In situ time-resolved SAXS study of the formation of mesostructured organically modified silica through modeling of micelles evolution during surfactant-templated self-assembly.

The mechanisms of formation of organically modified (phenyl, vinyl, and methyl) silica materials with cubic Pm3n and hexagonal p6m periodic mesostructures obtained in one step in the presence of the cetyltrimethylammonium bromide (CTA(+)B) surfactant are reported in this study. Understanding the way these complex materials form is difficult but undoubtedly necessary for controlling the material structure and its properties because of the combined presence of surface organic groups and large surface areas. Here, the mechanism of formation is clarified on the basis of the modeling of time-resolved in situ small angle X-ray scattering (SAXS) experiments, with a specific focus on the micelle evolution during material formation. Their fast self-assembly is followed for the first time with a quick temporal resolution of a few seconds using a third-generation synchrotron radiation source. To better understand the behavior of the complex organic-containing mesostructure, we perform a comparative study with the corresponding organo-free, isostructural materials obtained from three different surfactants (CTA(+), CTEA(+), and CTPA(+)) having a constant chain length (C(16)) and an increasing polar head volume (met-, et-, and prop-). Numerical modeling of SAXS data was crucial to highlighting a systematic sphere-to-rod micellar transition, otherwise undetected, before the formation of the 2D hexagonal phase in both organo-free and organo-containing systems. Then, two different pathways were found in the formation of the cubic Pm3n mesostructure: either an ordering transition from concentrated flocs of spherical micelles (from CTEA(+) or CTPA(+)) for pure TEOS systems or a structural transformation from an intermediate 2D hexagonal mesophase in organosilane systems (from CTA(+)). Combining the comparison between organo-free and organo-containing systems with numerical modeling, we find that the hexagonal-to-cubic phase transition in the organically modified materials seems to be strongly influenced not only by the obvious presence of the organic group but also by the quicker and more massive condensation kinetics of silicate oligomers on the CTA(+) micellar surface. Finally, quite unexpectedly, we find a wormlike-to-sphere micellar transition in the CTPA(+) system.

87Sr solid-state NMR as a structurally sensitive tool for the investigation of materials: antiosteoporotic pharmaceuticals and bioactive glasses.

Strontium is an element of fundamental importance in biomedical science. Indeed, it has been demonstrated that Sr(2+) ions can promote bone growth and inhibit bone resorption. Thus, the oral administration of Sr-containing medications has been used clinically to prevent osteoporosis, and Sr-containing biomaterials have been developed for implant and tissue engineering applications. The bioavailability of strontium metal cations in the body and their kinetics of release from materials will depend on their local environment. It is thus crucial to be able to characterize, in detail, strontium environments in disordered phases such as bioactive glasses, to understand their structure and rationalize their properties. In this paper, we demonstrate that (87)Sr NMR spectroscopy can serve as a valuable tool of investigation. First, the implementation of high-sensitivity (87)Sr solid-state NMR experiments is presented using (87)Sr-labeled strontium malonate (with DFS (double field sweep), QCPMG (quadrupolar Carr-Purcell-Meiboom-Gill), and WURST (wideband, uniform rate, and smooth truncation) excitation). Then, it is shown that GIPAW DFT (gauge including projector augmented wave density functional theory) calculations can accurately compute (87)Sr NMR parameters. Last and most importantly, (87)Sr NMR is used for the study of a (Ca,Sr)-silicate bioactive glass of limited Sr content (only ~9 wt %). The spectrum is interpreted using structural models of the glass, which are generated through molecular dynamics (MD) simulations and relaxed by DFT, before performing GIPAW calculations of (87)Sr NMR parameters. Finally, changes in the (87)Sr NMR spectrum after immersion of the glass in simulated body fluid (SBF) are reported and discussed.

Investigation of the interface in silica-encapsulated liposomes by combining solid state NMR and first principles calculations.

In the context of nanomedicine, liposils (liposomes and silica) have a strong potential for drug storage and release schemes: such materials combine the intrinsic properties of liposome (encapsulation) and silica (increased rigidity, protective coating, pH degradability). In this work, an original approach combining solid state NMR, molecular dynamics, first principles geometry optimization, and NMR parameters calculation allows the building of a precise representation of the organic/inorganic interface in liposils. {(1)H-(29)Si}(1)H and {(1)H-(31)P}(1)H Double Cross-Polarization (CP) MAS NMR experiments were implemented in order to explore the proton chemical environments around the silica and the phospholipids, respectively. Using VASP (Vienna Ab Initio Simulation Package), DFT calculations including molecular dynamics, and geometry optimization lead to the determination of energetically favorable configurations of a DPPC (dipalmitoylphosphatidylcholine) headgroup adsorbed onto a hydroxylated silica surface that corresponds to a realistic model of an amorphous silica slab. These data combined with first principles NMR parameters calculations by GIPAW (Gauge Included Projected Augmented Wave) show that the phosphate moieties are not directly interacting with silanols. The stabilization of the interface is achieved through the presence of water molecules located in-between the head groups of the phospholipids and the silica surface forming an interfacial H-bonded water layer. A detailed study of the (31)P chemical shift anisotropy (CSA) parameters allows us to interpret the local dynamics of DPPC in liposils. Finally, the VASP/solid state NMR/GIPAW combined approach can be extended to a large variety of organic-inorganic hybrid interfaces.