Steady-State Probe-Partitioning FRET: A Simple and Robust Tool for the Study of Membrane Phase Behavior

An experimental strategy has been developed specifically for the study of composition-dependent phase behavior in multi-component artificial membranes. The strategy is based on steady-state measurements of fluorescence resonance energy transfer between freely diffusing membrane probe populations, and it is well suited for the rapid generation of large data sets. Presented in this paper are the basic principles that guide the experiment's design, the derivation of an underlying mathematical model that serves to interpret the data, and experimental results that confirm the model's predictive power.Comment: 7 pages, 4 figure

Annealed Silver-Island Films for Applications in Metal-Enhanced Fluorescence: Interpretation in Terms of Radiating Plasmons

The effects of thermally annealed silver island films have been studied with regard to their potential applicability in applications of metal-enhanced fluorescence, an emerging tool in nano-biotechnology. Silver island films were thermally annealed between 75 and 250°C for several hours. As a function of both time and annealing temperature, the surface plasmon band at ≈420 nm both diminished and was blue shifted. These changes in plasmon resonance have been characterized using both absorption measurements, as well as topographically using Atomic Force Microscopy. Subsequently, the net changes in plasmon absorption are interpreted as the silver island films becoming spherical and growing in height, as well as an increased spacing between the particles. Interestingly, when the annealed surfaces are coated with a fluorescein-labeled protein, significant enhancements in fluorescence are osbserved, scaling with annealing temperature and time. These observations strongly support our recent hypothesis that the extent of metal-enhanced fluorescence is due to the ability of surface plasmons to radiate coupled fluorophore fluorescence. Given that the extinction spectrum of the silvered films is comprised of both an absorption and scattering component, and that these components are proportional to the diameter cubed and to the sixth power, respectively, then larger structures are expected to have a greater scattering contribution to their extinction spectrum and, therefore, more efficiently radiate coupled fluorophore emission. Subsequently, we have been able to correlate our increases in fluorescence emission with an increased particle size, providing strong experiment evidence for our recently reported metal-enhanced fluorescence, facilitated by radiating plasmons hypothesis

Microscopic theory of surface-enhanced Raman scattering in noble-metal nanoparticles

We present a microscopic model for surface-enhanced Raman scattering (SERS) from molecules adsorbed on small noble-metal nanoparticles. In the absence of direct overlap of molecular orbitals and electronic states in the metal, the main enhancement source is the strong electric field of the surface plasmon resonance in a nanoparticle acting on a molecule near the surface. In small particles, the electromagnetic enhancement is strongly modified by quantum-size effects. We show that, in nanometer-sized particles, SERS magnitude is determined by a competition between several quantum-size effects such as the Landau damping of surface plasmon resonance and reduced screening near the nanoparticle surface. Using time-dependent local density approximation, we calculate spatial distribution of local fields near the surface and enhancement factor for different nanoparticles sizes.Comment: 8 pages, 6 figures. Considerably extended final versio

Photonic mode density effects on single-molecule fluorescence blinking

We investigated the influence of the photonic mode density (PMD) on the triplet dynamics of individual chromophores on a dielectric interface by comparing their response in the presence and absence of a nearby gold film. Lifetimes of the excited singlet state were evaluated in ordet to measure directly the PMD at the molecules position. Triplet state lifetimes were simultaneously determined by statistical analysis of the detection time of the fluorescence photons. The observed singlet decay rates are in agreement with the predicted PMD for molecules with different orientations. The triplet decay rate is modified in a fashion correlated to the singlet decay rate. These results show that PMD engineering can lead to an important suppression of the fluorescence, introducing a novel aspect of the physical mechanism to enhance fluorescence intensity in PMD-enhancing systems such as plasmonic devices

Size-Dependence of the Wavefunction of Self-Assembled Quantum Dots

The radiative and non-radiative decay rates of InAs quantum dots are measured by controlling the local density of optical states near an interface. From time-resolved measurements we extract the oscillator strength and the quantum efficiency and their dependence on emission energy. From our results and a theoretical model we determine the striking dependence of the overlap of the electron and hole wavefunctions on the quantum dot size. We conclude that the optical quality is best for large quantum dots, which is important in order to optimally tailor quantum dot emitters for, e.g., quantum electrodynamics experiments.Comment: 5 pages, 3 figure

Studying Flow Close to an Interface by Total Internal Reflection Fluorescence Cross Correlation Spectroscopy: Quantitative Data Analysis

Total Internal Reflection Fluorescence Cross Correlation Spectroscopy (TIR-FCCS) has recently (S. Yordanov et al., Optics Express 17, 21149 (2009)) been established as an experimental method to probe hydrodynamic flows near surfaces, on length scales of tens of nanometers. Its main advantage is that fluorescence only occurs for tracer particles close to the surface, thus resulting in high sensitivity. However, the measured correlation functions only provide rather indirect information about the flow parameters of interest, such as the shear rate and the slip length. In the present paper, we show how to combine detailed and fairly realistic theoretical modeling of the phenomena by Brownian Dynamics simulations with accurate measurements of the correlation functions, in order to establish a quantitative method to retrieve the flow properties from the experiments. Firstly, Brownian Dynamics is used to sample highly accurate correlation functions for a fixed set of model parameters. Secondly, these parameters are varied systematically by means of an importance-sampling Monte Carlo procedure in order to fit the experiments. This provides the optimum parameter values together with their statistical error bars. The approach is well suited for massively parallel computers, which allows us to do the data analysis within moderate computing times. The method is applied to flow near a hydrophilic surface, where the slip length is observed to be smaller than 10nm, and, within the limitations of the experiments and the model, indistinguishable from zero.Comment: 18 pages, 12 figure

Rapid interrogation of the physical and chemical characteristics of salbutamol sulphate aerosol from a pressurised metered-dose inhaler (pMDI)

Individual micron-sized solid particles from a Salamols pharmaceutical inhaler are stably captured in air using an optical trap for the first time. Raman spectroscopy of the levitated particles allows online interrogation of composition and deliquescent phase change within a high humidity environment that mimics the particle’s travel from inhaler to lun

Nanoscale control of Ag nanostructures for plasmonic fluorescence enhancement of near-infrared dyes

Potential utilization of proteins for early detection and diagnosis of various diseases has drawn considerable interest in the development of protein-based detection techniques. Metal induced fluorescence enhancement offers the possibility of increasing the sensitivity of protein detection in clinical applications. We report the use of tunable plasmonic silver nanostructures for the fluorescence enhancement of a near-infrared (NIR) dye (Alexa Fluor 790). Extensive fluorescence enhancement of ∼2 orders of magnitude is obtained by the nanoscale control of the Ag nanostructure dimensions and interparticle distance. These Ag nanostructures also enhanced fluorescence from a dye with very high quantum yield (7.8 fold for Alexa Fluor 488, quantum efficiency (Qy) = 0.92). A combination of greatly enhanced excitation and an increased radiative decay rate, leading to an associated enhancement of the quantum efficiency leads to the large enhancement. These results show the potential of Ag nanostructures as metal induced fluorescence enhancement (MIFE) substrates for dyes in the NIR “biological window” as well as the visible region. Ag nanostructured arrays fabricated by colloidal lithography thus show great potential for NIR dye-based biosensing applications

A calibration method for broad-bandwidth cavity enhanced absorption spectroscopy performed with supercontinuum radiation

An efficient calibration method has been developed for broad-bandwidth cavity enhanced absorption spectroscopy. The calibration is performed using phase shift cavity ring-down spectroscopy, which is conveniently implemented through use of an acousto-optic tunable filter (AOTF). The AOTF permits a narrowband portion of the SC spectrum to be scanned over the full high-reflectivity bandwidth of the cavity mirrors. After calibration the AOTF is switched off and broad-bandwidth CEAS can be performed with the same light source without any loss of alignment to the set-up. We demonstrate the merits of the method by probing transitions of oxygen molecules O-2 and collisional pairs of oxygen molecules (O-2)(2) in the visible spectral range

Spin-boson models for quantum decoherence of electronic excitations of biomolecules and quantum dots in a solvent

We give a theoretical treatment of the interaction of electronic excitations (excitons) in biomolecules and quantum dots with the surrounding polar solvent. Significant quantum decoherence occurs due to the interaction of the electric dipole moment of the solute with the fluctuating electric dipole moments of the individual molecules in the solvent. We introduce spin boson models which could be used to describe the effects of decoherence on the quantum dynamics of biomolecules which undergo light-induced conformational change and on biomolecules or quantum dots which are coupled by Forster resonant energy transfer.Comment: More extended version, to appear in Journal of Physics: Condensed Matter. 13 pages, 3 figure