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In this communication, we report the second harmonic scattering from mass characterized 2D graphene oxide sheets dispersed in an aqueous suspension, in the femtosecond regime at 800 nm laser excitation. Charge-detection mass-spectrometry, performing at the single sheet level, allows for an exhaustive molar mass distribution and thus concentration for these 2D nanomaterials samples. The orientation-averaged hyperpolarizability value is (1.36 ± 0.15) × 10 -25 esu as determined by the concentration-dependent harmonic scattering signal. In addition, the multi-photon excited fluorescence spectrum is characterized by a broad band in the visible range between 350 and 700 nm centered at about 500 nm.

Gold nanoclusters (Au NCs) are an emerging class of luminescent nanomaterials but still suffer from moderate photoluminescence quantum yields. Recent efforts have focused on tailoring their emission properties. Introducing zwitterionic ligands to cap the metallic kernel is an efficient approach to enhance their one-photon excitation fluorescence intensity. In this work, we extend this concept to the nonlinear optical regime, i.e., two-photon excitation fluorescence. For a proper comparison between theory and experiment, both ligand and solvent effects should be considered. The effects of ligand shell size and of aqueous solvent on the optical properties of zwitterion functionalized gold nanoclusters have been studied by performing quantum mechanics/molecular mechanics (QM/MM) simulations.

The ability of gold(i) thiolates to self-assemble into supramolecular architectures opens the route for a new class of nanomaterials with a unique structure-optical property relationship. However, for a confirmed structure-optical property relationship, a control of the supramolecular architectures is required. In this work, we report a simple synthesis of sub-100 nanometer gold-cysteine and silver doped gold-cysteine supramolecular assemblies. We explore in particular silver-doping as a strategy to enhance the optical properties of these supramolecular assemblies. By an accurate characterization of as-synthesized supramolecular nanoparticles, we have been able to measure for the first time, their absolute two-photon absorption cross-section, two-photon excited fluorescence cross-section and first hyperpolarizabilities at different near-IR wavelengths. Huge values are obtained for silver doped gold-cysteine supramolecular assemblies, as compared to their corresponding undoped counterpart. In addition, we employ DFT and TD-DFT methods to study the geometric and electronic structures of model gold-cysteine and silver doped gold-cysteine compounds in order to address the structure-linear/nonlinear optical property relationship. The aim is to gain insights into the origin of the nonlinear optical enhancement of silver-doped gold supramolecular assemblies.

We report theoretical and experimental results on two-photon absorption (TPA) cross section of thiolated small silver cluster Ag15L11 exhibiting extraordinary large TPA in red. Our findings provide the responsible mechanism and allow proposing new classes of nanoclusters with large TPAs which are promising for biological and medical applications.

We present a new compact and versatile experimental set-up that has been designed to perform electron and ion imaging experiments on large multiply charged gas phase molecular and cluster species. It combines an electrospray ionization source, a quadrupole mass filter guiding ion optics and a velocity map imaging spectrometer. Characterization of the spectrometer has been performed on atomic ions. Results obtained on molecular species (stilbene 420 dianions) demonstrate the possibility offered by this experimental set-up.

We focus on the functional role of small silver clusters in model hybrid systems involving peptides in the context of a new generation of nanostructured materials for biosensing. The optical properties of hybrids in the gas phase and at support will be addressed with the aim to bridge fundamental and application aspects. We show that extension and enhancement of absorption of peptides can be achieved by small silver clusters due to the interaction of intense intracluster excitations with the π-π* excitations of chromophoric aminoacids. Moreover, we demonstrate that the binding of a peptide to a supported silver cluster can be detected by the optical fingerprint. This illustrates that supported silver clusters can serve as building blocks for biosensing materials. Moreover, the clusters can be used simultaneously to immobilize biomolecules and to increase the sensitivity of detection, thus replacing the standard use of organic dyes and providing label-free detection. Complementary to that, we show that protected silver clusters containing a cluster core and a shell liganded by thiolates exhibit absorption properties with intense transitions in the visible regime which are also suitable for biosensing applications.

The UV photoexcitation spectrum of deprotonated tryptophan anion is presented. Singly deprotonated amino-acid tryptophan has been produced in an electrospray ionization source, isolated in a quadrupole ion trap and photoexcited with a UV tunable laser, resulting in the photodetachment of the excess electron. Whereas no influence of the proton on the UV spectrum of tryptophan was previously reported (Phys. Chem. Chem. Phys., 2004, 6, 2633; J. Chem. Phys., 2005, 122, 074310), we observe a strong bathochromism due to the presence of the negatively charged group in the vicinity of the chromophore. An excellent agreement with TD-DFT (time dependent density functional theory) predictions for the absorption spectrum of the lowest energy conformer is found. The sensitivity of the tryptophan chromophore to the presence of a remote negative charge offers new perspectives for charge mapping in large biomolecules.