaggregates.The pcakprofrlesIntermolecularNOEs betweenprotonson the spokesof hubM3of the complexesare sharperthan that of the polystyrene:thisandthe bcnzylicprotonsof bcnzCArarc consistentwith the modelobservationreinforcesthc conclusionthat the 2 * 3 aggregatesproposedfor the 2 3 complex. The large magnitudesof theseare structurallyhomogeneous.NOEs indicatethat the structureof (hubM3)2(benzCA)3is2. Pertiel Decomplexationin GFC with CTICI3rs the Eluenlwelldefinedand stablein solution. We do not s eNOEs betweenof (hubM3)2(benzCA)3that occursduringtheDecomplexationprotonsin adjacentlayersof the complex. This observationisGPC analysisis irreversiblebecausefree hubM3and bcnzCA2by CPKwith the fferent molecularweights(2093 and 445,respectively)andmodels(-4.8 A).shouldseparate(in principle)on the column.rr The single,sharp3. Hydrogen-Bonddhotons. The imide prototlsof benzCA2peakin the GPC traccof (hubM3)t(benzCA)3with CH2CI2as(y, y') are equivalentin the uncomplexedmol@ule,appearingatthe eluentshowsthat this aggregatedoesnot decomplexduringtheyoccupy6 I1.6 ppmin DMSO-d6.In (hubM3)2(benzCA2)3the analysis.In contrast,the GPC traceof (hubM3)z(bcnzCAJrdifferent hydrogen-bondingsites and thus appearas separatewith CHCI3as the eluentshowsa sbarppeakat 8.3 min correresonancesat 6 14.8and 15.5ppm in CDCI3. The downfieldspondingto the 2 3 aggregate,alongwith a broadpeakat 9.3positionof al. Thisto someform(s) of decomplexedmin correspondingthe melaminering nitrogenatoms.doesdecomplexapresult indicatesthat (hubM3)2(benzCAz)r4. Dirstereotopichotons. Severalsetsof protonsthat arepreciablyduring GPC analysisin the more polar solvent.Theequivalentin hubM3(g,g';q, q'; andr, /) andbenzCA2(y,y';traceof hubM3complexedwith monomericneohexylCAis shownw, w'i and x, x') bccomediastereotopicin the 2 * 3 aggregatein Figure4 for comparison.This I * 3 complex[hubM3(neo(hubM3)2(bcnzCAJ3.The protongl is shiftedupfieldby 1.6ppmhexylCA)rl is lessstablethat the 2 3 aggregateandthusshowswith raspcctto g. Molecular modelssuggestthat this shift istailing.r2'r3shieldingfrom the neigbboringaromaticcauscdby througb-spacering of the 1,3-diaminobenzenemoiety.(10) Stable complexesgive sharp,symmctricalpcaksin GPC, while lcssD. Ctrncterizetion of (hSMr)2OenzCArr by GelPermeationstable complexesshow tailing of their peakscausedby dccomplcxationduringCtrometogrephy(GPIC). We usedGPC to determinewhetherthc analysis. Stevens,F. J. Biochemistry 19t6, 2J, 981. Stevens,F. J.the self-assembledstructuresexistas a mixture of speciesor asB i o p h y s J. . 1 9 t 9 , 5 J , 1 1 5 5 .singlespecieswith well-definedsize. The shapcsof peaksin GPC( I I ) The low solubility of bcnzCA2and the self-associationof hubM3 makcgivea qualitativemeasureof the stabilityof the self-assembled their
large supramolecular arrays. Flexible analogs of hubM3 lead to I * 3 aggregatc with monomeric isocyanurates that are less stable than aggregates formed by hubM3.2 We wanted to determine whether the enthalpy of formation the 2 3 complexes, which 0002-7863 193 I rsls-1321 04.00/0 @1993 American Chemical Societv
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