Intramolecular π–π Interactions in Flexibly Linked Partially Fluorinated Bisarenes in the Gas Phase

Three compounds with phenyl and pentafluorophenyl rings bridged by (CH₂)₃ and (CH₂)₂SiMe₂ units were synthesized by hydrosilylation and C−C coupling reactions. Their solid‐state structures are dominated by intermolecular π stacking interactions, primarily leading to dimeric or chain‐type aggregates. Analysis of free molecules in the gas phase by electron diffraction revealed the most abundant conformer to be significantly stabilized by intramolecular π–π interactions. For the silicon compounds, structures characterized by σ–π interactions between methyl and pentafluorophenyl groups are second lowest in energy and cannot be excluded completely by the gas electron diffraction experiments. C₆H₅(CH₂)₃C₆F₅, in contrast, is present as a single conformer. The gas‐phase structures served as a reference for the evaluation of a series of (dispersion‐corrected) quantum‐chemical calculations.     

Improving barrier properties of polyethylene/Fe2O3-modified nanographene nanocomposites in a magnetic field

The present work aims at improving the barrier properties of high molecular weight Polyethylene/ graphene nanoplatelets (HMWPE/GnP) nanocomposites by aligning the embedded modified graphene nanoparticles in a magnetic field. Graphene nanoplatelets (GnP) were modified by magnetic Fe₂O₃ to produce Fe₂O₃-modified Graphene, GnP-mFe₂O₃. The magnetic properties of Fe₂O₃ were previously characterized by the vibrating sample magnetometer (VSM) method and resulting GnP-mFe₂O₃ nanoparticles were characterized by Fourier transform infrared (FTIR) analysis. HMWPE/GnP nanocomposites were prepared via melt mixing. The prepared nanocomposites were sheeted at high temperatures in a magnetic field using a hot press. The barrier properties of prepared films, HMWPE/GnP and HMWPE/GnP-mFe₂O₃ were characterized by carrying out a permeation to oxygen experiment as a function of GnP and GnP-mFe₂O₃ contents. A decrease in gas transmission rate (GTR) was observed for the samples after being subjected to the magnetic field compared to the non-treated sample. The results of differential scanning calorimetry (DSC) and field emission electron microscopy (FESEM) experiments confirmed the orientation of GnP-mFe₂O₃ nanoparticles in nanocomposites.     

Bismuth triple-decker phthalocyanine: synthesis and structure

Triclinic crystals of bismuth(III) triple-decker phthalocyanine, Bi₂Pc₃, Pc=C₃₂H₁₆N₈²⁻, were grown directly by the reaction of Bi₂Se₃ with 1,2-dicyanobenzene at 220°C. The Bi₂Pc₃ molecule is centrosymmetric with the bismuth atoms located closer to the peripheral phthalocyaninato(2−) rings than to the central ring. Each bismuth(III) ion is connected by four N-isoindole atoms to the peripheral and by four N-isoindole to the central Pc ring with average distances of 2.333 and 2.747 Å, respectively. This indicates a stronger connection of Bi(III) to the peripheral saucer-shaped macrocyclic rings than to the central rings. The neighbouring phthalocyaninato(2−) moieties in the Bi₂Pc₃ molecule are separated by a distance of 3.101(5) Å. The central Pc ring is rotated by 36.4° with respect to the peripheral ones. Differences in Bi–N bond lengths are a result of interaction of the bismuth ion with peripheral and central rings as well as the repulsion forces between two bismuth ions in the same Bi₂Pc₃ molecule, which are separated by a distance of 3.839(2) Å. The crystal packing is characterized by a distance of 3.56 Å between Pc rings of neighbouring Bi₂Pc₃ molecules.     

Carbon Dynamics on the Molybdenum Carbide Surface during Catalytic Propane Dehydrogenation

The effect of the gas‐phase chemical potential on surface chemistry and reactivity of molybdenum carbide has been investigated in catalytic reactions of propane in oxidizing and reducing reactant mixtures by adding H₂, O₂, H₂O, and CO₂ to a C₃H₈/N₂ feed. The balance between surface oxidation state, phase stability, carbon deposition, and the complex reaction network involving dehydrogenation reactions, hydrogenolysis, metathesis, water‐gas shift reaction, hydrogenation, and steam reforming is discussed. Raman spectroscopy and a surface‐sensitive study by means of in situ X‐ray photoelectron spectroscopy evidence that the dynamic formation of surface carbon species under a reducing atmosphere strongly shifts the product spectrum to the C₃‐alkene at the expense of hydrogenolysis products. A similar response of selectivity, which is accompanied by a boost of activity, is observed by tuning the oxidation state of Mo in the presence of mild oxidants, such as H₂O and CO₂, in the feed as well as by V doping. The results obtained allow us to draw a picture of the active catalyst surface and to propose a structure–activity correlation as a map for catalyst optimization.     

Elimination of AsF3 from anhydrous HF using AgFAsF6 as a mediator

Elimination of the arsenic (III) impurity AsF₃ from anhydrous hydrogen fluoride has been demonstrated using a bench-scale apparatus (∼500 mL of HF), with a Ag(II) salt AgFAsF₆ as a mediator. In this process, AsF₃ is oxidized by AgFAsF₆ to AsF₅. In the next step, AsF₅ is eliminated from HF by reaction with NaF. The oxidizer, AgFAsF₆, is reduced to AgAsF₆ which is regenerated to AgFAsF₆ by F₂ in HF at room temperature. This method can reduce the arsenic content in HF from a few hundred ppm to the industrially required level (<3 ppm). The results for three other methods (distillation, oxidation by F₂ gas, and oxidation by K₂NiF₆) are reported and compared with the AgFAsF₆ method in a preliminary examination (using ∼4 mL of HF).     

New polyimide-polyaniline hollow fibers: Synthesis, characterization and behavior in gas separation

New polyimide-polyaniline hollow fibers were produced by dissolution of the polymers in NMP and dry/wet spinning of the resulting solution in a non-solvent (H₂O). The morphology and thermal properties of the fibers, were examined by means of SEM and TGA, and FTIR spectroscopy was used for the study of their chemical structure. Permeability and selectivity measurements in different gases (He, H₂, CH₄, CO₂, O₂ and N₂) were performed in order to evaluate the performance of the membrane in gas separation applications. The results indicate that the novel membrane is a well structured hollow fiber, thermally stable up to 500°. The introduction of polyaniline into the polyimide matrix, results in a great enhancement in fiber permeability (60-600 times) possibly due to increase of the total free volume due to the introduction of shorter polyaniline molecules in the matrix, allowing larger quantities of gases to pass through the composite membrane. Perm-selectivity ratios for the composite membranes H₂/CH₄, He/N₂, H₂/N₂ and H₂/CO₂ were found lower by a factor of 6.4, 8.9, 7.7 and 1.47, respectively, compared to membranes produced using only polyimide. The opposite effect was observed for CH₄/CO₂ and N₂/CO₂ perm-selectivity ratios that showed an increase by a factor of 3.52 and 5.2, respectively. The ratio CH₄/CO₂ is of particular interest for natural gas purification purposes.     

Effect of Al2O3 nanoparticles on the steel-glass/epoxy composite joint bonded by a two-component structural acrylic adhesive

This paper reports a study on the effect of Al₂O₃ nanoparticles on the adhesion strength of steel-glass/epoxy composite joints bonded by a two-component structural acrylic adhesive. The addition of Al₂O₃ nanoparticles to the two-component acrylic adhesive led to a remarkable enhancement in the shear and tensile strength of the composite joints. The shear and tensile strength of the adhesive joints increased by addition of Al₂O₃ up to 1.5 wt%, which decreased by further addition of the nanofiller. Introduction of the nanoparticles caused a reduction in the peel strength of the joints. DSC analysis revealed that the glass transition temperature (Tg) of the adhesives rose by increasing the nanofiller content. The advancing water contact angle was decreased for adhesives containing nanoparticles. SEM micrographs indicated good dispersions of the Al₂O₃ nanoparticles within the acrylic matrix in the specimens with up to 1.5 wt% Al₂O₃ and revealed that addition of nanoparticles altered the fracture morphology from smooth to rough fracture surfaces.     

Synthesis and x-ray crystal structure of the TiMgCl5(OOCCH2Cl) · (ClCH2COOC2H5)3 Adduct

The synthesis of the TiMgCl₅(OOCCH₂Cl) · (ClCH₂COOC₂H₅)₃ adduct, obtained by reacting TiCl₄ with a solution of MgCl₂ in dry ClCH₂COOC₂H₅, is reported together with its molecular and crystal structure as determined by x-ray diffraction. The structure was solved by direct and Fourier methods and refined by least-squares techniques to R = 0.057 for 1318 independent observed reflections. Crystals are monoclinic, space-group P2₁/c, with 4 formula units in a unit-cell of dimensions a = 10.480(4), b = 19.641(9), c = 16.597(6) Å, β = 120.21(5)°. The titanium(IV) atom is octahedrally coordinated by five chlorine atoms and an oxygen atom of a OOCCH₂Cl residue. The magnesium atom is similarly coordinated by two chlorine atoms, the carbonyl oxygen atoms of three ClCH₂COOC₂H₅ molecules and an oxygen atom of the OOCCH₂Cl residue. The two octahedra share an edge by a double chlorine bridge between the magnesium and the titanium atoms and are also connected by the COO group of the OOCCH₂Cl residue. Changes in the configurations and dimensions with respect to the free acceptor and donor molecules are discussed.     

Tunable Oxygen Activation for Catalytic Organic Oxidation: Schottky Junction versus Plasmonic Effects

The charge state of the Pd surface is a critical parameter in terms of the ability of Pd nanocrystals to activate O₂ to generate a species that behaves like singlet O₂ both chemically and physically. Motivated by this finding, we designed a metal–semiconductor hybrid system in which Pd nanocrystals enclosed by {100} facets are deposited on TiO₂ supports. Driven by the Schottky junction, the TiO₂ supports can provide electrons for metal catalysts under illumination by appropriate light. Further examination by ultrafast spectroscopy revealed that the plasmonics of Pd may force a large number of electrons to undergo reverse migration from Pd to the conduction band of TiO₂ under strong illumination, thus lowering the electron density of the Pd surface as a side effect. We were therefore able to rationally tailor the charge state of the metal surface and thus modulate the function of Pd nanocrystals in O₂ activation and organic oxidation reactions by simply altering the intensity of light shed on Pd–TiO₂ hybrid structures.     

Reaction‐Based and Single Fluorescent Emitter Decorated Ratiometric Nanoprobe to Detect Hydrogen Peroxide

A novel reaction‐based cross‐linked polymeric nanoprobe with a self‐calibrating ratiometric fluorescence readout to selectively detect H₂O₂ is reported. The polymeric nanoprobe is fabricated by using hydrophobic H₂O₂‐reactive boronic ester groups, crosslinker units, and environmentally sensitive 3‐hydroxyflavone fluorophores through a miniemulsion polymerization. On treatment with H₂O₂, the boronic esters in the polymer are cleaved to form hydrophilic alcohols and subsequently lead to a hydrophobic–hydrophilic transition. Covalently linked 3‐hydroxyflavones manifest the change in polarity as a ratiometric transition from green to blue, accompanied by a 500‐fold increase in volume. Furthermore, this nanoprobe has been used for ratiometric sensing of glucose by monitoring the H₂O₂ generated during the oxidation of glucose by glucose oxidase, and thus successfully distinguished between normal and pathological levels of glucose.     

Thermal evolution of ferromagnetic metallic glasses

A traditional TG apparatus was modified by placing two permanent magnets producing a controlled magnetic field (TG(M): Magneto Thermogravimetry). This technique proved to be useful to study both structural relaxation and crystallisation of ferromagnetic metallic glasses. Results obtained for the amorphous alloys Fe₄₀Ni₄₀P₁₄B₆ and Fe_62.5Co₆Ni_7.5Zr₆Nb₂Cu₁B₁₅, are reported in this paper. Structural relaxation can be evaluated by measuring changes in Curie temperature induced by thermal treatments. Crystallisation in TG(M) is detected through a change in the measured apparent mass (difference between the sample mass and magnetic force driving it upward). These results were confirmed by DSC analysis. Whether the obtained crystalline phase is ferromagnetic, it can be identified through its Curie temperature, measured by TG(M). In fact the value of 770°C measured as Curie temperature of crystallised Fe_62.5Co₆Ni_7.5Zr₆Nb₂Cu₁B₁₅led to conclude that the only ferromagnetic crystalline phase is a-Fe. These hypothesis was confirmed by XRD analysis, showing that the first crystallisation yields to a-Fe nanocrystals. This revised version was published online in July 2006 with corrections to the Cover Date.     

Tailoring of Electronic Structure and Thermoelectric Properties of a Topological Crystalline Insulator by Chemical Doping

Topological crystalline insulators (TCIs) are a new quantum state of matter in which linearly dispersed metallic surface states are protected by crystal mirror symmetry. Owing to its vanishingly small bulk band gap, a TCI like Pb_0.6Sn_0.4Te has poor thermoelectric properties. Breaking of crystal symmetry can widen the band gap of TCI. While breaking of mirror symmetry in a TCI has been mostly explored by various physical perturbation techniques, chemical doping, which may also alter the electronic structure of TCI by perturbing the local mirror symmetry, has not yet been explored. Herein, we demonstrate that Na doping in Pb_0.6Sn_0.4Te locally breaks the crystal symmetry and opens up a bulk electronic band gap, which is confirmed by direct electronic absorption spectroscopy and electronic structure calculations. Na doping in Pb_0.6Sn_0.4Te increases p‐type carrier concentration and suppresses the bipolar conduction (by widening the band gap), which collectively gives rise to a promising zT of 1 at 856 K for Pb_0.58Sn_0.40Na_0.02Te. Breaking of crystal symmetry by chemical doping widens the bulk band gap in TCI, which uncovers a route to improve TCI for thermoelectric applications.     

Synthesis and characterization of LiNi0.43Mn0.43Co0.13O2 by wet-chemical method

In the aim to obtain a new powder able to substitute oxide intensively used as a material for the positive electrode in the batteries Lithium-ion, the LiNi_0.43Mn_0.43Co_0.13O₂ material was synthesized by sol–gel method and characterized by XRD, RAMAN and TEM. The composition of our LiNi_0.43Mn_0.43Co_0.13O₂ oxide was checked by ICP analysis. The Rietveld refinement showed a very weak mixing cation disorder, probably due to the presence of nickel excess in this material. Electrochemical performances of LiNi_0.43Mn_0.43Co_0.13O₂ oxide were tested using this material as positive electrode in a battery of lithium.     

Breaking the Passivation: Sodium Borohydride Synthesis by Reacting Hydrated Borax with Aluminum

A significant obstacle in the large-scale applications of sodium borohydride (NaBH₄) for hydrogen storage is its high cost. Herein, we report a new method to synthesize NaBH₄ by ball milling hydrated sodium tetraborate (Na₂B₄O₇ ⋅ 10H₂O) with low-cost Al or Al₈₈Si₁₂, instead of Na, Mg or Ca. An effective strategy is developed to facilitate mass transfer during the reaction by introducing NaH to enable the formation of NaAlO₂ instead of dense Al₂O₃ on Al surface, and by using Si as a milling additive to prevent agglomeration and also break up passivation layers. Another advantage of this process is that hydrogen in Na₂B₄O₇ ⋅ 10H₂O serves as a hydrogen source for NaBH₄ generation. Considering the low cost of the starting materials and simplicity in operation, our studies demonstrate the potential of producing NaBH₄ in a more economical way than the commercial process.     

Direct Zinc Finger Protein Persulfidation by H2S Is Facilitated by Zn2+

H₂S is a gaseous signaling molecule that modifies cysteine residues in proteins to form persulfides (P‐SSH). One family of proteins modified by H₂S are zinc finger (ZF) proteins, which contain multiple zinc‐coordinating cysteine residues. Herein, we report the reactivity of H₂S with a ZF protein called tristetraprolin (TTP). Rapid persulfidation leading to complete thiol oxidation of TTP mediated by H₂S was observed by low‐temperature ESI‐MS and fluorescence spectroscopy. Persulfidation of TTP required O₂ , which reacts with H₂S to form superoxide, as detected by ESI‐MS, a hydroethidine fluorescence assay, and EPR spin trapping. H₂S was observed to inhibit TTP function (binding to TNFα mRNA) by an in vitro fluorescence anisotropy assay and to modulate TNFα in vivo. H₂S was unreactive towards TTP when the protein was bound to RNA, thus suggesting a protective effect of RNA.     

Semi-Continuous Heterophase Polymerization to Synthesize Nanocomposites of Poly(acrylic acid)-Functionalized Carbon Nanotubes

Two materials, pure poly(acrylic acid) (PAA) and nanocomposites with a matrix of PAA and carbon nanotubes (CNTs) as reinforcing agent were synthesized by semi-continuous heterophase polymerization (SHP). CNTs were prepared by a chemical vapor deposition technique and purified by steam. CNTs were characterized by a high resolution scanning electron microscopy (HRSEM) and Raman and Fourier transform infrared spectroscopies. Nanocomposites were prepared with: (i) purified CNTs (CNTs_p) or (ii) purified and functionalized CNTs possessing an acyl chloride moiety (CNTs_OCl). In both cases, the nanocomposites synthesis was carried out by in situ polymerization of acrylic acid (AA) by SHP. When CNTs_OCl were used previously to the polymerization of AA, a series of specific amounts of CNTs_OCl and AA were mixed to induce a chemical reaction between the carboxyl group of AA and the acyl chloride group of the CNTs_OCl. The product, acrylic acid grafted to CNTs_OCl (CNTs_OCl-AA), was used to prepare the PAA-CNTs_OCl nanocomposites. The PAA-CNTs_OCl nanocomposites were characterized by HRSEM, Raman, FTIR and CPMAS ¹³C-NMR spectroscopies and also by thermogravimetric analysis (TGA). The results reveal that PAA-CNTs_OCl nanocomposites were formed by PAA macromolecules grafted to CNTs_OCl. The kinetic behavior observed for the synthesis of pure PAA or PAA-CNTs_OCl nanocomposites by SHP was similar. Latexes of PAA-CNTs_OCl nanocomposites were stable without formation of a precipitate of CNTs_OCl for over 1.5 years, while latex prepared with CNTs_p and PAA, was unstable and formation of a precipitate of CNTs_p was observed immediately after its preparation. PAA-CNTs_p nanocomposites were characterized only by TGA. Moreover, latex of the PAA-CNTs_p nanocomposite that did not precipitate immediately after its preparation, turned into a gel; this gelation never occurred with the PAA-CNTs_OCl nanocomposite latex.     

Cooperative Catalysis of Ru(III)-Porphyrin in CO2-Involved Synthesis of Oxazolidinones

CO₂-transformations into high value-added products have become a fascinating area in green chemistry. Herein, a Ru(III)-porphyrin catalyst (RuCl₃ ⋅ 3H₂O−H₂TPP) was found highly efficient in the three-component reaction of CO₂, aliphatic amines and dichloroethane (or its derivative) for synthesis of oxazolidinones in the yields of 71∼91%. It was indicated by means of the control experiments and UV-vis spectra that CO₂ was stoichiometrically activated by the involved aliphatic amine substrates to form a stable carbamate salt while 1,2-dichloroethane (or its derivative) was independently activated by the involved Ru(III)-porphyrin catalyst. The combination of CO₂-activation by aliphatic amines with 1,2-dichloroethane activation by Ru(III)-porphyrin catalyst cooperatively contributed to this successful transformation.     

Second order incommensurate phase transition in 25L-Ta2O5

A new structural state 25L-Ta₂O₅, obtained from sintering and annealing treatments of a Ta₂O₅ powder, is identified both by electron diffraction and high resolution imaging on a transmission electron microscope (TEM). According to general rules for the different L-Ta₂O₅ structures proposed by Grey et al. (J. Solid State Chem. 178 (2005) 3308), a structural model is derived from their crystallographic data on 19L-Ta₂O₅. This model yields simulated images in agreement with high resolution TEM observations of the structure oriented along its [001] zone axis, but only for a very thin crystal thickness of less than 1.2 nm. Such a limitation is shown to be due to a modulation of the structure along its [001] axis. Actually, from an analysis of a diffuse scattering and of its evolution into satellites reflections as a function of the cooling rate, a second order incommensurate phase transition can be assumed to occur in this compound. The property of single phase samples observed by TEM is also verified by X-ray powder diffraction. In a discussion about studies performed by different authors on incommensurate structures in the system Ta₂O₅-WO₃, it is noticed that TEM results, similar to ours, indicate that phase transitions could be expected in these structures.     

Oxidation – Reduction Reactions of Tetrachloroaurate(III) Anion with Triphenyl Derivatives of Group V Elements

The reduction of the tetrachloroaurate (III) anion by L (L = PPh₃, AsPh₃, SbPh₃) is quantitative in non-aqueous solution. The products are the gold(I)-complexes AuClL (L = AsPh₃, SbPh₃) and Au(PPh₃)⁺₂ together with the corresponding oxidation product LCl₂. Kinetic studies show that the reactions are first order in AuCl^?₁ and L. In addition a path independent of PPh₃ was found in dichloromethane. These data are interpreted in terms of mechanisms which involve reduction of AuCl^?₄ to AuCl^?₂ followed by equilibrium formation of AuClL for L = AsPh₃ and SbPh₃. For PPh₃, the data are consistent with a chloride replacement by PPh₃ to give AuCl₃ PPh₃, which is followed by a rapid reduction by a second mole of PPh₃. Equilibrium formation constants are reported for several Au(I) complexes.     

Double Negatively Curved C70 Growth through a Heptagon‐Involving Pathway

All previously reported C₇₀ isomers have positive curvature and contain 12 pentagons in addition to hexagons. Herein, we report a new C₇₀ species with two negatively curved heptagon moieties and 14 pentagons. This unconventional heptafullerene[70] containing two symmetric heptagons, referred to as dihept‐C₇₀, grows in the carbon arc by a theoretically supported pathway in which the carbon cluster of a previously reported C₆₆ species undergoes successive C₂ insertion via a known heptafullerene[68] intermediate with low energy barriers. As identified by X‐ray crystallography, the occurrence of heptagons facilitates a reduction in the angle of the π‐orbital axis vector in the fused pentagons to stabilize dihept‐C₇₀. Chlorination at the intersection of a heptagon and two adjacent pentagons can greatly enlarge the HOMO–LUMO gap, which makes dihept‐C₇₀Cl₆ isolable by chromatography. The synthesis of dihept‐C₇₀Cl₆ offers precious clues with respect to the fullerene formation mechanism in the carbon‐clustering process.