Ionosilica ionogels have been lately introduced as emerging all-ionic designer materials. They consist of an ionic liquid (IL) guest trapped within a solid ionosilica support host. In this work, we investigate the influence of the (i) ionosilica nature and (ii) the ionosilica/IL ratio on the mobility of the confined IL. We report the elaboration of various ionosilica ionogels via a nonhydrolytic sol-gel process, using namely tris(3-(trimethoxysilyl)propyl)amine (TTA), Methyl-tris(3-(trimethoxysilyl)propyl)ammonium iodide (MTTA) and tetrakis(3-(trimethoxysilyl)-propyl)ammonium iodide (TKTA) as ionosilica precursors, with the IL butyl-methyl imidazolium bis-triflimide ([BMIM] TFSI). Various ionogels were prepared from different ratios between the ionosilica host and the IL guest. The host/guest interactions i.e. the change in the conformational contribution of the IL counter-anion were explored by means of Raman spectroscopy. In addition, the transport properties of the confined species were probed via spin echo solid-state NMR experiments and Complex Impedance Spectroscopy (CIS) measurements. Raman experiments revealed different conformational equilibrium for the TFSI anion in the various ionosilica ionogels, with an increase in the cisoid form compared to the bulk IL due to confinement effects. The TFSI anion seems to experience different degree of confinement and thus different interactions with the ionosilica scaffold as a function of the investigated parameters. Concomitantly, the 1H spin echo NMR and CIS measurements revealed a significantly higher ionic mobility in the materials synthesized in the presence of the tris-trialkoxysilylated ammonium precursor compared to the one synthesized in the presence of tetra-trialkoxysilylated ammonium precursor. These results may reflect stronger host-guest interactions in the latter case related to the higher degree of reticulation of the network. All these techniques give concordant results and highlight an effect of the chemical constitution of the ionosilica scaffold and the amount of confined IL on its dynamics within the network.

Low-dimensional boron nitride (BN) chains were prepared in the one-dimensional pores of the siliceous zeolites theta-one (TON) and Mobil-twelve (MTW) by the infiltration, followed by the dehydrocoupling and pyrolysis of ammonia borane under high-pressure, high-temperature conditions. High-pressure X-ray diffraction in a diamond anvil cell and in a large-volume device was used to follow in situ these different steps in order to determine the optimal conditions for this process. Based on these results, millimeter-sized samples of BN/TON and BN/MTW were synthesized. Characteristic B–N stretching vibrations of low-dimensional BN were observed by infrared and Raman spectroscopies. The crystal structures were determined using a combination of X-ray diffraction and density functional theory with one and two one-dimensional zig-zag (BN)x chains per pore in BN/TON and BN/MTW, respectively. These 1-D BN chains potentially have interesting photoluminescence properties in the far ultraviolet region of the electromagnetic spectrum.

Pancreatic cancer is one of the deadliest cancers with an increasing incidence due to a lack ofearly-stage diagnostics and effective treatment [1]. The RAS/RAF/ MAPK/CDK4 pathway is frequentlydysregulated in pancreatic cancer and CDK4 constitutes an attractive target since several drugs havebeen approved by the FDA to inhibit its activity: Abemaciclib, Ribociclib and Palbociclib [2,3] (Figure1) However these inhibitors are not efficient in monotherapy and have only been approved for breastcancer. In order to propose an efficient therapeutic strategy to target CDK4 in pancreatic cancer, wepropose to deliver Abemaciclib using carbon nanotubes.
Carbon nanotubes are promising materials for nanomedicine applications and especially fordrug delivery. [4] In this project, we adsorb Abemaciclib onto single-walled carbon nanotubes (SWNT)for delivery of the drug into pancreatic cancer cells. In order to study adsorption, we investigate thechanges in the optical signatures of SWNTs in the near-infrared (NIR) by coupling NIR absorption,photoluminescence and Raman spectroscopies. [5] Typical kinetic spectroscopic results, assigned tothe adsorption of Abemaciclib on SWNT, dispersed in water using carbomethylcellulose (CMC), arepresented in Figure 2. We discuss the results in terms of changes of the dielectric environment of thenanotubes, leading to modulation of their excitonic and optical properties. We have furtherinvestigated the inhibitory potential of SWNT-Abemaciclib on proliferation of PANC1 cells comparedto Abemaciclib alone and have determined the toxicthreshold of SWNT dispersed in CMC.

Poly(N-isopropyl acrylamide) (PNIPAM) is a thermo-responsive polymer which undergoes a reversible coil-to-globule transition in water at temperatures close to the human body temperature [1]. Consequently, PNIPAM-based microgels show a volume phase transition (VPT) under heating. Photo-responsive hybrid microgels have been prepared by incorporating gold nanoparticles in PNIPAM microgels [2]. The outstanding photo-thermal and optical properties of single-walled carbon nanotubes (SWNTs) make them promising candidates to prepare multi-responsive hybrid microgels. However, no thorough studies have been reported so far.
In this work, we report the preparation and properties of aqueous dispersions of PNIPAM/SWNTs hybrid microgels (Figure 1a). We study their structure by transmission electron microscopy and dynamic light scattering. We investigate their optical properties and changes when heated at the VPT by near infrared (NIR) absorption, Raman and photoluminescence (PL) spectroscopies [3]. Furthermore, we use optical microscopy (Figure 1b), light scattering and NIR Raman/PL spectroscopy to show that the VPT transition can be triggered by NIR photo-thermal excitation.

Density functional tight-binding calculations of the adsorption of OH − and other related diatomic anions on carbon nanotubes and graphene show that two adsorption states coexist: a physisorption state caused by Debye interactions, and a chemisorption state at shorter distances dominated by ionic-covalent interactions. For all anions, both adsorption energies scale linearly with the curvature of the carbon surface, and increase with decreasing anion polarizability but also, in metallic nanotubes, with chiral angle. At short distances, charge transfer modifies the attractive Debye forces into repulsive forces of the dipole-dipole type, tuning the strength of the chemisorption state, and may determine its existence and stability.

NaLa(SO4)2,H2O crystalline powder was obtained under hydrothermal conditions at 220°C. A coupled TGA/DTA experiment of NaLa(SO4)2,H2O exhibits a weight loss at 260°C corresponding to the dehydration and an endothermal peak at 774°C. To elucidate the transformation mechanism as a function of temperature, single crystals have been grown at 80°C, 300 and 800°C. For each phase, single crystals have been isolated and structure determination was performed. As already published, NaLa(SO4)2,H2O crystallizes in a P3121 space group. However, the dehydration at 260°C is not a simple loss of the water molecule but a radical change in the structure. The removal of the water molecules inside the tunnels formed by the framework leads to a change in the coordination of the LaO9 Lanthanum-based polyhedrons. The compound obtained after dehydration is a new triple sulfate of the formula Na3La(SO4)3 crystallizing in the R-3 space group (a = 14.0976(1) Å; c = 8.1267(1) Å) with LaO12 icosahedrons. Millimeter size single crystals of this new phase have been grown under hydrothermal conditions (300°C, 157 bars). After the endothermal peak at 774°C, Na3La(SO4)3 decomposes by forming the anhydrous double sulfate NaLa(SO4)2 crystallizing in the P-1 space group with LaO10 polyhedrons. The structure of the three (NaLa)-compounds at RT, 300°C and 800°C is compatible with the expected Raman signatures. Finally, a complete transformation of NaLa(SO4)2,H2O up to 800°C is proposed. After 1000°C, the compound decomposes chemically with a large weight loss.