Low loss negative index metamaterials with one type of meta-atom

Metamaterial building blocks from microwave to optical range are mainly based on metal-dielectric composites. In almost all structures with true negative index (not coming from losses), two kinds of meta-atoms (electric and magnetic) are mixed to drive simultaneously the effective permittivity and permeability to negative values leading in turn to a negative index of refraction. In this paper, we show that two coupled structures with localized plasmons modes (e.g. cut-wires or split ring resonators) can exhibit negative refractive index by their own, by appropriately controlling the hybridization scheme of the plasmons modes. Because of small metal filling factor and reduced optical losses, the resulting structures may pave the way to realistic applications of metamaterials at optical frequencies.     

Experimental/theoretical electrostatic properties of a styrylquinoline-type HIV-1 integrase inhibitor and its progenitors

We have established that polyhydroxylated styrylquinolines are potent inhibitors of HIV-1 integrase (IN). Among them, we have identified (E)-8-hydroxy-2-[2-(4,5-dihydroxy-3-methoxyphenyl)-ethenyl]-7-quinolinecarboxylic acid (1) as a promising lead. Previous molecular dynamics simulations and docking procedures have shown that the inhibitory activity involves one or two metal cations (Mg2+), which are present in the vicinity of the active center of the enzyme. However, such methods are generally based on a force-field approach and still remain not as reliable as ab initio calculations with extended basis sets on the whole system. To go further in this area, the aim of the present study was to evaluate the predictive ability of the electron density and electrostatic properties in the structure-activity relationships of this class of HIV-1 antiviral drugs. The electron properties of the two chemical progenitors of 1 were derived from both high-resolution X-ray diffraction experiments and ab initio calculations. The twinning phenomenon and solvent disorder were observed during the crystal structure determination of 1. Molecule 1 exhibits a planar s-trans conformation, and a zwitterionic form in the crystalline state is obtained. This geometry was used for ab initio calculations, which were performed to characterize the electronic properties of 1. The electron densities, electrostatic potentials, and atomic charges of 1 and its progenitors are here compared and analyzed. The experimental and theoretical deformation density bond peaks are very comparable for the two progenitors. However, the experimental electrostatic potential is strongly affected by the crystal field and cannot straightforwardly be used as a predictive index. The weak difference in the theoretical electron densities between 1 and its progenitors reveals that each component of 1 conserves its intrinsic properties, an assumption reinforced by a 13C NMR study. This is also shown through an excellent correlation of the atomic charges for the common fragments. The electrostatic potential minima in zwitterionic and nonzwitterionic forms of 1 are discussed in relation with the localization of possible metal chelation sites.     

Cognitive ability experiment with photosensitive organic molecular thin films

We present an optical experiment which permits us to evaluate the information exchange necessary to self-induce cooperatively a well-organized pattern in a randomly activated molecular assembly. A low-power coherent beam carrying polarization and wavelength information is used to organize a surface relief grating on a photochromic polymer thin film which is photoactivated by a powerful incoherent beam. We demonstrate experimentally that less than 1% of the molecules possessing information cooperatively transmit it to the entire photoactivated polymer film.     

Nonlinear behavior of vocal fold vibration: The role of coupling between the vocal folds

Coupling between the vocal folds is one of the nonlinear mechanisms allowing regulation and synchronization of mucosal vibration. The purpose of this study was to establish that modulations such as diplophonia and abnormalities observed in vocal signals that may be observed in some cases of laryngeal pathology can be considered as nonlinear behavior due to the persistence of some physical interaction (coupling). An experimental model using excised porcine larynx was designed to create tension asymmetry between the vocal folds and to obtain vocal signals with modulations. Signals were analyzed by spectral analysis and the phase portrait method. Results were compared with computer-generated synthetic signals corresponding to nonlinear combinations of sinusoid signals. Under these conditions, evidence of nonlinear behavior was detected in 85% of experimental signals. These findings were interpreted as a demonstration of vocal fold interaction. Based on these findings, the authors conclude that (1) coupling must be taken into account in physical models of laryngeal physiology, and that (2) methods of nonlinear dynamics may be used for objective voice analysis.     

Edge-strengthening of flat glass with acrylate coatings

Edge-strengthening is a novel technology used to strengthen glass by applying a coating only on the edges. In this work, edge flaws of flat glass articles were examined in detail via scanning electron microscope (SEM) imaging. Then the effect of using weatherable acrylate coatings on edge-strengthening of flat glass was determined. Four-point bending measurement showed that the coatings provided more than twofold increase of the mean flexural strength and a factor of about two increase of the tensile stress needed to reach 0.8% cumulative probability of failure. The coatings were found to cover the flaw zone at the glass edges and partially fill in the cracks. Different surface treatments led to different levels of strengthening, indicating the importance of coating adhesion. The coating’s thermal and mechanical properties affected the extent of strengthening effect. A coating formulation with a higher glass transition temperature tended to provide a better strengthening effect, indicating the importance of closure stress within cracks generated during film curing process. Challenges of applying the edge-strengthening technology are also discussed.     

Excited State Dynamics of Isolated 6- and 8-Hydroxyquinoline Molecules

The photoinduced dynamics of isolated n-hydroxyquinoline (nHQ) molecules (n=6,8) was investigated in femtosecond pump-probe experiments. A qualitative difference was found between 8HQ and 6HQ. After an initial rapid decay corresponding to the departure of the initial wavepacket out of the Franck-Condon region of the excitation, the 8HQ probe signal decays to zero in 0.37 ps whereas a much longer time constant of 10.4 ps is observed in 6HQ. This interrogates on the role played by the intramolecular H-bond N HO which is at play the 8HQ molecule. Ab-initio were performed at the MCSCF/aug-cc-pVDZ level on the 8HQ molecule to help the discussion. A complex energy landscape was found, which includes a conical intersection.     

Controlled proteolysis of normal and pathological prion protein in a microfluidic chip

A microreactor for proteinase K (PK)-mediated protein digestion was developed as a step towards the elaboration of a fully integrated microdevice for the detection of pathological prion protein (PrP). PK-grafted magnetic beads were immobilized inside a polydimethylsiloxane (PDMS) microchannel using a longitudinal magnetic field parallel to the flow direction and a magnetic field gradient, thereby forming a matrix for enzymatic digestion. This self-organization provided uniform pore sizes, a low flow resistance and a strong reaction efficiency due to a very thin diffusion layer. The microreactor's performance was first evaluated using a model substrate, succinyl-ala-ala-ala-paranitroanilide (SAAAP). Reaction kinetics were typically accelerated a hundred-fold as compared to conventional batch reactions. Reproducibility was around 98% for on-chip experiments. This microsystem was then applied to the digestion of prion protein from brain tissues. Controlled proteolysis could be obtained by varying the on-chip flow rate, while a complete proteolysis of normal protein was achieved in only three minutes. Extracts from normal and pathological brain homogenates were finally compared and strong discrimination between normal and pathological samples was demonstrated.     

Use of poly(ethylene terephtalate) film bag to sample and remove humidity from atmosphere containing volatile organic compounds

Nalophan bags made from poly(ethylene terephtalate) film are often used to collect odorous gases. In this paper, the sample water removal method, based on humidity diffusion through the sample bag film, was applied using Nalophan bags and Tedlar bags to sample volatile organic compounds (VOCs) at low concentration (10 microg/m(3)). The removal of water with Nalophan bags enabled a reduction in relative humidity (RH) in a 10-L air sample from 80% to 20% in 2h at 20 degrees C. The use of Nalophan bags for the removal of water did not involve significant VOC loss among the 11 compounds studied.     

Ultrafast dynamics of acetylacetone (2,4-pentanedione) in the S2 state

The dynamics of the enolic form of acetylacetone (E-AcAc) was investigated using a femtosecond pump-probe experiment. The pump at 266 nm excited E-AcAc in the first bright state, S2(pi pi*). The resulting dynamics was probed by multiphoton ionization at 800 nm. It was investigated for 80 ps on the S2(pi pi*) and S1(n pi*) potential energy surfaces. An important step is the transfer from S2 to S1 that occurs with a time constant of 1.4 +/- 0.2 ps. Before, the system had left the excitation region in 70 +/- 10 fs. An intermediate step was identified when E-AcAc traveled on the S2 surface. Likely, it corresponds to an accidental resonance in the detection scheme that is met along this path. More importantly, some clues are given that an intramolecular vibrational energy relaxation is observed, which transfers excess vibrational energy from the enolic group O-H to the other modes of the molecule. The present multistep evolution of excited E-AcAc probably also describes, at least qualitatively, the dynamics of other electronically excited beta-diketones.