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1.
Lithium Insertion Mechanism in Iron-Based Oxyfluorides with Anionic Vacancies Probed by PDF Analysis
Dr. Damien Dambournet Dr. Karena W Chapman Dr. Mathieu Duttine Dr. Olaf Borkiewicz Dr. Peter J Chupas Dr. Henri Groult 《ChemistryOpen》2015,4(4):443-447
The mechanism of lithium insertion that occurs in an iron oxyfluoride sample with a hexagonal–tungsten–bronze (HTB)-type structure was investigated by the pair distribution function. This study reveals that upon lithiation, the HTB framework collapses to yield disordered rutile and rock salt phases followed by a conversion reaction of the fluoride phase toward lithium fluoride and nanometer-sized metallic iron. The occurrence of anionic vacancies in the pristine framework was shown to strongly impact the electrochemical activity, that is, the reversible capacity scales with the content of anionic vacancies. Similar to FeOF-type electrodes, upon de-lithiation, a disordered rutile phase forms, showing that the anionic chemistry dictates the atomic arrangement of the re-oxidized phase. Finally, it was shown that the nanoscaling and structural rearrangement induced by the conversion reaction allow the in situ formation of new electrode materials with enhanced electrochemical properties. 相似文献
2.
Feng Ning Damien Delhomme Yann LeCun Fabio Piano Léon Bottou Paolo Emilio Barbano 《IEEE transactions on image processing》2005,14(9):1360-1371
We describe a trainable system for analyzing videos of developing C. elegans embryos. The system automatically detects, segments, and locates cells and nuclei in microscopic images. The system was designed as the central component of a fully automated phenotyping system. The system contains three modules 1) a convolutional network trained to classify each pixel into five categories: cell wall, cytoplasm, nucleus membrane, nucleus, outside medium; 2) an energy-based model, which cleans up the output of the convolutional network by learning local consistency constraints that must be satisfied by label images; 3) a set of elastic models of the embryo at various stages of development that are matched to the label images. 相似文献
3.
A new and easy protocol for the formation of substituted 4,5-dihydro-1,2,4-triazin-6(1H)-ones was developed on solid support. The heterocyclic compounds were formed by nucleophilic reaction of hydrazine on thioamide esters. As cyclization was concomitant with cleavage from the support, substituted 4,5-dihydrotriazinones were obtained in high purity. 相似文献
4.
Damien Thompson 《Chemphyschem》2007,8(11):1684-1693
Molecular recognition between guest ink molecules and beta-cyclodextrin (beta-CD) cavities at self-assembled monolayers provides a molecular printboard for nanopatterning applications. We recently used molecular dynamics (MD) simulations to describe the specificity of ink-printboard binding and here extend the simulations to include charged cyclodextrin hosts, necessary to broaden the chemistry of molecular printboards and bind charged inks such as the ferrocenium cation. Shifting to high pH, or alternatively grafting a charged sidearm onto beta-CD, created three distinct types of anionic beta-CD cavity and we used electronic structure calculations and MD simulations to measure host-guest charge transfer and binding strengths. We find that steric recognition of uncharged organic molecules is retained at the charged printboards, and that improved guest-host electrostatic contacts can strengthen binding of larger inks while penalising small inks, enhancing the level of discrimination. A prudent choice of complementary host-guest shape and charge states thus provides a means of tuning both ink binding strength and specificity at molecular printboards. 相似文献
5.
Wataru Ueda Kenzo Oshihara Damien Vitry Tokio Hisano Youhei Kayashima 《Catalysis Surveys from Japan》2002,6(1-2):33-44
Mo-V-M(=Al, Ga, Bi, Sb and Te)–O mixed oxide catalysts were synthesized hydrothermally for the first time, characterized structurally, and tested for ethane and propane oxidation after activation by various ways. These catalysts were black solids of rod-shaped (fiber like) crystals, which had a layer structure in the direction of fiber axis and a high dimensional arrangement of metal octahedra in the cross-section plane. These fresh crystalline materials became active for catalytic oxidation of alkanes after heat-treatment at 600 °C and subsequent grinding in order to increase exposed plane of the cross-section. The resulting catalysts were very active for an oxidative dehydrogenation of ethane with 80% of the ethylene selectivity in the reaction temperature range of 300 to 400 °C and also showed about 50% selectivity to acrylic acid in the propane oxidation. Multi-functional character which derived from the high dimensional structure of the catalysts and mechanism of the selective alkane oxidation were discussed. 相似文献
6.
The oxidative decomposition of various ketones (including acetone, 2-butanone, 4-heptanone, cyclopentanone and cyclohexanone) over dehydrated TiO(2) (P25) powder is investigated by electron paramagnetic resonance (EPR) spectroscopy. For the first time, a series of thermally unstable radical intermediates are observed both on the activated and reduced TiO(2) surface, depending on the adopted experimental conditions. These radical intermediates are identified as organoperoxy-based species of general formula ROO(.-) and RCO(3) (.-). They are formed by reaction of photogenerated charge carriers (either trapped electrons or trapped holes) with the adsorbed ketones in the presence of molecular oxygen. The organoperoxy intermediates are thermally unstable and decompose at temperatures in the region of 180-250 K. This work demonstrates that free-radical pathways involving both organoperoxy and superoxide radicals can be responsible for the thermal- and photodecomposition of ketones over polycrystalline TiO(2) (P25). 相似文献
7.
Alberola A Farley RD Humphrey SM McManus GD Murphy DM Rawson JM 《Dalton transactions (Cambridge, England : 2003)》2005,(24):3838-3845
Selective chlorination of thiophene-2,3-dithiol with SO(2)Cl(2) generates the corresponding sulfenyl chloride, 2,3-C(4)H(2)S(SCl)(2). Subsequent condensation with Me(3)SiN(3) yields the thiophenodithiazolylium salt [C(4)H(2)S(3)N]Cl, [TDTA]Cl. The structure of the cation, TDTA+, was established by X-ray diffraction as both its AsF(6)(-) and HSO(4)(-) salts. Reduction of [TDTA]Cl with Ag powder yields the radical TDTA* which was characterised by X- and Q-band (9 and 34 GHz) EPR and ENDOR studies. The spin density distributions estimated from the EPR/ENDOR measurements were found to be in very good agreement with those determined by DFT (B3LYP/6-31G*) indicating that ca 10% of the spin density is delocalised onto the thiophene ring. Comparison of the spin density distributions in TDTA* and the isoelectronic trithiatriazapentalenyl radical C(2)S(3)N(3), TTTA*, indicates that replacement of N by C-H leads to a localisation of the spin density on the dithiazolyl ring. 相似文献
8.
[reaction: see text] A synthesis of the glutarimide-derived metabolite of thalidomide, 5'-hydroxythalidomide (2), is described. The synthesis employed the lactone derivative of N-benzyloxycarbonyl (CBZ)-protected 4-hydroxyglutamic acid 12, which is prepared by a de novo route from diethyl acetamidomalonate. The reaction of 12 with 4-methoxybenzylamine gave the corresponding isoglutamine, which then provided the key CBZ-protected N-PMB-glutarimide 14 after dehydration. Deprotection of both the CBZ and PMB groups followed by phthalimidation and deacetylation of the 3-amino-5-acetoxyglutarimide 16 afforded 2. 相似文献
9.
We report on the coupling of a polymer-based microfluidic chip to a MALDI-TOF MS using a rotating ball interface. The microfluidic chips were fabricated by micromilling a mold insert into a brass plate, which was then used for replicating polymer microparts via hot embossing. Assembly of the chip was accomplished by thermally annealing a cover slip to the embossed substrate to enclose the channels. The linear separation channel was 50 microm wide, 100 microm deep, and possessed an 8 cm effective length separation channel with a double-T injector (V(inj) = 10 nL). The exit of the separation channel was machined to allow direct contact deposition of effluent onto a specially constructed rotating ball inlet to the mass spectrometer. Matrix addition was accomplished in-line on the surface of the ball. The coupling utilized the ball as the cathode transfer electrode to transport sample into the vacuum for desorption with a 355 nm Nd:YAG laser and analyzed on a TOF mass spectrometer. The ball was cleaned online after every rotation. The ability to couple poly(methylmethacrylate) microchip electrophoresis devices for the separation of peptides and peptide fragments produced from a protein digest with subsequent online MALDI MS detection was demonstrated. 相似文献
10.
N-Cyanomethyl and N-propargyl β-amino alcohols are chlorinated with SOCl2 and treated with NaN3 in DMSO. A substitution/cycloaddition process affords in good yields, with high diastereoselectivity and a regioselectivity depending on the substitution pattern of the starting amino alcohol, fused tri- and tetrazoles-piperazines. These heterocycles were further lithiated with n-BuLi at the benzylic position and reacted diastereoselectively with a range of electrophiles. 相似文献