DNA-Enabled Chiral Gold Nanoparticle–Chromophore Hybrid Structure with Resonant Plasmon–Exciton Coupling Gives Unusual and Strong Circular Dichroism

Lan, Xiang; Zhou, Xu; McCarthy, Lauren A.; Govorov, Alexander O.; Liu, Yan; Link, Stephan

doi:10.1021/jacs.9b08797

Title: DNA-Enabled Chiral Gold Nanoparticle–Chromophore Hybrid Structure with Resonant Plasmon–Exciton Coupling Gives Unusual and Strong Circular Dichroism

Full Record
Other Related Research

Abstract

Circular dichroism (CD) from hybrid complexes of plasmonic nanostructures and chiral molecules has recently attracted significant interest. Yet, the hierarchical chiral self-assembly of molecules on surfaces of metal nanostructures has remained challenging. As a result, a deep understanding of plasmon–exciton coupling between surface plasmons and chiral collective molecular excitations has not been achieved. In particular, the critical impact of resonant plasmon–exciton coupling within the hybrid is unclear. Here, we employed DNA-templated strategies to control the chiral self-assembly of achiral chromophores with rationally tuned exciton transitions on gold nanosphere (AuNP) or gold nanorod (AuNR) surfaces. Unlike many previous chiral plasmonic hybrids utilizing chiral biomolecules with CD signals in the UV range, we designed structures with the chiral excitonic resonances at visible wavelengths. The constructed hybrid complexes displayed strong chiroptical activity that depends on the spectral overlap between the chiral collective molecular excitations and the plasmon resonances. We find that when spectral overlap is optimized, the molecular CD signal originating from the chiral self-assemblies of chromophores was strongly enhanced (maximum enhancement of nearly an order of magnitude) and a plasmonic CD signal was induced. Surprisingly, the sign of the molecular CD was reversed despite different self-assembly mechanisms of the Au nanoparticle–chromophore hybrids.more »« less

Authors:

Lan, Xiang ^[1]; Zhou, Xu ^[2]; McCarthy, Lauren A. ^[1];

^[3];

^[2];

^[1]

Rice Univ., Houston, TX (United States)
Arizona State Univ., Tempe, AZ (United States)
Univ. of Electronic Science and Technology of China, Chengdu (China); Ohio Univ., Athens, OH (United States)

Publication Date:: 2019-11-14

Research Org.:: Rice Univ., Houston, TX (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

OSTI Identifier:: 1596647

Grant/Contract Number:: SC0016353; CHE-1507745; CHE-1903980

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 141; Journal Issue: 49; Related Information: Supporting Info: https://pubs.acs.org/doi/10.1021/jacs.9b08797.; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 77 NANOSCIENCE AND NANOTECHNOLOGY; Dyes and pigments; Metal nanoparticles; Oligomers; Plasmonics; Plasmons

Citation Formats


                    Lan, Xiang, Zhou, Xu, McCarthy, Lauren A., Govorov, Alexander O., Liu, Yan, and Link, Stephan. DNA-Enabled Chiral Gold Nanoparticle–Chromophore Hybrid Structure with Resonant Plasmon–Exciton Coupling Gives Unusual and Strong Circular Dichroism.  United States: N. p., 2019. 
Web.  doi:10.1021/jacs.9b08797.

Copy to clipboard


                    Lan, Xiang, Zhou, Xu, McCarthy, Lauren A., Govorov, Alexander O., Liu, Yan, & Link, Stephan. DNA-Enabled Chiral Gold Nanoparticle–Chromophore Hybrid Structure with Resonant Plasmon–Exciton Coupling Gives Unusual and Strong Circular Dichroism.  United States.  https://doi.org/10.1021/jacs.9b08797

Copy to clipboard


                    Lan, Xiang, Zhou, Xu, McCarthy, Lauren A., Govorov, Alexander O., Liu, Yan, and Link, Stephan. Thu .  
"DNA-Enabled Chiral Gold Nanoparticle–Chromophore Hybrid Structure with Resonant Plasmon–Exciton Coupling Gives Unusual and Strong Circular Dichroism".  United States.  https://doi.org/10.1021/jacs.9b08797.  https://www.osti.gov/servlets/purl/1596647.

Copy to clipboard


                    
@article{osti_1596647,

  title        = {DNA-Enabled Chiral Gold Nanoparticle–Chromophore Hybrid Structure with Resonant Plasmon–Exciton Coupling Gives Unusual and Strong Circular Dichroism},

  author       = {Lan, Xiang and Zhou, Xu and McCarthy, Lauren A. and Govorov, Alexander O. and Liu, Yan and Link, Stephan},

  abstractNote = {Circular dichroism (CD) from hybrid complexes of plasmonic nanostructures and chiral molecules has recently attracted significant interest. Yet, the hierarchical chiral self-assembly of molecules on surfaces of metal nanostructures has remained challenging. As a result, a deep understanding of plasmon–exciton coupling between surface plasmons and chiral collective molecular excitations has not been achieved. In particular, the critical impact of resonant plasmon–exciton coupling within the hybrid is unclear. Here, we employed DNA-templated strategies to control the chiral self-assembly of achiral chromophores with rationally tuned exciton transitions on gold nanosphere (AuNP) or gold nanorod (AuNR) surfaces. Unlike many previous chiral plasmonic hybrids utilizing chiral biomolecules with CD signals in the UV range, we designed structures with the chiral excitonic resonances at visible wavelengths. The constructed hybrid complexes displayed strong chiroptical activity that depends on the spectral overlap between the chiral collective molecular excitations and the plasmon resonances. We find that when spectral overlap is optimized, the molecular CD signal originating from the chiral self-assemblies of chromophores was strongly enhanced (maximum enhancement of nearly an order of magnitude) and a plasmonic CD signal was induced. Surprisingly, the sign of the molecular CD was reversed despite different self-assembly mechanisms of the Au nanoparticle–chromophore hybrids. Our findings offer new insight into plasmonic CD enhancements and will inspire further studies on chiral light–matter interactions in strongly coupled plasmonic–excitonic systems.},

  doi          = {10.1021/jacs.9b08797},

  journal      = {Journal of the American Chemical Society},

  number       = 49,

  volume       = 141,

  place        = {United States},

  year         = {2019},

  month        = {11}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/jacs.9b08797

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 2 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Excitation wavelength dependent photon anti-bunching/bunching from single quantum dots near gold nanostructures

Journal Article Dey, Swayandipta ; Zhou, Yadong ; Sun, Yonglei ; ... - Nanoscale

Here, we aim to investigate the change in photon emission statistics of single CdSe/CdS core/shell quantum dots (QDs) on dielectric modified gold nanoparticle (NP) substrates as a function of the excitation wavelength. Photons emitted from single QDs are typically “anti-bunched” and are independent of the excitation wavelength. However, when QDs are coupled to plasmonic substrates, even at the low excitation power regime, we observed a significant change in photoluminescence emission behavior of single QDs; i.e. the emission transformed from incomplete photon anti-bunched to bunched when the excitation was changed from “off” to “on” plasmon resonance. Theoretical studies based on electrodynamicsmore »« less
Cited by 5
https://doi.org/10.1039/C7NR05299E

Full Text Available
Circular Dichroism in Off-Resonantly Coupled Plasmonic Nanosystems

Journal Article Ferry, Vivian E. ; Hentschel, Mario ; Alivisatos, A. Paul - Nano Letters

Chiral plasmonic systems have been observed to exhibit large chiroptical responses, much larger than those found in molecular or solid state systems. Here, we investigate the role of resonant coupling in such systems and whether the formation of collective plasmonic modes in a chiral assembly of metallic nanostructures is a necessary condition for chiroptical response. We show in experiment and simulation that off-resonant coupling between spectrally detuned nanostructures arranged with structural chirality leads to a clear but weak chiroptical response. We interpret our results in the framework of scattering between the individual constituents that in turn leads to a chiropticalmore »« less
Cited by 31
https://doi.org/10.1021/acs.nanolett.5b03970

Full Text Available
Supramolecular Packing Controls H ₂ Photocatalysis in Chromophore Amphiphile Hydrogels

Journal Article Weingarten, Adam S. ; Kazantsev, Roman V. ; Palmer, Liam C. ; ... - Journal of the American Chemical Society

Light harvesting supramolecular assemblies are potentially useful structures as components of solar-to-fuel conversion materials. The development of these functional constructs requires an understanding of optimal packing modes for chromophores. Here, we investigated assembly in water and the photocatalytic function of perylene monoimide chromophore amphiphiles with different alkyl linker lengths separating their hydrophobic core and the hydrophilic carboxylate headgroup. We found that these chromophore amphiphiles (CAs) self-assemble into charged nanostructures of increasing aspect ratio as the linker length is increased. The addition of salt to screen the charged nanostructures induced the formation of hydrogels and led to internal crystallization within somemore »« less
Cited by 17
https://doi.org/10.1021/jacs.5b10027
Strong Coupling of Localized Surface Plasmons to Excitons in Light-Harvesting Complexes

Journal Article Tsargorodska, Anna ; Cartron, Michaël L. ; Vasilev, Cvetelin ; ... - Nano Letters

Gold nanostructure arrays exhibit surface plasmon resonances that split after attaching light harvesting complexes 1 and 2 (LH1 and LH2) from purple bacteria. The splitting is attributed to strong coupling between the localized surface plasmon resonances and excitons in the light-harvesting complexes. Wild-type and mutant LH1 and LH2 from Rhodobacter sphaeroides containing different carotenoids yield different splitting energies, demonstrating that the coupling mechanism is sensitive to the electronic states in the light harvesting complexes. Plasmon–exciton coupling models reveal different coupling strengths depending on the molecular organization and the protein coverage, consistent with strong coupling. Strong coupling was also observed formore »« less
Cited by 10
https://doi.org/10.1021/acs.nanolett.6b02661
Ligand Coverage and Exciton Delocalization Control Chiral Imprinting in Perovskite Nanoplatelets

Journal Article Georgieva, Zheni N. ; Zhang, Zhendian ; Zhang, Peng ; ... - Journal of Physical Chemistry. C

Chiral perovskites have generated significant recent interest, yet little is known about how their chiro-optical properties arise. In this study, chiral methylammonium lead halide perovskite nanoplatelets (NPLs) with varied halide and ligand compositions are prepared using direct synthetic methods. Circular dichroism (CD) and ¹H NMR studies find a non-linear relationship between the chiroptical properties and the ratio of chiral phenylethylammonium (PEA) to achiral octylamine (OA) ligands on the NPL surface. We use density functional theory (DFT) computations and a chiral imprinted particle-in-a-box model to rationalize the experimentally observed CD spectra and find that the saturation point of the induced chiralitymore »« less
https://doi.org/10.1021/acs.jpcc.2c04192

Similar Records