Redox-cleavable star cationic PDMAEMA by arm-first approach of ATRP as a nonviral vector for gene de

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Inthiswork,wesynthesizedastarcationicpolymer(s-PDMAEMA)consistingofcleavablepoly[N,Nbis(acryloyl)cystamine](PBAC)crosslinkedcoreandpoly(N,N-dimethyl-ethylaminemethacrylate)(PDMAEMA)armsbyatomictransferradicalpolymerizationusingone-pot‘‘armfirst’’method.Thes-PDMAEMAthatwasdegradableinamimicintracellularredoxenvironmentwasmoreefficientincondensingDNA.Itwasshownthats-PDMAEMAachievedhighergenetransfectionlevelsrelativetotheirlinearprecursorsands-PDMAEMA200withlongerandmorearmsexhibitedsuperiortransfectionefficienciesandlowercytotoxicitycomparedtoPEI25K.Thebuffercapacitieswereexaminedbyacidbasetitration;thepH-dependentmorphologicalevolutionandenzymestabilityofPDMAEMA/DNAcomplexeswereinvestigatedbyatomicforcemicroscopy(AFM)andtime-resolvedfluorescencespectroscopy,respectively.Theresultsindicatedthatthestarpolymersexhibitedastrongerbufferingabilitythantheirlinearprecursorsduetotheincreasedinnerosmoticpressure.BydecreasingthepHfrom7.4to5.0,thelinearPDMEMA/DNAcomplexesbecamemorecompact;incontrast,s-PDMAEMA200/DNAcomplexadoptedaloosemorphologyduetothestericbarrierofinter-armsandoutwardextensionofpositivelychargedarms.AnalysisofthefluorescencelifetimesoffreeandintercalatedethidiumbromideunveiledmoreeffectiveprotectionofDNAaffordedbys-PDMAEMA.TheeffectofmediumpHonthestarPDMAEMAsystemwassmallerowingtotheabilityofdenselytertiaryaminogroupsalongmultiplearmstoabsorbmoreprotons,whichwasfavorableforendosomolyticescapeofcomplexes.
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