Hierarchical Assemblies of Inorganic Nanoparticles (NPs) Nicholas A. - - PowerPoint PPT Presentation

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Hierarchical Assemblies of Inorganic Nanoparticles (NPs) Nicholas A. - - PowerPoint PPT Presentation

Sep 17, 2022 32 likes •443 views

U N I V E R S I T Y O F M I C H I G A N , A N N A R B O R Hierarchical Assemblies of Inorganic Nanoparticles (NPs) Nicholas A. Kotov Liquid Peptides Crystals Coordination Hydrophobic bonds interaction Supra DNA Molecular RNA

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Hierarchical Assemblies of Inorganic Nanoparticles (NPs)

U N I V E R S I T Y O F M I C H I G A N , A N N A R B O R

Nicholas A. Kotov

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SLIDE 2

Peptides Liquid Crystals DNA RNA

Supra Molecular Constructs Self‐Assem. Monolayers Micelles Coord. Assemblies Vesicles

Self‐ Assembled Layers

Micelles

Coord. Assemblies

Langmuir Blodgett Films

Hydrogen Bonding van der Waals interactions Covalent bonds Hydrophobic interaction Electrostatic interactions Coordination bonds

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I nteractions London dispersion attraction VLDF = A 121/12∙π∙d2 d

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I nteractions

A 121

d Metals and semiconductors 10 — 40 ∙ 10‐20 J Organic molecules 1 — 10 ∙ 10‐20 J

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I nteractions d 64 · kT∙ σ0 ε0ε Electrostatic Repulsion: VEL = ————— exp(‐κDd)

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I nteractions d

σ0

Metals and semiconductors 1 — 60 mC/m2 Organic materials, insulators 26 — 100 mC/m2

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SLIDE 7

Simplicity

Wide range of experimental conditions and building blocks

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Energy of Electrostatic Repulsion Energy of Attraction 3D Agglomerates Freely Dispersed NPs Chains Sheets

Sim ple Phase Diagram

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SLIDE 9

Supraparticles

CdSe stabilized by citrate no specific shape no monodispersity

Collaboration with Prof. Sharon Glotzer (UM)

  • Prof. ZhiyongTang, (National NanoCenter, Beijing)
  • Y. Xia,T. D. Nguyen, M. Yang, B. Lee, A. Santos, P. Podsiadlo, Z. Tang, S. C. Glotzer, N. A. Kotov,

Self assembly of virus‐like self‐limited inorganic supraparticles from nanoparticles, Nature Nanotechnology, 2011, 6, 580

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Mechanism of Supraparticle Self‐Assembly

  • -- - - - - --
  • Supraparticle is formed due to balance of electrostatic repulsion

and London dispersion attraction.

  • Y. Xia,T. D. Nguyen, M. Yang, B. Lee, A. Santos, P. Podsiadlo, Z. Tang, S. C. Glotzer, N. A. Kotov,

Self assembly of virus‐like self‐limited inorganic supraparticles from nanoparticles, Nature Nanotechnology, 2011, 6, 580

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Complex Assemblies with Au NP in the center Other Assemblies CdSe, PbS, PbSe Complex Assemblies with Au NanoRods in the center

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Colloidal Crystals from Supraparticles

Assembly combining the nanoscale and mesoscale structural motifs

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Capsid‐Like Biomimetic Nanoshells pH 9.5 pH 4.3

50 nm Collaborations with

  • Prof. Petr Kral, U. Illinois Chicago
  • Prof. Peijun Zhang, U. Pittsburg

Cryo‐TEM Tomography

  • M. Yang, H. Chan, G. Zhao, J.H. Bahng, P. Zhang, P.Král, N. A. Kotov, Self‐Assembly of Nanoparticles into

Biomimetic Capsid‐Like Nanoshells, Nature Chemistry, 2017, 9, 287–294.

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SLIDE 14

Assem blies of Chiral NPs into Nanohelixes

CdTe NP stabilized with D‐CYS CdTe NP stabilized with L‐CYS 150 nm 150 nm

  • J. Yeom, B.Yeom, H. Chan, K.W. Smith, S. Dominguez‐Medina , J.H.Bahng, G. Zhao, W.‐S.Chang,

S.J.Chang, A. Chuvilin, D. Melnikau,A.L. Rogach,P. Zhang, S.Link, P.Král,N. A. Kotov, Nature Materials, 2015, 14, 66–72

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SLIDE 15

Does self‐assembly

  • f complex systems require

monodispersity?

Energy landscape

  • f self‐assembly
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Polydispersed Building Blocks Au-S nanosheets

5.2 ± 1.9 nm

Jiang, W.; et al. Emergence of Complexity in Hierarchically Organized Chiral Particles. Science, 2020, 368, 6491, 642

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Self‐Assembled Chiral Hedgehog Particles

Au‐S 2D Material Strong Optical Emission

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Chiroptically Active Hedgehog Particles

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Self‐Assembled Hedgehog Particles

  • J. H. Bang, B. Yeom, Y. Wang, S. O. Tung, N.A. Kotov, Anomalous Dispersions of Hedgehog

Particles, Nature, 2015, 517, 596

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SLIDE 20

Self‐Assembled Hedgehog Particles

Strong Optical Emission Au‐S 2D Material

Jiang, W.; Qu, Z.; Kumar, P.; Vecchio, D.; Wang, Y.; Ma, Y.; Bahng, J. H.; Bernardino, K.; Gomes, W. R.; Colombari, F. M.; et al. Emergence of Complexity in Hierarchically Organized Chiral Particles. Second revision

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SLIDE 21

Unusual pH Stability

Jiang, W.; et al. Emergence of Complexity in Hierarchically Organized Chiral Particles. Science, 2020, 368, 6491, 642

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Chiroptically Active Hedgehog Particles

Jiang, W.; et al. Emergence of Complexity in Hierarchically Organized Chiral Particles. Science, 2020, 368, 6491, 642

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SLIDE 23

Chiroptically Active Hedgehog Particles

Jiang, W.; et al. Emergence of Complexity in Hierarchically Organized Chiral Particles. Science, 2020, 368, 6491, 642

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Phase diagram

Temperature, deg 0C Chirality, e.e.%

Jiang, W.; et al. Emergence of Complexity in Hierarchically Organized Chiral Particles. Science, 2020, 368, 6491, 642

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Phase diagram

Temperature, deg 0C Chirality, e.e.%

Jiang, W.; et al. Emergence of Complexity in Hierarchically Organized Chiral Particles. Science, 2020, 368, 6491, 642

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SLIDE 26

Phase diagram

Temperature, deg 0C Chirality, e.e.%

Jiang, W.; et al. Emergence of Complexity in Hierarchically Organized Chiral Particles. Science, 2020, 368, 6491, 642

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SLIDE 27

Phase diagram

Temperature, deg 0C Chirality, e.e.%

Jiang, W.; et al. Emergence of Complexity in Hierarchically Organized Chiral Particles. Science, 2020, 368, 6491, 642

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SLIDE 28

Phase diagram

Temperature, deg 0C Chirality, e.e.%

Jiang, W.; et al. Emergence of Complexity in Hierarchically Organized Chiral Particles. Science, 2020, 368, 6491, 642

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Graphs and Com plexity

GRAPH ‐ a set of nodes and edges COMPLEXITY ‐ information content

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Graphs and Com plexity

Multifractal parameters Connectivity index Complexity index (CI) Measures of Complexity

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Graphs and Com plexity

Multifractal parameters Connectivity index Complexity index (CI)

  • M. Randić, D. Plavšić On the Concept of Molecular

Complexity Croatica Chemica Acta, 2002, 75 (1) 107

Measures of Complexity

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SLIDE 32

Graphs and Com plexity Multifractal parameters Connectivity index Complexity index (CI)

  • M. Randić, D. Plavšić On the Concept of Molecular

Complexity Croatica Chemica Acta, 2002, 75 (1) 107

Measures of Complexity

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Nanoassem blies

Tang, Z.; Kotov, N. A.; Giersig, M.; Science, 2002, 297, 237. Cho, K.‐S.; Talapin, D. V.; Gaschler,

  • W. L.; Murray, C. B., J. Am. Chem.

Soc., 2005, 127, 7140

  • S. Blank, et al.. J. Microsc.

2003, 212, 280. Kotov, N.A.; Dékány, I.; Fendler, J.H. Adv. Mater. 1996, 8, 637.

  • Y. Xia,T. D. Nguyen, M. Yang, B. Lee, A.

Santos, P. Podsiadlo, Z. Tang, S. C. Glotzer,

  • N. A. Kotov, Nature Nanotech, 2011, 6, 580
  • W. H. Evers, B.Goris, S. Bals,

M.Casavola, J.de Graaf, R.van Roij, M. Dijkstra, D. Vanmaekelbergh, Nano Lett. 2013, 13, 2317

50 nm

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Graph Theory ( GT) of Nanoassem blies A generalized layer of organic ligands

NODES – represent zero‐dimensional nanoscale building blocks EDGE ‐ represents organic‐inorganic interface

Generalized nanoparticle

K1 graph

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GT Representation for Com plex Building Blocks

One‐dimensional nanorod Two‐dimensional nanosheet Three‐dimensional chiral building block

K2 K3 K5

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Connectivity Betw een Com plex Blocks EDGE ‐ represents organic‐inorganic interface

Jiang, W.; Qu, Z.; Kumar, P.; Vecchio, D.; Wang, Y.; Ma, Y.; Bahng, J. H.; Bernardino, K.; Gomes, W. R.; Colombari, F. M.; et al. Emergence of Complexity in Hierarchically Organized Chiral Particles.. Second revision

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Calculations of Com plexity I ndex

CI = 1 + [1/2] = 1.5

CI = N + ΣN (nearest neighbors)/2 + ΣN (next neighbors)/4 + … Number of edges for a node = N

CI = 4 + [16/2] = 12

Jiang, W.; Qu, Z.; Kumar, P.; Vecchio, D.; Wang, Y.; Ma, Y.; Bahng, J. H.; Bernardino, K.; Gomes, W. R.; Colombari, F. M.; et al. Emergence of Complexity in Hierarchically Organized Chiral Particles.. Second revision

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SLIDE 38

Calculations of Com plexity I ndex

… …

CI = 2 + [4/2] + [4/4] + [4/8] +… = 2 +Lim(Σ 4/2n) = 6

… …

  • M. Li, S. Johnson, H. Guo, E. Dujardin
  • S. Mann, A Generalized Mechanism for

Ligand‐Induced Dipolar Assembly of Plasmonic Gold Nanoparticle Chain Networks Advance Funct. Mater, 2011, 21, 851

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Graph Theory Models CI=24.0

3 µm

CI=6.0

  • S. Blank, et al.. J. Microsc. 2003, 212, 280.
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Graph Theory Models CI=40.0 CI=87.0

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Thank You!

NIH NSF DARPA ONR Dow Chemicals Boeing Dow Chemicals 3D Biomatrix AFOSR ARO DOE DTRA IMRA NicoTechnologies BASF Hyundai

and other contributors for generous support