TY - JOUR
T1 - Symmetry-breaking in patch formation on triangular gold nanoparticles by asymmetric polymer grafting
AU - Kim, Ahyoung
AU - Vo, Thi
AU - An, Hyosung
AU - Banerjee, Progna
AU - Yao, Lehan
AU - Zhou, Shan
AU - Kim, Chansong
AU - Milliron, Delia J.
AU - Glotzer, Sharon C.
AU - Chen, Qian
N1 - Synthesis and self-assembly experiments for this work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, under Award DE-SC0020723 (A.K. and Q.C.). Experiments were carried out in part in the Materials Research Laboratory Central Research Facilities, University of Illinois. Theory and simulation for this work was supported by the Department of the Navy, Office of Naval Research under ONR award number N00014-18-1-2497 (T.V. and S.C.G). This research utilized computational resources and services supported by Advanced Research Computing at the University of Michigan, Ann Arbor, and provided by the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation Grant ACI-1053575, XSEDE Award DMR 140129 (T.V. and S.C.G.). LSPR of this work was performed by P.B. at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, and was supported by the U.S. DOE, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. D.M. and P.B. acknowledge partial support from the Center for Dynamics and Control of Materials: an NSF Materials Research Science and Engineering Center (NSF MRSEC) under Cooperative Agreement DMR-1720595 and the Welch Foundation (F-1848). A.K and T.V. thank Prof. Kenneth S. Schweizer and Prof. Catherine J. Murphy for helpful discussions.
Synthesis and self-assembly experiments for this work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, under Award DE-SC0020723 (A.K. and Q.C.). Experiments were carried out in part in the Materials Research Laboratory Central Research Facilities, University of Illinois. Theory and simulation for this work was supported by the Department of the Navy, Office of Naval Research under ONR award number N00014-18-1-2497 (T.V. and S.C.G). This research utilized computational resources and services supported by Advanced Research Computing at the University of Michigan, Ann Arbor, and provided by the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by National Science Foundation Grant ACI-1053575, XSEDE Award DMR 140129 (T.V. and S.C.G.). LSPR of this work was performed by P.B. at the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility, and was supported by the U.S. DOE, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. D.M. and P.B. acknowledge partial support from the Center for Dynamics and Control of Materials: an NSF Materials Research Science and Engineering Center (NSF MRSEC) under Cooperative Agreement DMR-1720595 and the Welch Foundation (F-1848). A.K and T.V. thank Prof. Kenneth S. Schweizer and Prof. Catherine J. Murphy for helpful discussions.
PY - 2022/12
Y1 - 2022/12
N2 - Synthesizing patchy particles with predictive control over patch size, shape, placement and number has been highly sought-after for nanoparticle assembly research, but is fraught with challenges. Here we show that polymers can be designed to selectively adsorb onto nanoparticle surfaces already partially coated by other chains to drive the formation of patchy nanoparticles with broken symmetry. In our model system of triangular gold nanoparticles and polystyrene-b-polyacrylic acid patch, single- and double-patch nanoparticles are produced at high yield. These asymmetric single-patch nanoparticles are shown to assemble into self-limited patch‒patch connected bowties exhibiting intriguing plasmonic properties. To unveil the mechanism of symmetry-breaking patch formation, we develop a theory that accurately predicts our experimental observations at all scales—from patch patterning on nanoparticles, to the size/shape of the patches, to the particle assemblies driven by patch‒patch interactions. Both the experimental strategy and theoretical prediction extend to nanoparticles of other shapes such as octahedra and bipyramids. Our work provides an approach to leverage polymer interactions with nanoscale curved surfaces for asymmetric grafting in nanomaterials engineering.
AB - Synthesizing patchy particles with predictive control over patch size, shape, placement and number has been highly sought-after for nanoparticle assembly research, but is fraught with challenges. Here we show that polymers can be designed to selectively adsorb onto nanoparticle surfaces already partially coated by other chains to drive the formation of patchy nanoparticles with broken symmetry. In our model system of triangular gold nanoparticles and polystyrene-b-polyacrylic acid patch, single- and double-patch nanoparticles are produced at high yield. These asymmetric single-patch nanoparticles are shown to assemble into self-limited patch‒patch connected bowties exhibiting intriguing plasmonic properties. To unveil the mechanism of symmetry-breaking patch formation, we develop a theory that accurately predicts our experimental observations at all scales—from patch patterning on nanoparticles, to the size/shape of the patches, to the particle assemblies driven by patch‒patch interactions. Both the experimental strategy and theoretical prediction extend to nanoparticles of other shapes such as octahedra and bipyramids. Our work provides an approach to leverage polymer interactions with nanoscale curved surfaces for asymmetric grafting in nanomaterials engineering.
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UR - http://www.scopus.com/inward/citedby.url?scp=85141515120&partnerID=8YFLogxK
U2 - 10.1038/s41467-022-34246-0
DO - 10.1038/s41467-022-34246-0
M3 - Article
C2 - 36351911
AN - SCOPUS:85141515120
SN - 2041-1723
VL - 13
JO - Nature communications
JF - Nature communications
IS - 1
M1 - 6774
ER -