Mohammed Guendouz

Molecular dynamics of a short-range ordered smectic phase nanoconfined in porous silicon

4-n-octyl-4-cyanobiphenyl has been recently shown to display an unusual sequence of phases when confined into porous silicon (PSi). The gradual increase of oriented short-range smectic (SRS) correlations in place of a phase transition has been interpreted as a consequence of the anisotropic quenched disorder induced by confinement in PSi. Combining two quasielastic neutron scattering experiments with complementary energy resolutions, the authors present the first investigation of the individual molecular dynamics of this system. A large reduction of the molecular dynamics is observed in the confined liquid phase, as a direct consequence of the boundary conditions imposed by the confinement. Temperature fixed window scans reveal a continuous glasslike reduction of the molecular dynamics of the confined liquid and SRS phases on cooling down to 250 K, where a solidlike behavior is finally reached by a two-step crystallization process.

Relation between static short-range order and dynamic heterogeneities in a nanoconfined liquid crystal.

We analyze the molecular dynamics heterogeneity of the liquid crystal 4-n-octyl-4-cyanobiphenyl nanoconfined in porous silicon. We show that the temperature dependence of the dynamic correlation length xi_(wall) , which measures the distance over which a memory of the interfacial slowing down of the molecular dynamics persists, is closely related to the growth of the short-range static order arising from quenched random fields. More generally, this result may also shed some light on the connection between static and dynamic heterogeneities in a wide class of condensed and soft matter systems.

Towards a biosensor based on anti resonant reflecting optical waveguide fabricated from porous silicon.

Recently, we demonstrated that Anti Resonant Reflecting Optical Waveguide (ARROW) based on porous silicon (PS) material can be used as a transducer for the development of a new optical biosensor. Compared to a conventional biosensor waveguide based on evanescent waves, the ARROW structure is designed to allow a better overlap between the propagated optical field and the molecules infiltrated in the porous core layer and so to provide better molecular interactions sensitivity. The aim of this work is to investigate the operating mode of an optical biosensor using the ARROW structure. We reported here an extensive study where the antiresonance conditions were adjusted just before the grafting of the studied molecules for a given refractive index range. The interesting feature of the studied ARROW structure is that it is elaborated from the same material which is the porous silicon obtained via a single electrochemical anodization process. After oxidation and preparation of the inner surface of porous silicon by a chemical functionalization process, bovine serum albumin (BSA) molecules, were attached essentially in the upper layer. Simulation study indicates that the proposed sensor works at the refractive index values ranging from 1.3560 to 1.3655. The experimental optical detection of the biomolecules was obtained through the modification of the propagated optical field and losses. The results indicated that the optical attenuation decreases after biomolecules attachment, corresponding to a refractive index change Δn(c) of the core. This reduction was of about 2 dB/cm and 3 dB/cm for Transverse Electric (TE) and Transverse Magnetic (TM) polarizations respectively. Moreover, at the detection step, the optical field was almost located inside the core layer. This result was in good agreement with the simulated near field profiles.

Molecular dynamics of glycerol and glycerol-trehalose bioprotectant solutions nanoconfined in porous silicon.

Glycerol and trehalose-glycerol binary solutions are glass-forming liquids with remarkable bioprotectant properties. Incoherent quasielastic neutron scattering is used to reveal the different effects of nanoconfinement and addition of trehalose on the molecular dynamics in the normal liquid and supercooled liquid phases, on a nanosecond time scale. Confinement has been realized in straight channels of diameter D=8 nm formed by porous silicon. It leads to a faster and more inhomogeneous relaxation dynamics deep in the liquid phase. This confinement effect remains at lower temperature where it affects the glassy dynamics. The glass transitions of the confined systems are shifted to low temperature with respect to the bulk ones. Adding trehalose tends to slow down the overall glassy dynamics and increases the nonexponential character of the structural relaxation. Unprecedented results are obtained for the binary bioprotectant solution, which exhibits an extremely non-Debye relaxation dynamics as a result of the combination of the effects of confinement and mixing of two constituents.

Incoherent Quasielastic Neutron Scattering Study of Molecular dynamics of 4-n-cyano-4'-octylbiphenyl.

We report incoherent quasielastic neutron scattering experiments on the thermotropic liquid crystal 4-n-octyl-4-cyanobiphenyl. The combination of time-of-flight and backscattering data allows analysis of the intermediate scattering function over about three decades of relaxation times. Translational diffusion and uniaxial molecular rotations are clearly identified as the major relaxation processes in, respectively, the nanosecond and picosecond time scales.

Micro-resonators based on integrated polymer technology for optical sensing

Research on sensors has experienced a noticeable development over the last decades especially in label free optical biosensors. However, compact sensors without markers for rapid, reliable and inexpensive detection of various substances induce a significant research of new technological solutions. The context of this work is the development of a sensor based on easily integrated and inexpensive micro-resonator (MR) component in integrated optics, highly sensitive and selective mainly in the areas of health and food. In this work, we take advantage of our previous studies on filters based on micro-resonators (MR) to experiment a new couple of polymers in the objective to use MR as a sensing function. MRs have been fabricated by processing SU8 polymer as core and PMATRIFE polymer as cladding layer of the waveguide. The refractive index contrast reaches 0.16 @ 1550 nm. Sub-micronic ring waveguides gaps from 0.5 to 1 μm have been successfully achieved with UV (i-line) photolithography. This work confirms our forecasts, published earlier, about the resolution that can be achieved. First results show a good extinction coefficient of ~17 dB, a quality factor around 104 and a finesse of 12. These results are in concordance with the theoretical study and they allow us to validate our technology with this couple of polymers. Work is going on with others lower cladding materials that will be used to further increase refractive index contrast for sensing applications.

Sliding and translational diffusion of molecular phases confined into nanotubes

The remaining dynamical degrees of freedom of molecular fluids confined into capillaries of nano to sub-nanometre diameter are of fundamental relevance for future developments in the field of nanofluidics. These properties cannot be simply deduced from the bulk one since the derivation of macroscopic hydrodynamics most usually breaks down in nanoporous channels and additional effects have to be considered. In the present contribution, we review some general phenomena, which are expected to occur when manipulating fluids under confinement and ultraconfinement conditions.

Dynamics of 8CB confined into porous silicon probed by incoherent neutron backscattering experiments

Abstract.Confinement in the nanochannels of porous silicon stronglynaffects the phase behavior of the archetype liquid-crystaln4-n-octyl-4-cyanobiphenyl (8CB). Axa0very striking phenomenon is thendevelopment of a short-range smectic order, which occurs on a verynbroad temperature range. It suggests in this case that quenchedndisorder effects add to usual finite size and surface interactionneffects. We have monitored the temperature variation of thenmolecular dynamics of the confined fluid by incoherent quasielasticnneutron scattering. A strongly reduced mobility is observed at thenhighest temperatures in the liquid phase, which suggests that theninterfacial molecular dynamics is strongly hindered. A continuouslynincreasing slowdown appears on cooling together with a progressivengrowth of the static correlation length.

Bioprotectant glassforming solutions confined in porous silicon nanocapillaries

Glycerol and trehalose-glycerol binary solutions are glass-forming liquids with remarkable bioprotectant properties. In this paper, we address the effects of confining of these solutions in straight channels of diameter D=8 nm formed by porous silicon. Neutron diffraction and incoherent quasielastic neutron scattering are used to reveal the different effects of nanoconfinement and addition of trehalose on the intermolecular structure and molecular dynamics of the liquid and glassy phases, on a nanosecond timescale.