Self-regulated co-assembly of soft and hard nanoparticles

Cui, Yan; Zhu, Hongyan; Cai, Jiandong; Qiu, Huibin

doi:10.1038/s41467-021-25995-5

Self-regulated co-assembly of soft and hard nanoparticles

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Published: 28 September 2021

Volume 12, article number 5682, (2021)
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Self-regulated co-assembly of soft and hard nanoparticles

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Abstract

Controlled self-assembly of colloidal particles into predetermined organization facilitates the bottom-up manufacture of artificial materials with designated hierarchies and synergistically integrated functionalities. However, it remains a major challenge to assemble individual nanoparticles with minimal building instructions in a programmable fashion due to the lack of directional interactions. Here, we develop a general paradigm for controlled co-assembly of soft block copolymer micelles and simple unvarnished hard nanoparticles through variable noncovalent interactions, including hydrogen bonding and coordination interactions. Upon association, the hairy micelle corona binds with the hard nanoparticles with a specific valence depending exactly on their relative size and feeding ratio. This permits the integration of block copolymer micelles with a diverse array of hard nanoparticles with tunable chemistry into multidimensional colloidal molecules and polymers. Secondary co-assembly of the resulting colloidal molecules further leads to the formation of more complex hierarchical colloidal superstructures. Notably, such colloidal assembly is processible on surface either through initiating the alternating co-assembly from a micelle immobilized on a substrate or directly grafting a colloidal oligomer onto the micellar anchor.

Building blocks of order: block copolymer micelles and colloidal particles in complex packing structures

Article 05 April 2024

Self-assembly of microcapsules via colloidal bond hybridization and anisotropy

Article 08 June 2016

Tunable assembly of hybrid colloids induced by regioselective depletion

Article 27 July 2020

Introduction

Over the past few decades, solution self-assembly of nanoparticles (NPs) has created a series of fascinating colloidal architectures, such as low-dimensional clusters^1,2,3,4, one-dimensional (1D) chains^{5,6,Full size image}

The soft-hard co-assembly strategy developed in this work provides a versatile and tunable platform for controlled construction of colloidal molecules and polymers in solution and on surface. The unique self-regulated association behavior simplifies the sculpting of building blocks and enriches the topologies of assembled architectures. We envision this facile and distinctive assembly approach would facilitate the controlled bonding of arbitrary soft and hard NPs given the existence of effective complementary interparticle interactions, thereby enabling the creation of colloidal superstructures with high-level complexities and on-demand functionalities.

Methods

Co-assembly of soft NPs and hard NPs in solution

The soft and hard NPs were prepared based on literature reports with slight modifications (more details available in Supplementary Information). A general protocol for the soft-hard co-assembly was as follows. Varying amounts of soft NPs (S_mV_n micelles) in ethanol and hard NPs (such as silica NPs, Au NPs, silica-coated Au NPs, PDA NPs, and ZIF-8 NPs) in ethanol or deionized water were mixed under vigorous stirring to ensure uniformity. After aging for a period of time, the resultant solution was taken out for TEM, SEM, and AFM characterizations. Taking the formation of micelles-capped BA₂ trimers for example: an ethanol solution of 50-nm silica NPs were instantly injected into an ethanol solution of S₂₀₉₀V₃₈₀ micelles under vigorous stirring; subsequently, the mixture was kept under mild stirring at room temperature for 12 h. It should be noted that for the fabrication of relatively extended 2D networks, large-scale 3D stacked monoliths, and micelles-capped nanoclusters the co-assembly was performed at 80 °C in a sealed vial in order to weaken the H-bonding and retard the rapid association of soft and hard NPs^34,35.

Preparation of micelles-coated, fluorinated silicon wafers

A silicon wafer (0.5 cm × 0.5 cm) was sonicated in acetone and water for 30 min, respectively, and dried under a gentle stream of nitrogen. Then, the silicon wafer was subjected to O₂-plasma treatment for 10 min to enrich the surface silanol groups. Subsequently, 10 μL of a 20-fold diluted ethanol solution of S₂₀₉₀V₃₈₀ micelles was spin-coated onto the silicon wafer using a spin coater (6000 rpm, 1 min). The resulting silicon wafer was allowed to age at room temperature for 12 h. Subsequent fluorination treatment was conducted as previously reported with slight modifications³⁶. Typically, the micelles-coated silicon wafer was placed in a Petri dish and then the Petri dish was placed in a desiccator, together with another smaller Petri dish containing 100 μL of heptadecafluoro-1,1,2,2-tetrahydrodecyltrichlorosilane (FDTS). The desiccator was connected to the vacuum line of the fume hood to evacuate the air. After 2 h, the fluorinated silicon wafer was taken out and rinsed with ethanol. The surface of the resultant silicon wafer transformed from hydrophilic to hydrophobic, as revealed by the static water CA values (increased from 45° to 112°, Supplementary Fig. 49).

On-surface synthesis of AB dimers and BA₂ trimers

The micelles-coated, fluorinated silicon wafer was immersed into an ethanol solution of 60-nm silica NPs. After 2 h, the silicon wafer was taken out and rinsed with ethanol several times. Subsequently, the silicon wafer was immersed into an ethanol solution of S₂₁₆₀V₆₂₀ micelles. After 2 h, the silicon wafer was taken out and rinsed with ethanol several times, and dried under a gentle stream of nitrogen.

Preparation of colloidal brushes through a “grafting-to” approach

The micelles-coated, fluorinated silicon wafer was immersed into an ethanol solution of silica-NPs-capped colloidal oligomers (formed by 67-nm silica NPs and S₂₀₉₀V₃₈₀ micelles, with length roughly controlled by tuning the mixing number ratio of S₂₀₉₀V₃₈₀ micelles and 67-nm silica NPs, Supplementary Fig. 51) for 15 h. The resultant silicon wafer was taken out and rinsed with ethanol several times, and dried under a gentle stream of nitrogen.

Data availability

The authors declare that all the data supporting the findings of this study are available within the paper and Supplementary Information files, and are available from the corresponding author upon reasonable request.

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Acknowledgements

This work was financially supported by the National Key R&D Program of China (2020YFA0908100), the National Natural Science Foundation of China (22075180, 92056110), the Innovation Program of Shanghai Municipal Education Commission (202101070002E00084), and the Science and Technology Commission of Shanghai Municipality (195271040, 20JC1415000, 21XD1421900).

Author information

These authors contributed equally: Yan Cui and Hongyan Zhu.

Authors and Affiliations

School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China
Yan Cui, Hongyan Zhu, Jiandong Cai & Huibin Qiu
Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai, 200240, China
Huibin Qiu
State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai, 200240, China
Huibin Qiu

Authors

Yan Cui
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Hongyan Zhu
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Jiandong Cai
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Huibin Qiu
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Contributions

Y.C., H.Z. and H.Q. conceived the project; Y.C. and H.Z. performed the experiments with assistance from J.C.; Y.C., H.Z. and H.Q. analyzed the data and prepared the manuscript with input from J.C. The project was supervised by H.Q.

Corresponding author

Correspondence to Huibin Qiu.

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The authors declare no competing interests.

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Peer review information Nature Communications thanks Zhihong Nie, and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Cui, Y., Zhu, H., Cai, J. et al. Self-regulated co-assembly of soft and hard nanoparticles. Nat Commun 12, 5682 (2021). https://doi.org/10.1038/s41467-021-25995-5

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Received: 07 April 2021
Accepted: 30 August 2021
Published: 28 September 2021
DOI: https://doi.org/10.1038/s41467-021-25995-5
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Self-regulated co-assembly of soft and hard nanoparticles

From

Abstract

Similar content being viewed by others

Building blocks of order: block copolymer micelles and colloidal particles in complex packing structures

Self-assembly of microcapsules via colloidal bond hybridization and anisotropy

Tunable assembly of hybrid colloids induced by regioselective depletion

Introduction

Methods

Co-assembly of soft NPs and hard NPs in solution

Preparation of micelles-coated, fluorinated silicon wafers

On-surface synthesis of AB dimers and BA₂ trimers

Preparation of colloidal brushes through a “grafting-to” approach

Data availability

References

Acknowledgements

Author information

Authors and Affiliations

Contributions

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Competing interests

Additional information

Supplementary information

Supplementary Information

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About this article

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Self-regulated co-assembly of soft and hard nanoparticles

From

Abstract

Similar content being viewed by others

Building blocks of order: block copolymer micelles and colloidal particles in complex packing structures

Self-assembly of microcapsules via colloidal bond hybridization and anisotropy

Tunable assembly of hybrid colloids induced by regioselective depletion

Introduction

Methods

Co-assembly of soft NPs and hard NPs in solution

Preparation of micelles-coated, fluorinated silicon wafers

On-surface synthesis of AB dimers and BA2 trimers

Preparation of colloidal brushes through a “grafting-to” approach

Data availability

References

Acknowledgements

Author information

Authors and Affiliations

Contributions

Corresponding author

Ethics declarations

Competing interests

Additional information

Supplementary information

Supplementary Information

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On-surface synthesis of AB dimers and BA₂ trimers