Role of surface defects in colloidal cadmium selenide (CdSe) nanocrystals in the specificity of fluorescence quenching by metal cations.

This study aimed to answer the question as whether crystal defects at the surface of soluble capped CdSe nanocrystals (or quantum dots, QDs) in water colloidal suspension are involved in the mechanism of fluorescence quenching induced by metal cations. Nanocrystals of CdSe were synthesized by an aqueous protocol, varying the ratio between the CdSe precursors and the grafted ligand mercaptosuccinic acid (MSA). Changing the MSA/CdSe ratio during synthesis impacts the crystal nucleation growth, which plays an important role in surface construction of CdSe QDs and changes the surface state. In this way, we could modulate the crystal surface defects of CdSe, as verified by analysis of the individual bands which constitute the emission spectra and are associated with different relaxation processes. We found that the various tested metal cations, which interact in solution with the MSA ligand grafted on the QDs, quench their fluorescence differently, depending on the MSA/CdSe ratio used in synthesis. The crystal defects modulate the excitonic relaxation in CdSe and we demonstrated here that the surface defects intervene in the quenching of QDs induced by the binding of cations.

Strain engineering of photo-induced phase transformations in Prussian blue analogue heterostructures.

Heterostructures based on Prussian blue analogues (PBA) combining photo- and magneto-striction have shown a large potential for the development of light-induced magnetization switching. However, studies of the microscopic parameters that control the transfer of the mechanical stresses across the interface and their propagation in the magnetic material are still too scarce to efficiently improve the elastic coupling. Here, this coupling strength is tentatively controlled by strain engineering in heteroepitaxial PBA core-shell heterostructures involving the same Rb0.5Co[Fe(CN)6]0.8·zH2O photostrictive core and isostructural shells of similar thickness and variable mismatch with the core lattice. The shell deformation and the optical electron transfer at the origin of photostriction are monitored by combined in situ and real time synchrotron X-ray powder diffraction and X-ray absorption spectroscopy under visible light irradiation. These experiments show that rather large strains, up to +0.9%, are developed within the shell in response to the tensile stresses associated with the expansion of the core lattice upon illumination. The shell behavior is, however, complex, with contributions in dilatation, in compression or unchanged. We show that a tailored photo-response in terms of strain amplitude and kinetics with potential applications for a magnetic manipulation using light requires a trade-off between the quality of the interface (which needs a small lattice mismatch i.e. a small a-cubic parameter for the shell) and the shell rigidity (decreased for a large a-parameter). A shell with a high compressibility that is further increased by the presence of misfit dislocations will show a decrease in its mechanical retroaction on the photo-switching properties of the core particles.

Density of Grafted Chains in Thioglycerol-Capped CdS Quantum Dots Determines Their Interaction with Aluminum(III) in Water.

We aimed to quantify the interaction of water-soluble-functionalized CdS quantum dots (QDs) with metal cations from their composition and physical properties. From the diameter of thioglycerol-capped nanoparticles (TG-CdS QDs) measured by electronic microscopy ( D = 12.3 ± 0.3 nm), we calculated the molecular mass of the individual particle MAQD = (3 ± 0.5) × 106 g·mol-1 and its molar absorption coefficient ε450 = 21 × 106 M-1·cm-1. We built a three-dimensional model of the TG-CdS QDs in agreement with the structural data, which allowed us to quantify the number of thioglycerol grafted chains to ∼2000 per QD. This value fully matches the saturation binding curve of Al3+ cations interacting with TG-CdS QDs. The reaction occurred with a slow association rate ( kon = 2.1 × 103 M-1·s-1), as expected for heavy QDs. The photophysical properties of the functionalized QDs were studied using an absolute QD concentration of 7 nM, which allowed us to investigate the interaction with 14 metallic cations in water. The fluorescence intensity of TG-CdS QDs could be quenched only in the presence of Al3+ ions in the range 0.2-10 µM but not with other cations and was not observed with other kinds of grafting chains.

Organic functionalization of luminescent oxide nanoparticles toward their application as biological probes.

Luminescent inorganic nanoparticles are now widely studied for their applications as biological probes for in vitro or in vivo experiments. The functionalization of the particles is a key step toward these applications, since it determines the control of the coupling between the particles and the biological species of interest. This paper is devoted to the case of rare earth doped oxide nanoparticles and their functionalization through their surface encapsulation with a functional polysiloxane shell. The first step of the process is the adsorption of silicate ions that will act as a primary layer for the further surface polymerization of the silane, either aminopropyltriethoxysilane (APTES) or glycidoxypropyltrimethoxysilane (GPTMS). The amino- or epoxy- functions born by the silane allow the versatile coupling of the particles with bio-organic species following the chemistry that is commonly used in biochips. Special attention is paid to the careful characterization of each step of the functionalization process, especially concerning the average number of organic functions that are available for the final coupling of the particles with proteins. The surface density of amino or epoxy functions was found to be 0.4 and 1.9 functions per square nanometer for GPTMS and APTES silanized particles, respectively. An example of application of the amino-functionalized particles is given for the coupling with alpha-bungarotoxins. The average number (up to 8) and the distribution of the number of proteins per particle are given, showing the potentialities of the functionalization process for the labeling of biological species.