Radiosynthesis of the fluorinated sucrose analogue, 1-[18F]fluoro-1-deoxysucrose
N/A
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
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Results for “FLUORINATION”
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Phase Equilibria and Condensed Phase Properties of Fluorinated Alkanes via First Principles Simulations
Vapor liquid equilibria (VLE) of organic compounds is governed by weak non-covalent interactions. This presents a significant challenge in predicting VLE using a first principles approach where density functional theory is used to model system potential. However, a dispersion corrected approach has significantly improved the performance of traditional density functionals. Here, we predict the VLE for a nonpolar carbon tetrafluoride (R14) and polar 1,1,1,2-tetrafluoroethane (R134a)via first principles Gibbs ensemble Monte Carlo simulations using PBED3 density functional. We find that the saturated liquid density for R14 is slightly under predicted for subcritical temperatures, while for R134a it is under predicted at lower reduced temperatures and over predicted at higher reduced temperatures. In the liquid phase, angle-resolved pair correlation functions indicate slight preference for R143a to align in parallel and antiparallel orientation in the first solvation shell.The vibrational spectra reveal peak broadening in the condensed phase due to solvothermal effects. Altogether, we find thePBED3 functional performance is better for the nonpolar molecule as compared to the polar one.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Correction to: Podophyllum derivatives containing fluorine atom in the 3-position of 2-aminopyridine improved the antitumor activity by inducing P53-dependent apoptosis
The corrected version of the figure including P53 expression appears below. This correction does not change any conclusions of the paper.
60 APPLIED LIFE SCIENCES↗
Fabrication and Analysis of Tri-layer YBa{sub 2}Cu{sub 3}O{sub 7−δ} Thick Films by Low-Fluorine MOD Method
Improving the thickness of superconducting layer in coated conductors is an effective way to enhance its critical current. In this work, tri-layer YBCO/YBCO/YDyBCO films were successfully deposited on buffered Hastelloy substrate using the multi-coating lowfluorine metal-organic decomposition (LF-MOD) method and the thickness of the films can be up to 2.4 μ m. The effects of high-temperature annealing time on microstructures and superconducting properties of the films were systematically studied. Energy dispersive X-ray spectroscopy (EDS) results reveal that there remains a large amount of F element in the upper layer of the film when the annealing time is too short. With increasing the annealing time, the fluoride-containing precursor converts to YBCO grains completely. But the coarsening of grains appeared, and the critical current density (J{sub c}) of the film dropped slightly when the annealing time is too long. The cross-sectional scanning electron microscope (SEM) image and EDS plane analysis were applied to investigate the microstructure and element distribution of the final triple-layer YBCO films, respectively. The critical current of the final YBCO superconducting film could reach 316 A (77 k, self-field) for 1.2-cm-wide tapes with the optimal annealing conditions.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Enhanced Pinning Properties of the Bilayers of YDy{sub 0.5}Ba{sub 2}Cu{sub 3}O{sub 7−δ} by SrZrO{sub 3} Nanoparticles through Low Fluorine Metallorganic Solution Deposition
Bilayered YDy{sub 0.5}Ba{sub 2}Cu{sub 3.6}O{sub 7−δ} superconducting films with a thickness of about 1 μ were deposited by metallorganic deposition method, an interlayer of secondary phase of SrZrO{sub 3} (SZO) and BaZrO{sub 3} (BZO) were inserted. Detailed growth mechanism studies of these structures as well as superconducting properties in different temperatures and magnetic field range (0–5 T) were investigated. Structural analysis showed that bilayer structure changed clearly the growth mechanism of YBCO. The SZO interlayer smoothens the film surface. Magnetic measurements of superconducting properties demonstrated that the critical temperature decreases slightly when both of SZO and BZO interlayer were inserted. This indicates a growing strain effect at the layer interfaces. The critical current densities as well as pining forces of bilayered YDy{sub 0.5}Ba{sub 2}Cu{sub 3.6}O{sub 7−δ} in the entire applied temperature and magnetic field range were enhanced by the insertion of SZO layer and decreased when BZO layer is introduced. The enhancement of the pinning properties is explained by the dense flux pinning in layered YDyBCO superconductors; this result may give further improvements in the current-carrying capability.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Selective Fluorination and Separation of Metals with NF3 for Mass Spectrometry
We report recent progress on the development of a new methodology based on the generation of volatile metal fluorides through the use of nitrogen trifluoride (NF3), and the separation and measurement of these metal fluorides by electron ionization mass spectrometry. Though unreactive under ambient conditions, NF3 reacts selectively at specified temperatures with various metal-containing species to form volatile metal fluorides. Utilizing these species-dependent traits, elements of a sample may be sequentially produced and thus separated on-line. Metals were reacted inside a thermogravimetric analyzer, the gas outlet of which was directly coupled to a quadrupole mass spectrometer with an electron impact ionization source via a molecular leak valve. We present results of this project including the electron ionization mass spectrum of gaseous tellurium hexafluoride.
Fluorination↗
Intramolecular C—F→Ln dative interactions in lanthanide complexes with fluorinated ligands
Complexes reported in the literature and potentially capable of intramolecular C—F→Ln interactions were analyzed. It was proposed to use the ToposPro software for structural and topological analysis to search for intramolecular C—F→Ln interactions. The shortest detected Ln···F contact amounted to 2.374 Å, while the longest weak non-valence contact was 4.060 Å. For all lanthanide complexes with Ln···F distances shorter than 3.447 Å, only strong intramolecular (valence) interactions between these atoms were observed. These interactions can affect the physicochemical properties of complexes and they are to be taken into account in determination of the coordination environment of lanthanide atoms.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Surpassing Robeson Upper Limit for CO2/N2 Separation with Fluorinated Carbon Molecular Sieve Membranes
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Structure investigation of fluorinated aluminophosphate ULM-3 Al templated by 3-methylaminopropylamine
A single-crystal X-ray diffraction analysis of an open-framework aluminophosphate ULM-3 Al prepared by 3-methylaminopropylamine (MAPA) as structure-directing agent revealed an orthorhombic Pcab symmetry (a=9.9949(4) A, b=15.8229(7) A, c=18.1963(5) A, R=0.0648, Z=8, unit cell formula [Al{sub 24}P{sub 24}O{sub 96}F{sub 16}.C{sub 32}H{sub 112}N{sub 16}]), which differs from the Pbc2{sub 1} symmetry of the structural analogue prepared in the presence of 1,4-diaminobutane. The {sup 27}Al, {sup 31}P, {sup 19}F, {sup 13}C and {sup 1}H NMR investigations, which were performed to study in detail MAPA arrangement inside the framework as well as the interactions of MAPA with the aluminophosphate host, confirmed the crystal symmetry and the proposed hydrogen bonding scheme between the template and the framework. - Graphical abstract: The aluminophosphate analogue of open-framework gallophosphate ULM-3 was synthesized in the presence of 3-methylaminopropylamine. The Pcab crystal symmetry and hydrogen bonding scheme was determined by single-crystal X-ray diffraction and NMR spectroscopy.
36 MATERIALS SCIENCE↗
Enhanced superconductivity of SmFeAsO co-doped by Scandium and Fluorine to increase chemical inner pressure
Sm{sub 1-x/3}Sc{sub x/3}FeAsO{sub 1-x}F{sub x} (x=0.09-0.27) were synthesized by the mechanical alloying and subsequent low temperature rapid sintering (2 h at 950 Degree-Sign C). The superconducting transition temperature (T{sub c}) increased with the doping level of x. The optimal doping achieved a T{sub c} up to 53.5 K in Sm{sub 0.93}Sc{sub 0.07}FeAsO{sub 0.79}F{sub 0.21}. The higher T{sub c} value was attributed to the increased chemical inner pressure from local lattice distortion induced by smaller-size dopants, which was further confirmed by Sm{sub 1-x}Sc{sub x}FeAsO{sub 0.88}F{sub 0.12} (x=0.04, 0.08, 0.12). Accordingly, larger lattice distortion can enhance the superconductivity below the doping limit. Similar phenomenon was also observed in the La{sub 1-x}Y{sub x}FeAsO{sub 0.8}F{sub 0.2} (x=0.4, 0.5, 0.6). - Graphical abstract: The introduction of Sc{sup 3+} and F{sup -} in SmFeAsO leads to higher chemical inner pressure generated by larger lattice distortion, which is the reason of the improved T{sub c}. Highlights: Black-Right-Pointing-Pointer The superconducting properties of Sm{sub 1-x/3}Sc{sub x/3}FeAsO{sub 1-x}F{sub x} are investigated. Black-Right-Pointing-Pointer The co-doping of Sc{sup 3+} and F{sup -} in SmFeAsO leads to higher chemical inner pressure. Black-Right-Pointing-Pointer Higher chemical inner pressure is beneficial to the superconductivity. Black-Right-Pointing-Pointer The co-doped samples of La{sub 1-x}Y{sub x}FeAsO{sub 0.8}F{sub 0.2} further demonstrate the assumption.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Fluorinated co-solvent promises Li-S batteries under lean-electrolyte conditions
Practical lithium-sulfur batteries stipulate the use of a lean-electrolyte and a high Coulombic efficiency of the lithium metal anode. In this work, we employ 1,1,2,2-tetrafluoroethyl 2,2,2-trifluoroethyl ether as a co-solvent in the electrolyte of Li-S batteries to meet the demands. The co-solvent fosters the formation of a LiF-rich solid electrolyte interphase on lithium metal anode, as revealed by Ab initio molecular dynamics and Femtosecond Stimulated Raman spectroscopy. The co-solvent results in an average Coulombic efficiency of 99.4% for lithium plating/stripping cycles. Full cells with a capacity ratio of 2 between lithium anode and the S@PAN cathode (3 gs cm –2 ) exhibited a stable cycle life over 100 cycles at an electrolyte/sulfur ratio of 2 µL mg –1 , validating the high Coulombic efficiency of the lithium anode and demonstrating the compatibility of the electrolyte with both electrodes. To enhance the energy density, we prepared a hybrid cathode composed of 45 wt.% VS 2 mixed with ZnS-coated Li 2 S@graphene as the cathode. Based on the mass of both electrodes and the electrolyte, the full cell delivers an energy density of 483 Wh kg –1 , which demonstrates viable Li-S batteries with the lean-electrolyte.
25 ENERGY STORAGE↗
Operando Elucidation on the Working State of Immobilized Fluorinated Iron Porphyrin for Selective Aqueous Electroreduction of CO 2 to CO
Iron porphyrin-based molecular catalysts can electrocatalyze CO 2 reduction to CO at nearly 100% selectivity in water. Nevertheless, the associated active sites and reaction mechanisms remain debatable, impeding the establishment of design guidelines for effective catalysts. This study reports coupling in operando experiments and theoretical calculations for immobilized 5,10,15,20-tetrakis(pentafluorophenyl) porphyrin Fe(III) chloride (FeF 20 TPP) for electrocatalytic CO 2 reduction in an aqueous phase. In operando UV–vis and X-ray absorption near-edge structure spectra indicated the persisting presence of Fe(II) species during the cathodic reaction, acting as catalytic sites that accommodate CO as Fe(II)–CO adducts. Consistently, the density functional calculations pointed out that the ligand-reduced state with oxidized Fe, namely, [Fe(II)F 20 (TPP • )] - , prevails in the catalytic cycle prior to the rate-controlling step. This work provides the conclusive representation related to the working states of Fe-based molecular catalysts under reaction conditions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Dramatic Enhancement of Rare-Earth Metal–Organic Framework Stability Via Metal Cluster Fluorination
Not Available
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
High resolution IR diode laser study of collisional energy transfer between highly vibrationally excited monofluorobenzene and CO{sub 2}: The effect of donor fluorination on strong collision energy transfer
Collisional energy transfer between vibrational ground state CO{sub 2} and highly vibrationally excited monofluorobenzene (MFB) was studied using narrow bandwidth (0.0003 cm{sup −1}) IR diode laser absorption spectroscopy. Highly vibrationally excited MFB with E′ = ∼41 000 cm{sup −1} was prepared by 248 nm UV excitation followed by rapid radiationless internal conversion to the electronic ground state (S{sub 1}→S{sub 0}*). The amount of vibrational energy transferred from hot MFB into rotations and translations of CO{sub 2} via collisions was measured by probing the scattered CO{sub 2} using the IR diode laser. The absolute state specific energy transfer rate constants and scattering probabilities for single collisions between hot MFB and CO{sub 2} were measured and used to determine the energy transfer probability distribution function, P(E,E′), in the large ΔE region. P(E,E′) was then fit to a bi-exponential function and extrapolated to the low ΔE region. P(E,E′) and the biexponential fit data were used to determine the partitioning between weak and strong collisions as well as investigate molecular properties responsible for large collisional energy transfer events. Fermi's Golden rule was used to model the shape of P(E,E′) and identify which donor vibrational motions are primarily responsible for energy transfer. In general, the results suggest that low-frequency MFB vibrational modes are primarily responsible for strong collisions, and govern the shape and magnitude of P(E,E′). Where deviations from this general trend occur, vibrational modes with large negative anharmonicity constants are more efficient energy gateways than modes with similar frequency, while vibrational modes with large positive anharmonicity constants are less efficient at energy transfer than modes of similar frequency.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Fixed-node diffusion Monte Carlo potential energy curve of the fluorine molecule F{sub 2} using selected configuration interaction trial wavefunctions
The potential energy curve of the F{sub 2} molecule is calculated with Fixed-Node Diffusion Monte Carlo (FN-DMC) using Configuration Interaction (CI)-type trial wavefunctions. To keep the number of determinants reasonable and thus make FN-DMC calculations feasible in practice, the CI expansion is restricted to those determinants that contribute the most to the total energy. The selection of the determinants is made using the CIPSI approach (Configuration Interaction using a Perturbative Selection made Iteratively). The trial wavefunction used in FN-DMC is directly issued from the deterministic CI program; no Jastrow factor is used and no preliminary multi-parameter stochastic optimization of the trial wavefunction is performed. The nodes of CIPSI wavefunctions are found to reduce significantly the fixed-node error and to be systematically improved upon increasing the number of selected determinants. To reduce the non-parallelism error of the potential energy curve, a scheme based on the use of a R-dependent number of determinants is introduced. Using Dunning’s cc-pVDZ basis set, the FN-DMC energy curve of F{sub 2} is found to be of a quality similar to that obtained with full configuration interaction/cc-pVQZ.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Modelling of fluorine based high density plasma for the etching of silica glasses
An etching simulator has been developed to study the etching of commercial silica glass (Pyrex, D263, AF45, and Vycor) in a SF{sub 6}/Ar inductively coupled plasma (ICP) discharge. The etching model is based on the development of the plasma kinetic model coupled to a two dimensional (2D) Monte Carlo cellular surface model to predict the etched surface morphology as a function of the operating conditions. The SF{sub 6}/Ar plasma model allows us to predict the neutral and ion species fluxes, as well as the density and the temperature of electrons, as a function of the reactor operating conditions. Such output parameters are used as input parameters in both the sheath and etching models. The 2D Monte Carlo cellular model is based on the representation of both the substrate and the mask by uniform cells, which each represents a real number of sites. The preferential redeposition mechanism of the etched products on the metallic sites seems to play an important role on the formation and the propagation of the etched surface roughness. The results obtained by the model are compared with the experimental results for etching rate and roughness. A satisfactory agreement between the experimental results and the model concerning the etching rate and the etched surface morphology has been obtained for different glasses.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Low-Dispersion Multimode Fibers with a Core Made of Fluorine-Doped Quartz Glass
The causes of the occurrence and the method of the elimination of defects of non-bridging oxygen in multimode fluorosilicate optical fibers prepared by the modified method of chemical vapor deposition are considered. The solution is the use of support tubes obtained by quartz surfacing in a hydrogen atmosphere. In this case, there is no absorption band in a range of 630 nm caused by nonbridging oxygen in the spectrum of optical losses of gradient fluorosilicate optical fibers of W-type. Attenuation in a visible spectrum range is mainly determined by the level of Rayleigh scattering and the mode dispersions at a wavelength of 342 and 683 nm are 1.2 ± 0.1 and 0.7 ± 0.2 ps/m, respectively.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Fluorinated Covalent Organic Frameworks: A Novel Pathway to Enhance Hydrogen Sorption and Control Isosteric Heats of Adsorption; HyMARC Seed Project Final Report
Organic framework materials, as a unique sub-class of carbon-based sorbents, have gained increasing attention for promising attributes toward gas storage. Calculations of the hydrogen capacity of optimized frameworks show potential to achieve greater than 60 g/L storage of hydrogen, placing metal-organic frameworks (MOFs) and COFs near the top of the class of porous materials. However, at the ensemble level, poor stacking creates a quasi-amorphous material with low structural integrity and low effective surface area. The chemical versatility of COFs allows for additional methods for producing long-range order that specifically target the inter-layer interactions in COFs but that leave key pore-accessible linker sites open. These modifications (either during synthesis or post-synthetic) enable a host of strategies to both improve crystalline order for more stable and higher surface, as well as add metals with open coordination for enhanced H 2 binding enthalpy.
08 HYDROGEN↗