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Molecular-Level Control over Plasmonic Properties in Silver Nanoparticle/Self-Assembling Peptide Hybrids.

ABSTRACT: The plasmonic properties of silver nanoparticle (AgNP) arrays are directly controlled by AgNP size, shape, and spatial arrangement. Reported here is a strategy to prepare chiral AgNP arrays templated by two constitutionally isomeric aromatic peptide amphiphiles (APAs), K_SC'EK_S and C'EK_SK_S (K_S = S-aroylthiooxime-modified lysine, C' = citrulline, and E = glutamic acid). In phosphate buffer, both APAs initially self-assembled into nanoribbons with a similar geometry. However, in the presence of silver ions and poly(sodium 4-styrenesulfonate) (PSSS), one of the nanoribbons (K_SC'EK_S) turned into nanohelices with a regular twisting pitch, while the other (C'EK_SK_S) remained as nanoribbons. Both were used as templates for synthesis of arrays of ∼8 nm AgNPs to understand how small changes in molecular structure affect the plasmonic properties of these chiral AgNP/APA hybrids. Both hybrids showed improved colloidal stability compared to pure AgNPs, and both showed enhanced sensitivity as surface-enhanced Raman spectroscopy (SERS) substrates for model analytes, with nanohelices showing better SERS performance compared to their nanoribbon counterparts and pure AgNPs.

SUBMITTER: Wang Y

PROVIDER: S-EPMC7657666 | biostudies-literature | 2020 May

REPOSITORIES: biostudies-literature

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Molecular-Level Control over Plasmonic Properties in Silver Nanoparticle/Self-Assembling Peptide Hybrids.

Wang Yin Y Yang Xiaozhou X Liu Tianyu T Li Zhao Z Leskauskas David D Liu Guoliang G Matson John B JB

Journal of the American Chemical Society 20200511 20

The plasmonic properties of silver nanoparticle (AgNP) arrays are directly controlled by AgNP size, shape, and spatial arrangement. Reported here is a strategy to prepare chiral AgNP arrays templated by two constitutionally isomeric aromatic peptide amphiphiles (APAs), KSC'EKS and C'EKSKS (KS = S-aroylthiooxime-modified lysine, C' = citrulline, ...[more]

PMID: 32392041

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Project description:Nanomaterials possess unusually high surface area-to-volume ratios and surface-determined physicochemical properties. It is essential to understand their surface-dependent toxicity in order to rationally design biocompatible nanomaterials for a wide variety of applications. In this study, we have functionalized the surfaces of silver nanoparticles (Ag NPs, 11.7 ± 2.7 nm in diameter) with three biocompatible peptides (CALNNK, CALNNS, CALNNE) to prepare positively (Ag-CALNNK NPs(+ζ)), negatively (Ag-CALNNS NPs(-2ζ)), and more negatively charged NPs (Ag-CALNNE NPs(-4ζ)), respectively. Each peptide differs in a single amino acid at its C-terminus, which minimizes the effects of peptide sequences and serves as a model molecule to create positive, neutral, and negative charges on the surface of the NPs at pH 4-10. We have studied their charge-dependent transport into early developing (cleavage-stage) zebrafish embryos and their effects on embryonic development using dark-field optical microscopy and spectroscopy (DFOMS). We found that all three Ag-peptide NPs passively diffused into the embryos via their chorionic pore canals, and stayed inside the embryos throughout their entire development (120 h), showing charge-independent diffusion modes and charge-dependent diffusion coefficients. Notably, the NPs create charge-dependent toxic effects on embryonic development, showing that the Ag-CALNNK NPs(+ζ) (positively charged) are the most biocompatible while the Ag-CALNNE NPs(-4ζ) (more negatively charged) are the most toxic. By comparing with our previous studies of the same sized citrated Ag and Au NPs, the Ag-peptide NPs are much more biocompatible than the citrated Ag NPs, and nearly as biocompatible as the Au NPs, showing the dependence of nanotoxicity upon the surface charges, surface functional groups, and chemical compositions of the NPs. This study also demonstrates powerful applications of single NP plasmonic spectroscopy for quantitative analysis of single NPs in vivo and in tissues, and reveals the possibility of rational design of biocompatible NPs.

Dataset Information

Molecular-Level Control over Plasmonic Properties in Silver Nanoparticle/Self-Assembling Peptide Hybrids.

Publications

Molecular-Level Control over Plasmonic Properties in Silver Nanoparticle/Self-Assembling Peptide Hybrids.

Similar Datasets

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