3D Printing and Pyrolysis of Optical ZrO2 Nanostructures by Two-Photon Lithography: Reduced Shrinkage and Crystallization Mediated by Nanoparticles Seeds.

Two-photon lithography is a potential route to produce high-resolution 3D ceramics. However, the large shrinkage due to the elimination of an important organic counterpart of the printed material during debinding/sintering remains a lock to further development of this technology. To limit this phenomenon, an original approach based on a composite resin incorporating 45 wt% ultrasmall (5 nm) zirconia stabilized nanoparticles into the zirconium acrylate precursor is proposed to process 3D zirconia microlattices and nanostructured optical surfaces. Interestingly, the nanoparticles are used both as seeds allowing control of the crystallographic phase formed during the calcination process and as structural stabilizing agent preventing important shrinkage of the printed ceramic. After 3D photolithography and pyrolysis, the weight and volume loss of the microstructures are drastically reduced as compared to similar systems processed with the reference resin without nanoparticles, and stable 3D microstructures of cubic zirconia are obtained with high spatial resolution. In the case of a patterned surface, the refractive index of 2.1 leads to a diffraction efficiency large enough to obtain microfocusing with linewidths of 0.1 µm, and the demonstration of a microlens array with a period as small as 0.8 µm.

Gold NanoBipyramids Performing as Highly Sensitive Dual-Modal Optical Immunosensors.

In this work, we demonstrate the feasibility of gold bipyramidal-shaped nanoparticles (AuBPs) to be used as active plasmonic nanoplatforms for the detection of the biotin-streptavidin interaction in aqueous solution via both Localized Surface Plasmon Resonance and Surface Enhanced Raman Scattering (LSPR/SERS). Our proof of concept exploits the precise attachment of the recognition element at the tips of AuBPs, where the electromagnetic field is stronger, which is beneficial to the surface sensitivity of longitudinal LSPR on the local refractive index and to the electromagnetic enhancement of SERS activity, too. Indeed, successive red shifts of the longitudinal LSPR associated with increased local refractive index reveal the attachment of para-aminothiophenol (p-ATP) chemically labeled Biotin to the Au surface and the specific capture of the target protein by biotin-functionalized AuBPs. Finite-Difference Time-Domain simulations based on the reconstructed index of refraction confirm LSPR measurements. However, the molecular identification of the biotin-streptavidin interaction remains elusive by LSPR investigation alone. Remarkably, we succeeded to complement the LSPR detection with reliable SERS measurements which permitted to (a) certify the molecular identification of biotin-streptavidin interaction and (b) extend the limit of detection of streptavidin in solution toward 10-12 M. Finally, to further probe the possibility to implement the AuBPs as dual LSPR-SERS based immunoassays in solution for real clinical diagnostics, we additionally investigated the AuBP's performance to transduce the specific antihuman IgG- human IgG binding event, providing thus a reference design for building unique plasmonic immunoassays for dual-optical detection of target proteins in aqueous solution.

Programming crack patterns with light in colloidal plasmonic films.

Crack formation observed across diverse fields like geology, nanotechnology, arts, structural engineering or surface science, is a chaotic and undesirable phenomenon, resulting in random patterns of cracks generally leading to material failure. Limiting the formation of cracks or "programming" the path of cracks is a great technological challenge since it holds promise to enhance material durability or even to develop low cost patterning methods. Drawing inspiration from negative phototropism in plants, we demonstrate the capability to organize, guide, replicate, or arrest crack propagation in colloidal films through remote light manipulation. The key consists in using plasmonic photothermal absorbers to generate "virtual" defects enabling controlled deviation of cracks. We engineer a dip-coating process coupled with selective light irradiation enabling simultaneous deposition and light-directed crack patterning. This approach represents a rare example of a robust self-assembly process with long-range order that can be programmed in both space and time.

Room temperature synthesis of CdSe/CdS triangular nanoemitters and their stabilization in colloidal state and sol-gel glass.

Heterostructured cadmium-based core-shell nanoparticles (NPs) are the subject of research because of not only fundamental scientific advances but also a range of technological applications. To increase the range of applications of nanoparticles, it is possible to immobilise them in sol-gel glass that can be easily manufactured and shaped, keeping the properties of the dispersed particles. This allows the creation of new bulk optical materials with tailored properties, opening up opportunities for various technological applications such as lighting or sensing. Herein we report the synthesis of core-shell CdSe/CdS triangular-shaped nanoparticles under an atmosphere of oxygen and at room temperature. A detailed characterisation of the obtained NPs was carried out. The interesting effect of the gelling agent (tetra-n-butylammonium fluoride) on the triangular nanoparticles in solution and the stability of the emission properties over time was investigated. Sol-gel glasses with entrapped triangular NPs were prepared, and their photoluminescence properties were compared with those obtained in colloidal solutions.

Simulating Plasmon Resonances of Gold Nanoparticles with Bipyramidal Shapes by Boundary Element Methods.

Computational modeling and accurate simulations of localized surface plasmon resonance (LSPR) absorption properties are reported for gold nanobipyramids (GNBs), a class of metal nanoparticle that features highly tunable, geometry-dependent optical properties. GNB bicone models with spherical tips performed best in reproducing experimental LSPR spectra while the comparison with other geometrical models provided a fundamental understanding of base shapes and tip effects on the optical properties of GNBs. Our results demonstrated the importance of averaging all geometrical parameters determined from transmission electron microscopy images to build representative models of GNBs. By assessing the performances of LSPR absorption spectra simulations based on a quasi-static approximation, we provided an applicability range of this approach as a function of the nanoparticle size, paving the way to the theoretical study of the coupling between molecular electron densities and metal nanoparticles in GNB-based nanohybrid systems, with potential applications in the design of nanomaterials for bioimaging, optics and photocatalysis.

Au nanobipyramids@mSiO2 core-shell nanoparticles for plasmon-enhanced singlet oxygen photooxygenations in segmented flow microreactors.

The plasmonic features of gold nanomaterials provide intriguing optical effects which can find potential applications in various fields. These effects depend strongly on the size and shape of the metal nanostructures. For instance, Au bipyramids (AuBPs) exhibit intense and well-defined plasmon resonance, easily tunable by controlling their aspect ratio, which can act synergistically with chromophores for enhancing their photophysical properties. In Rose Bengal-nanoparticle systems it is now well established that the control of the dye-to-nanoparticle distance ranging from 10 to 20 nm as well as spectral overlaps is crucial to achieve appropriate coupling between the plasmon resonance and the dye, thus affecting its ability to generate singlet oxygen (1O2). We have developed AuBPs@mSiO2 core-shell nanostructures that provide control over the distance between the metal surface and the photosensitizers for improving the production of 1O2 (metal-enhanced 1O2 production - ME1O2). A drastic enhancement of 1O2 generation is evidenced for the resulting AuBPs and AuBPs@mSiO2 in the presence of Rose Bengal, using a combination of three indirect methods of 1O2 detection, namely in operando Electron Paramagnetic Resonance (EPR) with 2,2,6,6-tetramethylpiperidine (TEMP) as a chemical trap, photooxygenation of the fluorescence probe anthracene-9,10-dipropionic acid (ADPA), and photooxygenation of methionine to methionine sulfoxide in a segmented flow microreactor.

Beyond the Concentration Limitation in the Synthesis of Nanobipyramids and Other Pentatwinned Gold Nanostructures.

Gold nanoparticles offer unique optoelectronic properties relevant for a wide range of processes and products, in biology and medicine (therapeutic agents, diagnostic, drug delivery), as well as in electronics, photovoltaics, and catalysis. So far, various synthesis methods proposed have led to rather limited concentration and purity of the colloidal suspensions, severely hindering their use. Here, we present a simple and versatile procedure for the synthesis of gold pentatwinned nanostructures, including nanobipyramids based on a seed-mediated growth process that overcomes the concentration limitations of current methods by 2 orders of magnitude. Moreover, our novel process offers quantitative yields while easily allowing a fine control of the particles' shape, size (with a high monodispersity), and plasmonic properties. Finally, we demonstrate that our method can be easily upscaled to produce large amounts of nanostructures, up to the gram scale, with minimal waste and postprocessing, thus facilitating their use for further applications and industrial developments.

Plasmonic Nanoparticles Driven Enhanced Light Amplification in a Local 2D and 3D Self-Assembly.

We present fluorescence and a random lasing enhancement effect due to the interaction between gold nanoparticles (AuNPs) and Rhodamine 6G (Rh6G) dye. Non-covalently bounded dyes in the proximity of nanoparticles are studied in three systems of varying dimensionality: from (i) three-dimensional freely distributed suspensions, through (ii) quasi-two-dimensional multilamellar liposomes, to (iii) solid two-dimensional thin layers. Liposomes facilitate the formation of stable AuNPs/Rh6G composition showing enhanced fluorescence, while solid thin films exhibit plasmon-assisted random lasing.

Nanocarriers with ultrahigh chromophore loading for fluorescence bio-imaging and photodynamic therapy.

We describe the design of original nanocarriers that allows for ultrahigh chromophore loading while maintaining the photo-activity of each individual molecule. They consist in shells of charged biocompatible polymers grafted on gold nanospheres. The self-organization of extended polymer chains results from repulsive charges and steric interactions that are optimized by tuning the surface curvature of nanoparticles. This type of nano-scaffolds can be used as light-activated theranostic agents for fluorescence imaging and photodynamic therapy. We demonstrate that, labeled with a fluorescent photosensitizer, it can localize therapeutic molecules before triggering the cell death of B16-F10 melanoma with an efficiency that is similar to the efficiency of the polymer conjugate alone, and with the advantage of extremely high local loading of photosensitizers (object concentration in the picomolar range).

Silica hybrid sol-gel materials with unusually high concentration of Pt-organic molecular guests: studies of luminescence and nonlinear absorption of light.

The development of new photonic materials is a key step toward improvement of existing optical devices and for the preparation of a new generation of systems. Therefore synthesis of photonic hybrid materials with a thorough understanding and control of the microstructure-to-properties relationships is crucial. In this perspective, a new preparation method based on fast gelation reactions using simple dispersion of dyes without strong covalent bonding between dye and matrix has been developed. This new sol-gel method is demonstrated through synthesis of monolithic siloxane-based hybrid materials highly doped by various platinum(II) acetylide derivatives. Concentrations of the chromophores as high as 400 mM were obtained and resulted in unprecedented optical power limiting (OPL) performance at 532 nm of the surface-polished solids. Static and time-resolved photoluminescence of the prepared hybrid materials were consistent with both OPL data and previous studies of similar Pt(II) compounds in solution. The impacts of the microstructure and the chemical composition of the matrix on the spectroscopic properties, are discussed.