TY - JOUR
T1 - Facile preparation of supramolecular H-shaped (ter)polymers via multiple hydrogen bonding
AU - Altintas, Ozcan
AU - Schulze-Suenninghausen, David
AU - Luy, Burkhard
AU - Barner-Kowollik, Christopher
PY - 2013/3/27
Y1 - 2013/3/27
N2 - A well-defined Hamilton wedge (HW) midchain functionalized block copolymer, i.e., polyethylene glycol-b-polystyrene (PEG-HW-PS, Mn,GPC = 5600 Da, PDI = 1.03), was successfully synthesized via a combination of atom transfer radical polymerization (ATRP) and copper-catalyzed azide alkyne cycloaddition (CuAAC). An α,ω-cyanuric acid (CA) difunctional linear homopolymer poly(n-butylacrylate) (CA-PnBA-CA, Mn,GPC = 8100 Da, PDI = 1.09) was concomitantly prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. Supramolecular H-shaped macromolecules were - for the first time - prepared through supramolecular self-assembly between HW and CA recognition motifs to generate (PS-b-PEG)·PnBA·(PS-b-PEG) and (PS-b-PS)·PnBA·(PS-b-PS) in CH2Cl2 or dichloromethane-d2 at ambient temperature. The self-assembly process (at a total concentration of the two species of close to 4.5 mM) was evidenced by proton nuclear magnetic resonance (1H NMR) spectroscopy, diffusion-ordered NMR spectroscopy (DOSY), and dynamic light scattering (DLS) analyses. The results derived via DOSY NMR experiments and DLS combined with a Job plot analysis and in-depth NMR titration experiments indicate that the formation of supramolecular H-shaped macromolecules in 2:1 stoichiometry is efficiently occurring via the employed complementary recognition motifs with high binding constants (between 1.2 and 1.5 × 105 L mol -1 at ambient temperature).
AB - A well-defined Hamilton wedge (HW) midchain functionalized block copolymer, i.e., polyethylene glycol-b-polystyrene (PEG-HW-PS, Mn,GPC = 5600 Da, PDI = 1.03), was successfully synthesized via a combination of atom transfer radical polymerization (ATRP) and copper-catalyzed azide alkyne cycloaddition (CuAAC). An α,ω-cyanuric acid (CA) difunctional linear homopolymer poly(n-butylacrylate) (CA-PnBA-CA, Mn,GPC = 8100 Da, PDI = 1.09) was concomitantly prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. Supramolecular H-shaped macromolecules were - for the first time - prepared through supramolecular self-assembly between HW and CA recognition motifs to generate (PS-b-PEG)·PnBA·(PS-b-PEG) and (PS-b-PS)·PnBA·(PS-b-PS) in CH2Cl2 or dichloromethane-d2 at ambient temperature. The self-assembly process (at a total concentration of the two species of close to 4.5 mM) was evidenced by proton nuclear magnetic resonance (1H NMR) spectroscopy, diffusion-ordered NMR spectroscopy (DOSY), and dynamic light scattering (DLS) analyses. The results derived via DOSY NMR experiments and DLS combined with a Job plot analysis and in-depth NMR titration experiments indicate that the formation of supramolecular H-shaped macromolecules in 2:1 stoichiometry is efficiently occurring via the employed complementary recognition motifs with high binding constants (between 1.2 and 1.5 × 105 L mol -1 at ambient temperature).
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U2 - 10.1021/mz400066r
DO - 10.1021/mz400066r
M3 - Article
AN - SCOPUS:84875353118
SN - 2161-1653
VL - 2
SP - 211
EP - 216
JO - ACS Macro Letters
JF - ACS Macro Letters
IS - 3
ER -