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The polymeric glyco-linker controls the signal outputs for plasmonic gold nanorod biosensors due to biocorona formation

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Pancaro, Alessia, Szymonik, Michal, Georgiou, Panagiotis G., Baker, Alexander N., Walker, Marc, Adriaensens, Peter, Hendrix, Jelle, Gibson, Matthew I. and Nelissen, Inge (2021) The polymeric glyco-linker controls the signal outputs for plasmonic gold nanorod biosensors due to biocorona formation. Nanoscale, 13 (24). pp. 10837-10848. doi:10.1039/D1NR01548F

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Official URL: http://dx.doi.org/10.1039/D1NR01548F

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Abstract

Gold nanorods (GNRs) are a promising platform for nanoplasmonic biosensing. The localised surface plasmon resonance (LSPR) peak of GNRs is located in the near-infrared optical window and is sensitive to local binding events, enabling label-free detection of biomarkers in complex biological fluids. A key challenge in the development of such sensors is achieving target affinity and selectivity, while both minimizing non-specific binding and maintaining colloidal stability. Herein, we reveal how GNRs decorated with galactosamine-terminated polymer ligands display significantly different binding responses in buffer compared to serum, due to biocorona formation, and how biocorona displacement due to lectin binding plays a key role in their optical responses. GNRs were coated with either poly(N-(2-hydroxypropyl)methacrylamide) (PHPMA) or poly(N-hydroxyethyl acrylamide) (PHEA) prepared via reversible addition–fragmentation chain-transfer (RAFT) polymerisation and end-functionalised with galactosamine (Gal) as the lectin-targeting unit. In buffer Gal-PHEA-coated GNRs aggregated upon soybean agglutinin (SBA) addition, whereas Gal-PHPMA-coated GNRs exhibited a red-shift of the LSPR spectrum without aggregation. In contrast, when incubated in serum Gal-PHPMA-coated nanorods showed no binding response, while Gal-PHEA GNRs exhibited a dose-dependent blue-shift of the LSPR peak, which is the opposite direction (red-shift) to what was observed in buffer. This differential behaviour was attributed to biocorona formation onto both polymer-coated GNRs, shown by differential centrifugal sedimentation and nanoparticle tracking analysis. Upon addition of SBA to the Gal-PHEA coated nanorods, signal was generated due to displacement of weakly-bound biocorona components by lectin binding. However, in the case of Gal-PHPMA which had a thicker corona, attributed to lower polymer grafting densities, addition of SBA did not lead to biocorona displacement and there was no signal output. These results show that plasmonic optical responses in complex biological media can be significantly affected by biocorona formation, and that biocorona formation itself does not prevent sensing so long as its exact nature (e.g. ‘hard versus soft’) is tuned.

Item Type: Journal Article
Subjects: Q Science > QC Physics
Q Science > QD Chemistry
Q Science > QH Natural history
Q Science > QP Physiology
T Technology > TA Engineering (General). Civil engineering (General)
Divisions: Faculty of Science > Chemistry
Library of Congress Subject Headings (LCSH): Nanoparticles, Surface plasmon resonance, Biochemical markers , Lectins , Polymerization
Journal or Publication Title: Nanoscale
Publisher: Royal Society of Chemistry
ISSN: 2040-3364
Official Date: 28 June 2021
Dates:
DateEvent
28 June 2021Published
3 June 2021Available
3 June 2021Accepted
Volume: 13
Number: 24
Page Range: pp. 10837-10848
DOI: 10.1039/D1NR01548F
Status: Peer Reviewed
Publication Status: Published
Access rights to Published version: Open Access
RIOXX Funder/Project Grant:
Project/Grant IDRIOXX Funder NameFunder ID
814236 European Commissionhttp://dx.doi.org/10.13039/501100000780
BOF20TT06Universiteit Hasselthttp://dx.doi.org/10.13039/501100009550
Hercules project AUHL/15/2 - GOH3816NFonds Wetenschappelijk Onderzoekhttp://dx.doi.org/10.13039/501100003130
866056European Research Councilhttp://dx.doi.org/10.13039/501100000781
BB/M01116X/1[BBSRC] Biotechnology and Biological Sciences Research Councilhttp://dx.doi.org/10.13039/501100000268

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