Elastic wave propagation in smooth and wrinkled stratified polymer films.

Periodic materials with sub-micrometer characteristic length scale can provide means for control of propagation of hypersonic phonons. In addition to propagation stopbands for the acoustic phonons, distinct dispersive modes can reveal specific thermal and mechanical behavior under confinement. Here, we employ both experimental and theoretical methods to characterize the phonon dispersion relation (frequency versus wave vector). We employed Brillouin light scattering (BLS) spectroscopy to record the phonon dispersion in stratified multilayer polymer films. These films consist of 4-128 alternate polycarbonate (PC) and poly (methyl methacrylate) (PMMA) layers along and normal to the periodicity direction. The distinct direction-dependent phonon propagation was theoretically accounted for, by considering the polarization, frequency and intensity of the observed modes in the BLS spectra. Layer-guiding was also supported by the glass transition temperatures of the PC and PMMA layers. The number of phonon dispersion branches increased with the number of layers but only a few branches were observable by BLS. Introduction of an additional in-plane periodicity, through a permanent wrinkling of the smooth PC/PMMA films, had only subtle consequences in the phonon propagation. Using the frequencies of the periodicity induced modes and momentum conservation equation we were able to precisely back calculate the wrinkle periodicity. However, a wrinkling-induced acoustic stopband utilizing flexible layered materials is still a challenge.

Direction-dependent elastic properties and phononic behavior of PMMA/BaTiO3 nanocomposite thin films.

Determination of the anisotropic mechanical properties of nanostructured hybrid films is of great importance to improve fabrication and to enable reliable utility. Here, we employ spontaneous Brillouin light spectroscopy to record the phononic dispersion relation along the two symmetry directions in a supported PMMA (poly(methylmethacrylate))-BaTiO3 hybrid superlattice (SL) with a lattice constant of about 140 nm. Several dispersive elastic modes are resolved for in-plane wave propagation, whereas along the periodicity direction the SL opens a wide propagation stop band for hypersonic phonons and near UV photons both centered at about 280 nm. A thorough theoretical analysis based on the finite element method quantitatively captures the band diagrams along the two main symmetry directions, helps identify the large density mismatch effect on the unexpectedly low sound phase velocity, and reveals significant anisotropy of the SL elastic tensor. Phonon propagation is a sensitive index of the structure, density, and the mechanical moduli of nanocomposite films.

Collective hypersonic excitations in strongly multiple scattering colloids.

Unprecedented low-dispersion high-frequency acoustic excitations are observed in dense suspensions of elastically hard colloids. The experimental phononic band structure for SiO(2) particles with different sizes and volume fractions is well represented by rigorous full-elastodynamic multiple-scattering calculations. The slow phonons, which do not relate to particle resonances, are localized in the surrounding liquid medium and stem from coherent multiple scattering that becomes strong in the close-packing regime. Such rich phonon-matter interactions in nanostructures, being still unexplored, can open new opportunities in phononics.

One-dimensional hypersonic phononic crystals.

We report experimental observation of a normal incidence phononic band gap in one-dimensional periodic (SiO(2)/poly(methyl methacrylate)) multilayer film at gigahertz frequencies using Brillouin spectroscopy. The band gap to midgap ratio of 0.30 occurs for elastic wave propagation along the periodicity direction, whereas for inplane propagation the system displays an effective medium behavior. The phononic properties are well captured by numerical simulations. The porosity in the silica layers presents a structural scaffold for the introduction of secondary active media for potential coupling between phonons and other excitations, such as photons and electrons.

Optomechanical crystals for spatial sensing of submicron sized particles.

Optomechanical crystal cavities (OMC) have rich perspectives for detecting and indirectly analysing biological particles, such as proteins, bacteria and viruses. In this work we demonstrate the working principle of OMCs operating under ambient conditions as a sensor of submicrometer particles by optically monitoring the frequency shift of thermally activated mechanical modes. The resonator has been specifically designed so that the cavity region supports a particular family of low modal-volume mechanical modes, commonly known as -pinch modes-. These involve the oscillation of only a couple of adjacent cavity cells that are relatively insensitive to perturbations in other parts of the resonator. The eigenfrequency of these modes decreases as the deformation is localized closer to the centre of the resonator. Thus, by identifying specific modes that undergo a frequency shift that amply exceeds the mechanical linewidth, it is possible to infer if there are particles deposited on the resonator, how many are there and their approximate position within the cavity region. OMCs have rich perspectives for detecting and indirectly analysing biological particles, such as proteins, viruses and bacteria.

Does Brillouin light scattering probe the primary glass transition process at temperatures well above glass transition?

The primary alpha-relaxation time (tau(alpha)) for molecular and polymeric glass formers probed by dielectric spectroscopy and two light scattering techniques (depolarized light scattering and photon correlation spectroscopy) relates to the decay of the torsional autocorrelation function computed by molecular dynamics simulation. It is well known that Brillouin light scattering spectroscopy (BLS) operating in gigahertz frequencies probes a fast (10-100 ps) relaxation of the longitudinal modulus M*. The characteristic relaxation time, irrespective of the fitting procedure, is faster than the alpha-relaxation which obeys the non-Arrhenius Vogel-Fulcher-Tammann equation. Albeit, this has been noticed, it remains a puzzling finding in glass forming systems. The available knowledge is based only on temperature dependent BLS experiments performed, however, at a single wave vector (frequency). Using a new BLS spectrometer, we studied the phonon dispersion at gigahertz frequencies in molecular [o-terphenyl (OTP)] and polymeric [polyisoprene (PI) and polypropylene (PP)] glass formers. We found that the hypersonic dispersion does relate to the glass transition dynamics but the disparity between the BLS-relaxation times and tau(alpha) is system dependent. In PI and PP, the former is more than one order of magnitude faster than tau(alpha), whereas the two relaxation times become comparable in the case of OTP. The difference between the two relaxation times appears to relate to the "breadth" of the relaxation time distribution function. In OTP the alpha-relaxation process assumes a virtually single exponential decay at high temperatures well above the glass transition temperature, in clear contrast with the case of the amorphous bulk polymers.

Anisotropic propagation and confinement of high frequency phonons in nanocomposites.

We show that self-ordered anodic aluminum oxide containing hexagonal arrays of cylindrical nanopores with submicron periodicity is a versatile model system for the exploration of rich phononic phenomena at gigahertz frequencies, which are intimately linked to fluids located in the nanopores and their interactions with the pore walls. Using high-resolution Brillouin spectroscopy we report the first realization of directional flow of elastic energy parallel and perpendicular to the pore axes, phonon localization, and tunability of the phononic band structure.

Thermodynamic, structural, and nanomechanical properties of a fluorous biphasic material.

The dynamics of the amphiphilic semifluorinated F(CF2)12(CH2)12H (F12H12) alkane that undergoes two condensed phase transitions have been investigated by Brillouin light spectroscopy, shear rheometry, small- (SAXS) and wide-angle (WAXS) X-ray scattering, and thermodynamic PVT measurements. The solid (I)-solid (II) transition (Ts) is marked by a stronger temperature dependence of the sound velocity in phase II and by a 2 orders of magnitude drop of the shear modulus. Between the Ts and the melting transition (Tm), the presence of two phonons implies a coexistence of solid (II) and amorphous (liquid) regions in the submicrometer range at thermal equilibrium as revealed by the SAXS pattern of a single reflection superimposed on a very broad amorphous halo. This intriguing finding of a transient, very slow (over 10 h) solid/liquid coexistence within phase II is rationalized by a two-stage mechanism for melting of the smectic phase (II) of F12H12. A refinement of the known packing motifs for the two solid-state structures is proposed.

Solvent-Dependent Light-Induced Structures in Gem-Dichlorocyclopropanated Polybutadiene Solutions.

The formation of permanent structures upon mild red laser illumination in transparent polydiene solutions is examined in the case of gem-dichlorocyclopropanated polybutadiene ( gDCC-PB) polymers bearing 15% functional units of the dichlorocyclopropane groups. The response was found to be distinct from the precursor PB. Whereas fiber-like patterns were clearly observed in both precursor and gDCC-PB solutions in cyclohexane, these were absent in the case of gDCC-PB/chloroform but were present in the precursor PB/chloroform solutions. The involved mechanical stresses were not sufficient for the gDCC activation to be detected by NMR spectroscopy. Remarkably, addition of even 10 wt % gDCC-PB into the latter solution sufficed to suppress the light-induced patterning. The importance of the chemical environment on the response to light irradiation was further checked and confirmed by use of other PB copolymers. Different diameter patterns and kinetics were observed. The strong solvent and comonomer mediated effect was reflected neither in solvency nor in optical polarizability differences of the polymers solvent couples.

Robustness of elastic properties in polymer nanocomposite films examined over the full volume fraction range.

Polymers with nanoparticle inclusions are attractive materials because physical properties can be tuned by varying size and volume fraction range. However, elastic behavior can degrade at higher inclusion fractions when particle-particle contacts become important, and sophisticated measurement techniques are required to study this crossover. Here, we report on the mechanical properties of materials with BaTiO3 nanoparticles (diameters < 10 nm) in a polymer (poly(methyl methacrylate)) matrix, deposited as films in different thickness ranges. Two well-known techniques, time and frequency domain Brillouin light scattering, were employed to probe the composition dependence of their elastic modulus. The time domain experiment revealed the biphasic state of the system at the highest particle volume fraction, whereas frequency domain Brillouin scattering provided comprehensive information on ancillary variables such as refractive index and directionality. Both techniques prove complementary, and can in particular be used to probe the susceptibility of elastic properties in polymer nanocomposites to aging.

Kinetics of Light-Induced Concentration Patterns in Transparent Polymer Solutions.

When exposed to weak visible laser light, solutions of common polymers like poly(isoprene) and poly(butadiene) respond by local concentration variations, which in turn lead to refractive index changes. Various micropatterns have been recently reported, depending mostly on the solvent environment and the irradiation conditions. Here, we focused on the simpler case of single polymer-rich filaments and we employed phase contrast microscopy to systematically investigate the influence of laser illumination and material parameters on the kinetics of the optically induced local concentration increase in the polydiene solutions. The refractive index contrast of the formed filaments increased exponentially with the laser illumination time. The growth rate exhibited linear dependence on the laser power and increased with polymer chain length in semidilute solutions in good solvents. On the contrary, the kinetics of the formed filaments appeared to be rather insensitive to the polymer concentration. Albeit the origin of the peculiar light field-polymer concentration coupling remains yet elusive, the new phenomenology is considered necessary for the elucidation of its mechanism.

Directional elastic wave propagation in high-aspect-ratio photoresist gratings: liquid infiltration and aging.

Determination of the mechanical properties of nanostructured soft materials and their composites in a quantitative manner is of great importance to improve the fidelity in their fabrication and to enable the subsequent reliable utility. Here, we report on the characterization of the elastic and photoelastic parameters of a periodic array of nanowalls (grating) by the non-invasive Brillouin light scattering technique and finite element calculations. The resolved elastic vibrational modes in high and low aspect ratio nanowalls reveal quantitative and qualitative differences related to the two-beam interference lithography fabrication and subsequent aging under ambient conditions. The phononic properties, namely the dispersion relations, can be drastically altered by changing the surrounding material of the nanowalls. Here we demonstrate that liquid infiltration turns the phononic function from a single-direction phonon-guiding to an anisotropic propagation along the two orthogonal directions. The susceptibility of the phononic behavior to the infiltrating liquid can be of unusual benefits, such as sensing and alteration of the materials under confinement.

A new class of tunable hypersonic phononic crystals based on polymer-tethered colloids.

The design and engineering of hybrid materials exhibiting tailored phononic band gaps are fundamentally relevant to innovative material technologies in areas ranging from acoustics to thermo-optic devices. Phononic hybridization gaps, originating from the anti-crossing between local resonant and propagating modes, have attracted particular interest because of their relative robustness to structural disorder and the associated benefit to 'manufacturability'. Although hybridization gap materials are well known, their economic fabrication and efficient control of the gap frequency have remained elusive because of the limited property variability and expensive fabrication methodologies. Here we report a new strategy to realize hybridization gap materials by harnessing the 'anisotropic elasticity' across the particle-polymer interface in densely polymer-tethered colloidal particles. Theoretical and Brillouin scattering analysis confirm both the robustness to disorder and the tunability of the resulting hybridization gap and provide guidelines for the economic synthesis of new materials with deliberately controlled gap position and width frequencies.

Synthesis and antiviral activity evaluation of some aminoadamantane derivatives.

The synthesis of some spiro[cyclopropane-1,2'-adamantan]-2-amines and methanamines and some spiro[pyrrolidine-2,2'-adamantanes] is described. The title compounds were evaluated against a wide range of viruses (influenza A, influenza B, parainfluenza 3, RSV, HSV-1, TK- HSV-1, HSV-2, vaccinia, vesicular stomatitis, polio 1, coxsackie B4, sindbis, semliki forest, Reo 1, HIV-1, and HIV-2), and some of them (compounds 6b, 6c, 9a, 16a, 16b, and 17) inhibited the cytopathicity of influenza A virus at a concentration significantly lower than that of amantadine and also significantly lower than the concentrations at which they proved cytotoxic to the host cells. None of the new aminoadamantane derivatives was active against influenza B virus or any of the other viruses tested, which points to their specificity as anti-influenza A virus agents.

Synthesis and antiviral activity evaluation of some new aminoadamantane derivatives. 2.

The synthesis of some new aminoadamantane derivatives is described. The new compounds were evaluated against a wide range of viruses [influenza A H1N1, influenza A H2N2, influenza A H3N2, influenza B, parainfluenza 3, herpes simplex virus type 1 (HSV-1) and type 2 (HSV-2), thymidine kinase-deficient (TK-) HSV-1, vaccinia, vesicular stomatitis, polio 1, Coxsackie B4, Sindbis, Semliki forest, Reo 1, varicella-zoster virus (VZV), TK- VZV, human cytomegalovirus (HCMV), and human immunodeficiency virus type 1 (HIV-1) and type 2 (HIV-2)]. Some of them proved markedly active against the influenza A H2N2 (compounds 4a,b, 5a, 6a, and 7a), H3N2 (compounds 5a, 6a, and 7a), and H1N1 (compounds 4b,c and 6d). Since compounds 5a, 6a, and 7a, amantadine, and rimantadine showed the same comparative pattern of potency against influenza strains H2N2, H3N2, and B, it may postulated that they act according to a similar mechanism, with regard to their "amine" effect, on the M2 ion channel of influenza A (H1N1, H2N2, or H3N2). In general, no significant activity was noted with any of the new compounds against any of the other viruses tested, making their activity against influenza virus more specific and striking. Borderline activity was noted with some of the compounds (4b,c, 5a-c, and 8a) against HIV-1.

Acoustic excitations in suspensions of soft colloids

Vibrational modes in suspensions of soft colloids in a fluid can be detected experimentally by Brillouin light scattering. Besides the usual acoustic mode, being essentially the longitudinal phonon of the liquid matrix, an "opticlike" mode is observed in giant starlike micelles at low volume fractions. We propose that this opticlike mode is due mainly to the internal vibration of each hairy particle.

Dynamics of core-shell particles in concentrated suspensions.

The dynamics of soft colloidal particles in a concentrated suspension was studied by two color dynamic light scattering. The short-time diffusion coefficient, D(s)(q), revealed a weak slowing down around the peak of S(q) in contrast to the much stronger dependence observed in hard sphere systems, and the absence of any slowing down in ultrasoft diblock micelles. The low-q limit of the diffusion coefficient, D(s)(q=0), reflecting the cooperative nature of the dynamics was found to decrease from its dilute limit value in contrast to the weak increase observed in hard sphere systems. The behavior of D(s)(q) reflects distinct polymer-layer-induced hydrodynamic effects present in concentrated suspensions of core-shell particles.

Synthesis and pharmacological study of some new beta-(dialkylaminomethyl)- gamma-butyrolactones and their tetrahydrofuran analogues.

This paper describes the synthesis of beta-(dialkylaminomethyl)-gamma- butyrolactones (6 and 15) and their tetrahydrofuran analogs 7 and 16. Their convulsant activity was studied on mice and could display an antiGABAergic component, but, unlike the alpha-(dialkylaminomethyl)- gamma-butyrolactones, no antiglycinergic component was detected. The possibility of an activation of the glutamatergic receptors (NMDA), by indirect stimulation of their glycinergic site, by the tetrahydrofurans analogs 7 could be considered. These compounds exhibited, at low doses (1/3 to 1/20 of their convulsant doses), an anticonvulsant action in the maximal electroshock test and this is in agreement with the abovementioned possibility.

3-Cyclopentyl-1-adamantanamines and adamantanemethanamines. Antiviral activity evaluation and convulsions studies.

The synthesis of 3-cyclopentyl-1-adamantanamines and adamantanemethanamines and some of their thioureas is described. The antiviral activity examination of these compounds indicated that some of them inhibited Respiratory Syncytial Virus (RSV) infection at concentrations that were slightly (up to 5-fold) lower than the cytotoxic concentration. Behavioral and convulsions studies of the above mentioned amines, in mice, did not show any dopaminomimetic activity and argue in favor of the existence of a glutamatergic component in the action of these derivatives.

[Synthesis and pharmacological study of alpha-phenyl-1-adamantanemethanamine]. / Synthèse et étude pharmacologique de la alpha-phényl-1-adamantaneméthanamine.

The alpha-phenyl-1-adamantanemethanamine 2 was synthesized and its pharmacological action was studied on mice. The behavior effects obtained with this compound (at low dose) as well as the antagonism of the convulsions and the lethality (induced by the amine 2 at high dose) by desimipramine, N-linoleylGABA or N-linoleylglycine, could suggest the existence of glutamatergic (NMDA), anti-GABAergic and antiglycinergic components in the action mechanism of this adamantanamine.