Self-assembly of gold nanoparticles grafted with amphiphilic supramolecular block copolymers

Zichao Wei; Chung Hao Liu; Hanyi Duan; Qiang Luo; Margaret Huang; Srinivas Thanneeru; Mu Ping Nie; Jie He

doi:10.1016/j.giant.2022.100102

Self-assembly of gold nanoparticles grafted with amphiphilic supramolecular block copolymers

Zichao Wei, Chung Hao Liu, Hanyi Duan, Qiang Luo, Margaret Huang, Srinivas Thanneeru, Mu Ping Nie, Jie He

Research output: Contribution to journal › Article › peer-review

8 Scopus citations

Abstract

Design of polymer grafted plasmonic metal nanoparticles (PGNPs) has received continuous interest due to polymer-driven self-assembly of plasmonic nanoparticles (NPs) as a means to control interparticle plasmon coupling in ensembles. We report the use of supramolecular “V-shaped” block copolymers (VBCPs) as surface ligands of PGNPs to study their hydrophobicity-driven self-assembly. The amphiphilic VBCPs are prepared from two homopolymers, namely dipicolyamine (DPA)-terminated polystyrene (PS) and pyridine (Py)-terminated poly(N,N-dimethylacrylamide) (PDMA) where the two polymers are bridged with Cu²⁺ ions. Those supramolecular VBCPs formed spherical micelles in the range of 100–300 nm, much larger than those of linear BCPs with similar chemical composition as a result of Cu²⁺ ions at the hydrophobic/hydrophilic interface. Thioester-containing supramolecular polymers can modify plasmonic AuNPs through ligand exchange even in the presence of Cu²⁺ ions. Those supramolecular polymers can drive PGNPs to form giant vesicles and two-dimensional (2-D) layered nanosheets. Using in situ light scattering, the supramolecular dynamics is found to allow maximum chain reconformation of polymer ligands where the interparticle distance of PGNPs grafted with VBCPs is smaller compared to that of PGNPs with linear BCPs. The assembled nanostructures with VBCPs also showed similar stimuli-responsive properties where the dissociation of DPA-Cu²⁺-Py coordination results in the disruption of assembled nanostructures. The supramolecular approaches potentially provide a new toolbox to design PGNP assemblies with tunable nanostructures and interesting dynamic properties enabled by non-covalent interaction.

Original language	English
Article number	100102
Journal	Giant
Volume	10
DOIs	https://doi.org/10.1016/j.giant.2022.100102
State	Published - Jun 2022
Externally published	Yes

Funding

J.H. is grateful for the support from the University of Connecticut and the ACS Petroleum Research Fund (ACS PRF). This study was also partially supported by the Institute of Materials Science at the University of Connecticut through the IMMP project. The authors thank to the beamtime of 16ID-LiX at the NSLS-II (Brookhaven National Lab) through a beamtime proposal (BAG-302208). The LiX beamline is part of the Center for BioMolecular Structure (CBMS), which is primarily supported by the National Institutes of Health, National Institute of General Medical Sciences (NIGMS) through a P30 Grant (P30GM133893), and by the DOE Office of Biological and Environmental Research (KP1605010). LiX also received additional support from NIH Grant S10 OD012331. As part of NSLS-II, a national user facility at Brookhaven National Laboratory, work performed at the CBMS is supported in part by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences Program under contract number DE-SC0012704. J.H. is grateful for the support from the University of Connecticut and the ACS Petroleum Research Fund (ACS PRF). This study was also partially supported by the Institute of Materials Science at the University of Connecticut through the IMMP project. The authors thank to the beamtime of 16ID-LiX at the NSLS-II (Brookhaven National Lab) through a beamtime proposal (BAG-302208). The LiX beamline is part of the Center for BioMolecular Structure (CBMS), which is primarily supported by the National Institutes of Health , National Institute of General Medical Sciences (NIGMS) through a P30 Grant (P30GM133893), and by the DOE Office of Biological and Environmental Research (KP1605010). LiX also received additional support from NIH Grant S10 OD012331. As part of NSLS-II, a national user facility at Brookhaven National Laboratory, work performed at the CBMS is supported in part by the U.S. Department of Energy , Office of Science, Office of Basic Energy Sciences Program under contract number DE-SC0012704.

Funders	Funder number
Office of Basic Energy Sciences Program	DE-SC0012704
National Institutes of Health	S10 OD012331
U.S. Department of Energy
American Cancer Society
National Institute of General Medical Sciences	P30GM133893
Office of Science
Biological and Environmental Research	KP1605010
American Chemical Society Petroleum Research Fund
University of Connecticut
Viện Khoa học vật liệu, Viện Hàn lâm Khoa học và Công nghệ Việt Nam	BAG-302208

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10.1016/j.giant.2022.100102

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title = "Self-assembly of gold nanoparticles grafted with amphiphilic supramolecular block copolymers",

abstract = "Design of polymer grafted plasmonic metal nanoparticles (PGNPs) has received continuous interest due to polymer-driven self-assembly of plasmonic nanoparticles (NPs) as a means to control interparticle plasmon coupling in ensembles. We report the use of supramolecular “V-shaped” block copolymers (VBCPs) as surface ligands of PGNPs to study their hydrophobicity-driven self-assembly. The amphiphilic VBCPs are prepared from two homopolymers, namely dipicolyamine (DPA)-terminated polystyrene (PS) and pyridine (Py)-terminated poly(N,N-dimethylacrylamide) (PDMA) where the two polymers are bridged with Cu2+ ions. Those supramolecular VBCPs formed spherical micelles in the range of 100–300 nm, much larger than those of linear BCPs with similar chemical composition as a result of Cu2+ ions at the hydrophobic/hydrophilic interface. Thioester-containing supramolecular polymers can modify plasmonic AuNPs through ligand exchange even in the presence of Cu2+ ions. Those supramolecular polymers can drive PGNPs to form giant vesicles and two-dimensional (2-D) layered nanosheets. Using in situ light scattering, the supramolecular dynamics is found to allow maximum chain reconformation of polymer ligands where the interparticle distance of PGNPs grafted with VBCPs is smaller compared to that of PGNPs with linear BCPs. The assembled nanostructures with VBCPs also showed similar stimuli-responsive properties where the dissociation of DPA-Cu2+-Py coordination results in the disruption of assembled nanostructures. The supramolecular approaches potentially provide a new toolbox to design PGNP assemblies with tunable nanostructures and interesting dynamic properties enabled by non-covalent interaction.",

author = "Zichao Wei and Liu, {Chung Hao} and Hanyi Duan and Qiang Luo and Margaret Huang and Srinivas Thanneeru and Nie, {Mu Ping} and Jie He",

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doi = "10.1016/j.giant.2022.100102",

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AU - Liu, Chung Hao

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AU - Huang, Margaret

AU - Thanneeru, Srinivas

AU - Nie, Mu Ping

AU - He, Jie

PY - 2022/6

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AB - Design of polymer grafted plasmonic metal nanoparticles (PGNPs) has received continuous interest due to polymer-driven self-assembly of plasmonic nanoparticles (NPs) as a means to control interparticle plasmon coupling in ensembles. We report the use of supramolecular “V-shaped” block copolymers (VBCPs) as surface ligands of PGNPs to study their hydrophobicity-driven self-assembly. The amphiphilic VBCPs are prepared from two homopolymers, namely dipicolyamine (DPA)-terminated polystyrene (PS) and pyridine (Py)-terminated poly(N,N-dimethylacrylamide) (PDMA) where the two polymers are bridged with Cu2+ ions. Those supramolecular VBCPs formed spherical micelles in the range of 100–300 nm, much larger than those of linear BCPs with similar chemical composition as a result of Cu2+ ions at the hydrophobic/hydrophilic interface. Thioester-containing supramolecular polymers can modify plasmonic AuNPs through ligand exchange even in the presence of Cu2+ ions. Those supramolecular polymers can drive PGNPs to form giant vesicles and two-dimensional (2-D) layered nanosheets. Using in situ light scattering, the supramolecular dynamics is found to allow maximum chain reconformation of polymer ligands where the interparticle distance of PGNPs grafted with VBCPs is smaller compared to that of PGNPs with linear BCPs. The assembled nanostructures with VBCPs also showed similar stimuli-responsive properties where the dissociation of DPA-Cu2+-Py coordination results in the disruption of assembled nanostructures. The supramolecular approaches potentially provide a new toolbox to design PGNP assemblies with tunable nanostructures and interesting dynamic properties enabled by non-covalent interaction.

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Self-assembly of gold nanoparticles grafted with amphiphilic supramolecular block copolymers

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