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.     

Detection of single photoluminescent diamond nanoparticles in cells and study of the internalization pathway

Diamond nanoparticles are promising photoluminescent probes for tracking intracellular processes, due to embedded, perfectly photostable color centers. In this work, the spontaneous internalization of such nanoparticles (diameter 25 nm) in HeLa cancer cells is investigated by confocal microscopy and time-resolved techniques. Nanoparticles are observed inside the cell cytoplasm at the single-particle and single-color-center level, assessed by time-correlation intensity measurements. Improvement of the nanoparticle signal-to-noise ratio inside the cell is achieved using a pulsed-excitation laser and time-resolved detection taking advantage of the long radiative lifetime of the color-center excited state as compared to cell autofluorescence. The internalization pathways are also investigated, with endosomal marking and colocalization analyses. The low colocalization ratio observed proves that nanodiamonds are not trapped in endosomes, a promising result in prospect of drug delivery by these nanoparticles. Low cytotoxicity of these nanoparticles in this cell line is also shown.     

Retrieval of atmospheric ozone profiles from an infrared quantum cascade laser heterodyne radiometer: results and analysis

Following the recent development of a ground-based prototype quantum cascade laser heterodyne radiometer operating in the midinfrared, atmospheric ozone profile retrievals from a solar occultation measurement campaign performed at the Rutherford Appleton Laboratory on 21 September 2006 are presented. Retrieval is based on the optimal estimation method. High resolution (0.0073 cm(-1)) atmospheric spectra recorded by the laser heterodyne radiometer and covering a microwindow (1033.8-1034.5 cm(-1)) optimized for atmospheric ozone measurements were used as measurement vectors. As part of the evaluation of this novel instrument, a comprehensive analysis of the retrievals is presented, demonstrating the high potential of quantum cascade laser heterodyne radiometry for atmospheric sounding. Vertical resolutions of 2 km near the ground and about 3 km in the stratosphere were obtained. The information content of the retrieval was found to be up to 48 bits, which is much higher than any other passive ground-based instrument. Frequency mismatches of several absorption peaks between the forward model and experimental spectra have been observed and significantly contribute to the retrieval noise error in the upper-troposphere lower-stratosphere region. Retrieved ozone vertical profiles were compared to ozonesonde data recorded at similar latitudes. The agreement is generally excellent except for the 20 to 25 km peak in ozone concentration, where ozonesonde data were found to be 20% lower than the amount retrieved from the laser heterodyne radiometer spectra. Quantum cascade laser based heterodyne radiometry in the midinfrared has been demonstrated to provide high spectral resolution and unprecedented vertical resolution for a passive sounder in a highly compact and mechanically simple package.     

Mechanically responding nanovalves based on polyelectrolyte multilayers

The alternate deposition of exponentially and linearly growing polyelectrolyte multilayers leads to the formation of multicompartment films. In this study, a new system consisting in nanometer-sized multilayer barriers deposited on or between multilayer compartments was designed to respond to mechanical stimuli and to act as nanovalves. The diffusion of polyelectrolytes through the barrier from one compartment to another can be switched on/off by tuning the mechanical stretching and thereby opening or closing nanopores in the barrier. This work represents a first step toward the design of chemically or biologically active films responding to mechanical stresses.     

Optimization of Advanced Live-Cell Imaging through Red/Near-Infrared Dye Labeling and Fluorescence Lifetime-Based Strategies

Fluorescence microscopy is essential for a detailed understanding of cellular processes; however, live-cell preservation during imaging is a matter of debate. In this study, we proposed a guide to optimize advanced light microscopy approaches by reducing light exposure through fluorescence lifetime (τ) exploitation of red/near-infrared dyes. Firstly, we characterized key instrumental elements which revealed that red/near-infrared laser lines with an 86x (Numerical Aperture (NA) = 1.2, water immersion) objective allowed high transmission of fluorescence signals, low irradiance and super-resolution. As a combination of two technologies, i.e., vacuum tubes (e.g., photomultiplier) and semiconductor microelectronics (e.g., avalanche photodiode), type S, X and R of hybrid detectors (HyD-S, HyD-X and HyD-R) were particularly adapted for red/near-infrared photon counting and τ separation. Secondly, we tested and compared lifetime-based imaging including coarse τ separation for confocal microscopy, fitting and phasor plot analysis for fluorescence lifetime microscopy (FLIM), and lifetimes weighting for enhanced stimulated emission depletion (STED) nanoscopy, in light of red/near-infrared multiplexing. Mainly, we showed that the choice of appropriate imaging approach may depend on fluorochrome number, together with their spectral/lifetime characteristics and STED compatibility. Photon-counting mode and sensitivity of HyDs together with phasor plot analysis of fluorescence lifetimes enabled the flexible and fast imaging of multi-labeled living H28 cells. Therefore, a combination of red/near-infrared dyes labeling with lifetime-based strategies offers new perspectives for live-cell imaging by enhancing sample preservation through acquisition time and light exposure reduction.     

A fair method for centralized optimization of multi-TSO power systems

This paper addresses the problem of centralized optimization of an interconnected power system partitioned into several regions controlled by different transmission system operators (TSOs). It is assumed that those utilities have agreed to transferring some of their competencies to a centralized control center, which is in charge of setting the control variables in the entire system to satisfy every utility’s individual objective. This paper proposes an objective method for centralized optimization of such multi-TSO power systems, which relies on the assumption that each TSO has a real-valued optimization function focusing on its control area only. This method is illustrated on the IEEE 118 bus system partitioned into three TSOs. It is applied to the optimal reactive power dispatch problem, where the control variables are the voltage settings for generators and compensators. After showing that the method has some properties of fairness, namely freedom from envy, efficiency, accountability, and altruism, we emphasize its robustness with respect to certain biased behavior of the different TSOs.     

Electroanalytical behavior of poly-L-lysine dendrigrafts at the interface between two immiscible electrolyte solutions

In this work, the electrochemical behavior of nonredox-active poly-L-lysine dendrigraft molecules of four different generations was investigated at the interface between two immiscible electrolyte solutions (ITIES). The influence of the dendrigraft generation on the electrochemical response, sensitivity of the calibration curves, and limit of detection was studied. Cyclic voltammetry at the ITIES revealed that the sensitivity increased (1840 to 25?800 nA μM(-1)) and the limit of detection decreased (11.10 to 0.65 μM) as the dendrigraft generation increased from generation G2 through to generation G5, respectively. The results are compared to those for protein voltammetry at the ITIES. Our studies suggest that the sensitivity expected for a synthetic ionized macromolecule can be predicted on the basis of its net charge and its diffusion coefficient. However, electrochemistry at the ITIES demonstrates a greater sensitivity toward proteins, which is attributed to their tertiary structure.     

Mechanical properties of thin glassy polymer films filled with spherical polymer-grafted nanoparticles

It is commonly accepted that the addition of spherical nanoparticles (NPs) cannot simultaneously improve the elastic modulus, the yield stress, and the ductility of an amorphous glassy polymer matrix. In contrast to this conventional wisdom, we show that ductility can be substantially increased, while maintaining gains in the elastic modulus and yield stress, in glassy nanocomposite films composed of spherical silica NPs grafted with polystyrene (PS) chains in a PS matrix. The key to these improvements are (i) uniform NP spatial dispersion and (ii) strong interfacial binding between NPs and the matrix, by making the grafted chains sufficiently long relative to the matrix. Strikingly, the optimal conditions for the mechanical reinforcement of the same nanocomposite material in the melt state is completely different, requiring the presence of spatially extended NP clusters. Evidently, NP spatial dispersions that optimize material properties are crucially sensitive to the state (melt versus glass) of the polymeric material.     

Template-assisted synthesis of high packing density SrLi2Ti6O14 for use as anode in 2.7-V lithium-ion battery

SrLi₂Ti₆O₁₄ has been prepared by using mesoporous TiO₂ brookite as a template and reactant. The prepared particles retained the rounded shape of the precursor, leading to high dispersivity and high packing density. The material has been further electrochemically characterized in both half and full cells. It shows good cycling stability and rate capability. A 2.7-V cell has been built by combining a SrLi₂Ti₆O₁₄ anode with a 4-V spinel cathode of LiMn₂O₄. This cell has a higher voltage compared to the 2.5-V LiMn₂O₄/Li₄Ti₅O₁₂ system.