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SupportingInformationUrchin-likeHydroxyapatite/GrapheneHollowMicrospheresaspH-ResponsiveBoneDrugCarriersJieLia*,MiaomiaoLiua,YujuanQiua,YuanjingGana,HongkunJiangb,BoyueLiuc,HaoWeibandNingMab*a.CollegeofLightIndustryScienceandEngineering,TianjinUniversityofScienceandTechnology,Tianjin,Chinab.KeyLaboratoryofSuperlightMaterialandSurfaceTechnologyofMinistryofEducation,CollegeofMaterialScienceandChemicalEngineering,HarbinEngineeringUniversity,Harbin,Chinac.SchoolofEnvironmentalandMunicipalEngineering,TianjinChengjianUniversity,Tianjin,ChinaCorrespondingauthors：JieLi,jieli@tust.edu.cn;NingMa,nma@hrbeu.edu.cnNumberofpages:4Numberoffigures:5Tableofcontents1.ThepreparationandtheparticlesizedistributionofrGO-TEPA/HAhollowmicrospheres………………S22.Zetapotentialofdifferentmicrospheres…………………………………………………………………….S33.InvitrocytotoxicitytestofrGO-TEPA……………………………………………………………………S34.ThestandardcurveofDOXconcentration…………………………………………………………………S45.SEMimagesofmicrospheresofdrugcarrierswithreleasetimesatpHvaluesof5.0……………………S4S1
1PreparationofrGO-TEPA/CaCO3compositemicrospheres4mgrGO-TEPAandaCaCl2aqueoussolution(10mM,40mL)weremixedandstirredat200rpmfor10minat25°Cwaterbathheating.Then,anNa2CO3aqueoussolution(Ca2+andCO32-weremixedina1:1ratioduringthisstep)wasslowlyaddeddropwise(30dropsperminute)totheCaCl2/rGO-TEPAsolutionunderstirringat200rpm,andtheresultingmixturewasthenmaintainedunderstaticconditionsfor1h.Themixturewaswashedbyrepeatedcentrifugation,firstwithdistilledwaterandthenwithabsoluteethanol,anddriedat40°Cundervacuumfor24h.FigureS1theparticlesizedistributionofrGO-TEPA/HAhollowmicrospheresS2
2FigureS2ZetapotentialofrGO-TEPA/CaCO3microspheres(A),rGO-TEPA/CaCO3:HAmicrospheres(B)andrGO-TEPA/HAmicrospheres(C)FigureS3InvitrocytotoxicitytestofMC3T3-E1cellsexposedtorGO-TEPAS3
3FigureS4thestandardcurveofDOXconcentrationFigureS4shownthestandardcurveofDOXconcentrationwiththeabsorbanceoftheDOXinPBSat480nm.ThemassofDOXwasacquiredbyconversionoftheabsorbancetotheconcentrationwiththevolumemultiplied.FigureS5SEMimagesof(a-c)DOX@rGO-TEPA/CaCO3:HAmicrospheresand(d-f)DOX@rGO-TEPA/HAhollowmicrosphereswithreleasetimesatpHvaluesof5.0.(a)t=0;(b)t=4h;(c)t=12h;(d)t=0;(e)t=4h;(f)t=12hS4
