Higher Order Tunable Fano Resonances in Multilayer Nanocones

We present a computational study of the plasmonic response of a gold–silica–gold multilayered nanostructure based on truncated nanocones. Symmetry breaking is introduced by rotating the nanostructure and by offsetting the layers. Nanocones with coaxial multilayers show dipole–dipole Fano resonances with resonance frequencies depending on the polarization of the incident light, which can be changed by rotating the nanostructure. By breaking the axial symmetry, plasmonic modes of distinct angular momenta are strongly mixed, which provide a set of unique and higher order tunable Fano resonances. The plasmonic response of the multilayered nanocones is compared to that of multishell nanostructures with the same volume and the former are discovered to render visible high-order dark modes and to provide sharp tunable Fano resonances. In particular, higher order tunable Fano resonances arising in non-coaxial multilayer nanocones can vary the plasmon lines at various spectral regions simultaneously, which makes these nanostructures greatly suitable for plasmon line shaping both in the extinction and near field spectra.     

Fano Resonances Induced by Strong Interactions Between Dipole and Multipole Plasmons in T-Shaped Nanorod Dimer

A simple T-shaped plasmonic nanostructure composed of two perpendicular coupled nanorods is proposed to produce strong Fano resonances. By the near-field coupling between the “bright” dipole and “dark” quadrupole plasmons of the nanorods, a deep Fano dip is formed in the extinction spectrum, which can be well fitted by the Fano interference model. The effects of the geometry parameters including nanorod length, coupling gap size, and coupling location to the Fano resonances are analyzed in detail, and a very high refractive index sensitivity is achieved by the Fano resonance. Also by adjusting the incident polarization direction, double Fano resonances can be formed by the interferences of the dipole, quadrupole, and hexapole plasmons. The proposed nanorod dimer structure is agile, and a trimer which supports double Fano resonances can be easily formed by introducing a third perpendicular coupled nanorod. The proposed T-shaped nanorod dimer structure may have applications in the fields of biological sensing and plasmon-induced transparency.     

Single-Particle Spectroscopy of Supported Silver Clusters on Silicon: Substrate Effects on Localized Surface Plasmons

The presence of a surrounding medium strongly affects the spectral properties of localized surface plasmons at metallic nanoparticles. Vice versa, plasmonic resonances have large impact on the electric polarization in a surrounding or supporting material. For applications, e.g., in light-converting devices, the coupling of localized surface plasmons with polarizations in semiconducting substrates is of particular importance. Using photoemission electron microscopy with tunable laser excitation, we perform single-particle spectroscopy of silver nanoclusters directly grown on Si(100). Two distinct localized surface plasmon modes are observed as resonances in the two-photon photoemission signals from individual silver clusters. The strengths of these resonances strongly depend on the polarization of the exciting electric field, which allows us to assign them to plasmon modes with polarizations parallel and perpendicular, respectively, to the supporting silicon substrate. Our mode assignment is supported by simulations which provide insight into the mutual interaction of charge oscillations at the particle surface with electric polarizations at the silver/silicon interface.

     

Fluorescence Resonance Energy Transfer Near Thin Films on Surfaces

A theory is developed for resonant energy transfer between donor and acceptor molecules outside of a solid coated with a thin film. The energy transfer rate is expressed in terms of a second-rank tensor, allowing one to consider all possible orientations of the transition dipole moments of the molecules. The theory of images is employed to construct expressions valid in the near-field approximation. This theory is extended to the full electrodynamic theory valid over all distances. Connections are made between the expressions for the image charges and the Fresnel coefficients from optics. It is found that the energy transfer rates are strongly influenced by surface resonances, including the interfacial surface plasmons and the two-dimensional plasmon of a metallic film. The possibility of the film supporting Fabry–Perot resonator modes is discussed.     

Förster Energy Transfer in the Vicinity of Two Metallic Nanospheres (Dimer)

We present a detailed theoretical analysis of the Förster energy transfer process when a pair of molecules (donor and acceptor) is located nearby a cluster of two metallic nanospheres (dimer). We consider the case in which plasmonic resonances are within the overlap between the donor emission and acceptor absorption spectra, as well as the case that excludes such resonances from the aforementioned spectral overlap. Moreover, we explore the dependence of the Förster energy transfer rate on different dimer configurations (size and separation of nanospheres) and several dipole orientations of molecules. The dimer perturbs strongly the Förster energy transfer rate when plasmons are excited, donor dipole is oriented along the longitudinal axis of the dimer, and the radii of nanospheres and the sphere-gap distance are on the order of a few nanometers. In case of plasmonic excitation, the Förster energy transfer rate is degraded as the sphere-gap distance and size of the nanoparticles increase due to the dephasing of electronic motion arising from ohmic losses of metal. Also, we study the Förster efficiency influenced by the dimer, finding that the high efficiency region (delimited by the Förster radius curve) is reduced as a consequence of significant enhancement of the direct donor decay rate. Our study could impact applications that involve Förster energy transfer.     

Quantum Theory of Surface Plasmon Polaritons: Planar and Spherical Geometries

A quantum theory of retarded surface plasmons on a metal–vacuum interface is formulated, by analogy with the well-known and widely exploited theory of exciton-polaritons. The Hamiltonian for mutually interacting instantaneous surface plasmons and transverse electromagnetic modes is diagonalized with recourse to a Hopfield–Bogoljubov transformation, in order to obtain a new family of modes, to be identified with retarded plasmons. The interaction with nearby dipolar emitters is treated with a full quantum formalism based on a general definition of modal effective volumes. The illustrative cases of a planar surface and of a spherical nanoparticle are considered in detail. In the ideal situation of absence of dissipation, as an effect of the conservation of in-plane wavevector, retarded plasmons on a planar surface represent true stationary states (which are usually called surface plasmon polaritons), whereas retarded plasmons in a spherical nanoparticle, characterized by frequencies that overlap with the transverse electromagnetic continuum, become resonances with a finite radiative broadening. The theory presented constitutes a suitable full quantum framework for the study of nonperturbative and nonlinear effects in plasmonic nanosystems.     

Experimental Study on Localized Surface Plasmon Mode Hybridization in the Near and Mid Infrared

We investigate plasmon excitations within a regular grating of double-layered gold/insulator nanoparticles in the infrared and visible spectral region. Provided a flat gold film as substrate, strong coupling between the localized surface plasmon modes and their image-like excitations in the metal is observed. The interaction results in a strong red shift of the plasmon mode as well as the splitting of the modes into levels of different angular momenta, often referred to as plasmon hybridization. The diameters of the nanoparticles are designed in a way that the splitting of the resonances occurs in the spectral region between 0.1 and 1 eV, thus being accessible using an infrared microscope. Moreover, we investigated the infrared absorption signal of gratings that contain two differently sized nanoparticles. The interaction between two autonomous localized surface plasmon excitations is investigated by analyzing their crossing behavior. In contrast to the interaction between localized surface plasmons and propagating plasmon excitations which results in pronounced anticrossing, the presented structures show no interaction between two autonomous localized surface plasmons. Finally, plasmon excitations of the nanostructured surfaces in the visible spectral region are demonstrated through photographs acquired at three different illumination angles. The change in color of the gratings demonstrates the complex interaction between propagating and localized surface plasmon modes.     

Controllable Coupling of Localized and Propagating Surface Plasmons to Tamm Plasmons

We theoretically investigate the coupling between Tamm plasmons and localized surface plasmons (LSPs) as well as propagating surface plasmons (PSPs) in a multilayer structure consisting of a metallic nanowire array and a spatially separated metal–dielectric Bragg reflector (DBR). A clear anticrossing behavior of the resonances is observed in the dispersion diagram resulting from the coupling, which is well explained by the coupled oscillator model. The coupling also creates new hybrid LSP or PSP modes with narrow bandwidths and unique spectral features. Upon the excitation of these hybrid modes, the local fields underneath the nanowires for the hybrid LSPs or near the lower metal layer surface for the hybrid PSPs are both enhanced greatly as compared with those achieved in the structure without DBR, which has potential applications in nonlinear optics and surface-enhanced spectroscopies.     

Structure Effect on Sensitivity of Gold Nanoslits Studied by Spectral Integration Method

Gold nanoslit arrays have multiple resonances due to localized plasmons, Bloch wave surface plasmon polaritons, and Wood’s anomaly. Different structures result in different resonances and affect the detection sensitivity of the nanoslits. We systematically compared different structure parameters such as period, slit widths, and gold film thickness by using a spectral integration method. The experimental results show the detection sensitivity had an optimal value for a 500-nm period and 130-nm-thick nanoslits. Moreover, the sensitivity increases with the decrease of the slit widths. It was improved about three times when the size was reduced from 230 to 56 nm. The optimized structure can achieve a detection limit of 5 × 10⁻⁶ refractive index unit when the stability is 0.2%. Combining multispectral images and the spectral integration method, we demonstrate real-time and multiple detections of antigen–antibody interactions.     

Sensitive label-free biosensors by using gap plasmons in gold nanoslits

The detection sensitivities of gap plasmons in gold nanoslit arrays are studied and compared with surface plasmons on outside surface. The nanoslit arrays were fabricated in a 130 nm-thick gold film with various slit widths. For transverse-magnetic (TM) incident wave, the 600 nm-period nanoslit array shows two distinguishable transmission peaks corresponding to the resonances of gap plasmons and surface plasmons, respectively. The surface sensitivities for both modes were compared by coating thin SiO(2) film and different biomolecules on the nanoslit arrays. Our experimental results verify gap plasmons are more sensitive than conventional surface plasmons. Its detection sensitivity increases with the decrease of slit width. The gap plasmon is one order of magnitude sensitive than the surface plasmon for slit widths smaller than 30 nm. We attribute this high sensitivity to the large overlap between biomolecules and nanometer-sized gap plasmons.     

High-Performance Dye-Sensitized Solar Cells Based on Morphology-Controllable Synthesis of ZnO–ZnS Heterostructure Nanocone Photoanodes

High-density and well-aligned ZnO–ZnS core–shell nanocone arrays were synthesized on fluorine-doped tin oxide glass substrate using a facile and cost-effective two-step approach. In this synthetic process, the ZnO nanocones act as the template and provide Zn²⁺ ions for the ZnS shell formation. The photoluminescence spectrum indicates remarkably enhanced luminescence intensity and a small redshift in the UV region, which can be associated with the strain caused by the lattice mismatch between ZnO and ZnS. The obtained diffuse reflectance spectra show that the nanocone-based heterostructure reduces the light reflection in a broad spectral range and is much more effective than the bare ZnO nanocone and nanorod structures. Dye-sensitized solar cells based on the heterostructure ZnO–ZnS nanocones are assembled, and high conversion efficiency (η) of approximately 4.07% is obtained. The η improvement can be attributed primarily to the morphology effect of ZnO nanocones on light-trapping and effectively passivating the interface surface recombination sites of ZnO nanocones by coating with a ZnS shell layer.     

Time-resolved fluorescence of DAPI in solution and bound to polydeoxynucleotides

Fluorescence decay studies, obtained by multifrequency phase-modulation fluorometry, have been performed on DAPI in solution and complexed with natural and synthetic polydeoxynucleotides. DAPI decay at pH 7 was decomposed using two exponential components of 2.8 and 0.2 ns of lifetime values, respectively. The double exponential character of the decay was maintained over a large pH range. Phase- and modulation-resolved spectra, collected between 420 and 550 nm, have indicated at least two spectral components associated with the two lifetime values. This, plus the observation of the dependence of the emission spectrum on the excitation wavelength, suggests a lifetime heterogeneity originating from ground-state molecular conformers, partially affected by pH changes. DAPI complexed with natural polydeoxynucleotides retained most of the features of DAPI decay in solution, except for the value of the long lifetime component that was longer (approximately 4 ns) and the relative fractional fluorescence intensities of the two components that were inverted. AT polymers/DAPI complexes show single exponential decay. Solvent shielding when DAPI is bound to DNA changes the indole ring solvation and stabilizes the longer lifetime decay component. For poly(GC)/DAPI complex, the decay was similar to that of free DAPI in solution, proving the dependence on the polydeoxynucleotides sequence the different types of binding and the reliability of the fluorescence method to solve them.     

Mechanisms and Rates of Decay of Marine Viruses in Seawater

Loss rates and loss processes for viruses in coastal seawater from the Gulf of Mexico were estimated with three different marine bacteriophages. Decay rates in the absence of sunlight ranged from 0.009 to 0.028 h^-1, with different viruses decaying at different rates. In part, decay was attributed to adsorption by heat-labile particles, since viruses did not decay or decayed very slowly in seawater filtered through a 0.2-μm-pore-size filter (0.2-μm-filtered seawater) and in autoclaved or ultracentrifuged seawater but continued to decay in cyanide-treated seawater. Cyanide did cause decay rates to decrease, however, indicating that biological processes were also involved. The observations that decay rates were often greatly reduced in 0.8- or 1.0-μm-filtered seawater, whereas bacterial numbers were not, suggested that most bacteria were not responsible for the decay. Decay rates were also reduced in 3-μm-filtered or cycloheximide-treated seawater but not in 8-μm-filtered seawater, implying that flagellates consumed viruses. Viruses added to flagellate cultures decayed at 0.15 h^-1, corresponding to 3.3 viruses ingested flagellate^-1 h^-1. Infectivity was very sensitive to solar radiation and, in full sunlight, decay rates were 0.4 to 0.8 h^-1. Even when UV-B radiation was blocked, rates were as high as 0.17 h^-1. Calculations suggest that in clear oceanic waters exposed to full sunlight, most of the virus decay, averaged over a depth of 200 m, would be attributable to solar radiation. When decay rates were averaged over 24 h for a 10-m coastal water column, loss rates of infectivity attributable to sunlight were similar to those resulting from all other processes combined. Consequently, there should be a strong diel signal in the concentration of infectious viruses. In addition, since sunlight destroys infectivity more quickly than virus particles, a large proportion of the viruses in seawater is probably not infective.     

Fluorescence lifetime distributions of 1,6-diphenyl-1,3,5-hexatriene in phospholipid vesicles

The fluorescence emission properties of 1,6-diphenyl-1,3,5-hexatriene (DPH) in 1,2-dipalmitoyl-3-sn-phosphatidylcholine and 1,2-dimyristoyl-3-sn-phosphatidylcholine multilamellar vesicles have been measured by using multifrequency phase fluorometry. The fluorescence decay of DPH in the phospholipid vesicles has been analyzed by assuming either that the decay is made up of a discrete sum of exponential components or that the decay is made up of one or more continuous distributions of lifetime components. The fit of the decay curve using exponentials required at least two terms, and the reduced X2 was relatively large. The fit using a continuous distribution of lifetime values used two continuous components. Several symmetric distribution functions were used: uniform, Gaussian, and Lorentzian. The distribution function that best described the decay was the Lorentzian. The full width at half-maximum of the Lorentzian distribution was about 0.6 ns at temperatures below the phase transition temperature. At the phospholipid phase transition and at higher temperatures, the distribution became quite narrow, with a width of about 0.1 ns. It is proposed that the lifetime distribution is generated by a continuum of different environments of the DPH molecule characterized by different dielectric constants. Below the transition temperature in the gel phase, the dielectric constant gradient along the membrane normal determines the distribution of decay rates. Above the transition, in the liquid-crystalline phase, the translational and rotational mobility of the DPH molecule increases, and the DPH experiences an average environment during the excited-state lifetime. Consequently, the distribution becomes narrower.(ABSTRACT TRUNCATED AT 250 WORDS)     

Time-resolved single tryptophan fluorescence in photoactive yellow protein monitors changes in the chromophore structure during the photocycle via energy transfer

We show from time-resolved fluorescence intensity and depolarization experiments that the fluorescence of the unique tryptophan W119 of PYP is quenched by energy transfer to the 4-hydroxycinnamoyl chromophore. Whereas the intensity decay has a time constant of 0.18 ns in P, the decay in the absence of the cofactor (apo-PYP) has a single exponential lifetime of 4.8 ns. This difference in lifetime with and without acceptor can be explained quantitatively on the basis of energy transfer and the high-resolution X-ray structure of P, which allows an accurate calculation of the kappa2 factor. Fluorescence depolarization experiments with donor and acceptor indicate that both are immobilized so that kappa2 is constant on the fluorescence time scale. Using background illumination from an LED emitting at 470 nm, we measured the time-resolved fluorescence in a photostationary mixture of P and the intermediates I2 and I2'. The composition of the photostationary mixture depends on pH and changes from mainly I2 at low pH to predominantly I2' at high pH. The I2/I2' equilibrium is pH-dependent with a pKa of approximately 6.3. In I2 the lifetime increases to approximately 0.82 ns. This is not due to a change in distance or to the increase in spectral overlap but is primarily a consequence of a large decrease in kappa2. Kappa2 was calculated from the available X-ray structures and decreases from approximately 2.7 in P to 0.27 in I2. This change in kappa2 is caused by the isomerization of the acceptor, which leads to a reorientation of its transition dipole moment. We have here a rare case of the kappa2 factor dominating the change in energy transfer. The fluorescence decay in the light is pH-dependent. From an SVD analysis of the light/dark difference intensity decay at a number of pH values, we identify three species with associated lifetimes: P (0.18 ns), I2 (0.82 ns), and X (0.04 ns). On the basis of the pH dependence of the amplitudes associated with I2 and X, with a pKa of approximately 6.3, we assign the third species to the signaling state I2'. The absorption spectra of the 0.82 and 0.04 ns species were calculated from the pH dependence of their fluorescence amplitudes and of the photostationary light/dark difference absorption spectra. The lambda(max) values of these spectra (372 and 352 nm) identify the 0.82 and 0.04 ns components with I2 and I2', respectively, and validate the fluorescence data analysis. The mutant E46Q allows a further test of the energy transfer explanation, since lowering the pH in the dark leads to a bleached state with an increased spectral overlap but without the isomerization-induced decrease in kappa2. The measured lifetime of 0.04 ns is in excellent agreement with predictions based on energy transfer and the X-ray structure.     

Dimerization and inter-chromophore distance of Cph1 phytochrome from Synechocystis,as monitored by fluorescence homo and hetero energy transfer

We investigated the dimerization of phytochrome Cph1 from the cyanobacterium Synechocystis by fluorescence resonance energy transfer (FRET). As donor we used the chromophore analogue phycoerythrobilin (PEB) and as acceptor either the natural chromophore phycocyanobilin (PCB; hetero transfer) or PEB (homo transfer). Both chromophores bind in a 1:1 stoichiometry to apo-monomers expressed in Escherichia coli. Energy transfer was characterized by time-resolved fluorescence intensity and anisotropy decay after excitation of PEB by picosecond pulses from a tunable Ti-sapphire laser system. ApoCph1 was first assembled with PEB at a low stoichiometry of 0.1. The remaining sites were then sequentially titrated with PCB. In the course of this titration, the mean lifetime of PEB decreased from 3.33 to 1.25 ns in the P(r) form of Cph1, whereas the anisotropy decay was unaffected. In the P(fr)/P(r) photoequilibrium (about 65% P(fr)), the mean lifetime decreased significantly less, to 1.67 ns. These observations provide strong support for inter-chromophore hetero energy transfer in mixed PEB/PCB dimers. The reduced energy transfer in P(fr) may be due to a structural difference but is at least in part due to the difference in spectral overlap, which was 4.1 x 10(-13) and 1.6 x 10(-13) cm(3) M(-1) in P(r) and P(fr), respectively. From the changes in the mean lifetime, rates of hetero energy transfer of 0.68 and 0.37 ns(-1) were calculated for the P(r) form and the P(fr)/P(r) photoequilibrium, respectively. Sequential titration of apo Cph1 with PEB alone to full occupancy did not affect the intensity decay but led to a substantial increase in depolarization. This is the experimental signature of homo energy transfer. Values for the rate of energy transfer k(HT) (0.47 ns(-1)) and the angle 2theta between the transition dipole moment directions (2theta = 45 +/- 5 degrees) were determined from an analysis of the concentration dependence of the anisotropy at five different PEB/Cph1 stoichiometries. The independently determined rates of hetero and homo energy transfer are thus of comparable magnitude and consistent with the energy transfer interpretation. Using these results and exploiting the 2-fold symmetry of the dimer, the chromophore-chromophore distance R(DA) was calculated and found to be in the range 49 A < R(DA) < 63 A. Further evidence for energy transfer in Cph1 dimers was obtained from dilution experiments with PEB/PEB dimers: the lifetime was unchanged, but the anisotropy increased as the dimers dissociated with increasing dilution. These experiments allowed a rough estimate of 5 +/- 3 microM for the dimer dissociation constant. With the deletion mutant Cph1Delta2 that lacks the carboxy terminal histidine kinase domain less energy transfer was observed suggesting that in this mutant dimerization is much weaker. The carboxy terminal domain of Cph1 that is involved in intersubunit trans-phosphorylation and signal transduction thus plays a dominant role in the dimerization. The FRET method provides a sensitive assay to monitor the association of Cph1 monomers.     

Tryptophan fluorescence studies of melanotropins in the amphiphile-water interface of reversed micelles

We report studies on the interaction of α-melanocyte stimulating hormone (α-MSH) and a synthetic analogue (MSH-I) with reverse micelles prepared from the amphiphilic sodium bis(2-ethylhexyl)sulfosuccinate in isooctane. The tripeptide lysyl-tryptophyl- lysine and the isolated amino acid tryptophan were also investigated as simpler compounds interacting with the micelles. Tryptophan fluorescence parameters (spectral position of emission band, anisotropy, and lifetime decay) demonstrated that in the presence of reverse micelles the environment around the fluorophore is less polar and more rigid than bulk water. Those parameters are sensitive to the changes induced in the micelles by the presence of water. In large micelles having a water/amphiphile molar ratio above 10, the modifications detected by fluorescence are small and the location of the fluorophore is not affected by a further increase in the concentration of the bulk water. The results, with additional support from quenching experiments, indicated that the different compounds occupy different positions in the large reverse micelles, but in any case they are in the interface region, without dispersing into the bulk water. From decay associated spectra, conformations were identified showing different degrees of tryptophan exposition to polar and nonpolar local environments. The conformation related to the long lifetime has its tryptophan more exposed to water while that associated to the intermediate lifetime has that residue stabilized in nonpolar media. The native hormone α-MSH and the analogue MSH-I present similar conformations in dry micelles. However, in buffer and in the large hydrated micelles, differences in conformations are evident, and could be related to the different physiological activity of the peptides. Received: 4 August 1999 / Revised version: 17 December 1999 / Accepted: 4 January 2000     

A TROSY relayed HCCH-COSY experiment for correlating adenine H2/H8 resonances in uniformly 13C-labeled RNA molecules

A new TROSY relayed HCCH-COSY pulse sequence is introduced for correlating adenine H2 and H8 resonances in ¹³C-labeled RNA molecules. The pulse scheme provides substantial improvements in signal-to-noise compared to previously suggested experiments, and therefore will be suitable for NMR studies of larger RNA molecules. The experiment provides ¹³C chemical shifts for all carbon nuclei in the adenine base. This is advantageous for resolving spectral overlap in larger RNA molecules and provides a starting point for measuring additional parameters for these carbons in the adenine spin system.     

Electrostatic interactions between α-helix dipoles in crystals of an uncharged helical undecapeptide

The electrostatic interactions between α-helix dipoles in the crystals of an uncharged helical undecapeptide have been studied in detail. The electrostatic interaction energy between one helix dipole and its 26 nearest neighbors is approximately ?23 kcal mol^?1. A very similar result is obtained when calculating the interactions between one helix dipole and all 988 helix dipoles occurring within a distance of 75 Å. It therefore appears that in these crystals of completely uncharged molecules large, favorable electrostatic interactions occur.     

Highly Sensitive Plasmonic Sensor Based on Fano Resonance from Silver Nanoparticle Heterodimer Array on a Thin Silver Film

We investigate the optical spectrum of a multilayer metallic slab using multiple-scattering formalism. A thin silver film is attached to a periodic array of heterodimers consisting of two vertically spaced silver nanoparticles of different radii. Depending on the radius of nanoparticles, heterodimer array presents a simple nanoscale geometry which gives rise to remarkable plasmonic properties of multipolar resonances. Due to the coherent interference of the localized nanoparticle plasmons (discrete mode) and surface plasmon polaritons of metallic film (continuous mode), the reflection spectrum represents a sharp asymmetric Fano resonance dip, which is strongly sensitive to the refractive index of the surrounding embedded dielectric host. The physical features contribute to a highly efficient plasmonic sensor for refractive index sensing with sensitivity of ～1.5?×?10^?3 RIU/nm.