Macromolecules
Article
(31) Hu, M.; Xia, Y.; McKenna, G. B.; Kornfield, J. A.; Grubbs, R. H.
Linear Rheological Response of a Series of Densely Branched Brush
Polymers. Macromolecules 2011, 44, 6935−6943.
(32) Ahn, S.-k.; Carrillo, J.-M. Y.; Keum, J. K.; Chen, J.; Uhrig, D.;
Lokitz, B. S.; Sumpter, B. G.; Michael Kilbey, S. Nanoporous poly(3-
hexylthiophene) thin film structures from self-organization of a
tunable molecular bottlebrush scaffold. Nanoscale 2017, 9, 7071−
7080.
(49) Radzinski, S. C.; Foster, J. C.; Matson, J. B. Preparation of
Bottlebrush Polymers via a One-Pot Ring-Opening Polymerization
(ROP) and Ring-Opening Metathesis Polymerization (ROMP)
Grafting-Through Strategy. Macromol. Rapid Commun. 2016, 37,
616−621.
(50) Skey, J.; O’Reilly, R. K. Facile one pot synthesis of a range of
reversible addition-fragmentation chain transfer (RAFT) agents.
Chem. Commun. 2008, 4183−4185.
(33) Hu, H.; Gopinadhan, M.; Osuji, C. O. Directed self-assembly of
block copolymers: a tutorial review of strategies for enabling
nanotechnology with soft matter. Soft Matter 2014, 10, 3867−3889.
(34) Lin, T.-P.; Chang, A. B.; Luo, S.-X.; Chen, H.-Y.; Lee, B.;
Grubbs, R. H. Effects of Grafting Density on Block Polymer Self-
Assembly: From Linear to Bottlebrush. ACS Nano 2017, 11, 11632−
11641.
(35) Radzinski, S. C.; Foster, J. C.; Scannelli, S. J.; Weaver, J. R.;
Arrington, K. J.; Matson, J. B. Tapered Bottlebrush Polymers: Cone-
Shaped Nanostructures by Sequential Addition of Macromonomers.
ACS Macro Lett. 2017, 6, 1175−1179.
(51) Schneider, Y.; Azoulay, J. D.; Coffin, R. C.; Bazan, G. C. New
Polyethylene Macroinitiators and Their Subsequent Grafting by Atom
Transfer Radical Polymerization. J. Am. Chem. Soc. 2008, 130,
10464−10465.
(52) Radzinski, S. C.; Foster, J. C.; Chapleski, R. C.; Troya, D.;
Matson, J. B. Bottlebrush Polymer Synthesis by Ring-Opening
Metathesis Polymerization: The Significance of the Anchor Group.
J. Am. Chem. Soc. 2016, 138, 6998−7004.
(53) Arrington, K. J.; Matson, J. B. Assembly of a visible light
photoreactor: an inexpensive tool for bottlebrush polymer synthesis
via photoiniferter polymerization. Polym. Chem. 2017, 8, 7452−7456.
(54) Abel, B. A.; McCormick, C. L. One-Pot” Aminolysis/Thiol−
Maleimide End-Group Functionalization of RAFT Polymers:
Identifying and Preventing Michael Addition Side Reactions.
Macromolecules 2016, 49, 6193−6202.
̈
(36) Steinhaus, A.; Pelras, T.; Chakroun, R.; Groschel, A. H.;
Mullner, M. Self-Assembly of Diblock Molecular Polymer Brushes in
̈
the Spherical Confinement of Nanoemulsion Droplets. Macromol.
Rapid Commun. 2018, 39, 1800177.
(37) Neiser, M. W.; Muth, S.; Kolb, U.; Harris, J. R.; Okuda, J.;
Schmidt, M. Micelle Formation from Amphiphilic “Cylindrical
Brush”Coil Block Copolymers Prepared by Metallocene Catalysis.
Angew. Chem., Int. Ed. 2004, 43, 3192−3195.
(55) Radzinski, S. C.; Foster, J. C.; Matson, J. B. Synthesis of
bottlebrush polymers via transfer-to and grafting-through approaches
using a RAFT chain transfer agent with a ROMP-active Z-group.
Polym. Chem. 2015, 6, 5643−5652.
(56) Lin, T.-P.; Chang, A. B.; Chen, H.-Y.; Liberman-Martin, A. L.;
Bates, C. M.; Voegtle, M. J.; Bauer, C. A.; Grubbs, R. H. Control of
Grafting Density and Distribution in Graft Polymers by Living Ring-
Opening Metathesis Copolymerization. J. Am. Chem. Soc. 2017, 139,
3896−3903.
(57) Li, X.; ShamsiJazeyi, H.; Pesek, S. L.; Agrawal, A.; Hammouda,
B.; Verduzco, R. Thermoresponsive PNIPAAM bottlebrush polymers
with tailored side-chain length and end-group structure. Soft Matter
2014, 10, 2008−2015.
(58) Willcock, H.; O’Reilly, R. K. End group removal and
modification of RAFT polymers. Polym. Chem. 2010, 1, 149−157.
(59) Miki, K.; Oride, K.; Kimura, A.; Kuramochi, Y.; Matsuoka, H.;
Harada, H.; Hiraoka, M.; Ohe, K. Influence of Side Chain Length on
Fluorescence Intensity of ROMP-Based Polymeric Nanoparticles and
Their Tumor Specificity in In-Vivo Tumor Imaging. Small 2011, 7,
3536−3547.
́
(38) Zehm, D.; Laschewsky, A.; Gradzielski, M.; Prevost, S.; Liang,
H.; Rabe, J. P.; Schweins, R.; Gummel, J. Amphiphilic Dual Brush
Block Copolymers as “Giant Surfactants” and Their Aqueous Self-
Assembly. Langmuir 2010, 26, 3145−3155.
(39) Bolton, J.; Rzayev, J. Tandem RAFT-ATRP Synthesis of
Polystyrene−Poly(Methyl Methacrylate) Bottlebrush Block Copoly-
mers and Their Self-Assembly into Cylindrical Nanostructures. ACS
Macro Lett. 2012, 1, 15−18.
(40) Namba, S.; Tsukahara, Y.; Kaeriyama, K.; Okamoto, K.;
Takahashi, M. Bulk properties of multibranched polystyrenes from
polystyrene macromonomers: rheological behavior I. Polymer 2000,
41, 5165−5171.
(41) Pakula, T.; Zhang, Y.; Matyjaszewski, K.; Lee, H.-i.; Boerner,
H.; Qin, S.; Berry, G. C. Molecular brushes as Super-soft elastomers.
Polymer 2006, 47, 7198−7206.
(42) Fenyves, R.; Schmutz, M.; Horner, I. J.; Bright, F. V.; Rzayev, J.
Aqueous Self-Assembly of Giant Bottlebrush Block Copolymer
Surfactants as Shape-Tunable Building Blocks. J. Am. Chem. Soc.
2014, 136, 7762−7770.
(43) Lyubimov, I.; Wessels, M. G.; Jayaraman, A. Molecular
Dynamics Simulation and PRISM Theory Study of Assembly in
Solutions of Amphiphilic Bottlebrush Block Copolymers. Macro-
molecules 2018, 51, 7586−7599.
(44) Love, J. A.; Morgan, J. P.; Trnka, T. M.; Grubbs, R. H. A
Practical and Highly Active Ruthenium-Based Catalyst that Effects the
Cross Metathesis of Acrylonitrile. Angew. Chem., Int. Ed. 2002, 41,
4035−4037.
(60) Wanka, G.; Hoffmann, H.; Ulbricht, W. The aggregation
behavior of poly-(oxyethylene)-poly-(oxypropylene)-poly-(oxyethy-
lene)-block-copolymers in aqueous solution. Colloid Polym. Sci.
1990, 268, 101−117.
(61) Alexandridis, P.; Athanassiou, V.; Fukuda, S.; Hatton, T. A.
Surface Activity of Poly(ethylene oxide)-block-Poly(propylene oxide)-
block-Poly(ethylene oxide) Copolymers. Langmuir 1994, 10, 2604−
2612.
(62) Yoo, H. S.; Park, T. G. Biodegradable polymeric micelles
composed of doxorubicin conjugated PLGA−PEG block copolymer.
J. Controlled Release 2001, 70, 63−70.
(45) Liu, J.; Gao, A. X.; Johnson, J. A. Particles without a Box:
Brush-first Synthesis of Photodegradable PEG Star Polymers under
Ambient Conditions. J. Visualized Exp. 2013, No. e50874.
(46) Heller, W. T.; Cuneo, M.; Debeer-Schmitt, L.; Do, C.; He, L.;
Heroux, L.; Littrell, K.; Pingali, S. V.; Qian, S.; Stanley, C.; Urban, V.
S.; Wu, B.; Bras, W. The suite of small-angle neutron scattering
instruments at Oak Ridge National Laboratory. J. Appl. Crystallogr.
2018, 51, 242−248.
(63) Wilhelm, M.; Zhao, C. L.; Wang, Y.; Xu, R.; Winnik, M. A.;
Mura, J. L.; Riess, G.; Croucher, M. D. Poly(styrene-ethylene oxide)
block copolymer micelle formation in water: a fluorescence probe
study. Macromolecules 1991, 24, 1033−1040.
(64) Nagarajan, R.; Ganesh, K. Block copolymer self-assembly in
selective solvents: Spherical micelles with segregated cores. J. Chem.
Phys. 1989, 90, 5843−5856.
(65) Mai, Y.; Eisenberg, A. Self-assembly of block copolymers. Chem.
Soc. Rev. 2012, 41, 5969−5985.
(47) Manning, D. D.; Strong, L. E.; Hu, X.; Beck, P. J.; Kiessling, L.
L. Neoglycopolymer inhibitors of the selectins. Tetrahedron 1997, 53,
11937−11952.
(66) Chen, Y.; Zhou, H.; Sun, Z.; Li, H.; Huang, H.; Liu, L.; Chen,
Y. Shell of amphiphilic molecular bottlebrush matters as unimolecular
micelle. Polymer 2018, 149, 316−324.
(48) Kanao, M.; Otake, A.; Tsuchiya, K.; Ogino, K. Stereo-Selective
Synthesis of 5-Norbornene-2-exo-carboxylic Acid-Rapid Isomerization
and Kinetically Selective Hydrolysis. Int. J. Org. Chem. 2012, 2, 26−
30.
(67) Pesek, S. L.; Xiang, Q.; Hammouda, B.; Verduzco, R. Small-
angle neutron scattering analysis of bottlebrush backbone and side
chain flexibility. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 104−111.
K
Macromolecules XXXX, XXX, XXX−XXX