On-chip light sheet illumination for nanoparticle tracking in microfluidic channels.

A simple and inexpensive method is presented to efficiently integrate light sheet illumination in a microfluidic chip for dark-field microscopic tracking and sizing of nanoparticles. The basic idea is to insert an optical fiber inside a polydimethylsiloxane (PDMS) elastomer microfluidic chip and use it as a cylindrical lens. The optical fiber is in this case no longer seen as only an optical waveguide but as a ready-made micro-optical component that is inexpensive and easy to source.

Determination of photoluminescence quantum yields in dilute solution using non-monochromatic excitation light.

The photoluminescence (PL) quantum yields (QYs) of fluorophores in dilute solutions can be determined fluorimetrically according to the comparative method employing standards of known PLQY. This method has recently been demonstrated to become more robust when the absorption of the excitation light and the PL emission are measured simultaneously using a transmitted light detector integrated in the fluorimeter. Herein, aided by fiber-coupled spectroscopic equipment and computerized data processing, we elaborate on this method by measuring the full corrected intensity spectrum of the excitation light transmitted through the sample.

Brownian Motion and Large Electric Polarizabilities Facilitate Dielectrophoretic Capture of Sub-200 nm Gold Nanoparticles in Water.

Dielectrophoresis can move small particles using the force resulting from their polarization in a divergent electric field. In liquids, it has most often been applied to micrometric objects such as biological cells or latex microspheres. For smaller particles, the dielectrophoretic force becomes very small and the phenomenon is furthermore perturbed by Brownian motion.

Spectroscopic and Hydrodynamic Characterisation of DNA-Linked Gold Nanoparticle Dimers in Solution using Two-Photon Photoluminescence.

Two-photon photoluminescence (TPPL) emission spectra of DNA-gold nanoparticle (AuNP) monoconjugates and the corresponding DNA-linked AuNP dimers are obtained by photon time-of-flight spectroscopy. This technique is combined with two-photon photoluminescence fluctuation correlation spectroscopy (TPPL-FCS) to simultaneously monitor the optical and hydrodynamic behaviour of these nano-assemblies in solution, with single-particle sensitivity and microsecond temporal resolution. In this study, the AuNPs have an average core diameter of 12 nm, which renders their dark-field plasmonic light scattering too weak for single-particle imaging.

Photoluminescence spectra and quantum yields of gold nanosphere monomers and dimers in aqueous suspension.

The intrinsic one-photon excited photoluminescence (PL) of dimers and monomers of gold spheres suspended in water was studied by combining photon time-of-flight spectroscopy (PTOFS) and light scattering fluctuation correlation spectroscopy (LS-FCS). The samples are obtained by precisely controlling the dimerization of aqueous colloidal systems based on 50 and 80 nm gold nanospheres. The combination of PTOFS and LS-FCS enables the separate spectroscopic study of monomers and dimers even though they exist as a mixture in the samples.

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.

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.

Resonant light scattering spectroscopy of gold, silver and gold-silver alloy nanoparticles and optical detection in microfluidic channels.

Dark field resonant light scattering by gold and silver nanoparticles enables the detection and spectroscopy of such particles with high sensitivity, down to the single-particle level, and can be used to implement miniaturised optical detection schemes for chemical and biological analysis. Here, we present a straightforward optical spectroscopic methodology for the quantitative spectrometric study of resonant light scattering (RLS) by nanoparticles. RLS spectroscopy is complementary to UV-visible absorbance measurements, and we apply it to the characterisation and comparison of different types of gold, silver and gold-silver alloy nanoparticles.

Foam films in the presence of functionalized gold nanoparticles.

Dry aqueous foams made of anionic surfactant (SDS) and spherical gold nanoparticles are studied by small angle X-ray scattering and by optical techniques. To obtain stable foams, the surfactant concentration is well above the critical micelle concentration. The specular reflectivity signal obtained on a very thin film (thickness 20 nm) shows that functionalized nanoparticles (17 nm typical size) are trapped within the film in the form of a single monolayer.

Folic acid-targeted mesoporous silica nanoparticles for two-photon fluorescence.

New nanotools for the imaging of cancer cells have been synthesized. Two-photon dye-doped 3-aminopropyltriethoxysilane-grafted mesoporous silica nanoparticles (MSN) have been grafted with folic acid (FA) functionalized PEG groups. Amine-PEG groups were first reacted with an activated ester derivative of FA.

The effectiveness of essential-state models in the description of optical properties of branched push-pull chromophores.

In this paper we present the synthesis, spectroscopic characterization and theoretical modelling of two pairs of correlated dipolar and octupolar donor-acceptor conjugated chromophores, based on the triphenylamine branching centre. The two pairs of chromophores differ for the electron withdrawing end-groups. Linear absorption, fluorescence and two-photon absorption of all the compounds in different solvents can be well described by the use of charge-resonance theoretical models based on essential-state descriptions of the electronic structure, and taking into account the coupling to effective molecular vibrations and to polar solvation degrees of freedom.

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.

Probing the interactions between disulfide-based ligands and gold nanoparticles using a functionalised fluorescent perylene-monoimide dye.

The binding of disulfides to gold nanoparticles was investigated using fluorescence spectroscopy and a perylene-monoimide dye coupled to a dissymmetric disulfide via a tetraethyleneglycolalkyl chain (PMImSS). Quantum chemical calculations using the polarizable continuum model (PCM) predict a strong quenching of perylene-monoimide fluorescence by gold nanoparticles as a result of efficient excitation energy transfer from the dye to the particle. Such quenching is indeed observed when unfunctionalised gold nanoparticles are added to a solution of PMImSS.

[Mesoporous silica nanoparticles for two-photon fluorescence].

Mesoporous silica nanoparticles have unique properties: a specific large surface or a narrow casting of the sizes of pores. The perspectives of use are the creation of new tools for the premature diagnosis. For these potential biological applications, the harmlessness of these nanoparticles must be established.

Two-photon transitions in quadrupolar and branched chromophores: experiment and theory.

A combined experimental and theoretical study is conducted on a series of model compounds in order to assess the combined role of branching and charge symmetry on absorption, photoluminescence, and two-photon absorption (TPA) properties. The main issue of this study is to examine how branching of quadrupolar chomophores can lead to different consequences as compared to branching of dipolar chromophores. Hence, three structurally related pi-conjugated quadrupolar chromophores symmetrically substituted with donor end groups and one branched structure built from the assembly of three quadrupolar branches via a common donor moiety are used as model compounds.

Quenching of molecular fluorescence on the surface of monolayer-protected gold nanoparticles investigated using place exchange equilibria.

The insertion of fluorescently labeled thiols into the protecting self-assembled monolayer on the surface of gold nanoparticles through place exchange reactions and the effects of this insertion on the photophysical properties of the fluorophores are investigated. Analysis of solution-phase fluorescence data using a dynamic equilibrium model yields the equilibrium constant for the place exchange equilibrium, as well as the relative fluorescence brightness of the fluorophores on the particle surface. In all cases we find a significant quenching of the fluorescence, and potential reasons for this quenching are discussed.

A NADPH substitute for selective photo-initiation of reductive bioprocesses via two-photon induced electron transfer.

A NADPH substitute where the nicotinamide moiety is replaced by a chromophoric unit having much larger two-photon absorption cross-section and able to transfer electrons to flavins only upon excitation is described as an effective two-photon nanotrigger for selective photo-activation of electron transfer in bioreductive processes.

Effects of (multi)branching of dipolar chromophores on photophysical properties and two-photon absorption.

To investigate the effect of branching on linear and nonlinear optical properties, a specific series of chromophores, epitome of (multi)branched dipoles, has been thoroughly explored by a combined theoretical and experimental approach. Excited-state structure calculations based on quantum-chemical techniques (time-dependent density functional theory) as well as a Frenkel exciton model nicely complement experimental photoluminescence and one- and two-photon absorption findings and contribute to their interpretation. This allowed us to get a deep insight into the nature of fundamental excited-state dynamics and the nonlinear optical (NLO) response involved.

Making sense of lanthanide luminescence.

The luminescence of trivalent lanthanide ions has found applications in lighting, lasers, optical telecommunications, medical diagnostics, and various other fields. This introductory review presents the basics of organic and inorganic luminescent materials containing lanthanide ions, their applications, and some recent developments. After a brief history of the discovery, purification and early spectroscopic studies of the lanthanides, the radiative and nonradiative transitions of the 4f electrons in lanthanide ions are discussed.

Distance-dependent fluorescence quenching on gold nanoparticles ensheathed with layer-by-layer assembled polyelectrolytes.

We report on the preparation, characterization, and photophysical study of new fluorescent core/shell nanoparticles fabricated by electrostatic layer-by-layer assembly. On the basis of gold cores with a diameter of 13 nm, these nanocolloids possess different fluorescently labeled polymer corona layers at various distances from the surface of the core metal using nonfluorescent polyelectrolytes as spacer layers. UV-visible spectroscopy and transmission electron microscopy confirm that the particle suspensions of fluorescently labeled core/shell nanoparticles are stable at all stages of their construction.

A modular approach to two-photon absorbing organic nanodots: brilliant dendrimers as an alternative to semiconductor quantum dots?

Nanoscopic fluorescent dendrimers having up to 96 two-photon chromophores and showing very large two-photon absorption cross-sections (up to 56 000 GM) were designed as a complementary "organic" alternative to quantum dots.

Action cross sections of two-photon excited luminescence of some Eu(III) and Tb(III) complexes.

Four different luminescent lanthanide complexes have been studied with respect to multiphoton excitation using near-infrared femtosecond pulses. The method for measuring action cross sections of two-photon excited fluorescence in solution relative to a known standard is reviewed. Two refractive index-related corrections are necessary in this method: one for the multiphoton excitation process, the other for the collection of the emitted light.