Nanovectorization of TRAIL with single wall carbon nanotubes enhances tumor cell killing
International audience; Tumor necrosis factor-related apoptosis-inducing ligand (TRAIL or Apo2L) is a member of the tumor necrosis factor (TNF) superfamily. This type II transmembrane protein is able to bound specifically to cancer cell receptors (i.e., TRAIL-R1 (or DR4) and TRAIL-R2 (or DR5)) and to induce apoptosis without being toxic for healthy cells. Because membrane-bound TRAIL induces stronger receptor aggregation and apoptosis than soluble TRAIL, we proposed here to vectorize TRAIL using single-walled carbon nanotubes (SWCNTs) to mimic membrane TRAIL. Owing to their exceptional and revolutional properties, carbon nanotubes, especially SWCNTs, are used in a wide range of physical or,…
Comment on “Infrared and Raman selection rules for elastic vibrations of spherical nanoparticles”
This Comment demonstrates again that selection rules established several years ago for the infrared absorption and the Raman scattering by vibrations of a spherical nanoparticle are correct and that the claimed errors about them are wrong.
Number of observable features in the acoustic-Raman spectra of nanocrystals
Low-frequency Raman scattering spectra are presented for gold nanocrystals with diameters 3.5 and 13 nm. The frequencies of the Raman peaks but also their number are shown to vary with the nanocrystal size. These results are analyzed using both the continuous elastic medium approximation and an atomistic approach. We show that the number of atoms in the nanocrystal determines an upper limit of the number of observable Raman features. The frequency range in which the continuous elastic medium approximation is valid is defined by comparison with the calculations based on the atomistic approach.
Far infrared absorption by acoustic phonons in titanium dioxide nanopowders
We report spectral features of far infrared electromagnetic radiation absorption in anatase TiO2 nanopowders which we attribute to absorption by acoustic phonon modes of nanoparticles. The frequency of peak excess absorption above the background level corresponds to the predicted frequency of the dipolar acoustic phonon from continuum elastic theory. The intensity of the absorption cannot be accounted for in a continuum elastic dielectric description of the nanoparticle material. Quantum mechanical scale dependent effects must be considered. The absorption cross section is estimated from a simple mechanical phenomenological model. The results are in plausible agreement with the absorption b…
Contact laws between nanoparticles: the elasticity of a nanopowder
International audience; Studies of the mechanical contact between nanometer-scale particles provide fundamental insights into the mechanical properties of materials and the validity of contact laws at the nanoscale which are still under debate for contact surfaces approaching atomic dimensions. Using in situ Brillouin light scattering under high pressure, we show that effective medium theories successfully predict the macroscopic sound velocities in nanopowders if one takes into account the cementation of the contacts Our measurements suggest the relevance of the continuum approach and effective medium theories to describe the contact between nanoparticles of diameters as small as 4 nm, i.e…
Vibrations of weakly coupled nanoparticles
The vibrations of a coupled pair of isotropic silver spheres are investigated and compared with the vibrations of the single isolated spheres. Situations of both strong coupling and also weak coupling are investigated using continuum elasticity and perturbation theory. The numerical calculation of the eigenmodes of such dimers is augmented with a symmetry analysis. This checks the convergence and applicability of the numerical method and shows how the eigenmodes of the dimer are constructed from those of the isolated spheres. The frequencies of the lowest frequency vibrations of such dimers are shown to be very sensitive to the strength of the coupling between the spheres. Some of these mod…
Optimization of MCM-41 type silica nanoparticles for biological applications: Control of size and absence of aggregation and cell cytotoxicity
Abstract Mesoporous silica nanoparticles were synthesized at high pH using CTAB as a template and TEOS as a silica precursor. It was shown that varying the NaOH concentration between 5 and 27.5 mM allows the size, pore and silica structure of mesoporous nanoparticles to be precisely tuned. In particular, monodisperse nanoparticles with the MCM-41 structure with size ranging from 90 nm to 450 nm were obtained by increasing the NaOH concentration from 12.5 to 22.5 mM. It thus demonstrates that NaOH concentration must range between 12.5 and 15 mM in order to prepare MCM-41 silica nanoparticles with optimal size for nanovectorization. We also found that under usual conditions the aggregation of…
Long Lived Acoustic Vibrational Modes of an Embedded Nanoparticle
Classical continuum elastic calculations show that the acoustic vibrational modes of an embedded nanoparticle can be lightly damped even when the longitudinal plane wave acoustic impedances $Z_o=\rho v_L$ of the nanoparticle and the matrix are the same. It is not necessary for the matrix to be less dense or softer than the nanoparticle in order to have long lived vibrational modes. Continuum boundary conditions do not always accurately reflect the microscropic nature of the interface between nanoparticle and matrix, and a multi-layer model of the interface reveals the possibility of additional reduction of mode damping.
Direct Writing on Copper Ion Doped Silica Films by Electrogeneration of Metallic Microstructures
International audience; A facile and rapid localized electrochemical reduction of colloid copper particles is proposed using the scanning electrochemical,microscope (SECM), technique. In this purpose, thin films of composite silica :glass containing copper salts were prepared by the sol-gel method via the dip coating technique. Acid-catalyzed tetraethylorthosilane (TEOS) solutions charged with copper nitrate were used as precursors. This one-pot experiment can be performed in mild conditions. The localized generation of copper metallic nanostructures on silica film has been performed by electroreduction of methyl viologen on an ultramicroelectrode (UME). The UME generates reducing species, …
Surface plasmons and vibrations of self-assembled silver nanocolumns
6 pags. ; 5 figs. 1 tab.
The mass load effect on the resonant acoustic frequencies of colloidal semiconductor nanoplatelets
Resonant acoustic modes of ultrathin CdS and CdSe colloidal nanoplatelets (NPLs) with varying thicknesses were probed using low frequency Raman scattering. The spectra are dominated by an intense band ascribed to the thickness breathing mode of the 2D nanostructures. The measured Raman frequencies show strong deviations with respect to the values expected for simple bare plates, all the more so as the thickness is reduced. The deviation is shown to arise from the additional mass of the organic ligands that are bound to the free surfaces of the nanoplatelets. The calculated eigen frequencies of vibrating platelets weighed down by the mass of the organic ligands are in very good agreement wit…
Inelastic neutron scattering due to acoustic vibrations confined in nanoparticles: theory and experiment
The inelastic scattering of neutrons by nanoparticles due to acoustic vibrational modes (energy below 10 meV) confined in nanoparticles is calculated using the Zemach-Glauber formalism. Such vibrational modes are commonly observed by light scattering techniques (Brillouin or low-frequency Raman scattering). We also report high resolution inelastic neutron scattering measurements for anatase TiO2 nanoparticles in a loose powder. Factors enabling the observation of such vibrations are discussed. These include a narrow nanoparticle size distribution which minimizes inhomogeneous broadening of the spectrum and the presence of hydrogen atoms oscillating with the nanoparticle surfaces which enhan…
Effect of Reaction Parameters on Composition and Morphology of Titanate Nanomaterials
International audience; In the present article, we report the synthesis of titanate nanotubes and nanoribbons with controlled morphology, structure, and chemical composition depending on the main parameters of the synthesis. Hydrothermal processing time, grain size of the precursor, type of agitation, and acid treatment were investigated, and the principal controversies mentioned in the literature such as nanotube crystallographic structure, their chemical composition, and acid treatment impact are discussed. These controversies may be due to the heterogeneities present in all the samples and are rarely considered in the literature. These nanostructures were characterized by Raman spectrosc…
Simple model for the vibrations of embedded elastically cubic nanocrystals
The purpose of this work is to calculate the vibrational modes of an elastically anisotropic sphere embedded in an isotropic matrix. This has important application to understanding the spectra of low-frequency Raman scattering from nanoparticles embedded in a glass matrix. First some low frequency vibrational modes of a free cubically elastic sphere are found to be nearly independent of one combination of elastic constants. This is then exploited to obtain an isotropic approximation for these modes which enables to take into account the surrounding isotropic matrix. This method is then used to quantatively explain recent spectra of gold and copper nanocrystals in glasses.
Damping by Bulk and Shear Viscosity of Confined Acoustic Phonons for Nanostructures in Aqueous Solution
International audience; A nanoparticle in aqueous solution is modeled as a homogeneous elastic isotropic continuum sphere in contact with an infinite viscous compressible Newtonian fluid. The frequencies and damping of the confined vibrational modes of the sphere are calculated for the material parameters of a CdSe nanoparticle in water and a poly(methyl methacrylate) nanosphere in water. Although the effects of viscosity are found to be negligible for macroscopic objects, for nanoscale objects, both the frequency and damping of the vibrational modes are significantly affected by the viscosity of the liquid. Furthermore, both shear viscosity and bulk viscosity play an important role. A mode…
Vibrations of free and embedded anisotropic elastic spheres:Application to low-frequency Raman scattering of silicon nanoparticles in silica
Vibrational mode frequencies and damping are calculated for an elastic sphere embedded in an infinite, homogeneous, isotropic elastic medium. Anisotropic elasticity of the sphere significantly shifts the frequencies in comparison to simplified calculations that assume isotropy. New low-frequency Raman light scattering data are presented for silicon spheres grown in a ${\mathrm{SiO}}_{2}$ glass matrix. Principal features of the Raman spectrum are not correctly described by a simple model of the nanoparticle as a free, isotropic sphere, but require both matrix effects and the anisotropy of the silicon to be taken into account. Libration, not vibration, is the dominant mechanism.
Acousto-plasmonic coupling in engineered metal nanocomposites
This work shows the production of self-assembled elongated nano-objects embedded in an oxide host oriented perpendicular to the substrate and their acousto-plasmonic dynamics. Electromagnetic “hot spots” are created that activate anomalous Raman vibrational modes.
Acoustic vibrations of anisotropic nanoparticles
Acoustic vibrations of nanoparticles made of materials with anisotropic elasticity and nanoparticles with non-spherical shapes are theoretically investigated using a homogeneous continuum model. Cubic, hexagonal and tetragonal symmetries of the elasticity are discussed, as are spheroidal, cuboctahedral and truncated cuboctahedral shapes. Tools are described to classify the different vibrations and for example help identify the modes having a significant low-frequency Raman scattering cross-section. Continuous evolutions of the modes starting from those of an isotropic sphere coupled with the determination of the irreducible representation of the branches permit some qualitative statements t…
Quasi-free nanoparticle vibrations in a highly-compressed ZrO2 nanopowder
Several-nanometer-size mechanical oscillators, or nanoresonators, may complement electronic and optical technologies in future terahertz devices, but they can be useful only if they can be made to ...
Phonons in an inhomogeneous continuum: Vibrations of an embedded nanoparticle
The spectrum of acoustic vibrational modes of an inhomogeneous elastic continuum are analyzed with application to a spherical nanoparticle embedded in an infinite glass block. The relationship of these modes to the discrete vibrational spectrum of a free sphere is studied. The vibrational modes of a sphere with a fixed surface are relevant in some situations. Comparisons are also made to calculations of mode frequency and damping based on complex valued frequency.
Acoustic vibrations of monoclinic zirconia nanocrystals
International audience; Polarized low-frequency Raman spectra originating from confined acoustic vibrations are reported for monoclinic ZrO2 nanoparticles with a narrow size distribution synthesized from a continuous supercritical water process. The monoclinic lattice structure is taken into account for the interpretation of the spectra by comparing with isotropic and anisotropic continuum elasticity calculations for monodomain nanocrystals. The various mechanisms leading to the broadening of the Raman peaks are discussed. We demonstrate that an accurate determination of the size distribution of the nanoparticles is possible using the Raman peak due to the fundamental breathing vibration wh…
Environmental effects on the natural vibrations of nanoplatelets: a high pressure study.
International audience; Resonant acoustic modes from ultrathin CdS colloidal nanoplatelets (NPLs) are probed under high pressure using low frequency Raman spectroscopy. In particular we focus on the characterization of the recently evidenced mass load effect that is responsible for a significant downshift of the NPL breathing frequency due to the inert mass of organic ligands. We show that a key parameter in the observation of the mass effect is whether the surrounding medium is able to support THz acoustic wave propagation, at a frequency close to that of the inorganic vibrating core. At low pressures, surface organic molecules show a single particle-like behavior and a strong mass effect …
Acoustic modes in metallic nanoparticles: atomistic versus elasticity modeling
The validity of the linear elasticity theory is examined at the nanometer scale by investigating the vibrational properties of silver and gold nanoparticles whose diameters range from about 1.5 to 4 nm. Comparing the vibration modes calculated by elasticity theory and atomistic simulation based on the Embedded Atom Method, we first show that the anisotropy of the stiffness tensor in elastic calculation is essential to ensure a good agreement between elastic and atomistic models. Second, we illustrate the reduction of the number of vibration modes due to the diminution of the number of atoms when reducing the nanoparticles size. Finally, we exhibit a breakdown of the frequency-spectra scalin…
Acoustic vibrations of embedded spherical nanoparticles
Abstract A solid-matrix-embedded spherical nanoparticle has acoustic vibrational frequencies which are shifted and damped relative to modes of a free sphere. Not only the longitudinal plane wave acoustic impedances, but also the Poisson ratios of nanoparticle and matrix are important in determining the Q-factor of the “breathing” mode, for which frequencies and Q-factors with different material combinations are presented. High matrix sound speed (e.g. silica, titania, alumina, diamond) increases Q.
One step continuous hydrothermal synthesis of very fine stabilized superparamagnetic nanoparticles of magnetite
International audience; Stable suspensions of citrated SPIO nanoparticles were synthesised in one step using a hydrothermal continuous process. Citrates control the crystallite size and the oxidation degree of metallic ions despite the very short reaction time (4 s). Magnetite particles, Fe2.94O4, with an average size of 4 nm and good monodispersity were obtained.
THz nanocrystal acoustic vibrations from ZrO2 3D supercrystals
International audience; We report sharp low-frequency Raman spectral features of supercrystals synthesized via the "benzyl alcohol route" and consisting of either yttrium-stabilized or pure zirconia (ZrO2) nanocrystals. In situ formed benzoate species control the nanocrystal growth and act as organic glue leading to the assembly of the nanocrystals in highly ordered 3D supercrystals. We attribute some Raman peaks to THz acoustic vibrations of individual nanocrystals which are only weakly coupled due to the strong acoustic mismatch between the capping ligands and the nanocrystals. Peak positions are consistent with nanocrystal sizes estimated from transmission electron microscopy and X-ray p…
A comparative study of methanol carbonation on unsupported SnO2 and ZrO2
International audience; The aim of this work was to explore the catalytic properties of SnO2 in the coupling of methanol with carbon dioxide to afford dimethyl carbonate. SnO2 nanopowders were produced by hydrolysis of tin tetra-tert-butoxide dissolved in n-butanol. The samples were much more active than a commercial one due to their higher surface areas. In addition, they exhibited excellent recyclability. However, comparison with ZrO2, prepared and tested under the same experimental conditions, showed that zirconia-based catalysts were more selective and are, among the heterogeneous catalysts already reported, still the more selective. SnO2 also catalyzed the formation of dimethyl ether l…
Longitudinal versus transverse spheroidal vibrational modes of an elastic sphere
Analysis of the spheroidal modes of vibration of a free elastic sphere show that they can be qualitatively grouped into two categories: primarily longitudinal and primarily transverse. This is not a sharp distinction. However, there is a relatively stark contrast between the two kinds of modes. Primarily transverse modes have a small divergence and have frequencies that are almost functionally independent of the longitudinal speed of sound. Analysis of inelastic light scattering intensity from confined acoustic phonons in nanoparticles requires an understanding of this qualitative distinction between different spheroidal modes. In addition, some common misconceptions about spheroidal modes …