Self-Assembly of Chiral Nanoparticles into Semiconductor Helices with Tunable near-Infrared Optical Activity

Yan, Jiao; Feng, Wenchun; Kim, Ji-Young; Lü, Jun; Kumar, Prashant; Mu, Zhengzhi; Wu, Xiaochun; Mao, Xiaoming; Kotov, Nicholas A.

doi:10.1021/acs.chemmater.9b04143

Cited by 98 publications

(130 citation statements)

References 129 publications

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“…The same effect can also be traced in other assemblies of nanoparticles, such as chiral CdTe tetrahedrons and planar graphene quantum dots (40,46). Figure S34.…”

Section: Ementioning

confidence: 61%

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Emergence of complexity in hierarchically organized chiral particles

Jiang

Kumar

et al. 2020

Science

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219

252

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The structural complexity of composite biomaterials and biomineralized particles arises from the hierarchical ordering of inorganic building blocks over multiple scales. Although empirical observations of complex nanoassemblies are abundant, the physicochemical mechanisms leading to their geometrical complexity are still puzzling, especially for nonuniformly sized components. We report the self-assembly of hierarchically organized particles (HOPs) from polydisperse gold thiolate nanoplatelets with cysteine surface ligands. Graph theory methods indicate that these HOPs, which feature twisted spikes and other morphologies, display higher complexity than their biological counterparts. Their intricate organization emerges from competing chirality-dependent assembly restrictions that render assembly pathways primarily dependent on nanoparticle symmetry rather than size. These findings and HOP phase diagrams open a pathway to a large family of colloids with complex architectures and unusual chiroptical and chemical properties.

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“…The same effect can also be traced in other assemblies of nanoparticles, such as chiral CdTe tetrahedrons and planar graphene quantum dots (40,46). Figure S34.…”

Section: Ementioning

confidence: 61%

“…(https://doi.org/10.1021/acs.che mmater.9b04143) (46). high CI in this case corresponds to high degree of control over the structure of these particles.…”

mentioning

confidence: 93%

Emergence of complexity in hierarchically organized chiral particles

Jiang

Kumar

et al. 2020

Science

Self Cite

219

252

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“…Extending the functionalization strategy presented here, in combination with the self-assembly of various topologies or combinations of topologies, could lead to unusual and complex assemblies with emerging optical properties. 37…”

Section: Towards Responsive Optical Systemsmentioning

confidence: 99%

Light-responsive self-assembly of semi-conducting nanoplatelets

Arias¹,

Huang²,

Ryabchun³

et al. 2020

Preprint

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CdSe nanoplatelets are a recently discovered class of colloidal semiconducting nanocrystals. Atomic control over their thickness allows achieving control over quantum size effects, and in particular, these platelets exhibit monochromatic light emission because of the confinement of photo-generated excitons only in their thickness. These nanoplatelets can self-organize into supra-particular polymers, depending on their environment, which means that their shape anisotropy can be expressed at the microscale. Here, the self-assembly of semiconducting nanoplatelets is controlled remotely by light, in a dynamic nanoparticulate system that integrates light-responsive molecular switches covalently. Azobenzene ligands were thus designed to (i) be grafted on the nanoplatelets (ii) ensure their colloidal stability in chloroform when confined on their surface in the E-configuration. Upon irradiation, the ligands isomerize into their Z-configuration, leading to a modification of the dipolar moment of the particles and to the formation of one-dimensional stacks. The self-assembly is reversible, as thermal relaxation of the ligands yields the initial dispersion back. This reversible hybrid system can be used in the design of responsive optical systems, as illustrated by photo-patterning experiments leading to controlled spatial resolution of the luminescence intensity in thin films.

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“…Chirality is one of the most universal properties of the physical world 1–4 . Chiral nanoscale structures from inorganic materials with strongly polarizable plasmonic and excitonic electronic states provide an avenue to efficiently manipulate polarization of light 5–14 . Templated assemblies of plasmonic nanoparticles (NPs) using biomacromolecules can produce superstructures with nanoscale chiral geometries 14–20 .…”

Section: Introductionmentioning

confidence: 99%

Plasmonic nanoparticles assemblies templated by helical bacteria and resulting optical activity

et al. 2020

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Plasmonic nanoparticles (NPs) adsorbing onto helical bacteria can lead to formation of NP helicoids with micron scale pitch. Associated chiroptical effects can be utilized as bioanalytical tool for bacterial detection and better understanding of the spectral behavior of helical self‐assembled structures with different scales. Here, we report that enantiomerically pure helices with micron scale of chirality can be assembled on Campylobacter jejuni, a helical bacterium known for severe stomach infections. These organisms have right‐handed helical shapes with a pitch of 1–2 microns and can serve as versatile templates for a variety of NPs. The bacteria itself shows no observable rotatory activity in the visible, red, and near‐IR ranges of electromagnetic spectrum. The bacterial dispersion acquires chiroptical activity at 500–750 nm upon plasmonic functionalization with Au NPs. Finite‐difference time‐domain simulations confirmed the attribution of the chiroptical activity to the helical assembly of gold nanoparticles. The position of the circular dichroism peaks observed for these chiral structures overlaps with those obtained before for Au NPs and their constructs with molecular and nanoscale chirality. This work provides an experimental and computational pathway to utilize chiroplasmonic particles assembled on bacteria for bioanalytical purposes.

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Self-Assembly of Chiral Nanoparticles into Semiconductor Helices with Tunable near-Infrared Optical Activity

Cited by 98 publications

References 129 publications

Emergence of complexity in hierarchically organized chiral particles

Emergence of complexity in hierarchically organized chiral particles

Light-responsive self-assembly of semi-conducting nanoplatelets

Plasmonic nanoparticles assemblies templated by helical bacteria and resulting optical activity

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