Graphene-doped photo-patternable ionogels: tuning of conductivity and mechanical stability of 3D microstructures

This work reports for the first time the development of enhanced conductivity, graphene- doped photo-patternable hybrid organic-inorganic ionogels and the effect of the subsequent materials condensation on the conductivity and mechanical stability of three- dimensional microstructures fabricated by multi-photon polymerisation (MPP). Ionogels were based on photocurable silicon/zirconium hybrid sol-gel materials and phosphonium (trihexyltetradecylphosphonium dicyanamide [P6,6,6,14][DCA] ionic liquid (IL). To optimise the dispersion of graphene within the ionogel matrices, aqueous solutions of graphene were prepared, as opposed to the conventional graphene powder approach, and employed as catalysts of hydrolysis and condensation reactions occurring in the sol-gel process. Ionogels were prepared via a two step process by varying the hydrolysis degree from 25 to 50%, IL content between 0-50 w/w%, and the inorganic modifier (zirconate complex) concentration from 30 to 60 mol.% against the photocurable ormosil and they were characterised via Raman, Electrochemical Impedance Spectroscopy and Transmission Electron Microscopy. MPP was performed on the hybrid ionogels, resulting in three- dimensional microstructures that were characterised using scanning electron microscopy. It is clearly demonstrated that the molecular formulation of the ionogels, including the concentration of graphene and the zirconate network modifier, play a critical role in the conductivity of the ionogels and influence the resulting mechanical stability of the fabricated three-dimensional microstructures. This work aims to establish for the first time the relationship between the molecular design and condensation of materials in the physico-chemistry and dynamic of ionogels

Use of ionic liquids in sol-gel; ionogels and applications

International audienceThe current strong interest in ionic liquids is motivated by their unique combination of properties such as negligible vapour pressure, thermal stability, non-flammability, high ionic conductivity and wide electrochemical stability window. The first part of this short review deals with all the specific aspects of sol-gel in the presence of ionic liquid, which can act as drying control chemical additive, catalyst, porogenous agent and solvent or co-solvent. The second part is devoted to the properties of the gels in which the ionic liquid is kept confined (ionogels) and their applications as electrolyte membranes, optical devices, catalysts and sensors

Synthesis of titanium dioxide precursor by the hydrolysis of titanium oxychloride solution

[EN] This communication focuses on the development of an approach to improve the synthesis of [Ti8O12(H2O)24]Cl8.HCl.7H2O crystals which is one of the precursor for titanium dioxide TiO2 particles. This study provides a significant improvement in crystallization kinetics with a production rate increased by a factor nineteen by intensifying heat and mass transfers compared to the process in a close vessel. This enhancement was made possible by the development of a new reactor to control the heat and mass transfers involved. In parallel with the experimental set-up, a numerical model representative of the transfer phenomena was initiated. The first numerical results are encouraging and present a good agreement with the measurements.The authors acknowledge financial support from the French Agence Nationale de la Recherche (ANR) under reference ANR-12-EMMA-0023 (Nano-OxTi project).Le Bideau, P.; Richard-Plouet, M.; Glouannec, P.; Magueresse, A.; Iya-Sou, D.; Brohan, L. (2018). Synthesis of titanium dioxide precursor by the hydrolysis of titanium oxychloride solution. En IDS 2018. 21st International Drying Symposium Proceedings. Editorial Universitat Politècnica de València. 1333-1340. https://doi.org/10.4995/IDS2018.2018.75811333134

Structure and dynamics in protic ionic liquids: a combined optical Kerr-effect and dielectric relaxation spectroscopy study

The structure and dynamics of ionic liquids (ILs) are unusual due to the strong interactions between the ions and counter ions. These microscopic properties determine the bulk transport properties critical to applications of ILs such as advanced fuel cells. The terahertz dynamics and slower relaxations of simple alkylammonium nitrate protic ionic liquids (PILs) are here studied using femtosecond optical Kerr-effect spectroscopy, dielectric relaxation spectroscopy, and terahertz time-domain spectroscopy. The observed dynamics give insight into more general liquid behaviour while comparison with glass-forming liquids reveals an underlying power-law decay and relaxation rates suggest supramolecular structure and nanoscale segregation

Cracking Piles of Brittle Grains

A model which accounts for cracking avalanches in piles of grains subject to external load is introduced and numerically simulated. The stress is stochastically transferred from higher layers to lower ones. Cracked areas exhibit various morphologies, depending on the degree of randomness in the packing and on the ductility of the grains. The external force necessary to continue the cracking process is constant in wide range of values of the fraction of already cracked grains. If the grains are very brittle, the force fluctuations become periodic in early stages of cracking. Distribution of cracking avalanches obeys a power law with exponent $\tau = 2.4 \pm 0.1$.Comment: RevTeX, 6 pages, 7 postscript figures, submitted to Phys. Rev.

Angiotensin II Receptor Blockers (ARBs Antihypertensive Agents) Increase Replication of SARS-CoV-2 in Vero E6 Cells

Several comorbidities, including hypertension, have been associated with an increased risk of developing severe disease during SARS-CoV-2 infection. Angiotensin II receptor blockers (ARBs) are currently some of the most widely-used drugs to control blood pressure by acting on the angiotensin II type 1 receptor (AT1R). ARBs have been reported to trigger the modulation of the angiotensin I converting enzyme 2 (ACE2), the receptor used by the virus to penetrate susceptible cells, raising concern that such treatments may promote virus capture and increase their viral load in patients receiving ARBs therapy. In this in vitro study, we reviewed the effect of ARBs on ACE2 and AT1R expression and investigated whether treatment of permissive ACE2+/AT1R+ Vero E6 cells with ARBs alters SARS-CoV-2 replication in vitro in an angiotensin II-free system. After treating the cells with the ARBs, we observed an approximate 50% relative increase in SARS-CoV-2 production in infected Vero E6 cells that correlates with the ARBs-induced up-regulation of ACE2 expression. From this data, we believe that the use of ARBs in hypertensive patients infected by SARS-CoV-2 should be carefully evaluated

Organic electrochemical transistor incorporating an ionogel as solid state electolyte for lactate sensing

The bulk of currently available biosensing techniques often require complex liquid handling, and thus suffer from problems associated with leaking and contamination. We demonstrate the use 10 of an Organic Electrochemical Transistor (OECT) for detection of lactate (an essential analyte in physiological measurements of athlete performance) by integration of a RTIL in a gel-format, as a solid-state electrolyte

Cymantrene, Cyrhetrene and Ferrocene Nucleobase Conjugates: Synthesis, Structure, Computational Study, Electrochemistry and Antitrypanosomal Activity

A series of cymantrene- and cyrhetrene-nucleobase derivatives together with the ferrocene-adenine conjugates have been prepared and characterized. The key step in synthesis of all compounds involved an N1-regioselective Michael addition of the respective nucleobase nucleophile to an in situ generated organometallic acryloyl electrophile reagent. The mechanism of this reaction was examined by DFT calculations. A single crystal X-ray diffraction study of cymantrene-adenine (5) were carried out and revealed that the plane of the adenine and the cyclopentadienyl group are almost perpendicular to each other. The cyclic voltammetry measurements on the cymantrenyl-nucleobases showed irreversible behavior for all compounds which can be explain by a ligand exchange of carbonyls with the donor functionality of the nucleobases. Cymantrene and cyrhetrene ketone nucleobases displayed significant in vitro activity against Trypanosoma brucei a causative parasite of sleeping sickness. They showed no cytotoxicity against human HL-60 cancer cells