Bicarbonate de sodium | EPFL Graph Search

Le bicarbonate de sodium (ou carbonate monosodique ou carbonate acide de sodium, anciennement bicarbonate de soude), l'hydrogénocarbonate de sodium en nomenclature moderne, est un composé inorganique décrit par la formule brute . C'est un composé ionique blanc de l'anion hydrogénocarbonate et du cation sodium, qui se présente sous forme de poudres. La forme ultra pure, très rare, est constituée de cristaux prismatiques blancs. Ce corps minéral anhydre, sous l'appellation minéralogique de nahcolite, apparaît néanmoins dans la nature sous la forme d'agrégats de cristaux prismatiques, le plus souvent en veines fibreuses ou en concrétions. Au laboratoire, l'hydrogénocarbonate de sodium apparaît sous la forme de fins cristaux blancs, solubles dans l'eau. Historique Les Égyptiens de l'Antiquité connaissaient déjà la poudre blanche appelée natron, se présentant comme des efflorescences se formant sur les bords des eaux saumâtres lors de l'évaporation de nombreux lacs africain

Acidic tumor microenvironment abrogates the efficacy of mTORC1 inhibitors

Anne Planche, Tania Santoro

Background: Blocking the mechanistic target of rapamycin complex-1 (mTORC1) with chemical inhibitors such as rapamycin has shown limited clinical efficacy in cancer. The tumor microenvironment is characterized by an acidic pH which interferes with cancer therapies. The consequences of acidity on the anti-cancer efficacy of mTORC1 inhibitors have not been characterized and are thus the focus of our study. Methods: Cancer cell lines were treated with rapamycin in acidic or physiological conditions and cell proliferation was investigated. The effect of acidity on mTORC1 activity was determined by Western blot. The anticancer efficacy of rapamycin in combination with sodium bicarbonate to increase the intratumoral pH was tested in two different mouse models and compared to rapamycin treatment alone. Histological analysis was performed on tumor samples to evaluate proliferation, apoptosis and necrosis. Results: Exposing cancer cells to acidic pH in vitro significantly reduced the anti-proliferative effect of rapamycin. At the molecular level, acidity significantly decreased mTORC1 activity, suggesting that cancer cell proliferation is independent of mTORC1 in acidic conditions. In contrast, the activation of mitogen-activated protein kinase (MAPK) or AKT were not affected by acidity, and blocking MAPK or AKT with a chemical inhibitor maintained an anti-proliferative effect at low pH. In tumor mouse models, the use of sodium bicarbonate increased mTORC1 activity in cancer cells and potentiated the anti-cancer efficacy of rapamycin. Combining sodium bicarbonate with rapamycin resulted in increased tumor necrosis, increased cancer cell apoptosis and decreased cancer cell proliferation as compared to single treatment. Conclusions: Taken together, these results emphasize the inefficacy of mTORC1 inhibitors in acidic conditions. They further highlight the potential of combining sodium bicarbonate with mTORC1 inhibitors to improve their anti-tumoral efficacy.

Biomed Central Ltd2016

Stability and physical properties of alkylsilane and alkylphosphonate self-assembled monolayer (SAM) films on metal oxide substrates characterized at the micro- and nanoscale

Enamul Hoque

Self-assembled monolayer (SAM) films have attracted immense attention for both fundamental and applied research. A SAM is composed of a large number of molecules with a head group that chemisorbs onto a substrate, a tail group that interacts with the outer surface of the film, and a spacer (backbone) chain group that connects the head and tail groups resulting in a coating. Interactions between spacer groups of different molecules, such as van der Waals forces and/or hydrogen bonding, hasten SAM film formation and contribute to its stability. In this dissertation, SAM and thin films have been formed onto copper and aluminum oxide surfaces by reaction with 1H,1H,2H,2H-perfluorodecyldimethylchlorosilane (PFMS), 1H,1H,2H,2H-perfluorodecyltrichlorosilane (PFTS), 1H,1H,2H,2H-perfluorodecylphosphonic acid (PFDP), octylphosphonic acid (OP), decylphosphonic acid (DP), and octadecylphosphonic acid (ODP). The properties and stability of the films were investigated employing complementary surface analysis techniques: X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), friction force microscopy (FFM), a derivative of AFM, contact angle measurements (CAMs), and Fourier transform infrared reflection/absorption spectroscopy (FT-IRRAS). The perfluoroalkylsilane SAM on Cu is found to be extremely hydrophobic typically having sessile drop static contact angles of more than 130° for pure water and a surface energy of 14 mJ/m2 (mN/m). FFM showed a significant reduction in the adhesive force and friction coefficient of PFMS modified Cu (PFMS/Cu) compared to unmodified Cu. Treatment by exposure to harsh conditions showed that PFMS/Cu SAM can withstand boiling nitric acid (pH=1.8), boiling water, and warm sodium hydroxide (pH=12, 60 °C) solutions for at least 30 minutes. Furthermore, no SAM degradation was observed when PFMS/Cu was exposed to warm nitric acid solution for up to 70 min at 60 °C or 50 min at 80 °C. XPS and FT-IRRAS data reveal a coordination of the PFMS silicon (Si) atom with a cuprate (CuO) molecule present on the oxidized copper substrate. The data give good evidence that the stability of the SAM film on the PFMS modified oxidized Cu surface is largely due to the formation of a siloxy-copper (-Si-O-Cu-) bond via a condensation reaction between silanol (-Si-OH) and copper hydroxide (CuOH). For a PFTS modified Cu surface (PFTS/Cu), the sessile drop static contact angle of pure water has been measured to be more than 125° and the surface energy to be typically less than 16 mJ/m2. Stability tests show that the PFTS/Cu film can survive in boiling pure water for one hour, boiling nitric acid (pH 1.5 or 1.8) for 30 minutes, sodium hydroxide solution (pH 12, 70 °C) for 30 minutes, and autoclave conditions (steam at 134 °C and 3 atmospheres) for 15 minutes. The more commonly used self-assembled monolayer (SAM) modifications of Cu surfaces, e.g. thiol compounds, are significantly less stable than PFTS/Cu. Extremely hydrophobic (low surface energy) and stable PFMS/Cu SAMs and PFTS/Cu films could be useful as corrosion inhibitors in micro/nanoelectronic devices and/or as promoters for anti-wetting, low adhesion surfaces or drop-wise condensation on heat exchange surfaces. XPS analysis confirmed the presence of perfluorinated and non-perfluorinated alkylphosphonate molecules on the PFDP, DP, and ODP SAMs deposited at the aluminum oxide coated silicon (Al/Si) surfaces. The sessile drop static contact angle of pure water on PFDP SAMs was typically more than 130° and on DP and ODP typically more than 125° indicating that the phosphonic acid SAMs reacted with Al samples were very hydrophobic. The surface roughness for PFDP/Al, DP/Al, ODP/Al, and bare Al was approximately 35 nm, as determined by AFM. The surface energy for PFDP/Al was determined to be approximately 11 mJ/m2 by the Zisman plot method compared to 21 mJ/m2 and 20 mJ/m2 for DP/Al and ODP/Al, respectively. PFDP/Al gave the lowest adhesion and friction force while bare Al gave the highest. The adhesion and friction forces for ODP/Al and DP/Al SAMs were in between. ODP, DP, and OP SAMs have been studied in detail on relatively flat aluminum oxide surfaces. The rms surface roughness for ODP/Al, DP/Al, OP/Al, and bare Al was less than 15 nm, as determined by AFM. The sessile drop static contact angle of pure water on ODP/Al and DP/Al was typically more than 115° and on OP/Al typically less than 105°. The surface energy for ODP/Al and DP/Al was determined to be approximately 21 mJ/m2 and 22 mJ/m2, respectively, compared to 26 mJ/m2 for OP/Al. ODP/Al and OP/Al were studied by FFM to better understand their micro-/nano-tribological properties. ODP/Al gave the lowest coefficient of friction values while bare Al gave the highest. The adhesion forces for ODP/Al and OP/Al were comparable. The chemical stability of ODP/Al, PFDP/Al, DP/Al, OP/Al, and PFMS/Al SAMs has been inspected by exposure to warm nitric acid (pH 1.8, 30 min, 60-95 °C). The XPS data and stability against harsh chemical conditions indicate that a type of bond forms between a phosphonic acid (PA) or silane molecule and the oxidized Al surface. Stability tests using warm nitric acid (pH 1.8, 30 min, 60-95 °C) show ODP/Al SAMs to be most stable followed by PFDP/Al, DP/Al, PFMS/Al, and OP/Al SAMs. For PFTS/Al, stability tests demonstrate that modified aluminum is able to survive exposure to warm nitric acid (pH = 1.8, 60 °C, 30 min) indicating some degree of robustness. Hydrophobic, low adhesion, and robust aluminum surfaces have useful applications for micro/nano-electromechanical systems (MEMS/NEMS), such as digital micro-mirror devices (DMDs). These studies are expected to aid in the design and selection of proper lubricants for MEMS/NEMS.

EPFL2007

Carbon dioxide for hydrogen storage via formic acid derivatives and methanol

Katerina Stefania Sordakis

Securing our energy future while minimizing the associated environmental impacts is a challenging endeavor and the fundamental aspect of sustainable development. The choice of energy resource and the reduction of greenhouse gas emissions, primarily carbon dioxide (CO2), are key parameters in this process. Hydrogen gas (H2) is an energy carrier with the potential of "green" production and utilization, in addition to having attractive inherent fuel properties. However, complications during its storage arise from its intrinsically light nature. Chemical H2 fixation within liquid formic acid (FA) and its derivatives is therefore a promising approach. In the present dissertation, reversible H2 storage cycles based on homogeneous FA/formate dehydrogenation and CO2/bicarbonate hydrogenation, as well as the related CO2 transformation to methanol are investigated. The first chapter provides an overview of challenges underlying energy sustainability, prospects for integration of H2 with our energy infrastructure, the employment of FA as a liquid organic hydrogen carrier and state of the art homogeneous catalysts for selective FA dehydrogenation and CO2 hydrogenation. The combination of these reactions to form a closed CO2 loop is the basic concept behind a reversible H2 storage system as it is envisaged by our group. In the second chapter, FA dehydrogenation/formation in the presence of triethylamine is discussed. The results are summarized as equilibrium positions within this couple, which can be controlled by adjustment of the operating pressure and temperature. The basic additive promotes H2 fixation but also allows for on-demand H2 release from a triethylammonium formate substrate. The third chapter addresses H2 storage in basic media, i.e. aqueous bicarbonate hydrogenation, with a Ru(III) catalyst precursor and a number of water-soluble phosphine ligands. The latter are introduced to tailor the exhibited activity by affecting the steric and electronic parameters of the catalyst. All phosphines provide high bicarbonate conversions, albeit with low reaction rates. Chapter four summarizes the optimization and mechanistic studies of the reversible formate dehydrogenation reaction, in the presence of a Ru(II)-mTPPTS catalyst. Cesium is chosen as the cation for the formate/bicarbonate salts because it leads to their high solubility in the aqueous solvent and therefore an increase in the hydrogen storage capacity. The involved equilibria are determined and a reaction mechanism for the formate dehydrogenation step is proposed, based on NMR studies. Advantages of the presented approach include the utilization of water as the solvent, the absence of CO2 throughout the reactions and the successful in situ recycling of the environmentally benign hydrogen carrier. In Chapter five the feasibility of producing both FA and methanol directly from CO2, at room temperature, in a "one-pot" reaction using aqueous solvent is demonstrated. Formic acid formation occurs in water without additives or organic solvents with a homogeneous iridium catalyst. Formic acid also undergoes disproportionation into methanol, with the same complex. Under optimized conditions, FA conversions of 98% and methanol selectivities of 96% are achieved in the disproportionation reaction. These reactions are relevant to the field of sustainable H2 storage, but might also provide an alternative approach to the commercial fossil-fuel-dependent production of formic acid and methanol.

EPFL2016