Abstract  The coupling of gemcitabine with functionalized carboxylic acids (C9-C13) or reactions of 4-N-tosylgemcitabine with the corresponding alkyl amines afforded 4-N-alkanoyl and 4-N-alkyl gemcitabine derivatives. The analogues with a terminal hydroxyl group on the alkyl chain were efficiently fluorinated under conditions that are compatible with protocols for (18)F labeling. The 4-N-alkanoylgemcitabines showed potent cytostatic activities in the low nanomolar range against a panel of tumor cell lines, whereas cytotoxicity of the 4-N-alkylgemcitabines were in the low micromolar range. The cytotoxicity for the 4-N-alkanoylgemcitabine analogues was reduced approximately by 2 orders of magnitude in the 2'-deoxycytidine kinase (dCK)-deficient CEM/dCK(-) cell line, whereas cytotoxicity of the 4-N-alkylgemcitabines was only 2-5 times lower. None of the compounds acted as efficient substrates for cytosolic dCK; therefore, the 4-N-alkanoyl analogues need to be converted first to gemcitabine to display a significant cytostatic potential, whereas 4-N-alkyl derivatives attain modest activity without measurable conversion to gemcitabine.

Abstract  In the present work, a series of Al-containing spherical mesostructured cellular silica foams (SMCFs) with different ultra-large pore sizes were successfully synthesized by simply adjusting the mass ratio (x) of the swelling agent 1,3,5-trimethylbenzene (TMB) to P123. The as-synthesized Al-SMCFs-x were utilized as NiMo catalyst supports for the hydrodesulfurization of dibenzothiophene. The characterization results showed that, compared with other studied NiMo/Al-SMCFs-x catalysts, the NiMo/Al-SMCFs-1.25 catalyst exhibited higher sulfidation degree, higher dispersions of Ni and Mo species, shorter length, and lower stacking number of MoS2 slabs. It was also found that the NiMo/Al-SMCFs-1.25 catalyst possessed suitable physicochemical parameters [i.e., ultra-large pore size (27.5nm), high surface area (383m(2)g(-1)), and large pore volume (1.34cm(3)g(-1)), resulting in the formation of more typeII active sites with more brim active sites. Consequently, the NiMo/Al-SMCFs-1.25 catalyst displayed outstanding catalytic performance for the hydrodesulfurization of dibenzothiophene.

Abstract  The combination of a halogen-free solvent 1,2,4-trimethylbenzene and unmodified fullerene potentially provides a way to develop environmentally-friendly and cost-effective solution-processed organic photocells. In this paper, the thermal annealing effect on the optical absorption spectra in poly(3-hexylthiophene): unmodified-C-60 composites with various compositions is reported. It is found that the onset temperature of the absorption spectrum change is higher in the composites with higher fullerene content. It is speculated that strong interaction between the polymer main chain and C-60 tends to suppress the reorientation of polymer main chains in a composite with high C-60 content.

Abstract  With lab-scale solution-processed thin film photovoltaic (TFPV) devices attaining market relevant efficiencies, the demand for environmentally friendly and scalable deposition techniques is increasing. Replacing toxic halogenated solvents is a priority for the industrialization of solution-processed TFPV. In this work, a generalized five-step process is presented for fabricating high-performance devices from nonhalogenated inks. Resulting from this process, several new solvent systems are introduced based on thiophene, tetralin, 1,2,4-trimethylbenzene, o-xylene, and anisole for blade coating of three different diketopyrrolopyrrole-based (pDPP5T-2, pPDPP5T-2S, and P390) bulk heterojunctions applied in organic photovoltaic devices. Devices based on pDPP5T-2S and P390 attain 5.6% and 6.1% efficiency, respectively, greater than the efficiency either material reached when processed from the halogenated solvent system commonly used. These processes are implemented without post-deposition annealing treatments or additives. The Hansen solubility parameters of the pDPP5T-2 material are obtained, and are used, along with wettability data on a variety of substrates, to determine optimum solvent combinations and ratios for deposition. This generalized five-step process results in new nonhalogenated solvent pathways for the scalable deposition of thin film photovoltaic materials.

Abstract  We designed and synthesized several nanomaterials 3 of three-layered core-shell (γ-FeOx@AuNP)@[C60(>DPAF-C9) 1 or 2]n nanoparticles (NPs). These NPs having e(-)-polarizable fullerosome structures located at the outer layer were fabricated from highly magnetic core-shell γ-FeOx@AuNPs. Fullerosomic polarization of 3 was found to be capable of causing a large amplification of material permittivity that is also associated with the photoswitching effect in the frequency range of 0.5-4.0 GHz. Multilayered synthetic construction allows Förster resonance energy transfer (FRET) of photoinduced accumulative surface plasmon resonance (SPR) energy in the gold layer to the partially bilayered C60(>DPAF-C9) 1 or 2-derived fullerosome membrane shell layer in a near-field of direct contact without producing radiation heat, which is commonly associated with SPR.

Abstract  Inverse micelle templated mesoporous manganese oxide (University of Connecticut mesoporous material, UCT-1) and ion promoted mesoporous manganese oxides (UCT-18-X, X = Mg2+, Ca2+, K+, Na+ and Cs+) having trace amount of alkali metal ions as promoters with tunable porosity and crystallinity were synthesized. The synthesis was based on the use of inverse micelles as soft templates and unique NOx chemistry as established for recently discovered UCT materials. The materials were tested for selective aerobic alcohol oxidation and the catalytic activity followed the order of UCT-1 < UCT-18-Mg < UCT-18-Ca < UCT-18-K < UCT-18-Na < UCT-18-Cs. The catalytic activity was correlated to the promoter ion induced increase in basicity of the materials. The retention of an amorphous structure, low reducibility, and the effects of lattice oxygen are other key factors responsible for the enhanced catalytic activity. The UCT-18-Cs catalyst was found to oxidize various alcohols to corresponding aldehydes and ketones selectively (100% selectivity) with very high conversion (as high as 100%). The UCT-18-Cs also exhibited solvent free green oxidation of 1.3.5-trimethylbenzene to yield 3,5-dimethylbenzoic acid and (3,5-dimethylphenyl)methyl ester with >90% conversion and 90% selectivity for the acid and 9% selectivity for the ester. (C) 2014 Published by Elsevier B.V.

Abstract  A fast and reliable method was developed for the determination of fluoride in toothpaste based on the headspace single drop microextraction (HS-SDME) followed by gas chromatography/flame ionization detection (GC/FID). The method is based on the volatilization of fluoride using trimethylchlorosilane as the derivatization reagent to form trimethylfluorosilane at acidic pH. The trimethylfluorosilane formed is preconcentrated in a 0.8 mu L drop of mesitylene suspended from the tip of a common GC microsyringe to the headspace of the sample. Parameters such as nature of the extraction solvent, extraction time, size of the microdrop, sample volume, stirring rate, derivatization reaction time and pH of the sample solution were studied and optimized. The developed protocol was found to yield a linear calibration curve in the concentration range of 5.0-39.0 mg L-1 with a limit of detection of 4.4 mu g L-1 with a good enrichment factor of 58.8 for the analyte. The repeatability of the method was satisfactory (RSD <= 5.41%). The total analysis time including microextraction and gas chromatography analysis was less than 30 min. Because preconcentration and sampling are performed from the headspace of the sample, this method is suitable for the determination of trace amounts of fluoride in toothpastes and water samples.

Abstract  Pt and Gd loaded ZSM-5 catalysts were synthesized by ion exchange method to investigate the effect of metal promoters on catalyst activity, coking and regeneration during military aviation fuel (JP-8) cracking into petroleum gas (PG) at 723 K. Multiple cracking and regeneration cycles were performed over the ZSM-5 based catalysts and their crystalline structure, oxidation profile, coke band and acidity were characterized. It was revealed that addition of Gd metal to the ZSM-5 catalyst prevented formation of complex aromatic coke and increased the number of Lewis acid sites, while Pt promoted ZSM-5 catalyst showed a decrease in the coke oxidation temperature. The effect of Pt and Gd promoters enhanced the coke burn-off ability, formed hydrogen rich carbon species and reduced oxidation temperature of coke substantially. Furthermore, agglomeration of Pt particles was partially impeded by coexisting Gd metal on the regenerated ZSM-5 catalyst. Synergetic effects of Pt and Gd promoters stabilized the PG yield and product distribution over the Pt-Gd/ZSM-5 catalyst during the cracking and regeneration cycles. (C) 2014 Elsevier B.V. All rights reserved.

Abstract  Final rept. 30 Sep 2010-29 Sep 2013.

Abstract  The precise determination of water content is a very important issue and in high demand in many fields. To ensure precise and reliable measurements, certified reference materials (CRM) of water standards, whose concentrations are traceable to the International System of Units (SI), are required. The National Metrology Institute of Japan (NMIJ) has issued a CRM of water in mesitylene (0.1 mg g(-1)) (NMIJ CRM 4222-a), with a very small uncertainty, for use in controlling the quality of analyses of trace water contents and confirming the validity of Karl Fischer (KF) titrators. This CRM is homogeneous, stable and low-hygroscopic under normal laboratory conditions; therefore, complex sample handling is not required. Characterization of the CRM was performed by coulometric and volumetric KF titrations. The certified value of the CRM (mass fraction of water) is 0.134 mg g(-1), and its expanded uncertainty is 0.004 mg g(-1) with a coverage factor of 2, and is metrologically traceable to SI. We describe the measurement procedures and assays of trace water contents with linkage to SI and the technical details of the characterization of water in NMIJ CRM 4222-a. The developed CRM is particularly suitable for the quality control and validation of coulometric KF instruments and will be valuable in analyzing trace water contents.

Abstract  The catalytic performance of divanadium- and dititanium- substituted gamma-Keggin polyoxotungstates, TBA(4)H[gamma-PW10V2O40] (I, TBA = tetra-n-butylammonium), TBA(4)H(2)[gamma-SiW10V2O40] (II), and TBA(8)[{gamma-SiW10Ti2O36(OH)(2)}(2)(mu-O)(2)] (III) has been assessed in the selective oxidation of industrially important alkylphenols/naphthols with the green oxidant 35% aqueous H2O2. Phosphotungstate I revealed a superior catalytic performance in terms of activity and selectivity and produced alkylsubstituted p-benzo- and naphthoquinones with good to excellent yields. By applying the optimized reaction conditions, 2,3,5-trimethyl-p-benzoquinone (TMBQ vitamin E key intermediate) was obtained in a nearly quantitative yield via oxidation of 2,3,6-trimethylphenol (TMP). The efficiency of H2O2 utilization reached 90%. The catalyst retained its structure under turnover conditions and could be recycled and reused. An active peroxo vanadium complex responsible for the oxidation of TMP to TMBQ has been identified using V-51 and P-31 NMR spectroscopy.

Abstract  Two-dimensional hexagonal thick-walled mesoporous titanosilicate catalysts synthesized using various amounts of titanium were used for the synthesis of 2,3,5-trimethyl-1,4-benzoquinone (TMB=O) by liquid-phase oxidation of 2,3,6-trimethylphenol (TMP-OH). These catalysts were also used for the oxidation of di-/tri-substituted phenols to produce 2,6-disubstituted p-benzoquinones (DSBQs). A promising chemical treatment method, for the preparation of green mesoporous TiSBA-15(6) or Washed TiSBA-15(6), was used for removal of non-framework TiO2 nanoparticle species from the active surface, and the catalytic activity of the recovered mesoporous TiSBA-15(6) catalyst has been evaluated. To confirm the green aspects, recyclability and hot-catalytic filtration experiments were performed. Based on the experimental results, it was found that the green mesoporous TiSBA-15(6) is a highly active, recyclable, and promising heterogeneous catalyst for the selective synthesis of TMB=O and DSBQs and produces >99% TMB=O selectivity with 100% TMP-OH conversion at 353 K for 60 min and 90-100% DSBQs selectivity with 83-99% phenol conversion at 330 K for 1-5 h.

Abstract  The density functional theory with account for gradient correction (DFT/PBE) and periodical boundary conditions was used to model the main stages of processes occurring in hydrogen low-temperature fuel cells. Modeling was carried out at the example of calculation of catalytic anodic and cathodic processes occurring on the surface of the Pt-19 catalyst supported on a SnO2 and water adsorption processes on the surface of a membrane represented by a crystal of metisylene sulfonic acid dihydrate [(CH3)(3)C6H2SO (3) (-) center dot H5O (2) (+) ]. It was shown that the most energy-efficient process in the membrane is formation of crystals, in which two stoichiometric water molecules correspond to a single SO3H group. Superstoichiometric water is adsorbed on the crystal surface with the adsorption energy of 0.3-0.6 eV; its transition inside the crystal is energy-consuming (2 eV). Barriers of surface proton conductivity are 0.2-0.3 eV.

Abstract  The performance of two synthetic aviation fuels was evaluated in a meso-scale heat recirculating combustor and the respective results compared with the combustion characteristics of a conventional petroleum-based jet fuel. One of the alternative jet fuels was synthesized via a Fischer-Tropsch (F-.T fuel) process, while the other was produced from tallow (bin-jet fuel). The petroleum-based fuel used in this study was JP-8. The combustion and extinction behavior of the above fuels and their mixtures (50% synthetic fuel and 50% JP-8 by volume in JP-8) in the meso-scale combustor using oxygen under fuel-rich and fuel-lean non-premixed combustion conditions was examined. The synthetic fuels exhibited stable combustion over a range of equivalence ratios at each fuel flow rate; however, stable combustion was not achieved for JP-8 under any of the examined conditions. The mixtures also exhibited somewhat unstable combustion phenomena as those seen with JP-8, but dampened enough such that mostly stable combustion could occur. Fuel characterization analysis was performed for each fuel, and their respective thermal performances evaluated. Both the F-T and bio-jet fuels reached a maximum thermal efficiency of about 95% near their respective rich extinction limits. The mixtures exhibited somewhat poor thermal performances, with a maximum thermal efficiency of about 75%. The results reveal that composition of the fuel plays a prominent role in the flame stability and thermal performance in meso-scale combustors, as more complex species (such as aromatics, found in JP-8) have a slower reaction rate than simple species. The short residence time available in the combustion zone of the micro-combustion chamber does not allow to fully combust the complex fuel species, resulting in flame instability and formation of soot. (C) 2013 Elsevier Ltd. All rights reserved.

Abstract  Oxidation behavior of dodecane and two mixtures of dodecane and m-xylene (90/10 wt.% and 80/20 wt.%) over an Rh catalyst in a meso-scale heat recirculating combustor was examined to isolate the effect of aromatic content on performance. The fuel conversion, product selectivities, and reaction kinetics were calculated, and the global combustion behavior observed. The results showed that increasing the amount of m-xylene in the fuel increased the fuel conversion from 85% (pure dodecane) to 92% (90/10) and further to 98% (80/20). The presence of xylene also significantly increased CO2/H2O selectivity and decreased CO/H-2 selectivity. Global activation energy increased linearly with increase in xylene content, supporting that addition of aromatic species to fuel lowers the overall reactivity. The non-catalytic reaction was also simulated using Chemkin software to determine the effect of the Rh catalyst on the combustor performance and to analyze the difference in chemical mechanisms. The results revealed that the catalyst promotes total oxidation over partial oxidation, and lowers the global activation energy by up to 70%. (C) 2015 Elsevier Ltd. All rights reserved.

Abstract  The framework hydrophobicity and flexibility of ZIF-8 are investigated by a detailed adsorption and diffusion study of a series of probe molecules including ethanol, 1-butanol, water, hexane isomers, xylene isomers, and 1,2,4-trimethylbenzene. The prospects for using ZIF-8 in biofuel recovery and hydrocarbon separations are discussed in terms of adsorption or kinetic selectivities. ZIF-8 shows extremely low water vapor uptakes and is especially suitable for vapor phase butanol-based biofuel recovery. The extraordinary framework flexibility of ZIF-8 is demonstrated by the adsorption of hydrocarbon molecules that are much larger than its nominal pore size, such as m-xylene, o-xylene and 1,2,4-trimethylbenzene. The calculation of corrected diffusion coefficients reveals an interesting spectrum of promising kinetic hydrocarbon separations by ZIF-8. These findings confirm that a molecular sieving effect tends to occur in the sorbate molecular size range of 4-6 Å rather than around the nominal ZIF-8 pore size of 3.4 Å, due to its surprising framework flexibility. © 2013 American Chemical Society.

Abstract  Fuel cell technology has yet to realize widespread deployment, in part because of the hydrogen fuel infrastructure required for proton exchange membrane systems. One option to overcome this barrier is to produce hydrogen by reforming propane, which has existing widespread infrastructure, is widely used by the general public, easily transported, and has a high energy density. The present work combines thermodynamic modeling of propane catalytic partial oxidation (cPOx) and experimental performance of a Precision Combustion Inc. (PCI) Microlith (R) reactor with real-time soot measurement. Much of the reforming research using Microlith-based reactors has focused on fuels such as natural gas, JP-8, diesel, and gasoline, but little research on propane reforming with Microlith-based catalysts can be found in literature. The aim of this study was to determine the optimal operating parameters for the reformer that maximizes efficiency and minimizes solid carbon formation. The primary parameters evaluated were reformate composition, carbon concentration in the effluent, and reforming efficiency as a function of catalyst temperature and O-2/C ratio. Including the lower heating values for product hydrogen and carbon monoxide, efficiency of 84% was achieved at an O-2/C ratio of 0.53 and a catalyst temperature of 940 degrees C, resulting in near equilibrium performance. Significant solid carbon formation was observed at much lower catalyst temperatures, and carbon concentration in the effluent was determined to have a negative linear relationship at T < 750 degrees C. The Microlith reactor displayed good stability during more than 80 experiments with temperature cycling from 360 to 1050 degrees C. (C) 2014 Elsevier B.V. All rights reserved.

Abstract  Silicon quantum dots (QDs) have attracted much interest in recent years for their prospects in biology and opto-electronics; also, anthracene is a star material for being the first organic molecule to be used in an electroluminescence (EL) device. In this paper, we report dual-emissive Si QDs, with the QD surface modified by 9-ethylanthracene. This hybrid nanomaterial dispersed well in nonpolar solvents such as mesitylene, exhibiting a dual-emission spectrum with peaks centered at 431 and 824 nm, corresponding to the ligand and Si QD related fluorescence, respectively. This is a general strategy for preparing dual-emission Si QDs with wavelengths tunable either by the size of the Si nanocrystals or by the molecules. This dual-emissive hybrid nanomaterial exhibits possible application potential as an active material for visible to near infrared light emitting devices or bio-imaging.

Abstract  Based on the idea of structural design, a novel catalytic system was developed from a block copolymer for the oxidation reaction of 2,3,6-trimethylphenol (TMP). The block copolymer, poly(4-vinylpyridine)-block-poly(ethylene glycol)-block-poly(4-vinylpyridine) (P4VP-PEG-P4VP), was synthesized via anionic polymerization. After self-assembly in water-1-hexanol solution and shell cross linking, the block copolymer formed the shell cross-linked reverse micelles (SCRMs). The CuCl2 complexed SCRMs were used in the catalytic oxidation reaction of TMP. Through coordinating with metal ions, regulating the distribution of metal catalytic active centers, and with the cocatalysis effect of the immobilized water droplets, this polymer-supported catalyst system demonstrated an efficient catalytic activity and recoverability. This work not only provides a promising catalyst based on mesoscale structure design using block copolymers but is also an example for deeper understanding on the structure effect in catalysis.

Abstract  Hierarchically macro/mesa structured porous copper-oxide monoliths with and without additives (dextran, 1,3,5-trimethylbenzene and silica nanoparticles) were successfully synthesized via a facile sol get route and characterized by scanning electron microscopy (SEM/FESEM), powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), the Brunauer-Emmet-Teller (BET) adsorption technique and FT-IR study. The results obtained reveal that the effect of additives has enhanced the specific surface area from 0.558 m(2) g(-1) to 229.5 m(2) g(-1) and varied the pore size from 8 mu m to 39 nm. Furthermore, the hierarchically porous copper-oxide materials have shown excellent catalytic activity towards the wet oxidation of phenol and electrocatalytic performance of mesoporous copper oxide (mpCuO) against p-nitrophenol, demonstrating the significance of the porous nature of copper-oxide monoliths.

Abstract  Studies of reactivity of antibiotic oligomycin A in various alkaline conditions showed that the compound easily undergoes retroaldol degradation in β-hydroxy ketone fragments positioned in the C7-C13 moiety of the antibiotic molecule. Depending on reaction conditions, the retroaldol fragmentation of the 8,9 or 12,13 bonds or formation of a product through double retroaldol degradation, when the fragment C9-C12 was detached, took place followed by further transformations of the intermediate aldehydes formed. The structures of the obtained non-cyclic derivatives of oligomycin A were supported by NMR and MS methods. NMR parameters demonstrate the striking similarity of the geometry (conformation) of the fragment C20-C34 in the non-cyclic products of retroaldol degradation and the starting antibiotic 1. The compounds obtained had lower cytototoxic properties than oligomycin A for human leukemia cells K-562 and colon cancer cells HCT-116 and lower activity against growth inhibition of model object Streptomyces fradiae. It cannot be excluded that the products of retroaldol degradation participate in the biological effects of antibiotic oligomycin A.

Abstract  Siliceous mesocellular foam (MCF) with tunable cell and window size was synthesized by the acid catalyzed sol-gel reaction of tetraethoxysilane in the presence of triblock copolymer Pluronic P123 (EO20PO70EO20) as structure-directing agent. The cell's size of MCF is increased with the increase of 1,3,5-trimethylbenzene amount, while the window's size of MCF could be tailored between 4 and 18.2 nm without affecting the cells size by adding of NH4F. The obtained MCF materials were employed as carriers for catalase immobilization. FT-IR spectra and N-2 sorption show that the catalase is immobilized into the mesopores of MCF. MCF with window size of 12.9 nm shows high catalase loading and activity, suggesting that matching the window's size with enzyme molecular diameter is a critical factor in attaining efficient immobilization since smaller window size prevents larger enzyme from entering the pore and larger window size causes the leakage of enzyme. The thermal and storage stabilities of the immobilized catalase were also improved due to the shield of the mesopores of MCF.

Abstract  A 3D metal-organic framework [NH2(CH3)(2)][Cd-6(L)(4)(DMF)(6)(HCOO)] (DMF = N, N-dimethylformamide) (1) has been synthesized using a tripodal ligand H3L (2,4,6-tris[ 1-(3-carboxylphenoxy)ylmethyl] mesitylene). The obtained complex exhibits a 3D framework containing hexanuclear {Cd-6} building units formed by two trinuclear {Cd-3 clusters that are connected via HCOO- anions. For complex 1, the participation of the fluorescent ligand H3L not only gives rise to a strong photoluminescence emission as expected, but more interestingly, that ligand originated characteristic band could be quenched selectively by nitrobenzene with a low detection limit, showing its potential as a highly sensitive and selective sensor for nitrobenzene. Based on an electron transfer quenching mechanism, the fluorescence sensing ability of 1 is also applicable for other electron-deficient nitroaromatic compounds with high selectivity and sensitivity, i.e., 1,4-dinitrobenzene, 1,3-dinitrobenzene, 2,4-dinitrotoluene, and 4-nitrotoluene, suggesting 1 a promising fluorescence sensor for detecting and recognizing the same kind of chemicals. (C) 2014 Author(s).

Abstract  In France, two options can be considered to handle the Very Low Level Waste (VLLW) and the Low Level Waste (LLW). The first one is the incineration at CENTRACO facility and the second one is the disposal at ANDRA sites. The waste acceptance in these two channels is dependent upon the adequacy between the waste characteristics (physical chemistry and radiological) and the channel specifications. If the waste characteristics and the channel specifications (presence of significant quantities of halogens, complexants agents, organic components. or/and high activity limits) are incompatible, an alternative solution have to be identify. It consists of a waste pre-treatment process. For Cadarache LOR (Liquides Organiques Radioactifs) waste streams, two radioactive scintillation cocktails have to be treated. They are composed of a mix of organic liquids and water: for the first one, 19 % of organic compounds (xylene, mesitylene, diphenyloxazole, TBP ...) and 86.9 % of water, and for the second one, 23 % of organic compounds (TBP ...) and 77 % of water. They contain halogens (chlorine and fluorine), complexants agents (nitrate, sulphate, oxalate and formate) and have got alpha beta gamma. spectra with mass activities equal to some 100 Bq/g. Therefore, tritium is also present. As a consequence, in order for storage acceptance at the ANDRA site, it is necessary to pre-treat the waste. An adequate solution seems to be a solidification process using NOCHAR polymers.

Indeed, NOCHAR polymers correspond to an important variety of products applied to the treatment of radioactive aqueous and organic liquids (solvent, oil, solvent/oil mixing ...) and sludge through a mechanical and chemical solidification process. For Cadarache LOR, N910 and N960 respectively dedicated to the organic and aqueous liquids solidification are considered. With the N910, the organic waste solidification occurs in two steps. As the organic liquid travels moves through the polymer strands, the strands swell and immobilize the liquid. Then as the polymer-organic cure, over time, the polymer continues to collapse on the organic to create a permanent chemical bond. The N960 has the ability to absorb aqueous waste up to 100 times its own weight. It creates a strong mechanical bond which permanently traps the contamination imbedded in the aqueous liquids. Therefore, these two NOCHAR polymers seem to be able to constitute a suitable solidification matrix for a final acceptance in storage on ANDRA sites.

In order to validate the solidification process using NOCHAR polymers as an acceptable solution for Cadarache LOR treatment, some solidification tests realised with N910 and N960, have been carried out for different Waste/Polymer ratios. To determine the best Waste/Polymer ratio and the optimal experimental parameters, exudation tests have been made. Indeed, the process prevents leaching and it results in the absence residual free organic or aqueous liquid which is forbidden in storage by ANDRA specifications. With these results, the obtained scientific data constitute a fundamental basis of an ANDRA agreement.

As a conclusion, the aim of this study is to demonstrate that the pre-treatment by solidification using NOCHAR polymers can constitute a solution for Cadarache LOR handling and more generally, for various organic and mixed organic/aqueous waste which can not be directly acceptable at CENTRACO facility or at ANDRA storage sites. So then, this study is a solid background to demonstrate the feasibility of the waste pre-treatment by solidification with NOCHAR polymer and to encourage this process development.

Abstract  C3-arylated indazole and pyrazoles are privileged structural motifs in agrochemicals and pharmaceuticals. C-3 C-H arylation of (1H) indazole and pyrazole has been a significant challenge due to the poor reactivity of the C-3 position. Herein, we report a practical Pd(II)/Phen catalyst and conditions for direct C-3 arylation of indazole and pyrazole with ArI or ArBr without using Ag additives as halide scavengers. The use of toluene, chlorobenzene, trifluoromethylbenzene and mesitylene as the solvent was found to be crucial for the selectivity and reactivity. We further demonstrate the robustness of this protocol through the first total synthesis of Nigellidine hydrobromide as well as expedient preparation of heterocycles structurally related to pesticides and drug molecules.