ARe-mail
e-mail 时间:2021-01-11 阅读:()
1MemoryofChiralityinJ-TypeAggregatesofAchiralPeryleneDianhydrideDyeCreatedinaChiralAsymmetricCatalyticSynthesisJin-SongZhao,Yi-BinRuan,RongZhouandYun-BaoJiang*DepartmentofChemistry,CollegeofChemistryandChemicalEngineering,andtheMOEKeyLaboratoryofAnalyticalSciences,XiamenUniversity,Xiamen361005,ChinaE-mail:ybjiang@xmu.
edu.
cnElectronicSupportingInformationTableofcontents1.
Materials,MeasurementsandExperimentalProcedures…22.
ESI-MSofPDAaggregatesdissociatedinDMF(Fig.
S1)33.
AbsorptionandfluorescencespectraofPDAmonomerinDMF(Fig.
S2)44.
AbsorptionandCDspectraofPDAJ-aggregatesmediatedbyL-lacticacid(Fig.
S3)45.
CDspectraofPDAJ-aggregatesmediatedbyL-tartaricacidwithoutandwithlateradditionofexcessD-tartaricacid(Fig.
S4)56.
1HNMRspectraofPDAJ-aggregatesandofPTKandCTAB(Fig.
S5)57.
1HNMRspectrumofpotassiumL-tartrateinD2O(Fig.
S6)68.
1HNMRspectraofpotassiumtartrateinD2O(Fig.
S7)69.
CDandabsorptionspectraofPDAJ-aggregatesbeforeandafterpurification(Fig.
S8)710.
CDspectraofpurifiedPDAJ-aggregatesmediatedbyL-tartaricacidwithoutandwithlateradditionofD-tartaricacid(Fig.
S9)711.
XRDofpurifiedPDAJ-andH-aggregates(Fig.
S10)812.
CDandabsorptionspectraofPDAinL-tartaricacid/TTABsolutions(Fig.
S11)813.
References.
921.
Materials,MeasurementsandExperimentalProceduresMaterialsReagentsandsolventswereusedasreceivedfromcommercialsourceswithoutfurtherpurification.
L-(+)-tartaricacid(>99%),D-(-)-tartaricacid(>99%),andperylene-3,4,9,10-tetracarboxylicdianhydride(PDA,>98%)werepurchasedfromAcrosOganics.
Otherchemicals(AR)includingoctadecyltrimthylammoniumbromide(OcTAB),cetyltrimethylammoniumbromide(CTAB),tetradecyltrimethylammoniumbromide(TTAB),decyltrimethylammoniumbromide(DTAB),andHClandKOHwerepurchasedfromGuoyao(Shanghai,China).
Potassiumperylenetetracarboxylate(PTK)wasobtainedfromhydrolysisofPDA.
1Solutionof1.
96g(5mmol)PDAand1.
12g(20mmol)KOHin20mLwaterwasheatedat50°Cfor5hours,duringwhichthedarkredPDApowdergraduallydissolvedtoleadtoadarkredsolution.
Afterfiltration,ethanolwasaddedtothefiltratetoprecipitatePTKthatwasthencollectedthroughfiltrationanddriedundervacuum,affording2.
73gyellowPTKpowderwithayieldof93%.
MeasurementsAbsorptionandCDspectrawererecordedonVarianCary-300UV/VisspectrophotometerandJASCOJ-810spectropolarimeter,respectively.
FluorescencespectrawererecordedonHitachiF-4500fluorescencespectrophotometer.
Electrosprayionizationmassspectrometry(ESI-MS)wasperformedonBrukerESQUIRE-3000plusmassspectrometerbyinjectionofDMFsolutionofthesample.
1HNMRand13CNMRspectrainD2OwererecordedonBrukerAV400spectrometer.
X-raydiffraction(XRD)wasperformedonPanalyticalX'pertPROdiffractometerequippedwithCuKαradiation(λ=1.
5418).
ZetapotentialdatawereobtainedonZetaPALSZetapotentialanalyzer.
Thesemeasurementswerecarriedoutat25°C.
ForCDspectralmeasurements,thesamplesolutioninacellwasstirredbeforethemeasurement.
Thenthesamplewasazimuthallyrotated90oaroundthelightaxisforconsecutivemeasurementsandthusobtainedCDspectrawerefoundtobethesame.
ThereforetheCDsignalsoriginatedexclusivelyfromthemolecularphenomenabutnotfromopticalartifactssuchastheinterferenceoflineardichroism.
2ExperimentalProcedures8mLPTK(62.
5μM)inCTAB(5mM)solutionand2mLL-orD-tartaricacid(2.
5mM,10equiv)inCTAB(5mM)solutionweremixedin10mLflaskat17°C.
Theflaskwassealedandheldat17°Cfor36hours.
Thefinaltransparentsolutionwasinmagenta3colorandwashardlyluminescent.
ThefinalconcentrationofPDAinCTABsolutionwas50μM.
FormationofPDAwasconfirmedbyESI-MS(FigureS1).
PurificationofthesynthesizedchiralPDAJ-aggregateswasperformedusingprecipitationmethod.
Increasingionicstrength,e.
g.
byadditionofsaturatedKBrsolution,resultedinbrownprecipitate.
AfterfiltrationandwashingwithcoldsaturatedKBrsolutionfor3times,theprecipitatewascarefullywashedwithcoldwaterbyavoidingheavystirringanddriedundervacuumbelow15°C.
Theobtaineddarkredprecipitatecanbere-dissolvedinpurewaterunderstirringtoformtransparentmagentasolution.
ConcentrationofthepurifiedPDAJ-aggregatesre-dissolvedinwaterwasmeasuredbyabsorptionspectrophotometry.
3200μLPDAJ-aggregatessolutionwasinjectedinto1.
8mLaqueoussolutionofKOH(1mM)andCTAB(5mM),hydrolysisofPDAtoPTKoccurredimmediatelyandthesolutioncolorturnedtobrightgreen.
Theconcentrationofperylenederivativeswascalculatedbytheabsorbanceat472nmincomparisonwiththestandardworkingcurveoftheabsorbanceat472nmagainstPTKconcentration,independentlypreparedfromabsorptionspectralmeasurementsonstandardPTKsolutions.
2.
ESI-MSofPDAaggregatesdissociatedinDMFESI-MScharacterizationwasperformedinthenegativeionmode.
Samplesolutionwaspreparedbyquickinjectionof40μLPDA(50μM)CTABsolutioninto2mLDMF.
Fig.
S1ESI-MSofPDAmonomerinDMF43.
AbsorptionandfluorescencespectraofPDAmonomerinDMFFig.
S2Normalizedabsorption(solidtrace)andfluorescence(dashtrace,λex=480nm)spectraofPDA(2.
5μM)inDMF.
4.
AbsorptionandCDspectraofPDAJ-aggregatesmediatedbyL-lacticacidFig.
S3(a)CDand(b)absorptionspectraofPDA(50μM)J-aggregatesmediatedbyL-lacticacidinaqueousCTAB(5mM)solution.
55.
CDspectraofPDAJ-aggregatesmediatedbyL-tartaricacidwithoutandwithlateradditionofexcessD-tartaricacidFig.
S4CDspectrumofthePDA(10μM)J-aggregatesinthepresenceofL-tartaricacid(0.
1mM)(black)andthatoveroneweekafterlateradditionof10-foldexcessofD-tartaricacid(1mM)at10-15°C(red)inaqueousCTABsolutions.
6.
1HNMRspectraofPDAJ-aggregatesandofPTKandCTABFig.
S51HNMRspectraof(a)purifiedPDAJ-aggregatesinD2Oand(b)afterdissociationoftheaggregatesbyaddingexcesssolidKOHinthesameD2Osolution.
SignalsofprotonsinbothPTKandCTABaredistinct,whereasnoC*Hsignaloftartrateat4.
23ppm(Fig.
S6)wasobserved.
TheamountofpossiblyremainingtartaricacidinthepurifiedPDAJ-aggregateswasthereforeestimatedtobemuchlessthan0.
5%ofPDA(Fig.
S7).
67.
1HNMRspectrumofpotassiumL-tartrateinD2OFigS61HNMRspectrumofpotassiumtartrate(20mM)inD2O.
8.
1HNMRspectraofpotassiumtartrateinD2OFig.
S71HNMRspectraof(a)purifiedPDAaggregatesdissociatedbyKOH(portionofFig.
S5b,concentrationoftheformedPTKwasca.
20mM)andpotassiumtartarateatconcentrationof(b)0.
1mM(0.
5%ofPTK),(c)0.
2mM(1%ofPTK)and(d)1mM(5%ofPTK)inthepresenceofPTK(20mM)inD2O.
79.
CDandabsorptionspectraofPDAJ-aggregatesbeforeandafterpurificationFig.
S8(a)CDand(b)absorptionspectraofthePDA(50μM)J-aggregatesmediatedbyL-tartaricacidbefore(blacktrace,inaqueousCTABsolution)andafter(redtrace,inwater)purification.
10.
CDspectraofpurifiedPDAJ-aggregatesmediatedbyL-tartaricacidwithoutandwithlateradditionofD-tartaricacidFig.
S9CDspectraofpurifiedPDAJ-aggregates(10μM,blacktrace,inwater)mediatedbyL-tartaricacidandthePDAJ-aggregates(10μM)afterlateradditionofD-tartaricacid(1mM,redtrace,inwater).
Thetwotracesarealmostthesame.
811.
XRDofpurifiedPDAJ-andH-aggregatesFig.
S10PowderXRDpatternsofthepurifiedPDA(a)J-and(b)H-aggregates.
TheH-aggregatesderivedfromJ-toH-aggregatestransitioninwaterat30°C.
12.
CDandabsorptionspectraofPDAinL-tartaricacid/TTABsolutionsFig.
S11(a)CDand(b)absorptionspectraofPDA(50μM)inTTABsolutionofvaryingconcentrationinthepresenceof0.
5mML-tartaricacid.
913.
References1(a)W.
L.
Wang,Y.
Bando,C.
Y.
Zhi,W.
Y.
Fu,E.
G.
Wang,D.
Golberg,J.
Am.
Chem.
Soc.
,2008,130,8144-8145;(b)G.
H.
Fu,M.
L.
Wang,Y.
L.
Wang,N.
Xia,X.
J.
Zhang,M.
Yang,P.
Zheng,W.
Wang,C.
Burger,NewJ.
Chem.
,2009,33,784-792.
2(a)C.
Spitz,S.
Dahne,A.
Ouart,H.
W.
Abraham,J.
Phys.
Chem.
B,2000,104,8664-8669;(b)J.
Yuan,M.
H.
Liu,J.
Am.
Chem.
Soc.
,2003,125,5051-5056.
3D.
A.
Skoog,F.
J.
Holler,T.
A.
Nieman,PrinciplesofInstrumentalAnalysis,5thed.
,SaundersCollege,FortWorth,TX,1998,pp.
301-328.
edu.
cnElectronicSupportingInformationTableofcontents1.
Materials,MeasurementsandExperimentalProcedures…22.
ESI-MSofPDAaggregatesdissociatedinDMF(Fig.
S1)33.
AbsorptionandfluorescencespectraofPDAmonomerinDMF(Fig.
S2)44.
AbsorptionandCDspectraofPDAJ-aggregatesmediatedbyL-lacticacid(Fig.
S3)45.
CDspectraofPDAJ-aggregatesmediatedbyL-tartaricacidwithoutandwithlateradditionofexcessD-tartaricacid(Fig.
S4)56.
1HNMRspectraofPDAJ-aggregatesandofPTKandCTAB(Fig.
S5)57.
1HNMRspectrumofpotassiumL-tartrateinD2O(Fig.
S6)68.
1HNMRspectraofpotassiumtartrateinD2O(Fig.
S7)69.
CDandabsorptionspectraofPDAJ-aggregatesbeforeandafterpurification(Fig.
S8)710.
CDspectraofpurifiedPDAJ-aggregatesmediatedbyL-tartaricacidwithoutandwithlateradditionofD-tartaricacid(Fig.
S9)711.
XRDofpurifiedPDAJ-andH-aggregates(Fig.
S10)812.
CDandabsorptionspectraofPDAinL-tartaricacid/TTABsolutions(Fig.
S11)813.
References.
921.
Materials,MeasurementsandExperimentalProceduresMaterialsReagentsandsolventswereusedasreceivedfromcommercialsourceswithoutfurtherpurification.
L-(+)-tartaricacid(>99%),D-(-)-tartaricacid(>99%),andperylene-3,4,9,10-tetracarboxylicdianhydride(PDA,>98%)werepurchasedfromAcrosOganics.
Otherchemicals(AR)includingoctadecyltrimthylammoniumbromide(OcTAB),cetyltrimethylammoniumbromide(CTAB),tetradecyltrimethylammoniumbromide(TTAB),decyltrimethylammoniumbromide(DTAB),andHClandKOHwerepurchasedfromGuoyao(Shanghai,China).
Potassiumperylenetetracarboxylate(PTK)wasobtainedfromhydrolysisofPDA.
1Solutionof1.
96g(5mmol)PDAand1.
12g(20mmol)KOHin20mLwaterwasheatedat50°Cfor5hours,duringwhichthedarkredPDApowdergraduallydissolvedtoleadtoadarkredsolution.
Afterfiltration,ethanolwasaddedtothefiltratetoprecipitatePTKthatwasthencollectedthroughfiltrationanddriedundervacuum,affording2.
73gyellowPTKpowderwithayieldof93%.
MeasurementsAbsorptionandCDspectrawererecordedonVarianCary-300UV/VisspectrophotometerandJASCOJ-810spectropolarimeter,respectively.
FluorescencespectrawererecordedonHitachiF-4500fluorescencespectrophotometer.
Electrosprayionizationmassspectrometry(ESI-MS)wasperformedonBrukerESQUIRE-3000plusmassspectrometerbyinjectionofDMFsolutionofthesample.
1HNMRand13CNMRspectrainD2OwererecordedonBrukerAV400spectrometer.
X-raydiffraction(XRD)wasperformedonPanalyticalX'pertPROdiffractometerequippedwithCuKαradiation(λ=1.
5418).
ZetapotentialdatawereobtainedonZetaPALSZetapotentialanalyzer.
Thesemeasurementswerecarriedoutat25°C.
ForCDspectralmeasurements,thesamplesolutioninacellwasstirredbeforethemeasurement.
Thenthesamplewasazimuthallyrotated90oaroundthelightaxisforconsecutivemeasurementsandthusobtainedCDspectrawerefoundtobethesame.
ThereforetheCDsignalsoriginatedexclusivelyfromthemolecularphenomenabutnotfromopticalartifactssuchastheinterferenceoflineardichroism.
2ExperimentalProcedures8mLPTK(62.
5μM)inCTAB(5mM)solutionand2mLL-orD-tartaricacid(2.
5mM,10equiv)inCTAB(5mM)solutionweremixedin10mLflaskat17°C.
Theflaskwassealedandheldat17°Cfor36hours.
Thefinaltransparentsolutionwasinmagenta3colorandwashardlyluminescent.
ThefinalconcentrationofPDAinCTABsolutionwas50μM.
FormationofPDAwasconfirmedbyESI-MS(FigureS1).
PurificationofthesynthesizedchiralPDAJ-aggregateswasperformedusingprecipitationmethod.
Increasingionicstrength,e.
g.
byadditionofsaturatedKBrsolution,resultedinbrownprecipitate.
AfterfiltrationandwashingwithcoldsaturatedKBrsolutionfor3times,theprecipitatewascarefullywashedwithcoldwaterbyavoidingheavystirringanddriedundervacuumbelow15°C.
Theobtaineddarkredprecipitatecanbere-dissolvedinpurewaterunderstirringtoformtransparentmagentasolution.
ConcentrationofthepurifiedPDAJ-aggregatesre-dissolvedinwaterwasmeasuredbyabsorptionspectrophotometry.
3200μLPDAJ-aggregatessolutionwasinjectedinto1.
8mLaqueoussolutionofKOH(1mM)andCTAB(5mM),hydrolysisofPDAtoPTKoccurredimmediatelyandthesolutioncolorturnedtobrightgreen.
Theconcentrationofperylenederivativeswascalculatedbytheabsorbanceat472nmincomparisonwiththestandardworkingcurveoftheabsorbanceat472nmagainstPTKconcentration,independentlypreparedfromabsorptionspectralmeasurementsonstandardPTKsolutions.
2.
ESI-MSofPDAaggregatesdissociatedinDMFESI-MScharacterizationwasperformedinthenegativeionmode.
Samplesolutionwaspreparedbyquickinjectionof40μLPDA(50μM)CTABsolutioninto2mLDMF.
Fig.
S1ESI-MSofPDAmonomerinDMF43.
AbsorptionandfluorescencespectraofPDAmonomerinDMFFig.
S2Normalizedabsorption(solidtrace)andfluorescence(dashtrace,λex=480nm)spectraofPDA(2.
5μM)inDMF.
4.
AbsorptionandCDspectraofPDAJ-aggregatesmediatedbyL-lacticacidFig.
S3(a)CDand(b)absorptionspectraofPDA(50μM)J-aggregatesmediatedbyL-lacticacidinaqueousCTAB(5mM)solution.
55.
CDspectraofPDAJ-aggregatesmediatedbyL-tartaricacidwithoutandwithlateradditionofexcessD-tartaricacidFig.
S4CDspectrumofthePDA(10μM)J-aggregatesinthepresenceofL-tartaricacid(0.
1mM)(black)andthatoveroneweekafterlateradditionof10-foldexcessofD-tartaricacid(1mM)at10-15°C(red)inaqueousCTABsolutions.
6.
1HNMRspectraofPDAJ-aggregatesandofPTKandCTABFig.
S51HNMRspectraof(a)purifiedPDAJ-aggregatesinD2Oand(b)afterdissociationoftheaggregatesbyaddingexcesssolidKOHinthesameD2Osolution.
SignalsofprotonsinbothPTKandCTABaredistinct,whereasnoC*Hsignaloftartrateat4.
23ppm(Fig.
S6)wasobserved.
TheamountofpossiblyremainingtartaricacidinthepurifiedPDAJ-aggregateswasthereforeestimatedtobemuchlessthan0.
5%ofPDA(Fig.
S7).
67.
1HNMRspectrumofpotassiumL-tartrateinD2OFigS61HNMRspectrumofpotassiumtartrate(20mM)inD2O.
8.
1HNMRspectraofpotassiumtartrateinD2OFig.
S71HNMRspectraof(a)purifiedPDAaggregatesdissociatedbyKOH(portionofFig.
S5b,concentrationoftheformedPTKwasca.
20mM)andpotassiumtartarateatconcentrationof(b)0.
1mM(0.
5%ofPTK),(c)0.
2mM(1%ofPTK)and(d)1mM(5%ofPTK)inthepresenceofPTK(20mM)inD2O.
79.
CDandabsorptionspectraofPDAJ-aggregatesbeforeandafterpurificationFig.
S8(a)CDand(b)absorptionspectraofthePDA(50μM)J-aggregatesmediatedbyL-tartaricacidbefore(blacktrace,inaqueousCTABsolution)andafter(redtrace,inwater)purification.
10.
CDspectraofpurifiedPDAJ-aggregatesmediatedbyL-tartaricacidwithoutandwithlateradditionofD-tartaricacidFig.
S9CDspectraofpurifiedPDAJ-aggregates(10μM,blacktrace,inwater)mediatedbyL-tartaricacidandthePDAJ-aggregates(10μM)afterlateradditionofD-tartaricacid(1mM,redtrace,inwater).
Thetwotracesarealmostthesame.
811.
XRDofpurifiedPDAJ-andH-aggregatesFig.
S10PowderXRDpatternsofthepurifiedPDA(a)J-and(b)H-aggregates.
TheH-aggregatesderivedfromJ-toH-aggregatestransitioninwaterat30°C.
12.
CDandabsorptionspectraofPDAinL-tartaricacid/TTABsolutionsFig.
S11(a)CDand(b)absorptionspectraofPDA(50μM)inTTABsolutionofvaryingconcentrationinthepresenceof0.
5mML-tartaricacid.
913.
References1(a)W.
L.
Wang,Y.
Bando,C.
Y.
Zhi,W.
Y.
Fu,E.
G.
Wang,D.
Golberg,J.
Am.
Chem.
Soc.
,2008,130,8144-8145;(b)G.
H.
Fu,M.
L.
Wang,Y.
L.
Wang,N.
Xia,X.
J.
Zhang,M.
Yang,P.
Zheng,W.
Wang,C.
Burger,NewJ.
Chem.
,2009,33,784-792.
2(a)C.
Spitz,S.
Dahne,A.
Ouart,H.
W.
Abraham,J.
Phys.
Chem.
B,2000,104,8664-8669;(b)J.
Yuan,M.
H.
Liu,J.
Am.
Chem.
Soc.
,2003,125,5051-5056.
3D.
A.
Skoog,F.
J.
Holler,T.
A.
Nieman,PrinciplesofInstrumentalAnalysis,5thed.
,SaundersCollege,FortWorth,TX,1998,pp.
301-328.
HostYun 新增美国三网CN2 GIA VPS主机 采用美国原生IP低至月15元
在之前几个月中也有陆续提到两次HostYun主机商，这个商家前身是我们可能有些网友熟悉的主机分享团队的，后来改名称的。目前这个品牌主营低价便宜VPS主机，这次有可以看到推出廉价版本的美国CN2 GIA VPS主机，月费地址15元，适合有需要入门级且需要便宜的用户。第一、廉价版美国CN2 GIA VPS主机方案我们可看到这个类型的VPS目前三网都走CN2 GIA网络，而且是原生IP。根据信息可能后续...
ParkinHost：俄罗斯离岸主机，抗投诉VPS，200Mbps带宽/莫斯科CN2线路/不限流量/无视DMCA/55折促销26.4欧元 /年起
外贸主机哪家好？抗投诉VPS哪家好？无视DMCA。ParkinHost今年还没有搞过促销，这次parkinhost俄罗斯机房上新服务器，母机采用2个E5-2680v3处理器、128G内存、RAID10硬盘、2Gbps上行线路。具体到VPS全部200Mbps带宽，除了最便宜的套餐限制流量之外，其他的全部是无限流量VPS。ParkinHost，成立于 2013 年，印度主机商，隶属于 DiggDigi...
博鳌云¥799/月,香港110Mbps(含10M CN2)大带宽独立服务器/E3/8G内存/240G/500G SSD或1T HDD
博鳌云是一家以海外互联网基础业务为主的高新技术企业，运营全球高品质数据中心业务。自2008年开始为用户提供服务，距今11年，在国人商家中来说非常老牌。致力于为中国用户提供域名注册（国外接口）、免费虚拟主机、香港虚拟主机、VPS云主机和香港、台湾、马来西亚等地服务器租用服务，各类网络应用解決方案等领域的专业网络数据服务。商家支持支付宝、微信、银行转账等付款方式。目前香港有一款特价独立服务器正在促销，...
e-mail为你推荐
-
租用虚拟主机租用虚拟主机需要注意什么？vps虚拟主机请问VPS和虚拟主机有什么不一样，为什么VPS贵那么多。广告的别来！域名注册服务万网域名注册服务怎么样？免费vps服务器免费服务器有哪些美国服务器托管美国服务器租用有那些机房，他们的优缺点是什么？台湾vps虚拟主机，VPS，服务器，其中哪个流量最大？免费域名空间求速度快的 免费空间 带域名的 谢谢大家虚拟空间哪个好虚拟空间哪个好网站空间价格普通的网站空间要多少钱一年手机网站空间手机网页空间需要多大？