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/μm2. The emission from the nanoantenna-trapped single quantum dot shows 7× increased brightness, 50× reduced blinking, 2× 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.
The poor photostability and low brightness of protein autofluorescence have been major limitations preventing the detection of label-free proteins at the single-molecule level. Overcoming these ...issues, we report here a strategy to promote the photostability of proteins and use their natural tryptophan autofluorescence in the ultraviolet (UV) for fluorescence correlation spectroscopy (FCS). Combining enzymatic oxygen scavengers with antioxidants and triplet-state quenchers greatly promotes the protein photostability, reduces the photobleaching probability, and improves the net autofluorescence detection rate. Our results show that the underlying photochemical concepts initially derived for organic visible fluorescent dyes are quite general. Using this approach, we achieved UV fluorescence correlation spectroscopy on label-free streptavidin proteins containing only 24 tryptophan residues, 6.5× fewer than the current state-of-the-art. This strategy greatly extends the possibility of detecting single label-free proteins with the versatility of single-molecule fluorescence without requiring the presence of a potentially disturbing external fluorescent marker. It also opens new perspectives to improve the UV durability of organic devices.
Plasmonic nanotweezers 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 nanotweezers 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 20× higher using sodium dodecyl sulfate (SDS) as compared to Triton X-100. This work uncovers an important mechanism in plasmonic nanotweezers and provides guidelines to control and optimize the trap performance for different plasmonic designs.
Spontaneous emission of fluorescent molecules or quantum dots is radiated along all directions when emitters are diluted in a liquid solution, which severely limits the amount of collected light. ...Besides, the emission direction does not carry any useful information and cannot be used to sort different molecules. To go beyond these limits, optical antennas have been recently introduced as conceptual tools to control the radiation properties for nanoemitters fixed on a substrate. Despite intense recent research, controlling the luminescence directivity remains a challenge for emitters with random positions and orientations, which is a key for several biomolecular screening applications. Here, we present full directional control of the fluorescence emission from molecules in water solution by an optical antenna made of a nanoaperture surrounded by a periodic set of shallow grooves in a gold film. For each emission wavelength, the fluorescence beam can be directed along a specific direction with a given angular width, hereby realizing a micrometer-size dispersive antenna. We demonstrate the fluorescence beaming results from an interference phenomenon and provide physical optics guidelines to control the fluorescence directivity by tuning the groove–nanoaperture distance. This photon-sorting capability provides a new approach for high-sensitivity screening of molecular species in solution.
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° 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.
The development of quantum plasmonic circuitry requires efficient coupling between quantum emitters and plasmonic waveguides. A major experimental challenge is to simultaneously maximize the surface ...plasmon propagation length, the coupling efficiency into the plasmonic mode, and the Purcell factor. Addressing this challenge is also the key to enabling long-range energy transfer between quantum nanoemitters. Here, we use a dual-beam scanning confocal microscope to carefully investigate the interactions between fluorescent nanoparticles and surface plasmons on single-crystalline silver nanowires. By exciting the fluorescent nanoparticles via nanowire surface plasmons, we maximize the light–matter interactions and reach coupling efficiencies up to 44% together with 24× lifetime reduction and 4.1 μm propagation lengths. This improved optical performance enables the demonstration of long-range plasmon-mediated fluorescence energy transfer between two nanoparticles separated by micrometer distance. Our results provide guidelines toward practical realizations of efficient long-range fluorescence energy transfer for integrated plasmonics and quantum nano-optics.
Single molecule detection provides detailed information about molecular structures and functions but it generally requires the presence of a fluorescent marker which can interfere with the activity ...of the target molecule or complicate the sample production. Detecting a single protein with its natural UV autofluorescence is an attractive approach to avoid all the issues related to fluorescence labeling. However, the UV autofluorescence signal from a single protein is generally extremely weak. Here, we use aluminum plasmonics to enhance the tryptophan autofluorescence emission of single proteins in the UV range. Zero-mode waveguide nanoapertures enable the observation of the UV fluorescence of single label-free β-galactosidase proteins with increased brightness, microsecond transit times, and operation at micromolar concentrations. We demonstrate quantitative measurements of the local concentration, diffusion coefficient, and hydrodynamic radius of the label-free protein over a broad range of zero-mode waveguide diameters. Although the plasmonic fluorescence enhancement has generated a tremendous interest in the visible and near-infrared parts of the spectrum, this work pushes further the limits of plasmonic-enhanced single molecule detection into the UV range and constitutes a major step forward in our ability to interrogate single proteins in their native state at physiological concentrations.
Plasmonic antennas have a profound impact on nanophotonics as they provide efficient means to manipulate light and enhance light–matter interactions at the nanoscale. However, the large absorption ...losses found in metals can severely limit the plasmonic applications in the visible spectral range. Here, we demonstrate the effectiveness of an alternative approach using all-dielectric nanoantennas based on silicon dimers to enhance the fluorescence detection of single molecules. The silicon antenna design is optimized to confine the near-field intensity in the 20 nm nanogap and reach a 270-fold fluorescence enhancement in a nanoscale volume of λ3/1800 with dielectric materials only. Our conclusions are assessed by combining polarization resolved optical spectroscopy of individual antennas, scanning electron microscopy, numerical simulations, fluorescence lifetime measurements, fluorescence burst analysis, and fluorescence correlation spectroscopy. This work demonstrates that all-silicon nanoantennas are a valid alternative to plasmonic devices for enhanced single molecule fluorescence sensing, with the additional key advantages of reduced nonradiative quenching, negligible heat generation, cost-efficiency, and complementary metal–oxide–semiconductor (CMOS) compatibility.
Plasmonic nanoapertures generate strong field gradients enabling efficient optical trapping of nano-objects. However, because the infrared laser used for trapping is also partly absorbed into the ...metal leading to Joule heating, plasmonic nano-optical tweezers face the issue of local temperature increase. Here, we develop three independent methods based on molecular fluorescence to quantify the temperature increase induced by a 1064 nm trapping beam focused on single and double nanoholes milled in gold films. We show that the temperature in the nanohole can be increased by 10 °C even at the moderate intensities of 2 mW/μm2 used for nano-optical trapping. The temperature gain is found to be largely governed by the ohmic losses into the metal layer, independently of the aperture size, double-nanohole gap, or laser polarization. The techniques developed therein can be readily extended to other structures to improve our understanding of nano-optical tweezers and explore heat-controlled chemical reactions in nanoapertures.
Using the ultraviolet autofluorescence of tryptophan amino acids offers fascinating perspectives to study single proteins without the drawbacks of fluorescence labeling. 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.
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