Liquid-Crystalline Suspensions of Photosensitive Paramagnetic CeF3 Nanodiscs.

The design of high-performance energy-converting materials is an essential step for the development of sensors, but the production of the bulk materials currently used remains costly and difficult. Therefore, a different approach based on the self-assembly of nanoparticles has been explored. We report on the preparation by solvothermal synthesis of highly crystalline CeF3 nanodiscs. Their surface modification by bisphosphonate ligands led to stable, highly concentrated, colloidal suspensions in water. Despite the low aspect ratio of the nanodiscs (∼6), a liquid-crystalline nematic phase spontaneously appeared in these colloidal suspensions. Thanks to the paramagnetic character of the nanodiscs, the nematic phase was easily aligned by a weak (0.5 T) magnetic field, which provides a simple and convenient way of orienting all of the nanodiscs in suspension in the same direction. Moreover, the more dilute, isotropic, suspensions displayed strong (electric and magnetic) field-induced orientation of the nanodiscs (Kerr and Cotton-Mouton effects), with fast enough response times to make them suitable for use in electro-optic devices. Furthermore, an emission study showed a direct relation between the luminescence intensity and magnetic-field-induced orientation of the colloids. Finally, with their fast radiative recombination decay rates, the nanodiscs show luminescence properties that compare quite favorably with those of bulk CeF3. Therefore, these CeF3 nanodiscs are very promising building blocks for the development and processing of photosensitive materials for sensor applications.

Tuning dye-to-particle interactions toward luminescent gold nanostars.

Light-matter interactions are of great interest for potential biological applications (bioimaging, biosensing, phototherapy). For such applications, sharp nanostructures exhibit interesting features since their extinction bands (surface plasmon resonance) cover a large bandwidth in the whole visible wavelength region due to the existence of "hot spots" located at the end of the tips. In this context, gold nanostars appear to be interesting objects. However, their study remains difficult, mainly due to complicated synthetic methods and further functionalization. This paper reports the synthesis, functionalization, and photophysics of luminescent hybrid gold nanostars prepared using a layer-by-layer (LbL) deposition method for the tuning of chromophore-to-particle distances together with the impact of the spectral overlap between the plasmon and the emission/absorption of the dyes. Several luminescent dyes with different optical signatures were selectively adsorbed at the nanoparticle surface. The optimized systems, exhibiting the highest luminescence recovery, clearly showed that overlap must be as low as possible. Also, the fluorescence intensities were quenched in close vicinity of the metal surface and revealed a distance-dependence with almost full recovery of the dyes emission for 11 LbL layers, which corresponded to 15 nm distances evaluated on dried samples. The photophysics of the luminescent core-shell particles were carried out in suspension and correlated with the response of isolated single objects.

Functionalized silica-based nanoparticles for photodynamic therapy.

AIM: The strategy developed aims to favor the vascular effect of photodynamic therapy by targeting tumor-associated vascularization using peptide-functionalized nanoparticles. We previously described the conjugation of a photosensitizer to a peptide targeting neuropilin-1 overexpressed in tumor angiogenic vessels. MATERIALS & METHODS: In this study, we have designed and photophysically characterized a multifunctional nanoparticle consisting of a surface-localized tumor vasculature targeting peptides and encapsulated photodynamic therapy and imaging agents. RESULTS & CONCLUSION: The elaboration of these multifunctional silica-based nanoparticles is reported. Nanoparticles functionalized with approximately 4.2 peptides bound to recombinant neuropilin-1 protein. Nanoparticles conferred photosensitivity to cells overexpressing neuropilin-1, providing evidence that the chlorin grafted within the nanoparticle matrix can be photoactivated to yield photocytotoxic effects in vitro.

Labeling of fibronectin by fluorescent and paramagnetic nanoprobes for exploring the extracellular matrix: bioconjugate synthesis optimization and biochemical characterization.

In this study, fibronectin-nanoparticles bioconjugates are developed and characterized. Multilabeled nanoparticles are composed of a core of the rare-earth oxide Gd(2)O(3):Tb(3+), capped with a set of Rhodamine B isothiocyanate encapsulated in a silica matrix and functionalized by a carboxylated polyethylene glycol shell. These nanoparticles are stabilized in aqueous solution and are found to contain about 400 carboxyl groups on their surface. Nanoparticle bioconjugation with highly purified human plasma fibronectin (Fn) is mediated by 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide and N-hydroxysuccinimide, resulting in an amide linkage between the carboxylic acid-terminated surface of the nanoparticle and the primary amine of Fn. The bioconjugation temperature and pH are optimized. The Local structure and global conformation of fibronectin-nanoparticle bioconjugates (FnNP*) are studied by fluorescence spectroscopy and enzymatic sites accessibility. Protein biochemical functionalities are globally conserved, and the protein is actually labeled. Elaboration of such complexes provides a promising bimodal contrasting agent for in vivo imaging.

Control of the in vivo biodistribution of hybrid nanoparticles with different poly(ethylene glycol) coatings.

Fluorescent nanoparticles containing a gadolinium oxide core are very attractive because they are able to combine both imaging (fluorescence imaging, magnetic resonance imaging) and therapy (X-ray therapy and neutron-capture therapy) techniques. The exploitation of these multifunctional particles for in vivo applications requires accurate control of their biodistribution. The postfunctionalization of these particles by four different poly(ethylene glycol) derivatives, which differ by chain length and end group, exerts a great influence on the zeta potential of the nanoparticles and on their biodistribution after intravenous injection to HEK-beta3-tumor-bearing mice. This study reveals that the behavior of PEGylated nanoparticles, which was monitored by in vivo fluorescence imaging, depends on both the chain length and the end group of the PEG chain.

Functionalization of luminescent aminated particles for facile bioconjugation.

For labeling proteins (streptavidin and fibronectin) by luminescent aminated nanoparticles, an interesting strategy that requires neither activation nor chemical pre- or post-treatment was explored. Because biomolecules are easily rendered luminescent after reaction with organic dyes carrying isothiocyanate moiety, phenylene diisothiocyanate (DITC) was used for covalently binding proteins onto luminescent hybrid gadolinium oxide nanoparticles whose ability to combine imaging and therapy was recently demonstrated.

Core/shell nanoparticles for multiple biological detection with enhanced sensitivity and kinetics.

The paper shows the different methods to attach a molecule to detect streptavidin to a dielectric particle made of a rare-earth oxide core and a polysiloxane shell containing fluorescein. First, the detection of streptavidin binding on a biotinylated gold substrate can be achieved in three ways: the shift of the surface plasmon resonance of the substrate and the double luminescence (organic and inorganic) of the core/shell particle. Second, these detections are efficient even after elimination upon thermal annealing of all the undesired molecules that skew the assays. Finally, the particle that ballasts the protein enhances its binding kinetics and increases the localized surface plasmon resonance shift that detects the binding.

Hybrid gadolinium oxide nanoparticles: multimodal contrast agents for in vivo imaging.

Luminescent hybrid nanoparticles with a paramagnetic Gd2O3 core were applied as contrast agents for both in vivo fluorescence and magnetic resonance imaging. These hybrid particles were obtained by encapsulating Gd2O3 cores within a polysiloxane shell which carries organic fluorophores and carboxylated PEG covalently tethered to the inorganic network. Longitudinal proton relaxivities of these particles are higher than the positive contrast agents like Gd-DOTA which are commonly used for clinical magnetic resonance imaging. Moreover these particles can be followed up by fluorescence imaging. This study revealed that these particles suited for dual modality imaging freely circulate in the blood vessels without undesirable accumulation in lungs and liver.