Dynamic light scattering unveils stochastic degradation in large-pore mesoporous silica nanoparticles.

Mesoporous Silica Nanoparticles (MSNs) have been increasingly investigated as versatile drug delivery carriers. A particular challenge for the systemic use of MSNs lies in the control of their degradation, which has not been fully understood until now. We implemented standard dynamic light scattering (DLS) experiments and introduced a novel DLS technique in a confocal volume to track the dynamics of large-pore MSN degradation in situ. This unique DLS technique, which involves a small observation volume, was chosen for its ability to count particle by particle during the degradation process, a method that has not been commonly used in nanoparticle research. The experiments were performed in different media compositions at low particle concentrations, below the silica solubility limit. MSNs with large conical pores were prepared and studied as they offer the possibility to incorporate and release large-sized biomolecules. Large-pore MSNs followed a singular degradation mechanism following a stochastic-like behavior, a finding that challenges the common idea that all nanoparticles (NPs) degrade similarly and homogeneously over time. We showed that some NPs are observed intact over a prolonged period while most other NPs have already vanished or been transformed into swollen NPs. Thus, a heterogeneous degradation process occurs, while the total concentration of NPs undergoes an exponential decay. These large conical pores MSNs will be utilized as reliable biomolecule nanocarriers by predicting the factors underlying the NP hydrolytic stability.

Hybrid CdSe/ZnS Quantum Dot-Gold Nanoparticle Composites Assembled by Click Chemistry: Toward Affordable and Efficient Redox Photocatalysts Working with Visible Light.

A new modular, easy-to-synthesize photocatalyst was prepared by assembling colloidal CdSe/ZnS quantum dots (QD) and gold nanoparticles (AuNP) via their ligands thanks to copper-catalyzed azide to alkyne cycloaddition (CuAAC) click chemistry. The resulting composite (QD-AuNP) photocatalyst was tested with a benchmark photoredox system previously reported by our group, for which QD alone acted as a photocatalyst but with a modest quantum yield (QY = 0.06%) and turnover number (TON = 350 in 3 h) due to poor charge separation. After optimization, the QD-AuNP composites exhibited much improved photocatalytic performances: up to five times higher TON (2600 in 3 h) and up to 24 times faster reaction in the first 10 min of visible irradiation. Such an improvement is attributed to an efficient electron transfer from QD to AuNP in the photoexcited QD-AuNP composites, which ensures a much better charge separation than that in QD alone. This was confirmed by studying both (i) the quenching of the QD photoluminescence during the synthesis of the QD-AuNP composites and (ii) the blue shift of the AuNP plasmon absorption band due to the accumulation of up to 7400 electrons per AuNP in QD-AuNP composites under visible light irradiation in the presence of electron donors.

In Situ Identification of Spherical Ag Monomers and Dimers at Zeptomole Adsorbate Concentrations by Surface-Enhanced Raman Scattering Correlation Spectroscopy.

We have developed a bright optical setup, especially optimized for surface-enhanced Raman scattering (SERS) correlation spectroscopy. We show that the brightness of the experiment combined with the correlation approach permits in situ access to the size and shape of the SERS-active aggregates in solution despite a very weak SERS signal of the adsorbed molecules. As a result, we demonstrate that dimers and larger SERS-active aggregates can be identified through the temporal fluctuations of the SERS signal of only a few hundred of adsorbed molecules, that is, at zeptomole adsorbate concentrations. Monomers covered by a monolayer of MBA were also identified. These results open a way for single nanoparticle sensing, for single-molecule SERS-active aggregate characterization, or for quantitative monitoring of functionalization processes on metallic objects.

Microscope spectrometer for light scattering investigations.

We describe a setup including a microscope to study volumes of a few mum(3) by static and dynamic light scattering (DLS) in a backscattering configuration. Light scattered by individual objects of micrometric size can be analyzed in the 400-800?nm spectral range. This setup can also be employed to study both diluted and concentrated colloidal solutions by DLS measurements. For diluted solutions we found evidence of the fluctuations of the number of particles in a confocal volume. We discuss their contribution to the autocorrelation function of the scattered intensity measured as a function of time.

Plasmon dispersion diagram and localization effects in a three-cavity commensurate grating.

Commensurate gratings of deep-metallic grooves have highly localized cavity resonances which do not exist for purely periodic gratings. In this paper we present the experimental dispersion diagram of the resonances of a commensurate grating with three sub-wavelength cavities per period. We observe selective light localization within the cavities, transition from a localized to a delocalized mode and modifications of the coupling of modes with the external plane-wave that may lead to the generation of black modes. This unexpected complexity is analyzed via a theoretical study in full agreement with the experiments. These results open a way to the control of wavelength-dependent hot spot predicted in more complex commensurate gratings.