Journal: Macromolecules
Article Title: Design, Scalable Synthesis, and Characterization of Poly(Oligourethane Methacrylate)s Bottlebrushes with Discrete, Sequence-Defined, and Stereocontrolled Side-Chains
doi: 10.1021/acs.macromol.5c02117
Figure Lengend Snippet: CD spectra of poly(oligourethane methacrylate)s in water/acetonitrile (1/1, v/v) solution at a concentration of 0.5 mg/mL. (A) Polymers with increasing oligourethane side-chain length (RAFT, S and R polymer series: P5_HmS, P6_HmSS, P7_HmSSS, P8_HmSSSS and P16_HmR, P17_HmRR, P18_HmRRR, P19_HmRRRR) and (B) polymers with syndiotactic oligourethane side chains P15_HmSRSR and P20_HmRSRS. (C) Relationship of molar ellipticity ([θ]) at 187 nm as a function of the number of stereocenters present in discrete oligourethane methacrylates (HmR-HmRRRR, blue; and HmS-HmSSSS, red) in water/acetonitrile (1/1, v/v) at a concentration of 0.2 mg/mL. Dotted lines indicate the linear behavior ( R 2 = 0.98 for HmS-HmSSSS and R 2 = 0.97 for HmR-HmRRRR). (D) Molar ellipticity ([θ]) at 187 nm as a function of stereocenter number present in the side chains of poly(oligourethane methacrylate)s obtained by RAFT polymerization (P9_HmS, P10_HmSS, P11_HmSSS, P12_HmSSSS, red dots) and by FRP (P1_HmS, P2_HmSS, P3_HmSSS, P4_HmSSSS, green dots) in water/acetonitrile (1/1, v/v). Dotted lines indicate the linear fitting ( R 2 = 0.96 for RAFT).
Article Snippet: ( S )-(+)-2-amino-1-propanol (S, 99.7%, ee 99.0%, Kindchem, Nanjing, Co., Ltd.), ( R )-(−)-2-amino-1-propanol (R, 99.5%, ee 99.0%, Kindchem, Nanjing, Co., Ltd.), 2-hydroxyethyl methacrylate (Hm, ≥99%, contains ≤50 ppm monomethyl ether hydroquinone inhibitor, Sigma-Aldrich), N , N ′-disuccinimidyl carbonate (dSu, >97%, Apollo Scientific), pyridine (Pyr, 99.5%, extra dried over molecular sieves, Thermo Scientific), acetonitrile (ACN, 99.9%, anhydrous, dried over molecular sieves, Thermo Scientific), ethyl acetate (≥99.7%, Eurochem), N , N -dimethylformamide (DMF, 99.8%, Chemland), deuterated chloroform (CDCl 3 , 99.8 atom % D, Sigma-Aldrich), deuterated dimethyl sulfoxide (DMSO- d 6 , 99.9 atom % D, Sigma-Aldrich), azobisisobutyronitrile (AIBN, 98%, Aldrich), 2-cyano-2-propyl benzodithioate (CPDB, <97%, Aldrich) were used as received from suppliers.
Techniques: Circular Dichroism, Concentration Assay, Polymer