Antibiotic photocatalysis and antimicrobial activity of low-cost multifunctional Fe3O4@HAp nanocomposites.

Water contamination by multiple pollutants is a serious environmental issue originating from the many diverse sources of pollution. It has worsened with the appearance of new contaminants, named emerging micropollutants, such as drug residues which are considered a potential threat to human health and/or ecosystems. These require prior treatment before release into the environment. Simultaneous adsorption and photocatalysis as well as solid-liquid separation are promising technologies for water treatment. In order to obtain low cost photoactive nanocomposites, porous and magnetic Fe3O4-hydroxyapatite (wFeHAp) nanocomposites were prepared by soft chemistry from the dissociation of natural phosphate into Ca2+ and H3PO4 precursors, further neutralized by ammonia in the presence of preformed Fe3O4 particles. The magnetic nanocomposites were characterized and examined as effective antibacterial agents. Fe3O4 association with apatite modifies the surface properties of the wFeHAp nanocomposite materials, yielding efficient antimicrobial activity for S. aureus, B. subtilis, E. coli and K. pneumoniae strains. The photocatalytic removal of ciprofloxacin (CPF) and oxytetracyclin (OXT) antibiotics in water was also evaluated. The wFeHAp nanocomposites adsorbed and degraded the selected antibiotics successfully. Toxicity evaluation of the treated water after photodegradation using the four strains demonstrates the absence of toxic by-products at the end of the reaction. Therefore, Fe3O4@HAp nanoparticles are valuable for antimicrobial and photocatalysis applications.

Stimulated Brillouin scattering in dispersed graphene.

We explored the Stimulated Brillouin scattering (SBS) behavior of a transparent liquid containing a low concentration of strongly absorbing nanoparticles. We measured SBS energies in N-methyl-2-pyrrolidone (NMP) and water at 532 nm-wavelength. The previously unknown NMP Brillouin gain factor is gB = 18.6 ± 1.8 cm⋅GW-1. Graphene nanoflakes suspended in liquids strongly quench SBS. Linear dependence of the SBS-threshold on the graphene absorption coefficient (concentration) makes it suitable for the detection of small nanoparticles quantities in water, with a minimal detectable concentration of 5⋅10-8 g⋅cm-3. The effect is interpreted as an antagonism between electrostriction and thermal expansion, which is induced by the formation of carbon vapor bubbles. It is very sensitive to changes in density, refractive index and acoustic absorption coefficient, which parameters can be determined in the SBS method, including access to the bubbling nanosecond dynamics. SBS suppression may find applications in laser technologies and optical telecommunication networks.

An isomerization-induced cage-breaking process in a molecular glass former below T(g).

A recent experimental [P. Karageorgiev, D. Neher, B. Schulz, B. Stiller, U. Pietsch, M. Giersig, L. Brehmer, Nature Mater. 4, 699 (2005)] study has found liquidlike diffusion below the glass-transition temperature in azobenzene-containing materials under irradiation. This result suggests that the isomerization-induced massive mass transport that leads to surface relief gratings formation in these materials, is induced by this huge increase of the matrix diffusion coefficient around the probe. In order to investigate the microscopic origin of the increase of the diffusion, we use molecular dynamics simulations of the photoisomerization of probe dispersed red 1 molecules dispersed inside a glassy molecular matrix. Results show that the increased diffusion is due to an isomerization-induced cage-breaking process. A process that explains the induced cooperative motions recently observed in these photoactive materials.

Isomerization-induced surface relief gratings formation: A comparison between the probe and the matrix dynamics.

We report molecular dynamics simulations of the effect of the photoisomerization of probe molecules on the nonequilibrium dynamics of a bulk amorphous matrix. Is it the matrix or the probe that drives the dynamics in SRG formation? In the first picture, the probe isomerization induces the motion of the probe inside the matrix. The motion of the probe then induces molecular motions inside the matrix. In the second picture, the probe isomerization induces a modification of the matrix diffusion mechanism. The diffusion of the matrix then induces the motion of the embedded probe. To answer this question, we compare the motion of the probe molecules and the motion of the matrix molecules in various thermodynamic conditions. We show that when the isomerization is switched on, the matrix molecules surrounding the probe move faster than the probe. Around the probe, the structural relaxation time of the matrix molecules is shorter than the probe relaxation time and the diffusion of the matrix molecules is larger than the probe diffusion. These results show that the matrix motions drive the dynamics.

Isomerization-induced dynamic heterogeneity in a glass former below and above T(g).

We report the first molecular dynamics simulations of the effect of the photoisomerization of probe molecules on the nonequilibrium dynamics of a glassy or supercooled molecular material. We show that the isomerization of the probe molecules creates a new mobile dynamic heterogeneity inside the matrix. Together with these induced cooperative motions, we find an important increase of the diffusion coefficient leading to liquidlike diffusion below the glass-transition temperature. This result could explain the massive mass transport that leads to surface relief grating formation in azobenzene containing amorphous materials. We find that the isomerization process controls the heterogeneity and the non-gaussian parameter of the material, leading to extremely rapid variations of these quantities.

Incoherent light-induced self-organization of molecules.

Although coherent light is usually required for the self-organization of regular spatial patterns from optical beams, we show that peculiar light-matter interaction can break this evidence. In the traditional method of recording laser-induced periodic surface structures, a light intensity distribution is produced at the surface of a polymer film by an interference between two coherent optical beams. We report on the self-organization followed by propagation of a surface relief pattern. It is induced in a polymer film by using a low-power and small-size coherent beam assisted by a high-power and large-size incoherent and unpolarized beam. We demonstrate that we can obtain large size and well-organized patterns starting from a dissipative interaction. Our experiments open new directions to improving optical processing systems.

Multistate polarization addressing using a single beam in an azo polymer film.

Peculiar light-matter interactions can break the rule that a single beam polarization can address only two states in an optical memory device. Multistate storage of a single beam polarization is achieved using self-induced surface diffraction gratings in a photoactive polymer material. The grating orientation follows the incident light beam's polarization direction. The permanent self-induced surface relief grating can be read out in real time using the same laser beam.

Characterization of the two-photon absorption resonance that is due to the internal charge-transfer transition of a push pull molecule, 4-(diethylamino)-beta-nitrostyrene.

The two-photon absorption resonance that is due to the internal charge-transfer transition of an organic push-pull molecule has been characterized. A nonlinear absorption spectrum of the 4-(diethylamino)- beta-nitrostyrene molecule was measured in a tetrahydrofuran solution by optical Kerr ellipsometry. The shape and the amplitude of the two-photon absorption spectrum are well described by a model that uses the relevant one-photon absorption spectrum related to the internal charge-transfer transition.

All-optical induction of noncentrosymmetry in a transparent nonlinear polymer rod.

What is believed to be the first evidence of an all-optical orientation of a highly transparent polymer is presented. The samples are bulk rods of poly(methyl methacrylate) grafted with paranitroaniline (PNA) obtained by use of copolymerization of methyl methacrylate (MMA) monomers mixed with grafted MMA-PNA monomers. Bulk samples were obtained after molding and polishing of the copolymer with standard techniques. Experiments show that the photoinduced second-order(1) susceptibility chi((2)) may occur through molecular reorientation following selective polar excitation of the nonlinear chromophores by simultaneous two- and three-photon absorption on the same electronic level.

Light-induced second-harmonic generation in azo-dye polymers.

The permanent all-optical poling of an azo-aromatic acrylic copolymer is experimentally demonstrated by seeding preparation in a backward phase-conjugation geometry. The microscopic mechanism involves an orientational hole burning followed by orientational redistribution caused by trans-to-cis isomerization of the azo-dye chromophores. The characteristic kinetics of monitored by second-harmonic generation.

Phase and frequency resolution of picosecond optical Kerr nonlinearities.

We report on a method aimed at measuring both the real and imaginary parts of the third-order Kerr-type nonlinear-optical susceptibility of isotropic materials. It is based on Kerr ellipsometry in which analysis of the polarization state of transmitted light between a nearly crossed polarizer and an analyzer allows separation of pump-induced dichroism and birefringence. The method provides a natural measurement of nonlinear phase retardations in angle units, without any calibration procedure. By using a white-light continuum as a probe, this property is used to get a simultaneous measurement of the nonlinear dispersion in the whole visible spectrum. It is illustrated in tetramethylsilane, where stimulated Stokes and anti-Stokes Raman contributions to the nonlinearity are observed.