Light-driven directed motion of azobenzene-coated polymer nanoparticles in an aqueous medium.

Azobenzene-coated polymer nanoparticles in the 16-nm-diameter range act as phototriggered nanomotors combining photo to kinetic energy conversion with optical control through light intensity gradients. The grafted dyes act as molecular propellers: their photoisomerization supplies sufficient mechanical work to propel the particles in an aqueous medium toward the intensity minima with velocities of up to 15 µm/s. It is shown that nanoparticles can be driven over tens of micrometers by translating the intensity gradients in the plane. The analysis of the particles motion demonstrates the decisive role of photoisomerization in the transport with a measured driving force that is 3 to 4 orders of magnitude higher than optical forces.

Nanomosaic network for the detection of proteins without direct electrical contact.

A nanomosaic network of metallic nanoparticles for the detection of ultralow concentrations of proteins is reported, which uses two planar microelectrodes embedded in a microchip that permit generation of capacitive coupling to the nanomosaic system without the need for direct electrical contact with the channel. By tailoring the microchannel surface using a sandwich configuration of polyethylene terephthalate/gold nanoparticles/poly(L-lysine), the surface charge can be modified following biomolecular interactions and monitored using a noncontact admittance technique. This nanodevice system behaves like a tunable capacitor and can be employed for the detection of any kind of molecule. The femtomolar detection of an anionic protein, such as beta-lactoglobulin in phosphate-buffered saline medium, is taken as an example.

Enhanced magnetic field sensitivity of spin-dependent transport in cluster-assembled metallic nanostructures.

The emerging field of spintronics explores the many possibilities offered by the prospect of using the spin of the electrons for fast, nanosized electronic devices. The effect of magnetization acting on a current is the essence of giant or tunnel magnetoresistance. Although such spintronics effects already find technological applications, much of the underlying physics remains to be explored. The aim of this article is to demonstrate the importance of spin mixing in metallic nanostructures. Here we show that magnetic clusters embedded in a metallic matrix exhibit a giant magnetic response of more than 500% at low temperature, using a recently developed thermoelectric measurement. This method eliminates the dominating resistivity component of the magnetic response and thus reveals an intrinsic spin-dependent process: the conduction-electron spin precession about the exchange field as the electron crosses the clusters, giving rise to a spin-mixing mechanism with strong field dependence. This effect appears sensibly only in the smallest clusters, that is, at the level of less than 100 atoms per cluster.

Hot adsorbate-induced retardation of the internal thermalization of nonequilibrium electrons in adsorbate-covered metal nanoparticles.

Femtosecond transient absorption spectroscopy has been used to investigate the electron-electron scattering dynamics in sulfate-covered gold nanoparticles of 2.5 and 9.2 nm in diameter. We observe an unexpected retardation of the absolute internal thermalization time compared to bulk gold, which is attributed to a negative feedback by the vibrationally excited sulfate molecules. These hot adsorbates, acting as a transient energy reservoir, result from the back and forth inelastic scattering of metal nonequilibrium electrons into the pi orbital of the sulfate. The vibrationally excited adsorbates temporarily govern the dynamical behavior of nonequilibrium electrons in the metal by re-emitting hot electrons. In other terms, metal electrons reabsorb the energy deposited in the hot sulfates by a mechanism involving the charge resonance between the sulfate molecules and the gold NPs. The higher surface-to-volume ratio of sulfate-covered gold nanoparticles of 2.5 nm leads to a stronger inhibition of the internal thermalization. Interestingly, we also note an analogy between the mechanism described here for the slow-down of electron-electron scattering in metal nanoparticles by the hot adsorbates and the hot phonon-induced retardation of hot charge carriers cooling in semiconductors.

Supercapacitive admittance tomoscopy.

A sensor for measuring adsorption on a substrate has been designed including a contactless detection scheme, called supercapacitive admittance tomoscopy (SCAT). The sensor comprises a thin dielectric layer with two parallel band electrodes on the one side and a chemically modified surface on the other onto which the adsorption of molecules occurs. Upon application of a high frequency ac voltage between the two electrodes, a capacitive coupling is established across the dielectric layer, and the admittance measured depends on the surface state of the chemically modified interface. On the basis of this principle, a flow sensor has been developed to measure sensorgrams to follow the dynamics of the adsorption and has been tested for the adsorption of IgG on the modified surface.

Size-selective separation of gold nanoparticles using isoelectric focusing electrophoresis (IEF).

Isoelectric focusing in a polyacrylamide pH gradient gel is used to analyze the size distribution of gold nanoparticles synthesized by a chemical route with mercaptosuccinic acid as a ligand. The isoelectric point of the nanoparticles is shown to be size dependent, allowing fractionation by electrophoresis. Each fraction has a narrow size distribution with a standard deviation lower than 0.4 nm.

Pure surface plasmon resonance enhancement of the first hyperpolarizability of gold core-silver shell nanoparticles.

We report the optical second harmonic (SH) response from gold core-silver shell nanoparticles supported at a liquid-liquid interface in the spectral region where the second harmonic generation (SHG) frequency is resonant with the surface plasmon (SP) resonance excitation of the nanoparticles. We compare these results with that obtained by classical linear optical absorption spectroscopy and show that the nonlinear optical response is dominated by the SP resonance enhancement with negligible contributions from the interband transitions. As a result, the SH spectrum exhibits two clear SP resonance bands attributed to the two SP resonances of the composite nanostructure formed by the gold core-silver shell nanoparticles. Absolute values of the hyperpolarizabilities are measured by hyper Rayleigh scattering (HRS) and compared that of pure gold nanoparticles. The hyperpolarizability measured at a harmonic energy of 3.0 eV, enhanced through excitation of the high energy SP resonance of the nanoparticle, increases with the silver content whereas the hyperpolarizability measured at a harmonic energy of 2.4 eV, enhanced through the excitation of the low energy SP resonance of the nanoparticle, decreases because of the shift of this resonance away from the harmonic frequency. The hyperpolarizability determined by HRS and the square root of the SHG intensities, scaling with the nanoparticle hyperpolarizability, have similar trends with respect to the silver content indicative of closely related adsorption properties yielding similar surface concentrations at the liquid-liquid interface.

Ultrafast chemical interface scattering as an additional decay channel for nascent nonthermal electrons in small metal nanoparticles.

The use of 4.2 nm gold nanoparticles wrapped in an adsorbates shell and embedded in a TiO2 metal oxide matrix gives the opportunity to investigate ultrafast electron-electron scattering dynamics in combination with electronic surface phenomena via the surface plasmon lifetimes. These gold nanoparticles (NPs) exhibit a large nonclassical broadening of the surface plasmon band, which is attributed to a chemical interface damping. The acceleration of the loss of surface plasmon phase coherence indicates that the energy and the momentum of the collective electrons can be dissipated into electronic affinity levels of adsorbates. As a result of the preparation process, gold NPs are wrapped in a shell of sulfate compounds that gives rise to a large density of interfacial molecules confined between Au and TiO2, as revealed by Fourier-transform-infrared spectroscopy. A detailed analysis of the transient absorption spectra obtained by broadband femtosecond transient absorption spectroscopy allows separating electron-electron and electron-phonon interaction. Internal thermalization times (electron-electron scattering) are determined by probing the decay of nascent nonthermal electrons (NNEs) and the build-up of the Fermi-Dirac electron distribution, giving time constants of 540 to 760 fs at 0.42 and 0.34 eV from the Fermi level, respectively. Comparison with literature data reveals that lifetimes of NNEs measured for these small gold NPs are more than four times longer than for silver NPs with similar sizes. The surprisingly long internal thermalization time is attributed to an additional decay mechanism (besides the classical e-e scattering) for the energy loss of NNEs, identified as the ultrafast chemical interface scattering process. NNEs experience an inelastic resonant scattering process into unoccupied electronic states of adsorbates, that directly act as an efficient heat bath, via the excitation of molecular vibrational modes. The two-temperature model is no longer valid for this system because of (i) the temporal overlap between the internal and external thermalization process is very important; (ii) a part of the photonic energy is directly transferred toward the adsorbates (not among "cold" conduction band electrons). These findings have important consequence for femtochemistry on metal surfaces since they show that reactions can be initiated by nascent nonthermal electrons (as photoexcited, out of a Fermi-Dirac distribution) besides of the hot electron gas.

Reversible voltage-induced assembly of au nanoparticles at liquid/liquid interfaces.

The voltage-induced assembly of mercaptosuccinic acid-stabilized Au nanoparticles of 1.5 +/- 0.4 nm diameter is investigated at the polarizable water/1,2-dichloroethane interface. Admittance measurements and quasi-elastic laser scattering (QELS) studies reveal that the surface concentration of the nanoparticle at the liquid/liquid boundary is reversibly controlled by the applied bias potential. The electrochemical and optical measurements provide no evidence of irreversible aggregation or deposition of the particles at the interface. Analysis of the electrocapillary curves constructed from the dependence of the frequency of the capillary waves on the applied potential and bulk particle concentration indicates that the maximum particle surface density is 3.8 x 10(13) cm(-2), which corresponds to 67% of a square closed-pack arrangement. This system provides a unique example of reversible assembly of nanostructures at interfaces, in which the density can be effectively tuned by the applied potential bias.

Hyper-Rayleigh scattering of gold nanorods and their relationship with linear assemblies of gold nanospheres.

The surface plasmon enhanced hyper-Rayleigh scattering light collected from an aqueous solution of gold nanorods is reported. A non negligible part of the signal is attributed to a photoluminescence background attributed to the electron hole recombination following multiphoton excitation of d-valence band electrons into the sp-conduction band. This radiative relaxation process is likely favored by the presence of the organic species adsorbed at the surface of the nanorods. The absolute value for the hyperpolarisability of nanorods is also compared by the external reference method to that of para-nitroaniline and found to be rather large although an absolute value cannot be given because the exact number density of the gold nanorods is unaccessible. This value is however compared with values reported for linear assemblies of gold spherical nanoparticles and further support the simple model of gold metal ellipsoids to describe the hyper-Rayleigh light intensities. The polarisation analysis of the hyper-Rayleigh scattering light is also determined for gold nanorods and compared to the expected one for gold nanospheres. For the latter spheres, the weakness of the signal intensities precludes a definite comparison with the model. On the opposite, for the nanorods, the polarisation dependence of the hyper-Rayleigh scattered light clearly deviates from the one expected for nanospheres.

Electrochemical and optical properties of two dimensional electrostatic assembly of Au nanocrystals.

The spectroscopic and electrochemical properties of two-dimensional electrostatic assembly of Au nanocrystals are examined on poly-L-lysine (pLys) modified gold electrodes. The surface preparation for the nanoparticle deposition involved the self-assembly of a monolayer of 11-mercaptoundecanoic acid on the electrode surface, followed by the electrostatic deposition of pLys from aqueous solution. The polyelectrolyte layer acts as the electrostatic anchor for the Au particles. Electrostatically stabilised Au particles were prepared by homogeneous reduction in the presence of citrate, yielding monodispersed colloidal suspension with an average diameter of 18 +/- 2 nm. After 4 h of deposition, the citrate-stabilised particles reach a maximum surface density of (8.2 +/- 0.1) x 10(10) particles cm(-2), with an average edge-to-edge distance of 25 nm. The particle surface density was estimated from scanning electron micrographs. Kelvin probe measurements were employed for examining changes in surface dipole introduced by the 2D array of nanocrystals. From simple electrostatic arguments, the apparent static dipole moment per particle was estimated of the order of 2700 D. The strong interaction between the nanocrystals and the pLys layer is responsible for the surface charge displacement, leading to changes in the surface dipole of 0.35 eV. These electrostatic interactions also manifest itself by the red shift of the plasmon resonance of the assembly with respect to the aqueous colloidal suspension. Analysis of the spectral broadening was attempted within the framework of the so-called coherent-potential approximation. Finally, electrochemical studies in 1,2-dichloroethane show a large electronic overlap between the nanocrystals and the metal substrate. Results obtained from electrochemical impedance spectroscopy strongly suggest that the electrostatic assembly of nanocrystal behaves like a 2D array of randomly distributed spherical nanoelectrodes.