Doru Constantin

Photochromic hybrid organic-inorganic liquid- crystalline materials built from nonionic surfactants and polyoxometalates: elaboration and structural study

This work reports the elaboration and structural study of new hybrid organic-inorganic materials constructed via the coupling of liquid-crystalline nonionic surfactants and polyoxometalates (POMs). X-ray scattering and polarized light microscopy demonstrate that these hybrid materials, highly loaded with POMs (up to 18 wt %), are nanocomposites of liquid-crystalline lamellar structure (Lalpha), with viscoelastic properties close to those of gels. The interpretation of X-ray scattering data strongly suggests that the POMs are located close to the terminal -OH groups of the nonionic surfactants, within the aqueous sublayers. Moreover, these materials exhibit a reversible photochromism associated to the photoreduction of the polyanion. The photoinduced mixed-valence behavior has been characterized through ESR and UV-visible-near-IR spectroscopies that demonstrate the presence of W(V) metal cations and of the characteristic intervalence charge transfer band in the near-IR region, respectively. These hybrid nanocomposites exhibit optical properties that may be useful for applications involving UV-light-sensitive coatings or liquid-crystal-based photochromic switches. From a more fundamental point of view, these hybrid materials should be very helpful models for the study of both the static and dynamic properties of nano-objects confined within soft lamellar structures.

Magnetic nanorods confined in a lamellar lyotropic phase.

The dilute lamellar phase of the nonionic surfactant C 12EO 5 was doped with goethite (iron oxide) nanorods up to a fraction of 5 vol %. The interaction between the inclusions and the host phase was studied by polarized optical microscopy (with or without an applied magnetic field) and by small-angle X-ray scattering. We find that, when the orientation of the nanorods is modified using the magnetic field, the texture of the lamellar phase changes accordingly; one can thus induce a homeotropic-planar reorientation transition. On the other hand, the lamellar phase induces an attractive interaction between the nanorods. In more concentrated lamellar phases (under stronger confinement) the particles form aggregates. This behavior is not encountered for a similar system doped with spherical particles, emphasizing the role of particle shape in the interaction between doping particles and the host phase.

Real-Time in Situ Probing of High-Temperature Quantum Dots Solution Synthesis

Understanding the formation mechanism of colloidal nanocrystals is of paramount importance in order to design new nanostructures and synthesize them in a predictive fashion. However, reliable data on the pathways leading from molecular precursors to nanocrystals are not available yet. We used synchrotron-based time-resolved in situ small and wide-angle X-ray scattering to experimentally monitor the formation of CdSe quantum dots synthesized in solution through the heating up of precursors in octadecene at 240 °C. Our experiment yields a complete movie of the structure of the solution from the self-assembly of the precursors to the formation of the quantum dots. We show that the initial cadmium precursor lamellar structure melts into small micelles at 100 °C and that the first CdSe nuclei appear at 218.7 °C. The size distributions and concentration in nanocrystals are measured in a quantitative fashion as a function of time. We show that a short nucleation burst lasting 30 s is followed by a slow decrease of nanoparticle concentration. The rate-limiting process of the quantum dot formation is found to be the thermal activation of selenium.

Norovirus capsid proteins self-assemble through biphasic kinetics via long-lived stave-like intermediates.

The self-assembly kinetics for a norovirus capsid protein were probed by time-resolved small-angle X-ray scattering and then analyzed by singular value decomposition and global fitting. Only three species contribute to the total scattering intensities: dimers, intermediates comprising some 11 dimers, and icosahedral T = 3 capsids made up of 90 dimers. Three-dimensional reconstructions of the intermediate robustly show a stave-like shape consistent with an arrangement of two pentameric units connected by an interstitial dimer. Upon triggering of self-assembly, the biphasic kinetics consist of a fast step in which dimers are assembled into intermediates, followed by a slow step in which intermediates interlock into capsids. This simple kinetic model reproduces experimental data with an excellent agreement over 6 decades in time and with nanometer resolution. The extracted form factors are robust against changes in experimental conditions. These findings challenge and complement currently accepted models for the assembly of norovirus capsids.

Diffusion coefficients in a lamellar lyotropic phase: evidence for defects connecting the surfactant structure

We measure diffusion coefficients in the lamellar phase of the nonionic binary system C(12)EO(6)/H(2)O using fluorescence recovery after photobleaching. The diffusion coefficient across the lamellae shows an abrupt increase upon approaching the lamellar-isotropic phase transition. We interpret this feature in terms of defects connecting the surfactant structure. An estimation of the defect density and of the variation in defect energy close to the transition is given in terms of a simple model.

Lyotropic Lamellar Phase Doped with a Nematic Phase of Magnetic Nanorods

We report the elaboration of a hybrid mesophase combining the lamellar order of a lyotropic system of nonionic surfactant and the nematic order of a concentrated solution of inorganic nanorods confined between the surfactant layers. Highly aligned samples of this mesophase can be obtained by thermal annealing, and the orientation of the nanorods is readily controlled with a magnetic field. High-resolution synchrotron X-ray scattering and polarized optical microscopy show that, compared to their isolated counterparts, both the nematic and lamellar orders are altered, demonstrating their interplay.

Biomimetic membranes of lipid-peptide model systems prepared on solid support

The structure of membrane-active peptides and their interaction with lipid bilayers can be studied in oriented lipid membranes deposited on solid substrates. Such systems are desirable for a number of surface-sensitive techniques. Here we focus on structural characterization by x-ray and neutron reflectivity and give an account of recent progress in sample preparation and measurements. We show that the degree of mesoscopic disorder in the films can significantly influence the scattering curves. Static defects should be minimized by optimization of the preparation techniques and their presence must be taken into account in the modelling. Examples are given for alamethicin and magainin in bilayers of different phosphocholines.

Solid-supported lipid multilayers: Structure factor and fluctuations

Abstract.We present a theoretical description of the thermal fluctuations in a solid-supported stack of lipid bilayers, for the case of vanishing surface tension

Interaction of Alamethicin Pores in DMPC Bilayers

\gamma = 0

Bilayer Elasticity at the Nanoscale: The Need for New Terms

and in the framework of continuous smectic elasticity. The model is successfully used to model the reflectivity profile of a thin (16 bilayers) DMPC sample under applied osmotic pressure and the diffuse scattering from a thick (800 bilayers) stack. We compare our model to previously existing theories.