Strong plasmonic fluorescence enhancement of individual plant light-harvesting complexes

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, accompanied by a 109-fold decrease in the average (amplitude-weighted) fluorescence lifetime from approximately 3.5 ns down to 32 ps, corresponding to an excitation enhancement of 63-fold and emission enhancement of up to 3.8-fold. This large enhancement is due to the strong spectral overlap of the longitudinal localized surface plasmon resonance of the utilized AuNRs and the absorption or emission bands of LHCII. This study provides an inexpensive strategy to explore the fluorescence dynamics of weakly emitting photosynthetic light-harvesting complexes at the single molecule level.Comment: 23 pages, 6 figures, 2 supplementary figures, and supplementary equation

Spectrally selective fluorescence imaging of Chlorobaculum tepidum reaction centers conjugated to chelator-modified silver nanowires

A polyhistidine tag (His-tag) present on Chlorobaculum tepidum reaction centers (RCs) was used to immobilize photosynthetic complexes on a silver nanowire (AgNW) modified with nickel-chelating nitrilo-triacetic acid (Ni-NTA). The optical properties of conjugated nanostructures were studied using wide-field and confocal fluorescence microscopy. Plasmonic enhancement of RCs conjugated to AgNWs was observed as their fluorescence intensity dependence on the excitation wavelength does not follow the excitation spectrum of RC complexes in solution. The strongest effect of plasmonic interactions on the emission intensity of RCs coincides with the absorption spectrum of AgNWs and is observed for excitation into the carotenoid absorption. From the absence of fluorescence decay shortening, we attribute the emission enhancement to increase of absorption in RC complexes

Silver Nanoparticle Aggregates as Highly Efficient Plasmonic Antennas for Fluorescence Enhancement

The enhanced local fields around plasmonic structures can lead to enhancement of the excitation and modification of the emission quantum yield of fluorophores. So far, high enhancement of fluorescence intensity from dye molecules was demonstrated using bow-tie gap antenna made by e-beam lithography. However, the high manufacturing cost and the fact that currently there are no effective ways to place fluorophores only at the gap prevent the use of these structures for enhancing fluorescence-based biochemical assays. We report on the simultaneous modification of fluorescence intensity and lifetime of dye-labeled DNA in the presence of aggregated silver nanoparticles. The nanoparticle aggregates act as efficient plasmonic antennas, leading to more than 2 orders of magnitude enhancement of the average fluorescence. This is comparable to the best-reported fluorescence enhancement for a single molecule but here applies to the average signal detected from all fluorophores in the system. This highlights the remarkable efficiency of this system for surface-enhanced fluorescence. Moreover, we show that the fluorescence intensity enhancement varies with the plasmon resonance position and measure a significant reduction (300×) of the fluorescence lifetime. Both observations are shown to be in agreement with the electromagnetic model of surface-enhanced fluorescence

Characterization of the aggregation-induced enhanced emission of N,N'-bis(4-methoxysalicylide)benzene-1,4-diamine

© 2015 Springer Science+Business Media New York. N,N′-bis(4-methoxysalicylide)benzene-1,4-diamine (S1) was synthesized from 4-methoxysalicylaldehyde and p-phenylenediamine and it was found to exhibit interesting aggregation-induced emission enhancement (AIEE) characteristics. In aprotic solvent, S1 displayed very weak fluorescence, whilst strong emission was observed when in protic solvent. The morphology characteristics and luminescent properties of S1 were determined from the fluorescence and UV absorption spectra, SEM, fluorescence microscope and grading analysis. Analysis of the single crystal diffraction data infers that the intramolecular hydrogen bonding constitutes to a coplanar structure and orderly packing in aggregated state, which in turn hinders intramolecular C-N single bond rotation. Given that the three benzene rings formed a large plane conjugated structure, the fluorescence emission was significantly enhanced. The absolute fluorescence quantum yield and fluorescence lifetime also showed that radiation transition was effectively enhanced in the aggregated state. Moreover, the AIEE behavior of S1 suggests there is a potential application in the fluorescence sensing of some volatile organic solvents

Strong antenna-enhanced fluorescence of a single light-harvesting complex shows photon antibunching

The nature of the highly efficient energy transfer in photosynthetic light-harvesting complexes is a subject of intense research. Unfortunately, the low fluorescence efficiency and limited photostability hampers the study of individual light-harvesting complexes at ambient conditions. Here we demonstrate an over 500-fold fluorescence enhancement of light-harvesting complex 2 (LH2) at the single-molecule level by coupling to a gold nanoantenna. The resonant antenna produces an excitation enhancement of circa 100 times and a fluorescence lifetime shortening to ~\n20 ps. The radiative rate enhancement results in a 5.5-fold-improved fluorescence quantum efficiency. Exploiting the unique brightness, we have recorded the first photon antibunching of a single light-harvesting complex under ambient conditions, showing that the 27 bacteriochlorophylls coordinated by LH2 act as a non-classical single-photon emitter. The presented bright antenna-enhanced LH2 emission is a highly promising system to study energy transfer and the role of quantum coherence at the level of single complexes

Interference-induced splitting of resonances in spontaneous emission

We study the resonance fluorescence from a coherently driven four-level atom in the Y-type configuration. The effects of quantum interference induced by spontaneous emission on the fluorescence properties of the atom are investigated. It is found that the quantum interference resulting from cascade emission decays of the atom leads to a splitting of resonances in the excited level populations calculated as a function of light detuning. For some parameters, interference assisted enhancement of inner sidebands and narrowing of central peaks may also occur in the fluorescence spectrum. We present a physical understandingof our numerical results using the dressed state description of the atom-light interaction.Comment: 7 pages including 7 figure

Spatial imaging of modifications to fluorescence lifetime and intensity by individual Ag nanoparticles

Highly ordered periodic arrays of silver nanoparticles have been fabricated which exhibit surface plasmon resonances in the visible spectrum. We demonstrate the ability of these structures to alter the fluorescence properties of vicinal dye molecules by providing an additional radiative decay channel. Using fluorescence lifetime imaging microscopy (FLIM), we have created high resolution spatial maps of the molecular lifetime components; these show an order of magnitude increase in decay rate from a localized volume around the nanoparticles, resulting in a commensurate enhancement in the fluorescence emission intensity.Comment: 3 pages, 2 figures, submitted Applied Physics Letter

Surface plasmon enhanced fluorescence: self-consistent classical treatment in the quasi-static limit

The problem of enhanced molecular emission in close proximity to dielectric and metallic interfaces is of great importance for many physical and biological applications. Here we present an exact treatment of the problem from the view point of classical electromagnetism. Self-consistent analytical theory of the surface fluorescence enhancement is developed for configurations consisting of an emitter in proximity to core-shell metal-dielectric nanoparticles. The dependence of the fluorescence enhancement on the excitation laser and fluorescence frequencies and distance of the emitter to the nanoparticle interface are studied. The developed theory predicts enhanced fluorescence at intermediate distances as well as emission quenching into non-radiative surface plasmon (SP) modes dominating the response for short distances. The conditions for optimal emission enhancement for two core-shell configurations are determined. The theory can be applied toward analyzes and optimization of various applications related to SP enhance fluorescence spectroscopy