Carbon nanotubes (CNTs) possess extraordinary mechanical, thermal, and electrical properties due to their atomically perfect structure and sp2-hybridization. Recently, Single-wall CNTs (SWCNTs) have become an interesting host for the nanoscale confinement of fluids, with a wealth of surprising phenomena appearing: spontaneous filling, frictionless mass transport, unusual phase diagram, etc[1]. Most of these phenomena are still under debate and call for experimental confirmation. But the field is struggling with finding experimental approaches sensitive enough to carry out measurements at the level of individual nanotubes. SWCNT field effect transistors (SWCNT-FETs) showed that the electronic properties of SWCNTs are sensitive to their diameter, defects, doping, adsorbates, and environment [2], [3].In this contribution, we demonstrate that individual carbon nanotube field effect transistors (CNTFET) are excellent tools for this aim, for the first time allowing to precisely identify water confined inside the nanotube. By studying the electrical performances of several unopened and opened CNTFETs submitted to various atmosphere and temperature treatments, i.e. dry air, humidity, secondary vacuum, and current annealing, we show that it is possible to distinguish water being outside and inside the nanotube, just outside, or the nanotube free from water. We thus observed that for opened SWCNT both secondary vacuum and current annealing move threshold gate voltage towards more negative values, while for closed SWCNT secondary vacuum had no effect compared to current annealing. To sum up, the current annealing treatment is essential to distinguish water adsorbed outside from water confined inside. We show that this behavior is universal, as all devices' metallicities behave similarly, provided that the surface of the nanotube is pre-cleaned by current annealing. We will also discuss the mechanisms behind the coupling of electronic transport and the presence of water.Our results open up the possibility to use CNTFET for instance reliable, selective, and sensitive chemical and biological sensors, and also, to resolve the long-standing questions in the nanofluidic community about the behavior of water under nanoscale confinement.Reference:[1] T. A. Pascal, W. A. Goddard, and Y. Jung, “Entropy and the driving force for the filling of carbon nanotubes with water,” Proc. Natl. Acad. Sci., vol. 108, no. 29, pp. 11794–11798, 2011, doi: 10.1073/pnas.1108073108.[2] D. Cao et al., “Electronic sensitivity of carbon nanotubes to internal water wetting,” ACS Nano, vol. 5, no. 4, pp. 3113–3119, 2011, DOI: 10.1021/nn200251z.[3] I. Heller, A. M. Janssens, J. Männik, E. D. Minot, S. G. Lemay, and C. Dekker, “Identifying the mechanism of biosensing with carbon nanotube transistors,” Nano Lett., vol. 8, no. 2, pp. 591–595, 2008, DOI: 10.1021/nl072996i.

The synthesis of multifunctional poly(amidoamine)(PAMAM)-based dendrimers containing a cleavable disulfide linkerwithin each armof the dendrimer, together with condensable triethoxysilyl groups on the periphery of the dendrimer, isdescribed. The dendrimers were mixed with bis(triethoxysilyl)benzene and subsequently transformed into silsesquioxanegels or periodic mesoporous organosilicas (PMOs) to generate materials with dendrimers covalently embedded within theinterior of the silsesquioxane networks. Subsequent treatment of the gels with dithiothreitol enabled the core of thedendrimers to be selectively cleaved at the disulfidesite, thus generating thiol functions localised within the pores.The effect of different dendrimer generations on the reactivity of the pendant thiol functions was probed by impregnationwith gold salts, which were reduced to obtain gold nanoparticleswithin the pore networks of the gels and PMOs. The gelsyielded polydisperse gold nanoparticles (2 to 70 nm) with dimensions modulated by the generation of thedendrimer,together with well-defined gold/thiolate clusters with Au...S distances of 2.3 Å. Suchclusters were also observed in the PMOsystem, together with monodispersed gold nanoparticles with diameters comparable to that of the organised pores in thePMO. The role of surface functionalisation in controlling the formation of gold clusters and/or nanoparticles is discusse

Polarized fluorescence emission of nanoscale emitters has been extensively studied for applications such as bioimaging, display, and optical communication. Extending the polarization properties in large assemblies of compact emitters is, however, challenging because of self-aggregation processes, which can induce depolarization effects, quenching, and cancellations of molecular dipoles. Here we use a-sexithiophene (6T) molecules confined inside boron nitride nanotubes (6T@BNNTs) to induce fluorescence anisotropy in a transparent host. The experiments first indicate that individual 6T@BNNTs exhibit a high polarization extinction ratio, up to 700, at room temperature. Using aberration- corrected HRTEM, we show that the fluorescence anisotropy is consistent with a general alignment of encapsulated 6T molecules along the nanotube axis. The molecular alignment is weakly influenced by the nanotube diameter, a phenomenon ascribed to stronger molecule-to-sidewall interactions compared to intermolecular interactions. By stretching a flexible thin film made of transparent polymers mixed with 6T@BNNTs, we induce a macroscopic fluorescence anisotropy within the film. This work demonstrates that the dyes@BNNT system can be used as an easy-to-handle platform to induce fluorescence anisotropy in photonic materials.

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.