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At least 1,135 records · Page 63

Pyrolysis Vapor and Bio-Oil Preconditioning via Ex Situ Hydrodeoxygenation and Alkylation Using a Heteropolyacid Catalyst

Ex situ catalytic preconditioning of biomass pyrolysis vapors (partial deoxygenation) has the potential for both reducing the oxygen content and beneficially influencing the oxygen speciation of condense bio-oils for enhancement of downstream condensed phase upgrading processes. Here, condensed phase upgrading processes may refer to both coprocessing and hydroprocessing with vacuum gas-oil (VGO). Reduction of oxygen content to produce bio-oils with greater hydrophobicity can enhance VGO-solubility while tailoring of oxygen speciation by removal of reactive carbonyls (e.g., acetic acid) can lessen catalytic deactivation via coking reactions. 1,2 Furthermore, enhanced VGO-solubility and reduced coking leads to greater biogenic carbon incorporation in end-products from condensed phase upgrading processes. By leveraging the hydrodeoxygenation and alkylation activity of a titania-supported molybdenum-heteropolyacid (Mo-HPA/TiO2) catalyst, pyrolysis vapors and resulting condensed bio-oils were effectively preconditioned for downstream upgrading. 3 Data regarding the use of Mo-HPA/TiO2 for pyrolysis vapor preconditioning will be presented on, including method of employment, catalyst characterization, and impacts on bio-oil in relation to downstream condensed phase upgrading processes. Our approach is to: Compare Mo-HPA/TiO2 product distribution to HZSM-5; Investigate Mo-HPA/TiO2 regeneration and characterize changes in acid site character; Assess product differences in terms of enhanced VGO-solubility.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Rechargeable alkaline battery using organic materials as negative electrodes

An energy storage device may provide a positive electrode, an electrolyte, and a negative electrode. The energy storage device may utilize an aqueous alkaline electrolyte, which may be nonflammable. The energy storage device may utilize organic material(s) as the negative electrode, such as, but not limited to, poly(anthraquinonyl sulfide) (PAQS), organic carbonyl compounds, organosulfur compounds, redox polymers, or radical polymers.

25 ENERGY STORAGE↗

BETO 2021 Peer Review - Analytical Development and Standardization for Biomass-Derived Thermochemical Liquids

This project began in FY14 to address the lack of standard chemical characterization analytical methods for bio-oils. Bio-oils are very complex and present numerous analytical challenges; yet reliable chemical information (quantification of both individual compounds and chemical functional groups) is needed to inform upgrading research and refinery co-processing. In this project, analysis needs are first determined from engaging the bioenergy community. Next, standard methods are developed to meet these needs, and then subsequently validated via inter-laboratory studies. Methods that are successfully validated (< 10% variability) are then shared as Laboratory Analytical Procedures (LAPs), which are free and publicly available. We have been tracking LAP use and have seen sustained usage as evidenced by an average of 500 pages views and 100 downloads per quarter, demonstrating the value of these methods to the bioenergy community. LAP methods that are particularly useful and reliable will be chosen for the next-level of standardization through ASTM. We have recently achieved approval by ASTM for our carbonyl titration method. This method (ASTM E3146) is the first example of an ASTM standard solely focused on the chemical characterization of bio-oils. Work in this project is meeting the analysis needs of the bioenergy community and will ultimately help enable the commoditization of bio-oils.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Feedstock and Catalyst Impact on Bio-Oil Production and FCC Co-Processing to Fuels

NREL’s thermochemical biomass conversion research is focused on ex-situ upgrading of biomass fast-pyrolysis (FP) vapors as an efficient and economical route to completely biogenic pyrolysis-based fuel precursors, potential fuels, and value-added chemicals depending on catalyst choice and process conditions. In this approach, biomass vapors are generated via fast pyrolysis with destabilizing vapor components (char, inorganics, tar aerosols) removed by hot gas filtration to produce conditioned vapors more responsive to catalytic upgrading. A Davison Circulating Riser (DCR), a petroleum industry standard for fluidized catalytic cracking (FCC) catalyst evaluation, was coupled with a custom pyrolyzer system designed to produce consistent composition pyrolysis vapors as feed to the DCR. The coupled system is shown below (Figure 1). Pyrolysis vapors, derived from pure hardwood and softwood, were upgraded using commercially available and laboratory modified zeolite-based catalysts. Upgraded oils were analyzed via 31P and 13C NMR spectroscopy, GCxGC-TOF/MS, carbonyl and ultimate analysis (CHNO), and micro distillation to assess both oil chemistry and distillation behavior as they relate to catalyst and feedstock type for producing fungible hydrocarbon product liquids. Measured process parameters identified from technoeconomic process analysis included achieving oil oxygenate contents of 20% or less, carbon-conversion efficiencies of 30% or more, and catalyst coking rates of 10% or less. A proprietary modified zeolite catalyst from Johnson Matthey produced oils that met these requirements. Using the DCR equipped with a proprietary nozzle system, a second approach focused on reducing the carbon intensity of petroleum-derived hydrocarbon fuels by FCC co-processing these CFP oils with petroleum vacuum gas oil (VGO) to produce biogenic carbon containing fuels. The vapor-phase upgrading results demonstrated for the first time the feasibility of producing refinery-compatible hydrocarbon fuel intermediates entirely from biomass-derived fast-pyrolysis vapors using an industry-accepted DCR system for catalytic upgrading. The co-processing results demonstrated the feasibility of using CFP oils with VGO feeds in FCC refinery operations to produce biogenic carbon containing fuels.

bio-oil↗

Conversion of lignin to ionic liquids

Disclosed herein are lignin-derived ionic liquids and methods for preparing them. The methods include forming a reaction mixture comprising a lignin-derived starting material, a carbonyl compound, and an amine; maintaining the reaction mixture under conditions sufficient to form a lignin-derived aminophenol; and converting the lignin derived aminophenol to the lignin-derived ionic liquid. Monomeric phenols, oligomeric phenols, and polymeric phenols can be used as lignin-derived starting materials.

Dutta, Tanmoy↗

Method for conversion of diols to olefin products

A method for converting a diol in solution to an olefin fraction, the method comprising: (i) reacting a diol of the formula HO—R—OH in solution with a carbonyl-containing molecule of the formula: in the presence of an acid catalyst to result in a dioxolane molecule of the formula: wherein R is a hydrocarbon linker containing 1-12 carbon atoms, and R 1 and R 2 are independently selected from hydrogen atom and hydrocarbon groups containing 1-12 carbon atoms, wherein R 1 and R 2 optionally interconnect; (ii) removing the dioxolane molecule from the solution by phase separation; and (iii) contacting the dioxolane molecule with a metal-loaded zeolite at a temperature of 100-500° C. to convert the dioxolane molecule to an olefin fraction.

Li, Zhenglong↗

In Situ Quantification of [Re(CO) 3 ] + by Fluorescence Spectroscopy in Simulated Hanford Tank Waste

A pretreatment protocol is presented that allows for the quantitative conversion and subsequent in situ spectroscopic analysis of [Re(CO)3]+ species in simulated Hanford tank waste. The protocol encompasses adding a simulated waste sample containing the non-emissive [Re(CO)3]+ species to a developer solution that enables the rapid, quantitative conversion of the non-emissive species to a luminescent species which can then be detected spectroscopically. The [Re(CO)3]+ species concentration in an alkaline, simulated Hanford tank waste supernatant can be quantified by the standard addition method. In a test case, the [Re(CO)3]+ species was measured to be at a concentration of 38.9 µM, which was a difference of 2.01% from the actual concentration of 39.7 µM.

fluorescence detection↗

Backbonding in Thorium(IV) and Uranium(IV) Diarsenido Complexes with t BuNC and CO

The coordination of tBuNC and CO with the diarsenido complexes (C 5 Me 5 ) 2 An(η 2 -As 2 Mes 2 ), An=Th, U, has been investigated. For the first time, a comparison between isostructural complexes of Th IV and U IV has been possible with CO; density functional calculations indicated an appreciable amount of π backbonding that originates from charge transfer from an actinide-arsenic sigma bond. The calculated CO stretching frequencies in the Th IV and U IV diarsenido complexes are consistent with the experimental measurements, both show large shifts to lower frequency. We demonstrate that the π backbonding is crucial to explaining the red shifts of CO frequency upon An IV complex formation. Interestingly, this interaction essentially correlates to the parallel orientation of π*(C-O) orbitals relative to the An-As bond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stabilization of Softwood-Derived Pyrolysis Oils for Continuous Bio-oil Hydroprocessing

The use of fast pyrolysis as a potential renewable liquid transportation fuel alternative to crude oil depends on successful catalytic upgrading to produce a refinery-ready product with oxygen content and qualities (i.e. specific functional group or compound content) that is compatible with the product’s proposed insertion point. Catalytic upgrading of bio-oil requires high temperature and pressure, while similar to crude oil hydrotreating, is not as straightforward for the thermally unstable pyrolysis oil. For years, a two-temperature zone, downflow trickle bed reactor was the state-of-the art for continuous operation. However, pressure excursion due to plug formation still occurred, typically at the high temperature transition zone, leading to a process shutdown within 140 h. Recently, a bio-oil pre-treatment process, together with a robust commercial catalyst, was found to be enabling the continuous operation of the two-zone hydroprocessing system. Here, we report the results on pre-treating bio-oil at 413 K and 8.4 MPa of flowing H2 (500 L H2/L bio-oil, 0.5 L bio-oil/L catalyst bed) and the attempts to characterize this oil product to understand the chemistry which enabled the long-term processing of bio-oil.

carbonyls↗

Oxidative stress suppresses the cellular bioenergetic effect of the 3-mercaptopyruvate sulfurtransferase/hydrogen sulfide pathway

Highlights: •Oxidative stress impairs 3-MST-derived H{sub 2}S production in isolated enzyme and in isolated mitochondria. •This impairs the stimulatory bioenergetic effects of H{sub 2}S in hepatocytes. •This has implications for the pathophysiology of diseases with oxidative stress. -- Abstract: Recent data show that lower concentrations of hydrogen sulfide (H{sub 2}S), as well as endogenous, intramitochondrial production of H{sub 2}S by the 3-mercaptopyruvate (3-MP)/3-mercaptopyruvate sulfurtransferase (3-MST) pathway serves as an electron donor and inorganic source of energy to support mitochondrial electron transport and ATP generation in mammalian cells by donating electrons to Complex II. The aim of our study was to investigate the role of oxidative stress on the activity of the 3-MP/3-MST/H{sub 2}S pathway in vitro. Hydrogen peroxide (H{sub 2}O{sub 2}, 100–500 μM) caused a concentration-dependent decrease in the activity of recombinant mouse 3-MST enzyme. In mitochondria isolated from murine hepatoma cells, H{sub 2}O{sub 2} (50–500 μM) caused a concentration-dependent decrease in production of H{sub 2}S from 3-MP. In cultured murine hepatoma cells H{sub 2}O{sub 2}, (3–100 μM), did not result in overall cytotoxicity, but caused a partial decrease in basal oxygen consumption and respiratory reserve rapacity. The positive bioenergetic effect of 3-MP (100–300 nM) was completely abolished by pre-treatment of the cells with H{sub 2}O{sub 2} (50 μM). The current findings demonstrate that oxidative stress inhibits 3-MST activity and interferes with the positive bioenergetic role of the 3-MP/3-MST/H{sub 2}S pathway. These findings may have implications for the pathophysiology of various conditions associated with increased oxidative stress, such as various forms of critical illness, cardiovascular diseases, diabetes or physiological aging.

60 APPLIED LIFE SCIENCES↗

Deletion of the calmodulin-binding domain of Grb7 impairs cell attachment to the extracellular matrix and migration

Highlights: •Grb7 is a calmodulin (CaM)-binding protein. •Deleting the CaM-binding site impairs cell attachment and migration. •CaM antagonists inhibit Grb7-mediated cell migration. •We conclude that CaM controls Grb7-mediated cell migration. -- Abstract: The adaptor Grb7 is a calmodulin (CaM)-binding protein that participates in signaling pathways involved in cell migration, proliferation and the control of angiogenesis, and plays a significant role in tumor growth, its metastatic spread and tumor-associated neo-vasculature formation. In this report we show that deletion of the CaM-binding site of Grb7, located in the proximal region of its pleckstrin homology (PH) domain, impairs cell migration, cell attachment to the extracellular matrix, and the reorganization of the actin cytoskeleton occurring during this process. Moreover, we show that the cell-permeable CaM antagonists N-(6-aminohexyl)-5-chloro-1-naphthalenesulfonamide (W-7) and N-(4-aminobutyl)-5-chloro-2-naphthalenesulfonamide (W-13) both retard the migration of cells expressing wild type Grb7, but not the migration of cells expressing the mutant protein lacking the CaM-binding site (Grb7Δ), underscoring the proactive role of CaM binding to Grb7 during this process.

60 APPLIED LIFE SCIENCES↗

Cancer cells recovering from damage exhibit mitochondrial restructuring and increased aerobic glycolysis

Highlights: • Some cancer cells recover from severe damage that causes cell death in majority of cells. • Damage-Recovered (DR) cancer cells show reduced mitochondria, mDNA and mitochondrial enzymes. • DR cells show increased aerobic glycolysis, ATP, cell proliferation, and resistance to damage. • DR cells recovered from in vivo damage also show increased glycolysis and proliferation rate. - Abstract: Instead of relying on mitochondrial oxidative phosphorylation, most cancer cells rely heavily on aerobic glycolysis, a phenomenon termed as “the Warburg effect”. We considered that this effect is a direct consequence of damage which persists in cancer cells that recover from damage. To this end, we studied glycolysis and rate of cell proliferation in cancer cells that recovered from severe damage. We show that in vitro Damage-Recovered (DR) cells exhibit mitochondrial structural remodeling, display Warburg effect, and show increased in vitro and in vivo proliferation and tolerance to damage. To test whether cancer cells derived from tumor microenvironment can show similar properties, we isolated Damage-Recovered (T{sup DR}) cells from tumors. We demonstrate that T{sup DR} cells also show increased aerobic glycolysis and a high proliferation rate. These findings show that Warburg effect and its consequences are induced in cancer cells that survive severe damage.

60 APPLIED LIFE SCIENCES↗

Synthesis, characterization, anticancer evaluation and mechanisms of cytotoxic activity of novel 3-hydroxy-3-pyrrolin-2-ones bearing thenoyl fragment: DNA, BSA interactions and molecular docking study

In order to make a progress in discovering a new agents for chemotherapy with improved properties and bearing in mind the fact that substituted 3-hydroxy-3-pyrrolin-2-ones belong to a class of biologically active compounds, series of novel 1,5-diaryl-4-(2-thienylcarbonyl)-3-hydroxy-3-pyrrolin-2-ones were synthesized and characterized by spectral (UV–Vis, IR, NMR, ESI-MS), X-ray and elemental analysis. All compounds were examined for their cytotoxic effect on human cancer cell lines HeLa and MDA-MB 231 and normal fibroblasts (MRC-5). Four compounds, 3-hydroxy-1-(p-tolyl)-4-(2-thienylcarbonyl)-5-(4-chlorophenyl)-2,5-dihydro-1H-pyrrol-2-one (D10), 3-hydroxy-1-(3-nitrophenyl)-4-(2-thienylcarbonyl)-5-(4-(benzyloxy)phenyl)-2,5-dihydro-1H-pyrrol-2-one (D13), 3-hydroxy-1-(4-nitrophenyl)-4-(2-thienylcarbonyl)-5-(4-(benzyloxy)phenyl)-2,5-dihydro-1H-pyrrol-2-one (D14), and 3-hydroxy-1-(4-chlorophenyl)-4-(2-thienylcarbonyl)-5-(4-(benzyloxy)phenyl)-2,5-dihydro-1H-pyrrol-2-one (D15), that showed the highest cytotoxicity against malignant cells and the best selectivity towards normal cells were selected for further experiments. Results obtained by investigating mechanisms of cytotoxic activity suggest that selected 3-hydroxy-3-pyrrolin-2-one derivatives in HeLa cells induce apoptosis that is associated with S phase arrest (D13, D15, and D10) or unrelated to cell cycle distribution (D14). Additionally, to better understand their suitability for potential use as anticancer medicaments we studied the interactions between biomacromolecules (DNA or BSA) and D13 and D15. The results indicated that D13 and D15 have great affinity to displace EB from the EB-DNA complex through intercalation [K sv = (3.7 ± 0.1) and (3.4 ± 0.1) × 10 3 M -1 , respectively], an intercalative mode also confirmed through viscosity measurements. K a values, obtained as result of fluorescence titration of BSA with D13 and D15 [K a = (4.2 ± 0.2) and (2.6 ± 0.2) × 10 5 M, respectively], support the fact that a significant amount of the tested compounds could be transported and distributed through the cells. In addition, by DNA and BSA molecular docking study for D13, D14 and D15 is determined and predicted the binding mode and the interaction region. © 2019 Elsevier Inc.

60 APPLIED LIFE SCIENCES↗

Enhanced properties of graphene/fly ash geopolymeric composite cement

This paper reports for the first time the incorporation of in-situ reduced graphene oxide (rGO) into geopolymers. The resulting rGO–geopolymeric composites are easy to manufacture and exhibit excellent mechanical properties. Geopolymers with graphene oxide (GO) concentrations of 0.00, 0.10, 0.35 and 0.50% by weight were fabricated. The functional groups, morphology, void filling mechanisms and mechanical properties of the composites were determined. The Fourier transform infrared (FTIR) spectra revealed that the alkaline solution reduced the hydroxyl/carbonyl groups of GO by deoxygenation and/or dehydration. Concomitantly, the spectral absorbance related to silica type cross-linking increased in the spectra. The scanning electron microscope (SEM) micrographs indicated that rGO altered the morphology of geopolymers from a porous nature to a substantially pore filled morphology with increased mechanical properties. The flexural tests showed that 0.35-wt.% rGO produced the highest flexural strength, Young's modulus and flexural toughness and they were increased by 134%, 376% and 56%, respectively.

36 MATERIALS SCIENCE↗

Synthesis of N-trifluoromethyl amides from carboxylic acids

Found in biomolecules, pharmaceuticals, and agrochemicals, amide-containing molecules are ubiquitous in nature, and their derivatization represents a significant methodological goal in fluorine chemistry. Trifluoromethyl amides have emerged as important functional groups frequently found in pharmaceutical compounds. To date, there is no strategy for synthesizing N -trifluoromethyl amides from abundant organic carboxylic acid derivatives, which are ideal starting materials in amide synthesis. Here, we report the synthesis of N -trifluoromethyl amides from carboxylic acid halides and esters under mild conditions via isothiocyanates in the presence of silver fluoride at room temperature. Through this strategy, isothiocyanates are desulfurized with AgF, and then the formed derivative is acylated to afford N -trifluoromethyl amides, including previously inaccessible structures. This method shows broad scope, provides a platform for rapidly generating N -trifluoromethyl amides by virtue of the diversity and availability of both reaction partners, and should find application in the modification of advanced intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular models of site-isolated cobalt, rhodium, and iridium catalysts supported on zeolites: Ligand bond dissociation energies

The chemistry of zeolite-supported site-isolated cobalt, rhodium, and iridium complexes that are essentially molecular was investigated with density functional theory (DFT) and the results compared with experimentally determined spectra characterizing rhodium and iridium species formed by the reactions of Rh(C 2 H 4 ) 2 (acac) and Ir(C 2 H 4 ) 2 (acac) (acac = acetylacetonate) with acidic zeolites such as dealuminated HY zeolite. The experimental results characterize ligand exchange reactions and catalytic reactions of adsorbed ligands, including olefin hydrogenation and dimerization. Two molecular models were used to characterize various binding sites of the metal complexes in the zeolites, and the agreement between experimental and calculated infrared frequencies and metal-ligand distances determined by extended X-ray absorption fine structure spectroscopy was generally very good. The calculated structures and energies indicate a metal-support-oxygen (M(I)-O) coordination number of two for most of the supported complexes and a value of three when the ligands include the radicals C 2 H 5 or H. The results characterizing various isomers of the supported metal complexes incorporating hydrocarbon ligands indicate that some carbene and carbyne ligands could form. Ligand bond dissociation energies (LDEs) are reported to explain the observed reactivity trends. The experimental observations of a stronger M-CO bond than M-(C 2 H 4 ) bond for both Ir and Rh match the calculated LDEs, which show that the single-ligand LDEs of the mono and dual-ligand complexes for CO are similar to 12 and similar to 15 kcal/mol higher in energy (when the metal is Rh) and similar to 17 and similar to 20 kcal/mol higher (when the metal is Ir) than the single-ligand LDEs of the mono and dual ligand complexes for C 2 H 4 , respectively. The results provide a foundation for the prediction of the catalytic properties of numerous supported metal complexes, as summarized in detail here.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Room-temperature synthesis and characterization of carbon-encapsulated molybdenum nanoparticles

Highlights: • Carbon-encapsulated molybdenum nanoparticles were synthesized at room temperature. • Different hydrocarbons were used as carbon source for shell formation. • Increase of hydrocarbon mole ratio resulted in decrease of Mo-based nanoparticle cores. • Increase of laser pulses number resulted in increase of Mo content in CEMNPs. • Carbon shells prevented Mo nanoparticles from aggregation. - Abstract: Carbon-encapsulated molybdenum nanoparticles were synthesized by laser-assisted photolysis of gaseous precursors. In the proposed method, gas mixtures containing various hydrocarbons and molybdenum hexacarbonyl vapor diluted in argon were irradiated with a nanosecond pulsed UV laser at room temperature. Particle samples were analyzed by transmission electron microscopy (TEM), electron microdiffraction (EMD), energy-dispersive X-ray spectroscopy (EDS), and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) techniques to observe the morphology and composition of the Mo/C nanoparticles. The influence of the type of hydrocarbon, its mole fraction, and the number of UV laser pulses on the resulting nanoparticles was investigated. The nanoparticles were heavily aggregated and consisted of Mo-based cores surrounded by carbon. The type of hydrocarbon did not have any visible effects on the nanoparticle structure and the size of the Mo-based cores or aggregates. Increasing the hydrocarbon mole fraction in the precursor mixture led to an increase in the carbon content and decrease of the Mo-based core size. Increasing the number of UV laser pulses led to larger Mo cores.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Simvastatin induces apoptosis by a Rho-dependent mechanism in cultured cardiac fibroblasts and myofibroblasts

Several clinical trials have shown the beneficial effects of statins in the prevention of coronary heart disease. Additionally, statins promote apoptosis in vascular smooth muscle cells, in renal tubular epithelial cells and also in a variety of cell lines; yet, the effects of statins on cardiac fibroblast and myofibroblast, primarily responsible for cardiac tissue healing are almost unknown. Here, we investigated the effects of simvastatin on cardiac fibroblast and myofibroblast viability and studied the molecular cell death mechanism triggered by simvastatin in both cell types. Methods: Rat neonatal cardiac fibroblasts and myofibroblasts were treated with simvastatin (0.1-10 {mu}M) up to 72 h. Cell viability and apoptosis were evaluated by trypan blue exclusion method and by flow cytometry, respectively. Caspase-3 activation and Rho protein levels and activity were also determined by Western blot and pull-down assay, respectively. Results: Simvastatin induces caspase-dependent apoptosis of cardiac fibroblasts and myofibroblasts in a concentration- and time-dependent manner, with greater effects on fibroblasts than myofibroblasts. These effects were prevented by mevalonate, farnesylpyrophosphate and geranylgeranylpyrophosphate, but not squalene. These last results suggest that apoptosis was dependent on small GTPases of the Rho family rather than Ras. Conclusion: Simvastatin triggered apoptosis of cardiac fibroblasts and myofibroblasts by a mechanism independent of cholesterol synthesis, but dependent of isoprenilation of Rho protein. Additionally, cardiac fibroblasts were more susceptible to simvastatin-induced apoptosis than cardiac myofibroblasts. Thus simvastatin could avoid adverse cardiac remodeling leading to a less fibrotic repair of the damaged tissues. - Research Highlights: > Simvastatin decreases CF and CMF viability independent of cholesterol synthesis. > Simvastatin induces CF and CMF apoptosis in a caspase-dependent manner being CMF more resistant than CF. > CMF has higher expression and active RhoA protein levels.

60 APPLIED LIFE SCIENCES↗