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Peptide-directed assembly of single-helical gold nanoparticle superstructures exhibiting intense chiroptical activity

Abstract:
Chiral nanoparticle assemblies are an interesting class of materials whose chiroptical properties make them attractive for a variety of applications. Here, C18-(PEPAu(M-ox))2 (PEPAu(M-ox) = AYSSGAPPM(ox)PPF) is shown to direct the assembly of single-helical gold nanoparticle superstructures that exhibit exceptionally strong chiroptical activity at the plasmon frequency with absolute g-factor values up to 0.04. Transmission electron microscopy (TEM) and cryogenic electron tomography (cryo-ET) results indicate that the single helices have a periodic pitch of approximately 100 nm and consist of oblong gold nanoparticles. The morphology and assembled structure of C18-(PEPAu(M-ox))2 are studied using TEM, atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, circular dichroism (CD) spectroscopy, X-ray diffraction (XRD), and solid-state nuclear magnetic resonance (ssNMR) spectroscopy. TEM and AFM reveal that C18-(PEPAu(M-ox))2 assembles into linear amyloid-like 1D helical ribbons having structural parameters that correlate to those of the single-helical gold nanoparticle superstructures. FTIR, CD, XRD, and ssNMR indicate the presence of cross-β and polyproline II secondary structures. A molecular assembly model is presented that takes into account all experimental observations and that supports the single-helical nanoparticle assembly architecture. This model provides the basis for the design of future nanoparticle assemblies having programmable structures and properties.
Publication status:
Published
Peer review status:
Peer reviewed

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Publisher copy:
10.1021/jacs.6b07322

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Publisher:
American Chemical Society
Journal:
Journal of the American Chemical Society More from this journal
Volume:
138
Issue:
41
Pages:
13655-13663
Publication date:
2016-09-29
Acceptance date:
2016-07-11
DOI:
EISSN:
1520-5126
ISSN:
0002-7863


Language:
English
Keywords:
Pubs id:
pubs:665109
UUID:
uuid:f517b04e-a022-48c3-afc9-32a690ea15ff
Local pid:
pubs:665109
Source identifiers:
665109
Deposit date:
2016-12-14
ARK identifier:

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