Photobleaching of Fluorophores on the Surface of Nanoantennas

Galloway, C. M.; Artur, Camille; Grand, Johan; Ru, Eric C. Le

doi:10.1021/jp510105z

Cited by 35 publications

(64 citation statements)

References 58 publications

(146 reference statements)

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“…However, the lower photon output could be compensated by a concomitant reduction of photobleaching. 47,48,49 Finally, as a further development of the NP-STED concept, we envision the possibility of combining plasmonic particles with quantum dots (as fluorophores) in order to have a robust probe in terms of photobleaching 14 with the plasmon modes enhancing the depletion of the emission, 39,40 thus, requiring less power for STED nanoscopy.…”

Section: Discussionmentioning

confidence: 99%

Plasmonic Nanoprobes for Stimulated Emission Depletion Nanoscopy

Cortés¹,

Huidobro²,

Sinclair³

et al. 2016

ACS Nano

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Plasmonic nanoparticles influence the absorption and emission processes of nearby emitters due to local enhancements of the illuminating radiation and the photonic density of states. Here, we use the plasmon resonance of metal nanoparticles in order to enhance the stimulated depletion of excited molecules for super-resolved nanoscopy. We demonstrate stimulated emission depletion (STED) nanoscopy with gold nanorods with a long axis of only 26 nm and a width of 8 nm that provide an enhancement of up to 50% of the resolution compared to fluorescent-only probes without plasmonic components irradiated with the same depletion power. The nanoparticle-assisted STED probes reported here represent a ~2x10 3 reduction in probe volume compared to previously used nanoparticles. Finally, we demonstrate their application toward plasmon-assisted STED cellular imaging at low-depletion powers and we also discuss their current limitations. Key-words: STED nanoscopy, nanorods, super-resolution, plasmonic nanoparticles, bio-imagingThe diffraction limit has ceased to be a practical limit to resolution in far-field microscopy, following the demonstration of STED, 1,2,3 RESOLFT 4 and localisation microscopies 5,6,7 and the subsequent development of a plethora of super-resolved nanoscopy techniques. 8 In particular, stimulated emission depletion (STED) nanoscopy, which builds on the advantages of laser scanning confocal microscopy, is a powerful technique for super-resolved imaging in complex biological samples including live organisms. 9,10 STED nanoscopy uses stimulated emission to turn off the spontaneous fluorescence emission of dye molecules, typically overlapping a focused excitation beam with a "doughnut" shaped beam that deexcites emitters to the ground state everywhere except for the area within the centre of the doughnut, thus providing theoretically diffraction-unlimited resolution in the transverse plane by reducing the fullwidth half-maximum (FWHM) of the point spread function. By increasing the power of the depletion beam the emission region can be can be drastically reduced -theoretically allowing for sub-nanometre resolution -with resolutions of less than 10 nm being demonstrated. 11 The scaling of resolution with the square root of the depletion beam power means that relatively high-power lasers are typically used for STED nanoscopy. In practice, however, the use of high-power irradiation can result in problems such as photobleaching of the fluorophores and phototoxicity, and so the achievable resolution is compromised by the need to limit the intensity of the depletion laser radiation. Furthermore, high power lasers can add cost and complexity to STED microscopes and so the requirement for high power depletion beams presents challenges for parallelizing STED measurements 12,13 in terms of the lasers required, thus, limiting the potential for faster super-resolved imaging.To some extent the issue of photobleaching can be addressed with the development of more robust fluorescent labels such as quantum dots 14 as ...

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Section: Discussionmentioning

confidence: 99%

Plasmonic Nanoprobes for Stimulated Emission Depletion Nanoscopy

Cortés¹,

Huidobro²,

Sinclair³

et al. 2016

ACS Nano

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“…More recent applications are emerging, leveraging this understanding of plasmonic optical properties and relying on the rigorous modelling offered by electromagnetic theory: we can cite for example the development of new types of chiroptical spectroscopies [12], the enhancement of photochemical reactions on surfaces [13][14][15][16], enhanced light emission in LEDs [17], or improved photovoltaics [18][19][20]. Many of these existing and emerging applications are underpinned by the fact that the optical (electronic) absorption of molecules on the surface of metallic NPs is enhanced.…”

mentioning

confidence: 99%

Modified optical absorption of molecules on metallic nanoparticles at sub-monolayer coverage

Darby¹,

Auguié²,

Meyer³

et al. 2015

Nature Photon

138

192

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Enhanced optical absorption of molecules in the vicinity of metallic nanostructures is key to a number of surface-enhanced spectroscopies and of great general interest to the fields of plasmonics and nano-optics. Yet, experimental access to this absorbance has long proven elusive. We here present direct measurements of the intrinsic absorbance of dye-molecules adsorbed onto silver nanospheres, and crucially, at sub-monolayer concentrations where dye-dye interactions become negligible. With a large detuning from the plasmon resonance, distinct shifts and broadening of the molecular resonances reveal the intrinsic properties of the dye in contact with the metal colloid, in contrast to the often studied strong-coupling regime where the optical properties of the dye-molecules cannot be isolated. The observation of these shifts together with the ability to routinely measure them has broad implications in the interpretation of experiments involving resonant molecules on metallic surfaces, such as surface-enhanced spectroscopies and many aspects of molecular plasmonics.Over the last two decades, the optical properties of metallic nanoparticles (NPs) of various sizes and shapes [1] [18][19][20]. Many of these existing and emerging applications are underpinned by the fact that the optical (electronic) absorption of molecules on the surface of metallic NPs is enhanced. But spectral changes induced by molecular adsorption are often ignored because of the experimental challenge of measuring surface absorbance spectra on nanoparticles, despite early attempts more than 30 years ago [21].This question is not directly addressed in the great number of recent studies devoted to the topic of strongcoupling between plasmons and molecules [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36]; in this regime, the plasmon-molecule interaction is evidenced by a typical anti-crossing of the two resonances as a function of detuning [25,33], but in such a strongly interacting system the molecular response cannot be isolated. Moreover, in such studies the dye concentration is often large (typically monolayer coverage and above) to maximize dye/plasmon interactions. Dye-dye interactions cannot therefore be neglected and are expected to induce resonance shifts of the dye layer independently of any plas- * Eric.LeRu@vuw.ac.nz monic effects; in fact many studies specifically work with J-aggregates rather than isolated dyes [22, 25-27, 31, 33]. As a result, the intrinsic effect (chemical and/or electromagnetic) of the NP on an isolated adsorbed molecule cannot be elucidated. To this aim, we will show that it is necessary to measure the absorbance of the dye when the dye and plasmon resonances are detuned (to avoid dye-plasmon interaction effects) and at low surface coverage (to avoid dye-dye interaction effects). This low surface coverage poses a significant experimental challenge because the dye absorbance is then very small and obscured by the large optical response (absorption and scattering) of the NPs.We here propose to measure NP/d...

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“…After that, for a fluorophore in its excited state, M Rad leads to the enhancement of the radiative decay rate. Furthermore, there is a factor, M NR ,that demonstrates the nonradiative emission into the metal and is responsible for the fluorescence quenching . The modified total excited state decay rate is therefore M Tot = M Rad + M NR .…”

Section: Theoretical Framework: Photobleaching Of Fluorophoresmentioning

confidence: 99%

“…So, both fluorescence and Raman signals of the fluorophores are modified on the metal surface and affected by PB effect. The time‐dependent intensity of Raman signal for molecules experiencing the same enhancements is given by

I_{SERS} ((),, t, S_{normalL}) = μ_{m} σ_{Raman}^{0} P_{normalL} M^{2} exp ((), - α_{B} M S_{L} t)

where

α_{B} = \frac{γ_{normalB}^{0}}{Q^{0} M_{Tot}}

…”

Section: Theoretical Framework: Photobleaching Of Fluorophoresmentioning

confidence: 99%

“…However, this experimental issue is always ignored in determination of the RS‐EF. Only Galloway et al investigated the PB effect of the dye molecule on the RS‐EF of nanodisc array structures where concentration of hot spots is not great. It is known that the local electromagnetic field and concentration of hot spots determine the amount of RS‐EF .…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Surface‐enhanced Raman spectroscopy of dye molecules on Ag‐modified silicon nanowire substrates: influence of photoinduced probe degradation on enhancement factors

Mehrvar

Sadeghipari

Tavassoli

et al. 2017

J Raman Spectroscopy

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Photobleaching effect is an immense problem in optical spectroscopy, especially when fluorophores are adsorbed on metal nanoparticles (NPs). Nevertheless, little effort has been assigned to the study of fluorophore photostability under this condition. In this paper, the effect of photobleaching on the Raman signal enhancement factor (RS‐EF) of dye molecules on Ag‐modified silicon nanowire (SiNW) substrates is investigated. For this purpose, SiNWs are fabricated by using the vapor–liquid–solid growth mechanism and decorated with Ag NPs by means of electroless deposition method. This process provides the possibility of forming uniformly and tightly packed Ag NPs on SiNWs. The effect of photostability of the crystal violet as analyte molecules on surface‐enhanced Raman spectroscopy is investigated as a function of time evolution and laser power. The influence of Ag NP deposition time on Raman signal enhancement is explored. Our work shows how we can optimize the excitation power for achievement of higher RS‐EF and, consequently, lower detectable concentration. Time evolution of surface‐enhanced Raman spectroscopy signal shows an exponential decay behavior, which indicates an almost uniform distribution of EFs. Capability of our nanostructure is assessed for different concentration, and subsequently, limit of detection of 10 pm with RS‐EF of 2.4×109 is obtained. Copyright © 2017 John Wiley & Sons, Ltd.

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Photobleaching of Fluorophores on the Surface of Nanoantennas

Cited by 35 publications

References 58 publications

Plasmonic Nanoprobes for Stimulated Emission Depletion Nanoscopy

Plasmonic Nanoprobes for Stimulated Emission Depletion Nanoscopy

Modified optical absorption of molecules on metallic nanoparticles at sub-monolayer coverage

Surface‐enhanced Raman spectroscopy of dye molecules on Ag‐modified silicon nanowire substrates: influence of photoinduced probe degradation on enhancement factors

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