000232374 001__ 232374
000232374 005__ 20180913064552.0
000232374 0247_ $$2doi$$a10.1021/acsmacrolett.7b00383
000232374 022__ $$a2161-1653
000232374 02470 $$2ISI$$a000411653600001
000232374 037__ $$aARTICLE
000232374 245__ $$aCellulose Nanocrystals with Tethered Polymer Chains: Chemically Patchy versus Uniform Decoration
000232374 260__ $$aWashington$$bAmer Chemical Soc$$c2017
000232374 269__ $$a2017
000232374 300__ $$a6
000232374 336__ $$aJournal Articles
000232374 520__ $$aThe site-specific surface modification of colloidal substrates, yielding "patchy" nanoparticles, is a rapidly expanding area of research as a result of the new complex structural hierarchies that are becoming accessible to chemists and materials scientists through colloidal self-assembly. The inherent directionality of cellulose chains, which feature a nonreducing and a reducing end, within individual cellulose nanocrystals (CNCs) renders them an interesting experimental platform for the synthesis of asymmetric nanorods with end-tethered polymer chains. Here, we present water-tolerant reaction pathways toward patchy and uniformly modified CNC hybrids based on atom transfer radical polymerization (ATRP) and initiators that were linked to the CNCs with carbodiimide-mediated coupling and Fischer esterification, respectively. Various monomers, including N-isopropylacrylamide (NIPAM), [2-(methacryloyloxy)ethyl]trimethylammonium chloride (METAC), and sodium 4-vinylbenzenesulfonate (4-SS), were polymerized from both types of initiator-modified CNCs, yielding chemically patchy and uniform CNC hybrids, via surface-initiated ATRP (SI-ATRP). Interestingly, the stereochemistry of tethered PNIPAM was affected by the precise location of ATRP initiating sites, as evidenced by H-1 NMR and circular dichroism (CD) spectroscopy. This effect may be related to the inherent right-handed chirality of CNCs. CNC/PMETAC hybrids were labeled with gold nanoparticles (AuNPs) in order to visualize the precise location of polymer tethers via cryo-electron microscopy. In some instances, the AuNPs were indeed concentrated at the end groups of the patchy CNC hybrids.
000232374 700__ $$aZoppe, Justin O.$$uEcole Polytech Fed Lausanne, Inst Mat, Batiment MXD,Stn 12, CH-1015 Lausanne, Switzerland
000232374 700__ $$aDupire, Alix Vaimiti Marie$$uEcole Polytech Fed Lausanne, Inst Mat, Batiment MXD,Stn 12, CH-1015 Lausanne, Switzerland
000232374 700__ $$aLachat, Theo Gaston Gerard$$uEcole Polytech Fed Lausanne, Inst Mat, Batiment MXD,Stn 12, CH-1015 Lausanne, Switzerland
000232374 700__ $$aLemal, Philipp
000232374 700__ $$aRodriguez-Lorenzo, Laura
000232374 700__ $$aPetri-Fink, Alke
000232374 700__ $$aWeder, Christoph
000232374 700__ $$0240029$$aKlok, Harm-Anton$$g156848
000232374 773__ $$j6$$k9$$q892-897$$tAcs Macro Letters
000232374 909C0 $$0252017$$pLP$$xU10342
000232374 909CO $$ooai:infoscience.tind.io:232374$$pSTI$$particle
000232374 917Z8 $$x156848
000232374 937__ $$aEPFL-ARTICLE-232374
000232374 973__ $$aEPFL$$rREVIEWED$$sPUBLISHED
000232374 980__ $$aARTICLE