Development Of Spatial Modulation Spectroscopy Of Single Nano-Objects In Liquid Environments For Biosensing Applications

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1 title Development Of Spatial Modulation Spectroscopy Of ngle Nano-Objects In Liquid Environments For Biosensing Applications J-M. Rye 1,2, C. Bonnet 1, F. Lerouge 2, J. Lermé 1, A. Mosset 1, M. Broyer 1, M. Pellarin 1, S. Parola 2, E. Cottancin 1 1 Institute of Light and Matter, Université Claude Bernard Lyon 1, CNRS UMR 5306, University of Lyon, Villeurbanne, France 2 Laboratory of Chemistry, École Normale Supérieure de Lyon, CNRS UMR 5182, University of Lyon, Lyon, France

2 Outline Introduction Localized Surface Plasmon Resonance (LSPR) Biosensing Applications? Probe Development Properties of Gold Bipyramids Sample Preparation SMS in a Liquid Environment Principles of SMS Adaptation to a Liquid Environment Results Gold Nanospheres Gold Bipyramids Other Work and Perspectives Interferometric Backscattering Looking Ahead

3 Localized Surface Plasmon Resonance Electric field +++ Metal sphere Collective oscillation of conduction electrons. Electron cloud Resonance occurs when the frequency of incident radiation approaches the natural frequency of electron oscillation. Adapted from K. A. Willets and R. P. Van Duyne. Localized Surface Plasmon Resonance Spectroscopy and Sensing. Annual Review of Physical Chemistry, 58(1): , May 2007 Extinction in Transmission The resonance frequency depends on several factors: composition size shape local environment SENSING APPLICATIONS

4 Biosensing Applications? Detect target analytes in solution. Sensitive plasmonic probe. Functionalized for label-free sensing. Fixed on a substrate. Detect changes in the optical response. of individual objects... in liquid! Probe Development: Nano-object synthesis. Sample preparation. Development of an experimental setup. Sample characterization optical electron microscopy Sensing Assays Numerical mulations

5 Gold Bipyramids TEM Image Ensemble Spectra in Solution Prepared by chemical synthesis Resonance is controllable via synthesis parameters. Optical response of Navarro, J. R. G. et al. Nanotechnology 23, (2012) a single bipyramid? y (nm) x (nm) E 0 E Hot spots near tips E k FEM simulation with COMSOL Multiphysics v. 5.1

6 Overview of Spatial Modulation Spectroscopy (SMS) Principle: relative spatial oscillation between object and spot P scat object oscillation P trans = P inc - P abs - P scat P inc P inc P abs P trans detector time sample mapping by stage translation Sample Map 2f) wide range optical spectra with white light source Navarro, J. R. G. et al. Nanotechnology 23, (2012) y(µm) 10 µm x(µm) correlation with electron microscopy

7 oscillating mirror SMS in a Liquid Environment dynamic fluid cell with sample on translatable stage objective objective lens spectrometer lock-in amplifier collimated white light source Fluid cell. Suitable objectives. Oscillating mirror. Samples unstable in water.

8 Stable Sample Preparation chemical washing surface functionalization H 2 N OH OH OH OH OH O 2 O 2 O O O 2 O O O O bipyramid deposition rinsing & drying O O O O O O O O O O O O gold bipyramid Object density, precipitates, etc.

9 SEM of lanized Sample Clean, stable samples with suitable density for SMS.

10 Gold Spheres: Maps in Air and Water E k 100 nm Au Spheres SMS Map in Air SMS Map in H 2 O Same constellation of objects found in air and H 2 O Individual objects may be studied in both environments.

11 Gold Spheres: Spectra in Air/H2O Δλ 45 nm R = 50 nm E k

12 Gold Bipyramids: Spectra in Air/H2O E k Δλ 57 nm l ~ 100 nm w ~ 30 nm

13 Gold Bipyramids: Spectra in H2O/Glycerol+H2O ngle Au Bipyramid in Water and 2:1 Water/Glycerol Δλ 20 nm E k l ~ 100 nm w ~ 30 nm

14 Forced Oscillation Phase Shifts Classical forced oscillator Mie Theory, Au sphere (R=40nm) E Fixed ions Free electrons Can we exploit this?

15 Interferometric Backscattering oscillating mirror dynamic fluid cell with sample on translatable stage splitter cube objective objective lens spectrometer lock-in amplifier lens spectrometer lock-in amplifier collimated white light source abrupt change in reflection signal reflection X/DC transmission X/DC (5x) wavelength (nm)

16 Looking Ahead The Next Steps Prepare functionalized samples (protocol ready). Add a pumping system for dynamic measurements. Add a CCD strip for faster spectra measurements. Preliminary tests with biotin-streptavidin system. Further Ahead Biosensing assays (e.g. detection of beta-amyloid protein). Use lithography techniques to arrange different probes. Test other objects (rods, cube dimers, lithographed samples). Sensing in gases.

17 Impact of the imust Labex probe synthesis setup development H2N H2N H2N H2N H2N sample preparation sms measurements in liquid y (nm) electron microscopy x (nm) numerical simulations 60 conferences H2N

18 Acknowledgements Christophe Bonnet Emmanuel Cottancin Jean Lermé Michel Pellarin Marie-Ange Lebeault Alexis Mosset Michel Broyer Alain Bourgey Christian Clavier Ph. D. Supervisors Frédéric Lerouge Stéphane Parola Thank you for your attention!

19 Questions Questions?