Plasmonically enhanced fluorescence is a widely studied and applied phenomenon, however only a comparative theoretical and experimental analyses of coupled fluorophores and plasmonic nanoresonators makes it possible to uncover, how this phenomenon can be controlled. A numerical optimization method was applied to design configurations that are capable of resulting in an enhancement of excitation and emission, moreover of both phenomena simultaneously in coupled Cy5 dye molecule and gold nanorod systems. Parametric sensitivity studies revealed, how the fluorescence enhancement depends on the molecule's location, distance and orientation. Coupled systems designed for simultaneous improvement exhibited the highest (intermediate directional) total fluorescence enhancement, which is accompanied by intermediate sensitivity to the molecule's parameters, except the location and orientation sensitivity at the excitation wavelength. Gold nanorods with a geometry corresponding to the predicted optimal configurations were synthesized, and DNA strands were used to control the Cy5 dye molecule distance from the nanorod surface via hybridization of the Cy5-labelled oligonucleotide. State-of-the-art dSTORM microscopy was used to accomplish a proof-of-concept experimental demonstration of the theoretically predicted (directional) total fluorescence enhancement. The measured fluorescence enhancement was in good agreement with theoretical predictions, thus providing a complete kit to design and prepare coupled nanosystems exhibiting plasmonically enhanced fluorescence.
Optical response of silicon (SiV) and nitrogen (NV) vacancy diamond color centers coupled to silver and gold nanorod dimers was numerically inspected. Optimization of the coupled emitter - nanorod dimer configurations was performed to attain the highest possible fluorescence enhancement by enhancing the excitation and emission of color centers simultaneously through plasmonic antenna resonances. To minimize losses conditional optimization was realized by setting a criterion regarding the minimum quantum efficiency of the coupled system (cQE). Restricted symmetric and allowed asymmetric antenna…
A novel numerical methodology has been developed, which makes possible to optimize arbitrary emitting dipole and plasmonic nano-resonator configuration with an arbitrary objective function. By selecting quantum efficiency as the objective function that has to be maximized at preselected Purcell factor criteria, optimization of plasmonic nanorod based configurations has been realized to enhance fluorescence of NV and SiV color centers in diamond. Gold and silver nanorod based configurations have been optimized to enhance excitation and emission separately, as well as both processes simultaneous…
We report on the dynamics of photodegradation and subsequent recovery of two-photon fluorescence in a dye-doped polymer. The energy dependence suggests that photo-degradation is a linear process while recovery is entropic. Such recovery could be useful to high-intensity devices such as two-photon absorbers, which can be used in many applications.
Tunable composite materials with interesting physical behavior can be designed through integrating unique optical properties of solid nanostructures with the facile responses of soft matter to weak external stimuli, but this approach remains challenged by their poorly controlled co-assembly at the mesoscale. Using scalable wet chemical synthesis procedures, we fabricated anisotropic gold-silica-dye colloidal nanostructures and then organized them into the device-scale (demonstrated for square inch cells) electrically tunable composites by simultaneously invoking molecular and colloidal self-as…
Body-of-Revolution Finite-Element Model of Plasmon-Enhanced Fluorescence
University of Birmingham（伯明翰大学）；Kyambogo University（坎博戈大学）；University of Pretoria（比勒陀利亚大学）；National Institute for Theoretical and Computational Sciences (NITheCS)（国家理论与计算科学研究所）
We propose to achieve super-resolution in far-field imaging by use of dual-dye-doped nanoparticles. The nanoparticles with a diameter of a few nanometers are co-doped with two types of dye molecules, namely, Cy3 and Cy5, at a controllable ratio. Due to the short distances between the dye molecules confined in the nanoparticles, Forster resonant energy transfer can occur between the Cy3 and Cy5 molecules with high efficiency. Therefore, the Cy5 molecules can quench the fluorescence emission from the Cy3 molecules in the outer region of focal spot of the excitation beam, thereby enhancing the re…
In this work, we use a site-selective functionalization strategy to decorate plasmonic nanopores with one or more fluorescent dyes. Using an easy and robust fabrication method, we manage to build single plasmonic rings on top of dielectric nanotubes with different inner diameters. The modulation of the dimension of the nanopores allows us to both tailor their field confinement and their Purcell Factor in the visible spectral range. In order to investigate how the changes in geometry influence the fluorescence emission efficiency, thiol-conjugated dyes are anchored on the plasmonic ring, thus f…
Electromagnetic coupling between subradiant plasmons and dye molecular excitons analyzed by spectral changes in ultrafast surface-enhanced fluorescence
We report a comparison of two photonic techniques for single-molecule sensing: fluorescence nanoscopy and optoplasmonic sensing. As the test system, oligonucleotides with and without fluorescent labels are transiently hybridized to complementary docking strands attached to gold nanorods. Comparing the measured single-molecule kinetics helps to examine the influence of fluorescent labels as well as factors arising from different sensing geometries. Our results demonstrate that DNA dissociation is not significantly altered by the fluorescent label, while DNA association is affected by geometric …
We used fluorescence spectroscopic measurements as a probe to study the self-healing properties of anthraquinone derivative molecules doped in poly(methyl methacrylate) (PMMA). 2,4-dibromo anthraquinone dye doped in PMMA recovers after photodegradation. Its dynamics differs from other anthraquinone derivative molecules. This could be due to the relatively heavier bromine atom attached to one of the carbon atoms of the benzene ring. In this paper, we will discuss the self-healing properties of 2,4-dibromo anthraquinone doped in PMMA matrix. We also tested the correlated chromophore domain model…
We report on the generation, and momentum space distribution of fluorescence emission from individual SiO2 microsphere on dye coated Au mirror. The molecular fluorescence emission mediated via whispering gallery modes of the sphere is studied using polarization resolved optical energy-momentum micro-spectroscopy. Our experiments reveal intensity dependence of split modes of the cavity as a function of in-plane wavevector and emission polarization in the far field. The exotic far-field distribution can be understood by sphere-image sphere model that further reveals the polarization dependence o…
A surrounding electromagnetic environment can engineer spontaneous emissions from quantum emitters through the Purcell effect. For instance, a plasmonic antenna can efficiently confine an electromagnetic field and enhance the fluorescent process. In this study, we demonstrate that a photonic microcavity can modulate plasmon-enhanced fluorescence by engineering the local electromagnetic environment. Consequently, we constructed a plasmon-enhanced emitter (PE-emitter), which comprised a nanorod and a nanodiamond, using the nanomanipulation technique. Furthermore, we controlled a polystyrene sphe…
Over the last decade, single-molecule optical microscopy has become the gold-standard approach to decipher complex molecular processes in cellular environments. [1-3] Single-molecule fluorescence microscopy has several advantages such as ease of application, high sensitivity, low invasiveness and versatility due the large number of available fluorescent probes. It bears however some drawbacks related to the poor photostability of organic dye molecules [4] and auto-fluorescent proteins [5-7] and and to the relatively large size of semiconductor nanoparticles in the context of live cell applicat…
Zero mode waveguide (ZMW) nanoapertures efficiently confine the light down to the nanometer scale and overcome the diffraction limit in single molecule fluorescence analysis. However, unwanted adhesion of the fluorescent molecules on the ZMW surface can severely hamper the experiments. Therefore a proper surface passivation is required for ZMWs, but information is currently lacking on both the nature of the adhesion phenomenon and the optimization of the different passivation protocols. Here we monitor the influence of the fluorescent dye (Alexa Fluor 546 and 647, Atto 550 and 647N) on the non…
Scanning microphotoluminescence is used to characterise the fluorescence from a dye-loaded polymer deposited on a 5 x 5 nanoantenna dipole array. Vertical and horizontal scans show anisotropic emission patterns.
Current optical detection schemes for single molecules require light absorption, either to produce fluorescence or direct absorption signals. This severely limits the range of molecules that can be detected, because most molecules are purely refractive. Metal nanoparticles or dielectric resonators detect non-absorbing molecules by a resonance shift in response to a local perturbation of the refractive index, but neither has reached single-protein sensitivity. The most sensitive plasmon sensors to date detect single molecules only when the plasmon shift is amplified by a highly polarizable labe…
We present indications of thermalization and cooling of quasi-particles, a precursor for quantum condensation, in a plasmonic nanoparticle array. We investigate a periodic array of metallic nanorods covered by a polymer layer doped with an organic dye at room temperature. Surface lattice resonances of the array---hybridized plasmonic/photonic modes---couple strongly to excitons in the dye, and bosonic quasi-particles which we call plasmon-exciton-polaritons (PEPs) are formed. By increasing the PEP density through optical pumping, we observe thermalization and cooling of the strongly coupled PE…
Background-free fluorescence detection in multidimensional electronic spectroscopy promises high sensitivity compared to conventional approaches. Here we explore the sensitivity limits of multidimensional electronic spectroscopy. We present a fluorescence-detected multidimensional electronic spectrometer based on a visible white-light continuum. As a demonstration of sensitivity, we report room temperature two-dimensional coherence maps of vibrational quantum coherences in a laser dye at optical densities ~2-3 orders of magnitude lower than conventional approaches. This high sensitivity is ena…
Plasmonic coupling of metallic nanoparticles and adjacent pigments can dramatically increase the brightness of the pigments due to the enhanced local electric field. Here, we demonstrate that the fluorescence brightness of a single plant light-harvesting complex (LHCII) can be significantly enhanced when coupled to single gold nanorods (AuNRs). The AuNRs utilized in this study were prepared via chemical reactions, and the hybrid system was constructed using a simple and economical spin-assisted layer-by-layer technique. Enhancement of fluorescence brightness of up to 240-fold was observed, acc…
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 inten…
We have fabricated layered nanocomposite consisting of a nanoporous anodic alumina sublayer (AOA), an ultrathin metal-containing polymer Langmuir-Blodgett (LB) film coating AOA, and multi-walled carbon nanotube (MCNT) - bundles which are arranged on the LB-film. MCNTs were preliminarily chemically modified by carboxyl groups and functionalized by stearic acid. We have experimentally observed an enhancement of Raman light scattering on surface plasmons in the LB-monolayers. This enhancement is due to charge and energy transfer. We demonstrate that propidium iodide (PI) fluorescence is quenched …
The detection of single molecules has facilitated many advances in life- and material-sciences. Commonly, it founds on the fluorescence detection of single molecules, which are for example attached to the structures under study. For fluorescence microscopy and sensing the crucial parameters are the collection and detection efficiency, such that photons can be discriminated with low background from a labeled sample. Here we show a scheme for filtering the excitation light in the optical detection of single stranded labeled DNA molecules. We use the narrow-band filtering properties of a hot atom…
We present a novel experimental setup in which magnetic and optical tweezers are combined for torque and force transduction onto single filamentous molecules in a transverse configuration to allow simultaneous mechanical measurement and manipulation. Previously we have developed a super-resolution imaging module which in conjunction with advanced imaging techniques such as Blinking assisted Localisation Microscopy (BaLM) achieves localisation precision of single fluorescent dye molecules bound to DNA of ~30 nm along the contour of the molecule; our work here describes developments in producing…
We demonstrated remote plasmonic enhancement (RPE) by a dense random array of Ag nanoislands (AgNIs) that were partially gold-alloyed and attached with column-structured silica (CSS) overlayer of more than 100 nm in thickness. The physical and chemical protection of the CSS layer could lead to reducing the mutual impact between analyte molecules and metal nanostructures. RPE plate was realized just by sputtering and chemical immersion processes, resulting in high productivity. We found a significant enhancement on the order of 10$^7$-fold for Raman scattering and 10$^2$-fold for fluorescence b…
