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Jérôme Wenger

Publications and source records attributed to Jérôme Wenger.

At least 19 recordsLinked to original sources

Sequential Multi-Step Nanoimprint Lithography Fabrication of Zero-Mode Waveguide Nanoaperture Arrays to Enhance Single Molecule Fluorescence Detection

Zero-mode waveguides (ZMWs) enable single-molecule fluorescence detection at micromolar concentrations by confining light to nanoscale volumes, overcoming the diffraction limit of confocal microscopy. However, their widespread adoption is hindered by high fabrication costs and limited throughput of traditional methods like focused ion beam or electron-beam lithography. Here, we introduce a scalable cost-effective approach using sequential nanoimprint lithography (NIL) combined with hydrofluoric acid etching to fabricate ZMW arrays with tunable diameters from a single initial master. In our sequential nanoimprint approach, each stamped NIL output serves as a master for the next nanoimprint generation. By leveraging the shrinkage of sol-gel nanopatterns during annealing, we achieve a cumulative diameter reduction from 230 nm to 115 nm over four successive imprints, all based on the same initial master. The resulting ZMWs exhibit detection volumes reduced by up to 1000-fold and fluorescence enhancement exceeding 16x, achieving performance comparable to state-of-the-art focused ion beam-fabricated devices. Eliminating the need for multiple master structures significantly expands the scalability of nanoimprint lithography approaches. By lowering the nanofabrication barriers and making ZMW arrays more accessible, the sequential NIL method paves the way towards broader adoption of nanophotonic devices in single-molecule biophysics, biosensing, and surface patterning applications.

physics.optics↗

Single Nanoparticle Dynamics in Opto-Thermal Tweezers: Resolving the Temporal Resolution of Depletion Force Trapping

Optothermal tweezers enable the manipulation of a wide range of nano-objects through optically induced depletion forces. Despite significant advances, the temporal dynamics of optothermal trapping remain elusive, as existing methodologies rely almost exclusively on time and ensemble averaging. Consequently, stable trapping cannot be distinguished from local transient accumulation, where the time-averaged concentration increases but particles exhibit rapid, dynamic motion in and out of the trap. Here we investigate optothermal trapping with single-nanoparticle-level analysis and sub-millisecond temporal resolution. Our data resolve the elusive dynamics of 40 nm polystyrene nanoparticles trapped within depletion force potentials in polyethylene glycol solutions, enabling to differentiate the conditions leading to extended trapping times from those leading to transient localization. Numerical simulations corroborate our experimental findings, elucidating how the interplay between thermophoresis and diffusiophoresis governs nanoparticle dynamics. These insights deepen our mechanistic understanding of optothermal trapping and unlock opportunities for single-molecule studies, nanoscale assembly, and targeted drug delivery.

physics.optics↗

Reconfigurable Magnetic Nanopore Platform for Selective Trapping

Solid-state nanopores offer a powerful platform for nanoscale analysis of individual analytes, including biomolecules and functionalized nanoparticles, by confining them within a precisely defined sensing region. However, their inherently passive operation restricts practical applications, as they cannot precisely control particle position or dynamics inside the pore. Here, we introduce magnetic nanopore architectures that integrate a ferromagnetic layer into the nanopore system. Acting as a magnetic discontinuity within an otherwise uniformly magnetized film, the nanopore generates localized stray magnetic fields that enable magnetic tweezing of magnetic nanoparticles, which can be functionalized with fluorescent biomolecules. Importantly, the nanopore geometry is designed to reversibly switch between a nearly uniform magnetization state and a magnetic flux-closure state through the application of short magnetic field pulses of controlled amplitude. This capability allows the magnetic tweezing effect to be selectively activated or deactivated, enabling controlled capture and release of tagged biomolecules on demand. As a proof of concept, we demonstrate the selective magnetic trapping of fluorescent magnetic particles. These findings pave the way for reconfigurable, on-chip magnetic nanopore platforms capable of selective trapping and high-throughput single-particle detection. KEYWORDS: Nanopores, magnetic tweezers, fluorescence microscopy, vortex state, active control, magnetic nanoparticles

physics.optics↗

DNA-Origami-Assembled Rhodium Nanoantennas for Deep-UV Label-Free Single-Protein Detection

Nanoparticles of plasmonic metals have significantly to the development of spectroscopic techniques, enabling strong confinement of electromagnetic fields at the nanoscale and corresponding signal amplification. However, to date, plasmonic applications have been limited mainly to the visible and near-infrared range, as materials supporting ultraviolet resonances typically exhibit poor chemical stability and lack robust surface functionalisation methods. In this work, we address these limitations by introducing a fully programmable approach to UV plasmonics based on rhodium nanocube dimers assembled using DNA origami templates. We have developed a reliable ligand exchange strategy that allows the functionalisation of rhodium nanocubes with DNA while maintaining their colloidal stability. These DNA-modified nanocubes act as modular building blocks that can be assembled into dimers with 69% efficiency and an average gap size of 10 nm. The DNA origami design also allows for the deterministic placement of a single streptavidin protein in the plasmonic gap, unlike previous methods based on stochastic diffusion. Experiments with single-molecule autofluorescence in UV, supported by numerical simulations, show an increase in brightness of up to 22, a reduction in fluorescence lifetime, and a more than tenfold increase in the total number of detected photons. By creating a robust and versatile platform for the production of UV-resonant plasmonic nanoantennas, this work extends the functionality of plasmonics to the deep UV spectrum and opens up new possibilities for labelling-free single-protein spectroscopy.

physics.optics↗

Breaking the Low Concentration Barrier of Single-Molecule Fluorescence Quantification to the Sub-Picomolar Range

Single-molecule fluorescence techniques provide exceptional sensitivity to probe biomolecular interactions. However, their application to accurately quantify analytes at the picomolar concentrations relevant for biosensing remains challenged by a severe degradation in the signal-to-background ratio. This so-called 'low concentration barrier' is a major factor hindering the broad application of single-molecule fluorescence to biosensing. Here we break into the low concentration limit while keeping intact the confocal microscope architecture and without requiring complex microfluidics or preconcentration stages. Using fluorescence lifetime correlation spectroscopy (FLCS) and adding a diaphragm to the laser excitation beam, we achieve a limit of quantitation (LOQ) down to 0.1 pM, significantly below the state-of-the-art. We identify the physical parameters setting the LOQ and introduce a broadly applicable figure of merit (FoM) that determines the LOQ and allows for a clear comparison between experimental configurations. Our approach preserves the ability to monitor dynamic interactions, diffusion times, and distinguish species in complex mixtures. We illustrate this feature by measuring the biotin-streptavidin association rate constant which is highly challenging to assess quantitatively due to the strong affinity of the biotin-streptavidin interaction. These findings push the boundaries of single-molecule fluorescence detection for biosensing applications at sub-picomolar concentrations with high accuracy and simplified systems.

physics.optics↗

Watching lanthanide nanoparticles one at a time: characterization of their photoluminescence dynamics at the single nanoparticle level

Lanthanide nanoparticles (LnNPs) feature sharp emission lines together with millisecond emission lifetimes which makes them promising luminescent probes for biosensing and bioimaging. Although LnNPs are gathering a large interest, their photoluminescence properties at the single nanoparticle level remain largely unexplored. Here, we employ fluorescence correlation spectroscopy (FCS) and photoluminescence burst analysis to investigate the photodynamics of Sm and Eu-based LnNPs with single nanoparticle sensitivity and microsecond resolution. By recording the photoluminescence intensity and the number of contributing LnNPs, we compute the photoluminescence brightness per individual nanoparticle, and estimate the actual number of emitting centers per nanoparticle. Our approach overcomes the challenges associated with ensemble-averaged techniques and provides insights into LnNP photodynamics. Moreover, we demonstrate our microscope capability to detect and analyze LnNPs at the single nanoparticle level, monitoring both photoluminescence brightness and burst duration. These findings expand our understanding of LnNPs and pave the way for their advanced biosensing applications at the single nanoparticle level.

physics.optics↗

Unveiling the photoluminescence dynamics of gold nanoclusters with fluorescence correlation spectroscopy

Gold nanoclusters (AuNCs) have captured significant interest for their photoluminescent properties; however, their rapid photodynamics remain elusive while probed by ensemble-averaging spectroscopy techniques. To address this challenge, we use fluorescence correlation spectroscopy (FCS) to uncover the photoluminescence dynamics of colloidal Au18(SG)14 nanoclusters. Our FCS analysis reveals the photoluminescence (PL) brightness per nanocluster, elucidating the impact of photoexcitation saturation and ligand interactions. Unlike DNA-encapsulated silver nanoclusters, the gold counterparts notably exhibit minimal blinking, with moderate amplitudes and 0.2 ms characteristic times. Our data also clearly reveal the occurrence of photon antibunching in the PL emission, showcasing the quantum nature of the PL process, with each AuNC acting as an individual quantum source. Using zero-mode waveguide nanoapertures, we achieve a 16-fold enhancement of the PL brightness of individual AuNCs. This constitutes an important enabling proof-of-concept for tailoring emission properties through nanophotonics. Overall, our study bridges the gap between ensemble-averaged techniques and single-molecule spectroscopy, offering new insights into AuNC photodynamics for biosensing and imaging applications.

physics.optics↗

Ultraviolet Resonant Nanogap Antennas with Rhodium Nanocube Dimers for Enhancing Protein Intrinsic Autofluorescence

Plasmonic optical nanoantennas offer compelling solutions for enhancing light-matter interactions at the nanoscale. However, until now, their focus has been mainly limited to the visible and near-infrared regions, overlooking the immense potential of the ultraviolet (UV) range, where molecules exhibit their strongest absorption. Here, we present the realization of UV resonant nanogap antennas constructed from paired rhodium nanocubes. Rhodium emerges as a robust alternative to aluminum, offering enhanced stability in wet environments and ensuring reliable performance in the UV range. Our results showcase the nanoantenna ability to enhance the UV autofluorescence of label-free streptavidin and hemoglobin proteins. We achieve significant enhancements of the autofluorescence brightness per protein by up to 120-fold, and reach zeptoliter detection volumes enabling UV autofluorescence correlation spectroscopy (UV-FCS) at high concentrations of several tens of micromolar. We investigate the modulation of fluorescence photokinetic rates and report excellent agreement between experimental results and numerical simulations. This work expands the applicability of plasmonic nanoantennas into the deep UV range, unlocking the investigation of label-free proteins at physiological concentrations.

physics.optics↗

Achieving High Temporal Resolution in Single-Molecule Fluorescence Techniques using Plasmonic Nanoantennas

Single-molecule fluorescence techniques are essential for investigating the molecular mechanisms in biological processes. However, achieving sub-millisecond temporal resolution to monitor fast molecular dynamics remains a significant challenge. The fluorescence brightness is the key parameter that generally defines the temporal resolution for these techniques. Conventional microscopes and standard fluorescent emitters fall short in achieving the high brightness required for sub-millisecond monitoring. Plasmonic nanoantennas have been proposed as a solution, but despite huge fluorescence enhancement have been obtained with these structures, the brightness generally remains below 1 million photons/s/molecule. Therefore, the improvement of temporal resolution has been overlooked. In this article, we present a method for achieving high temporal resolution in single-molecule fluorescence techniques using plasmonic nanoantennas, specifically optical horn antennas. We demonstrate about 90% collection efficiency of the total emitted light, reaching a high fluorescence brightness of 2 million photons/s/molecule in the saturation regime. This enables observations of single molecules with microsecond binning time and fast fluorescence correlation spectroscopy (FCS) measurements. This work expands the applications of plasmonic antennas and zero-mode waveguides in the fluorescence saturation regime towards brighter single-molecule signal, faster temporal resolutions and improved detection rates to advance fluorescence sensing, DNA sequencing and dynamic studies of molecular interactions.

physics.optics↗

Ultraviolet Nanophotonics Enables Autofluorescence Correlation Spectroscopy on Label-Free Proteins With a Single Tryptophan

Using the ultraviolet autofluorescence of tryptophan aminoacids offers fascinating perspectives to study single proteins without the drawbacks of fluorescence labelling. However, the low autofluorescence signals have so far limited the UV detection to large proteins containing several tens of tryptophan residues. This limit is not compatible with the vast majority of proteins which contain only a few tryptophans. Here we push the sensitivity of label-free ultraviolet fluorescence correlation spectroscopy (UV-FCS) down to the single tryptophan level. Our results show how the combination of nanophotonic plasmonic antennas, antioxidants and background reduction techniques can improve the signal-to-background ratio by over an order of magnitude and enable UV-FCS on thermonuclease proteins with a single tryptophan residue. This sensitivity breakthrough unlocks the applicability of UV-FCS technique to a broad library of label-free proteins.

physics.optics↗

Fluorescence Brightness, Photostability and Energy Transfer Enhancement of Immobilized Single Molecules in Zero-Mode Waveguides Nanoapertures

Zero-mode waveguide (ZMW) nanoapertures are widely used to monitor single molecules beyond the range accessible to normal microscopes. However, several aspects of the ZMW influence on the photophysics of fluorophores remain inadequately documented and sometimes controversial. Here, we thoroughly investigate the ZMW influence on the fluorescence of single immobilized Cy3B and Alexa 647 molecules, detailing the interplays between brightness, lifetime, photobleaching time, total number of emitted photons and Förster resonance energy transfer (FRET). Despite the plasmonic-enhanced excitation intensity in the ZMW, we find that the photostability is preserved with similar photobleaching times as on the glass reference. Both the fluorescence brightness and the total numbers of photons detected before photobleaching are increased, with an impressive gain near five times found for Alexa 647 dyes. Finally, the single-molecule data importantly allow a loophole-free characterization of the ZMW influence on the FRET process. We show that the FRET rate constant is enhanced by 50%, demonstrating that nanophotonics can mediate the energy transfer. These results deepen our understanding of the fluorescence enhancement in ZMWs and are of immediate relevance for single-molecule biophysical applications.

physics.optics↗

Ultraviolet optical horn antennas for label-free detection of single proteins

Single-molecule fluorescence techniques have revolutionized our ability to study proteins. However, the presence of a fluorescent label can alter the protein structure and/or modify its reaction with other species. To avoid the need for a fluorescent label, the intrinsic autofluorescence of proteins in the ultraviolet offers the benefits of fluorescence techniques without introducing the labelling drawbacks. Unfortunately, the low autofluorescence brightness of proteins has greatly challenged single molecule detection so far. Here we introduce optical horn antennas, a dedicated nanophotonic platform enabling the label-free detection of single proteins in the UV. This design combines fluorescence plasmonic enhancement, efficient collection up to 85{\textdegree} angle and background screening. We detect the UV autofluorescence from immobilized and diffusing single proteins, and monitor protein unfolding and dissociation upon denaturation. Optical horn antennas open up a unique and promising form of fluorescence spectroscopy to investigate single proteins in their native states in real time.

physics.bio-ph↗

Single Photon Source from a Nanoantenna-Trapped Single Quantum Dot

Single photon sources with high brightness and subnanosecond lifetimes are key components for quantum technologies. Optical nanoantennas can enhance the emission properties of single quantum emitters, but this approach requires accurate nanoscale positioning of the source at the plasmonic hotspot. Here, we use plasmonic nanoantennas to simultaneously trap single colloidal quantum dots and enhance their photoluminescence. The nano-optical trapping automatically locates the quantum emitter at the nanoantenna hotspot without further processing. Our dedicated nanoantenna design achieves a high trap stiffness of 0.6 fN/nm/mW for quantum dot trapping, together with a relatively low trapping power of 2 mW/$μ$m$^2$. The emission from the nanoantenna-trapped single quantum dot shows 7x increased brightness, 50x reduced blinking, 2x shortened lifetime and a clear antibunching below 0.5 demonstrating true single photon emission. Combining nano-optical tweezers with plasmonic enhancement is a promising route for quantum technologies and spectroscopy of single nano-objects.

physics.optics↗

Purcell radiative rate enhancement of label-free proteins with ultraviolet aluminum plasmonics

The vast majority of proteins are intrinsically fluorescent in the ultraviolet, thanks to the emission from their tryptophan and tyrosine amino-acid constituents. However, the protein autofluorescence quantum yields are generally very low due to the prevailing quenching mechanisms by other amino acids inside the protein. This motivates the interest to enhance the radiative emission rate of proteins using nanophotonic structures. Although there have been numerous reports of Purcell effect and local density of optical states (LDOS) control in the visible range using single dipole quantum emitters, the question remains open to apply these concepts in the UV on real proteins containing several tryptophan and tyrosine amino acids arranged in a highly complex manner. Here, we report the first complete characterization of the Purcell effect and radiative rate enhancement for the UV intrinsic fluorescence of label-free \b{eta}-galactosidase and streptavidin proteins in plasmonic aluminum nanoapertures. We find an excellent agreement with a calibration performed using a high quantum yield UV fluorescent dye. Demonstrating and intensifying the Purcell effect is essential for the applications of UV plasmonics and the label-free detection of single proteins.

physics.optics↗

Preventing Corrosion of Aluminum Metal with Nanometer-Thick Films of Al2O3 Capped with TiO2 for Ultraviolet Plasmonics

Extending plasmonics into the ultraviolet range imposes the use of aluminum to achieve the best optical performance. However, water corrosion is a major limiting issue for UV aluminum plasmonics, as this phenomenon occurs significantly faster in presence of UV light, even at low laser powers of a few microwatts. Here we assess the performance of nanometer-thick layers of various metal oxides deposited by atomic layer deposition (ALD) and plasma-enhanced chemical vapor deposition (PECVD) on top of aluminum nanoapertures to protect the metal against UV photocorrosion. The combination of a 5 nm Al2O3 layer covered by a 5 nm TiO2 capping provides the best resistance performance, while a single 10 nm layer of SiO2 or HfO2 is a good alternative. We also report the influence of the laser wavelength, the laser operation mode and the pH of the solution. Properly choosing these conditions significantly extends the range of optical powers for which the aluminum nanostructures can be used. As application, we demonstrate the label-free detection of streptavidin proteins with improved signal to noise ratio. Our approach is also beneficial to promote the long-term stability of the aluminum nanostructures. Finding the appropriate nanoscale protection against aluminum corrosion is the key to enable the development of UV plasmonic applications in chemistry and biology.

physics.optics↗

Plasmonic nano-optical trap stiffness measurements and design optimization

Plasmonic nano-optical tweezers enable the non-invasive manipulation of nano-objects under low illumination intensities, and have become a powerful tool for nanotechnology and biophysics. However, measuring the trap stiffness of nanotweezers remains a complicated task, which hinders the development of plasmonic trapping. Here, we describe an experimental method to measure the trap stiffness based on the temporal correlation of the fluorescence from the trapped object. The method is applied to characterize the trap stiffness in different double nanohole apertures and explore the influence of their design parameters in relationship with numerical simulations. Optimizing the double nanohole design achieves a trap stiffness 10x larger than the previous state-of-the-art. The experimental method and the design guidelines discussed here offer a simple and efficient way to improve the performance of nano-optical tweezers.

physics.optics↗

Quantifying the Role of the Surfactant and the Thermophoretic Force in Plasmonic Nano-Optical Trapping

Plasmonic nano-tweezers use intense electric field gradients to generate optical forces able to trap nano-objects in liquids. However, part of the incident light is absorbed into the metal, and a supplementary thermophoretic force acting on the nano-object arises from the resulting temperature gradient. Plasmonic nano-tweezers thus face the challenge of disentangling the intricate contributions of the optical and thermophoretic forces. Here, we show that commonly added surfactants can unexpectedly impact the trap performance by acting on the thermophilic or thermophobic response of the nano-object. Using different surfactants in double nanohole plasmonic trapping experiments, we measure and compare the contributions of the thermophoretic and the optical forces, evidencing a trap stiffness 20x higher using sodium dodecyl sulfate (SDS) as compared to Triton X-100. This work uncovers an important mechanism in plasmonic nano-tweezers and provides guidelines to control and optimize the trap performance for different plasmonic designs.

physics.optics↗

Long-range Single Molecule Förster Resonance Energy Transfer Between Alexa Dyes in Zero-Mode Waveguides

Zero-mode waveguides (ZMW) nanoapertures milled in metal films were proposed to improve the FRET efficiency and enable single molecule FRET detection beyond the 10 nm barrier, overcoming the restrictions of diffraction-limited detection in a homogeneous medium. However, the earlier ZMW demonstrations were limited to the Atto 550 - Atto 647N fluorophore pair, asking the question whether the FRET enhancement observation was an artefact related to this specific set of fluorescent dyes. Here, we use Alexa Fluor 546 and Alexa Fluor 647 to investigate single molecule FRET at large donor-acceptor separations exceeding 10 nm inside ZMWs. These Alexa fluorescent dyes feature a markedly different chemical structure, surface charge and hydrophobicity as compared to their Atto counterparts. Our single molecule data on Alexa 546 - Alexa 647 demonstrate enhanced FRET efficiencies at large separations exceeding 10 nm, extending the spatial range available for FRET and confirming the earlier conclusions. By showing that the FRET enhancement inside a ZMW does not depend on the set of fluorescent dyes, this report is an important step to establish the relevance of ZMWs to extend the sensitivity and detection range of FRET, while preserving its ability to work on regular fluorescent dye pairs.

physics.optics↗