Time-of-Flight Photon Spectroscopy: A Simple Scheme To Monitor Simultaneously Spectral and Temporal Fluctuations of Emission on Single Nanoparticles

Here we report on a novel scheme for spectral analysis that exploits the wavelength dependence of the time-of-flight of a photon in a dispersive medium. This versatile and cost-effective method, named time-of-flight photon spectroscopy (TOFPS), has the major advantage of being compatible with time-correlated single-photon counting experiments. Consequently, each photon acquired during an experiment is characterized by two parameters, its absolute time of arrival and its color, respectively. As a result, the spectral and temporal fluctuations of the emission of a single nano-object can be derived from a single measurement. As a proof of the concept, we demonstrate in the paper that the method can be used to perform Raman spectroscopy as well as fluorescence spectroscopy. We emphasize that TOFPS proves to be very efficient for improving signal-to-noise ratio in fluorescence correlation spectroscopy measurements by subsequent spectral filtering and to record luminescence spectra from single metallic particles. We demonstrate that the opportunity of simultaneously recording spectral and temporal fluctuations could be used to sort particles of different shapes inside a sample. TOFPS furthermore allows developing a new type of time interval distribution analysis which correlates the time interval between two photons and their corresponding color shift. It is applied to the analysis of the two-photon excited luminescence of a single gold nanorod. This method has a potential for a broad range of applications, among which time-resolved SERS spectroscopy and analysis of the dynamics of emission processes can be handled with new statistical approaches based on the correlation of spectral and temporal fluctuations

One-photon excited luminescence of single gold particles diffusing in solution under pulsed illumination

Here we report on the visible luminescence of single gold nanospherical particles diffusing in water excited by a pulsed-laser at 488 nm. The signal studied by fluorescence correlation spectroscopy does not display the expected characteristics. The main deviation is obtained for the diffusion time that depends on the laser irradiance. Additional advanced methods of measurements have been implemented to further characterize the emission. These methods have allowed us to demonstrate that the luminescence does not blink even in the picosecond domain and that it does not photobleach either. The comparison between the signals obtained under pulsed and continuous excitations at the same wavelength suggests that the increase in the particle temperature plays a role in the non-linear increase in the luminescence intensity with the excitation power. As in the case of two-photon excited luminescence, it implies that a model describing the luminescence process for a single particle diffusing in liquid must take into account the whole system composed of the gold particle, the capping ligands and the surrounding water

Influence of polarization and wavelength on two-photon excited luminescence of single gold nanospheres

The Brownian rotation of a nearly spherical gold particle capped with ligands can be observed in the correlation profile of the intensity of the two-photon excited luminescence. Here we report on a multi-parameter study of the luminescence properties, including spectral and polarization analysis of the signal at the single particle level. First, the data confirm the role of the radiative de-excitation of the surface plasmons in the luminescence process. Secondly, the results obtained at low power indicate that the capped particle in water can be approximatively described as a spherical rotor acting in the far-field as a point-like absorption and emission dipole of fixed directions. In addition, we show that the dynamics of the ligands, induced by the heat transfer from the particle to its environment, can be partly controlled by the choice of excitation wavelength

Manipulation and Optical Detection of Colloidal Functional Plasmonic Nanostructures in Microfluidic Systems

The very strong optical resonances of plasmonic nanostructures can be harnessed for sensitive detection of chemical and biomolecular analytes in small volumes. Here we describe an approach towards optical biosensing in microfluidic systems using plasmonic structures (functionalized gold nanoparticles) in colloidal suspension. The plasmonic nanoparticles provide the optical signal, in the form of resonant light scattering or absorption, and the microfluidic environment provides means for selectively manipulating the nanoparticles through fluid dynamics and electric fields. In the first part we discuss recent literature on functionalized colloidal particles and the methods for handling them in microfluidic systems. Then we experimentally address aspects of nanoparticle functionalization, detection through plasmonic resonant light scattering under dark-field illumination and the electrokinetic behavior of the particles under the action of an alternating electric field

Ligand-Induced Anisotropy of the Two-Photon Luminescence of Spherical Gold Particles in Solution Unraveled at the Single Particle Level

Here we report on the visible luminescence properties of individual spherical gold particles in solution, obtained by two-photon excited fluorescence correlation spectroscopy and by an original dual Rayleigh-fluorescence method, correlating the Rayleigh scattering and the luminescence fluctuations of the same particle. The results demonstrate that the power needed to observe the two-photon excited visible luminescence depends on the illuminated particle and that the corresponding emission is anisotropic at low power. These observations combined with the evolution of the dynamics of the luminescence with respect to excitation power are interpreted by the presence of unique emissive surface states that are randomly switched off and on by the heat-induced movement of the molecular coating. These characteristics, which remain hidden in macroscopic experiments, have important implications with respect to the potential use of the particles as labels in two-photon imaging in aqueous samples

The intrinsic luminescence of individual plasmonic nanostructures in aqueous suspension by photon time-of-flight spectroscopy

We have studied the intrinsic one-photon excited luminescence of freely diffusing gold nanoparticles of different shapes in aqueous suspension. Gold nanospheres were used as a reference, since their luminescence has been investigated previously and their light absorption and scattering properties are described analytically by Mie theory. We then studied gold nanobipyramids and nanostars that have recently gained interest as building blocks for new plasmonic nanosensors. The aim of our study is to determine whether the luminescence of gold nanoparticles of complex shape (bipyramids and nanostars) is a plasmon-assisted process, in line with the conclusions of recent spectroscopic studies on spheres and nanorods. Our study has been performed on particles in suspension in order to avoid any artefact from the heterogeneous environment created when particles are deposited on a substrate. We employ a recently developed photon time-of-flight method in combination with correlation spectroscopy of the light scattered by the particles to probe the luminescent properties of individual particles based on a particle-by-particle spectral analysis. Furthermore, we have performed resonant light scattering spectroscopic measurements on the same samples. Our work demonstrates the power of our time-of flight method for uncovering the plasmonic signatures of individual bipyramids and nanostars during their brief passage in the focal volume of a confocal set-up. These spectral features of individual particles remain hidden in macroscopic measurements. We find that the intrinsic photoluminescence emission of gold bipyramids and gold nanostars is mediated by their localized surface plasmons

Fluorescence correlation spectroscopy reveals strong fluorescence quenching of FITC adducts on PEGylated gold nanoparticles in water and the presence of fluorescent aggregates of desorbed thiolate ligands

Colloidal gold particles functionalised with oligoethylene-glycolated disulfide ligands and fluorescent moieties derived from fluorescein isothiocyanate (FITC) have been prepared and studied in aqueous suspension using fluorescence correlation spectroscopy (FCS). FCS probes the dynamics of the particles at the single object level, and reveals the desorption of fluorescent ligands which subsequently aggregate into larger (slower diffusing) objects. Cross-correlation spectroscopy of the FITC fluorescence and the Rayleigh-Mie scattering (RM-FCCS) of the gold cores shows that the only detectable fluorescent objects are free ligands and aggregates not associated with a gold particle. The fluorescence of bound fluorophores is quenched making their fluorescence too weak to be detected. FCS and RM-FCCS are useful tools for characterising functionalised noble metal particles in solution, under conditions similar to those used in optical bio-imaging. Desorption of thiolates from gold nanoparticles needs to be taken into account when working with these materials at low concentration

Optical extinction and scattering cross sections of plasmonic nanoparticle dimers in aqueous suspension

Absolute extinction and scattering cross sections for gold nanoparticle dimers were determined experimentally using a chemometric approach involving singular-value decomposition of the extinction and scattering spectra of slowly aggregating gold nanospheres in aqueous suspension. Quantitative spectroscopic data on plasmonic nanoparticle assemblies in liquid suspension are rare, in particular for particles larger than 40 nm, and in this work we demonstrate how such data can be obtained directly from the aggregating suspension. Our method can analyse, non invasively, the evolution of several sub-populations of nanoparticle assemblies. It may be applied to other self-assembling nanoparticle systems with an evolving optical response. The colloidal systems studied here are based on 20, 50 and 80 nm gold nanospheres in aqueous solutions containing sodium lipoate. In these systems, the reversible dimerisation process can be controlled using pH and ionic strength, and this control is rationalised in terms of DLVO theory. The dimers were identified in suspension by their translational and rotational diffusion through scattering correlation spectroscopy. Moreover, their gigadalton molecular weight was measured using electrospray charge-detection mass spectrometry, demonstrating that mass spectrometry can be used to study nanoparticles assemblies of very high molecular mass. The extinction and scattering cross sections calculated in the discrete-dipole approximation (DDA) agree very well with those obtained experimentally using our approach