for UV Accelerated Assemblies Constructed Using Calixpyridinium in Aqueous Solution - Wang et al. - Unknown - Unknown

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SupportingInformationforUVAcceleratedAssembliesConstructedUsingCalixpyridiniuminAqueousSolutionKuiWang,*Mi-NiWang,Qi-QiWang,ChangLiu,Yu-HanDu,SiyangXing,*andBolinZhu*TianjinKeyLaboratoryofStructureandPerformanceforFunctionalMolecules,CollegeofChemistry,TianjinNormalUniversity,Tianjin300387,Chinahxxywk@tjnu.edu.cn(KuiWang);hxxyxsy@tjnu.edu.cn(SiyangXing);hxxyzbl@gmail.com(BolinZhu)NumberofPages:18NumberofFigures:24

1(a)(b)FigureS1.1HNMRspectrum(a)and13CNMRspectrum(b)ofcalixpyridiniuminD2O.FigureS2.Crystalstructureofcalixpyridinium.Itisinaccordancewiththepreviousreportedcrystalstructureofcalixpyridinium.1

2Thecalixpyridinium-complexation-inducedcriticalaggregationconcentration(CAC)ofsuraminsodiumcouldbeacquiredbymeasuringtheUV-visabsorptionspectraofcalixpyridiniuminthepresenceofdifferentconcentrationsofsuraminsodium.AsshowninFig.S3,addingasmallamountofsuraminsodiumtotheaqueoussolutionofcalixpyridiniumcouldnotleadtoanychangeoftheabsorbanceover400nm.Withthefurtheradditionofsuraminsodium,abroadabsorptionover400nmappearedduetotheformationofabundantsupramolecularnanoparticlesbythecomplexationofcalixpyridiniumwithsuraminsodium.Therefore,thecalixpyridinium-complexation-inducedCACofsuraminsodiumcouldbedeterminedbyobservingtheinflectionpointontheplotoftheabsorbanceat400nmversustheconcentrationofsuraminsodium:0.72μMat30μMcalixpyridinium,4.6μMat50μMcalixpyridinium,and1.6μMat80μMcalixpyridinium.

30.150.0100.05M0.10M0.12m0.0080.15Mn0.3M0e0cn0.090.5M4t0.006ab0.7Maerco1.0Mnsb0.061.5Mab0.004[Suraminsodium]=0.72MAr2.0MosbA0.0020.030.0000.000.11400500600700800[Suraminsodium]/MWavelength/nm(a)(b)0.300.0250.25M0.250.5M0.020m1.0Mn0.202.0M00ec40.015n3.0Mtab5.0Maer0.15cos7.0Mna0.010[Suraminsodium]=4.6Mb10MbrA0.10o13Msb0.005A0.050.0000.00400500600700800110Wavelength/nm[Suraminsodium]/M(c)(d)0.200.0140.1M0.0120.2M0.16m0.3Mne0.5M000.010cn0.121.0M4tab1.5Ma0.008reo2.0Mcnsab0.083.0Mb0.006[Suraminsodium]=1.6MAr4.0Mosb0.0040.04A0.0020.004005006007008000.11Wavelength/nm[Suraminsodium]/M(e)(f)FigureS3.UV-Visabsorptionspectraofaqueoussolutionsofsuraminsodiumatdifferentconcentrationsinthepresenceof30μM(a),50μM(c),and80μM(e)calixpyridiniumatroomtemperature.Dependenceoftheabsorbanceat400nmontheconcentrationofsuraminsodiuminthepresenceof30μM(b),50μM(d),and80μM(f)calixpyridinium.

4Basedonthesameprinciple,thesuraminsodium-complexation-inducedCACofcalixpyridiniumcouldalsobeobtainedbymeasuringtheUV-visabsorptionspectraofsuraminsodiuminthepresenceofdifferentconcentrationsofcalixpyridinium:8.0μMat80μMsuraminsodium,6.4μMat100μMsuraminsodium,and6.3μMat120μMsuraminsodium(Fig.S4).0.300.0160.5M0.251.0M0.0142.0Mmn0.012e0.203.0M00cna5.0M4t0.010br0.157.0Maeoc0.008s10MnbaA13Mbr0.0060.10[Calixpyridinium]=8.0M15Mosb0.004A0.050.0020.0000.00110400500600700800[Calixpyridinium]/MWavelength/nm(a)(b)0.300.0180.25M0.0160.250.5M1.0Mm0.014ne0.202.0M000.012cn3.0M4tab5.0Ma0.010r0.15eo7.0Mcn0.008sb10MabA0.10ro0.006[Calixpyridinium]=6.4M13MsbA0.0040.050.0020.000.000400500600700800110Wavelength/nm[Calixpyridinium]/M(c)(d)0.300.0161.0M0.0140.251.5M2.0Mm0.012ne0.204.0M00cn6.0M4t0.010ab8.0Mar0.15eco10Mn0.008sab12MbA0.10ro0.006[Calixpyridinium]=6.3MsbA0.0040.050.0020.00400500600700800110Wavelength/nm[Calixpyridinium]/M(e)(f)

5FigureS4.UV-Visabsorptionspectraofaqueoussolutionsofcalixpyridiniumatdifferentconcentrationsinthepresenceof80μM(a),100μM(c),and120μM(e)suraminsodiumatroomtemperature.Dependenceoftheabsorbanceat400nmontheconcentrationofcalixpyridiniuminthepresenceof80μM(b),100μM(d),and120μM(f)suraminsodium.0.50.10.40.20.3e0.4cn0.30.5abr0.6os0.7b0.20.8A0.90.10.0400500600700800Wavelength/nmFigureS5.UV-Visabsorptionspectraofaqueoussolutionsofcalixpyridiniumandsuraminsodiumwithdifferentmixingmolarratios{[Calixpyridinium]/([Calixpyridinium]+[suraminsodium])}.[calixpyridinium]+[suraminsodium]=50μM.

6TheCACof3:2calixpyridiniumandsuraminsodiumforconstructingthecalixpyridinium–suraminsodiumsupramolecularaggregatescouldalsobedeterminedbyobservingtheinflectionpointontheplotoftheabsorbanceat400nmversustheconcentrationofcalixpyridinium:4.5μMcalixpyridinium(Fig.S6).Furtherstudiesonthecalixpyridinium–suraminsodiumaggregateswerefocusedonaconcentrationthatwashigherthanthisCACtoensurethecompleteaggregationbetweenthem.0.50.0300.09M0.15M0.0250.40.30Mmn0.60M000.020ec1.50M4tn0.3a3.00Maebrc0.015o6.00Mnsb0.29.00Mab[Calixpyridinium]=4.5MA12.0Mro0.010sb0.1A0.0050.0000.03004005006007008000.1110Wavelength/nm[Calixpyridinium]/M(a)(b)FigureS6.(a)UV-Visabsorptionspectraofaqueoussolutionsofcalixpyridinium–suraminsodiumatdifferentconcentrationswithafixed3:2stoichiometry.(b)Dependenceoftheabsorbanceat400nmoncalixpyridiniumconcentrationinthecalixpyridinium–suraminsodiumsolutionwithafixed3:2stoichiometry.Theconcentrationofcalixpyridiniumchangedfrom0.09to12μM.

7FigureS7.High-resolutionTEMimageofthecalixpyridinium–suraminsodiumassemblies.[calixpyridinium]=6μM,[suraminsodium]=4μM.

8TheUV-visabsorptionspectraofthecalixpyridinium–suraminsodiumsolutionshowednochangewithin1.5hafteritspreparation(Fig.S8),whichsuggestedthatthissupramolecularassemblyachievedbalancequicklyaftertheirmixture.0.200.0h0.5h0.161.0h1.5hecn0.12abrosb0.08A0.040.00300400500600700800Wavelength/nmFigureS8.UV-Visabsorptionspectraofthecalixpyridinium–suraminsodiumassemblyatdifferenttimewithin1.5hatroomtemperatureinwater.[calixpyridinium]=6μM,and[suraminsodium]=4μM.

9Centrifugingthecalixpyridinium–suraminsodiumsolutioncouldnotaffectitsUV-visabsorptionspectrumandTyndalleffect(Fig.S9),implyingthatthecalixpyridinium–suraminsodiumsupramolecularaggregateshadsufficientstability.FigureS9.UV-Visabsorptionspectraofthecalixpyridinium–suraminsodiumassemblybeforeandaftercentrifugationforoneminuteat1000r/mininaqueoussolution.Inset:photographshowingtheTyndalleffectofthecalixpyridinium–suraminsodiumsolutionbefore(I)andaftercentrifugationforoneminute(II).[calixpyridinium]=6μM,and[suraminsodium]=4μM.

10FigureS10.UV-Visabsorptionspectraofaqueoussolutionsofcalixpyridinium–suraminsodiumassemblyatpH6and4.Inset:photographshowingtheTyndalleffectofthecalixpyridinium–suraminsodiumsolutionatpH6and4atroomtemperatureinwater.[calixpyridinium]=6μM,and[suraminsodium]=4μM.1.01.0pH=6pH=6pH=4pH=40.80.8eeccn0.6na0.6abbrroossb0.4b0.4AA0.20.20.00.0300400500600700800300400500600700800Wavelength/nmWavelength/nm(a)(b)FigureS11.(a)UV-VisabsorptionspectraofaqueoussolutionsofcalixpyridiniumatpH6and4.(b)UV-VisabsorptionspectraofaqueoussolutionsofsuraminsodiumatpH6and4.[calixpyridinium]=6μM,and[suraminsodium]=4μM.

11FigureS12.PhotographshowingtheTyndalleffectofthecalixpyridinium–suraminsodiumassemblyatpH6and8.[calixpyridinium]=6μM,and[suraminsodium]=4μM.FigureS13.1HNMRspectra(400MHz,D2O,298K)ofcalixpyridiniumatpD6andpD11,[calixpyridinium]=5mM.

121.0pH=6pH=80.8ecn0.6abrosb0.4A0.20.0300400500600700800Wavelength/nm(a)(b)FigureS14.(a)UV-VisabsorptionspectraofaqueoussolutionsofcalixpyridiniumatpH6and8.Inset:photographshowingthecolorofthecalixpyridiniumsolutionatpH6and8atroomtemperatureinwater.(b)UV-VisabsorptionspectraofaqueoussolutionsofsuraminsodiumatpH6and8.[calixpyridinium]=6μM,and[suraminsodium]=4μM.

13FigureS15.Photographsshowingthecolorofthecalixpyridinium+suraminsodiumsolution(I)andthefreecalixpyridiniumsolution(II)atpH8.[calixpyridinium]=6μM,and[suraminsodium]=4μM.FigureS16.PhotographshowingtheTyndalleffectofthecalixpyridiniumandsuraminsodiummixturesolutionpreparedatpH11.[calixpyridinium]=21μM,and[suraminsodium]=14μM.

14FigureS17.High-resolutionTEMimageofthecalixpyridiniumandsuraminsodiummixturesolutionpreparedatpH11.[calixpyridinium]=21μM,and[suraminsodium]=14μM.2.5o20c2.0o30ceocn1.540cabrosb1.0A0.50.0200300400500600700800Wavelength/nmFigureS18.UV-Visabsorptionspectraofthedepro-calixpyridiniumandsuraminsodiummixturesolutionatpH5.5atdifferenttemperaturesinwater.[calixpyridinium]=21μM,and[suraminsodium]=14μM.

15FigureS19.PhotographshowingtheTyndalleffectofthedepro-calixpyridiniumandsuraminsodiummixturesolutionatpH5.5aftertheUVirradiationat254nmfor2h.[calixpyridinium]=21μM,and[suraminsodium]=14μM.(a)(b)FigureS20.Photographsshowingthecolor(a)andtheTyndalleffect(b)oftheadditionproductofdepro-calixpyridiniumandsuraminsodiummixturesolutionatpH5.5(I)and11(II).[calixpyridinium]=21μM,and[suraminsodium]=14μM.

16FigureS21.High-resolutionTEMimageofthesupramolecularassemblyconstructedbythecomplexationofsuraminsodiumwiththeadditionproductofdepro-calixpyridinium.[calixpyridinium]=21μMand[suraminsodium]=14μM.2.02h1.63hand10minec1.2nabrosb0.8A0.40.0200300400500600700800Wavelength/nmFigureS22.UV-Visabsorptionspectraofaqueoussolutionsofdepro-calixpyridiniumatpH5.5aftertheUVirradiationat254nmfordifferenttimes.[calixpyridinium]=21μM.

17FigureS23.PhotographshowingtheTyndalleffectoftheaqueoussolutionsofcalixpyridiniumatpH5.5before(I)andafter(II)theUVirradiationat254nmfor3hand10min.[calixpyridinium]=21μM.FigureS24.High-resolutionTEMimagesoftheself-assemblyconstructedbytheadditionproductofdepro-calixpyridiniuminwater,[calixpyridinium]=21μM.(1)Shinoda,S.;Tadokoro,M.;Tsukube,H.;Arakawa,R.One-StepSynthesisofaQuaternaryTetrapyridiniumMacrocycleasaNewSpecificReceptorofTricarboxylateAnions.Chem.Commun.1998,181−182.