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

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 exh...

Full description

Bibliographic Details
Main Authors: Merg, A, Boatz, J, Mandal, A, Zhao, G, Mokashi-Punekar, S, Liu, C, Wang, X, Zhang, P, van der Wel, P, Rosi, N
Format: Journal article
Language:English
Published: American Chemical Society 2016
_version_ 1797104044900089856
author Merg, A
Boatz, J
Mandal, A
Zhao, G
Mokashi-Punekar, S
Liu, C
Wang, X
Zhang, P
van der Wel, P
Rosi, N
author_facet Merg, A
Boatz, J
Mandal, A
Zhao, G
Mokashi-Punekar, S
Liu, C
Wang, X
Zhang, P
van der Wel, P
Rosi, N
author_sort Merg, A
collection OXFORD
description 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.
first_indexed 2024-03-07T06:28:19Z
format Journal article
id oxford-uuid:f517b04e-a022-48c3-afc9-32a690ea15ff
institution University of Oxford
language English
last_indexed 2024-03-07T06:28:19Z
publishDate 2016
publisher American Chemical Society
record_format dspace
spelling oxford-uuid:f517b04e-a022-48c3-afc9-32a690ea15ff2022-03-27T12:24:43ZPeptide-directed assembly of single-helical gold nanoparticle superstructures exhibiting intense chiroptical activityJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:f517b04e-a022-48c3-afc9-32a690ea15ffEnglishSymplectic Elements at OxfordAmerican Chemical Society2016Merg, ABoatz, JMandal, AZhao, GMokashi-Punekar, SLiu, CWang, XZhang, Pvan der Wel, PRosi, NChiral 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.
spellingShingle Merg, A
Boatz, J
Mandal, A
Zhao, G
Mokashi-Punekar, S
Liu, C
Wang, X
Zhang, P
van der Wel, P
Rosi, N
Peptide-directed assembly of single-helical gold nanoparticle superstructures exhibiting intense chiroptical activity
title Peptide-directed assembly of single-helical gold nanoparticle superstructures exhibiting intense chiroptical activity
title_full Peptide-directed assembly of single-helical gold nanoparticle superstructures exhibiting intense chiroptical activity
title_fullStr Peptide-directed assembly of single-helical gold nanoparticle superstructures exhibiting intense chiroptical activity
title_full_unstemmed Peptide-directed assembly of single-helical gold nanoparticle superstructures exhibiting intense chiroptical activity
title_short Peptide-directed assembly of single-helical gold nanoparticle superstructures exhibiting intense chiroptical activity
title_sort peptide directed assembly of single helical gold nanoparticle superstructures exhibiting intense chiroptical activity
work_keys_str_mv AT merga peptidedirectedassemblyofsinglehelicalgoldnanoparticlesuperstructuresexhibitingintensechiropticalactivity
AT boatzj peptidedirectedassemblyofsinglehelicalgoldnanoparticlesuperstructuresexhibitingintensechiropticalactivity
AT mandala peptidedirectedassemblyofsinglehelicalgoldnanoparticlesuperstructuresexhibitingintensechiropticalactivity
AT zhaog peptidedirectedassemblyofsinglehelicalgoldnanoparticlesuperstructuresexhibitingintensechiropticalactivity
AT mokashipunekars peptidedirectedassemblyofsinglehelicalgoldnanoparticlesuperstructuresexhibitingintensechiropticalactivity
AT liuc peptidedirectedassemblyofsinglehelicalgoldnanoparticlesuperstructuresexhibitingintensechiropticalactivity
AT wangx peptidedirectedassemblyofsinglehelicalgoldnanoparticlesuperstructuresexhibitingintensechiropticalactivity
AT zhangp peptidedirectedassemblyofsinglehelicalgoldnanoparticlesuperstructuresexhibitingintensechiropticalactivity
AT vanderwelp peptidedirectedassemblyofsinglehelicalgoldnanoparticlesuperstructuresexhibitingintensechiropticalactivity
AT rosin peptidedirectedassemblyofsinglehelicalgoldnanoparticlesuperstructuresexhibitingintensechiropticalactivity