Adsorption of anionic dyes on chitosan beads. 1. The influence of the chemical structures of dyes and temperature on the adsorption kinetics

In this work, chitosan beads were synthesized in acidic medium and cross-linked in 1% glutaraldehyde solution. The characterization of the materials using TG/DTG, XRD, and BET surface areas showed that the beads did not modify their characteristics after the cross-linking reaction. The cross-linked beads were utilized as adsorbents for the removal of the yellow-, blue-, and red-anionic reactive dyes from aqueous solutions at pH 2.0. Adsorption of the yellow-dye increased from 25 to 50 degrees C. However, adsorption of the blue-dye decreased from 25 to 50 degrees C. Interestingly, the adsorption of the red-dye decreased from 25 to 35 degrees C and increased from 45 to 50 degrees C. The kinetic data were evaluated using an Avrami kinetic model, where the parameter n was related to the determination of changes in the adsorption mechanisms. Adsorption data of the dyes in relation to the contact time, the chemical structures of the dyes, and temperature were presented and were discussed.     

Sulphate preconcentration by anion exchange resin in flow injection and its turbidimetric determination in water

A preconcentration procedure was established for sulphate determination in rain waters at the mg/l level, employing a small column packed with the AG1-X8 (200-400 mesh) anionic resin inserted into a flow injection system. Sulphate determination was performed by using the turbidimetric method based on reaction with barium. For concentrations within 0.10 and 2.0 MgSO(2-)(4)/l, a throughput of 50 determinations/hr was achieved, and the relative standard deviation of results was better than 2%.     

The reaction of N-aminophthalimide with isothiocyanates

N-Aminophthalimide ( I ) reacted in refluxing isopropyl alcohol with a number of isothiocyanates to give the related 1:1 addition products, N-(3-substitutedthioureido)phthalimides III. On the other hand, heating I directly with an excess of neat arylisothiocyanates produced the N-arylphthalimides IV. As shown for IIIa, the 1:1 addition products are conveniently deblocked by the Ing-Manske procedure to yield the 4-substituted thiosemicarbazide.     

A concise and regioselective synthesis of 1-alkyl-4-imidazolecarboxylates

Reaction between ethyl 3-N,N-(dimethylamino)-2-isocyanoacrylate (1) and a primary amine (2) regioselectively affords 1-alkyl-4-imidazolecarboxylates (3) in good yields (52-89%). The method is applicable to unhindered and hindered amine substrates, as well as those containing reactive functionality such as alcohols and secondary and tertiary amines. [reaction: see text]     

Structure cristalline de SmZrF7. Relations structurales avec le type ReO3

The crystal structure of the fluorozirconate SmZrF₇ has been determined from single crystal X-ray data; the final R value is 0.028. In this compound, isotypic with all the fluorozirconates LnZrF₇ (Ln = rare earth), the symmetry of the cell is monoclinic (space group: P₂₁). The Zr atoms are surrounded by six fluorine atoms forming an almost perfect octahedron: the average distance ZrF is 2.006 Å. The Sm atoms are surrounded by a 8 fluorine atoms polyhedron, the distances SmF lie from 2.221 to 2.411 Å. The association of these two polyhedra by sharing corner forms slabs with an approximately ReO₃ type arrangement: the thickness of the slabs is two octahedra.These slabs with the composition M₂X₇ are held together so that the top fluorine atoms at the surface of a slab increase the coordination of the Sm atom of an adjacent slab. This MX_3.5 phase corresponds to a new structural type between MX₃ (ReO₃ type) and MX₄ (SnF₄ type).     

A theoretical investigation of the interaction between H,Li, Na,K, and fullerenes

We studied the interaction between H, Li, Na, and K with one and two C₆₀ molecules using unrestricted Hartree–Fock (UHF) methods. We investigated the effects of distances between the doping atoms and the C₆₀ clusters, total charges, interaction energies, stabilities, HOMO‐LUMO energy differences, charge distribution, and potential energy surfaces. The effect of each doping atom was analyzed and potential technological applications discussed. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Mixed-metal cluster chemistry. 26 . Proclivity for “all-terminal” or “plane-of-bridging-carbonyls” ligand disposition in tungsten-triiridium clusters

Reaction of WH(CO)₃(η-C₅Me₅) with IrCl(CO)₂(4-H₂NC₆H₄Me) affords WIr₃(μ-CO)₃(CO)₈(η-C₅Me₅) in low yield. A structural study reveals a WIr₂-centred plane of bridging carbonyls, in contrast to the crystal structure of WIr₃(CO)₁₁(η-C₅H₅) (all-terminal carbonyl distribution). DFT calculations reveal an increasing proclivity to adopt an all-terminal CO disposition for clusters MIr₃(CO)₁₁(η-C₅H₅) in the gas phase on proceeding from M=Cr to Mo and then W, consistent with structural studies in the solid state for which the tungsten-containing cluster is the only all-terminal example. Increasing electron donation from the ligands in the tungsten system (either from phosphine substitution or cyclopentadienyl permethylation) suffices to impose a plane of bridging carbonyls in the ground state structure. ¹³C NMR fluxionality studies reveal that CO exchange mechanism(s) for WIr₃(CO)₁₁(η-C₅H₅) and the related tetrahedral cluster W₂Ir₂(CO)₁₀(η-C₅H₅)₂ are very fast and involve all carbonyls on the clusters. DFT calculations on MIr₃(CO)₁₁(η-C₅H₅) (M=Cr, Mo) substantiate a ‘merry-go-round’ mechanism for carbonyl scrambling in these systems, a result which is consistent with the scrambling behaviour seen in the NMR fluxionality studies on the W-containing congener.     

Mixed-metal cluster chemistry. 19. Crystallographic, spectroscopic, electrochemical, spectroelectrochemical, and theoretical studies of systematically varied tetrahedral group 6-iridium clusters

A systematically varied series of tetrahedral clusters involving ligand and core metal variation has been examined using crystallography, Raman spectroscopy, cyclic voltammetry, UV-vis-NIR and IR spectroelectrochemistry, and approximate density functional theory, to assess cluster rearrangement to accommodate steric crowding, the utility of metal-metal stretching vibrations in mixed-metal cluster characterization, and the possibility of tuning cluster electronic structure by systematic modification of composition, and to identify cluster species resultant upon electrochemical oxidation or reduction. The 60-electron tetrahedral clusters MIr(3)(CO)(11-x)(PMe(3))(x)(eta(5)-Cp) [M = Mo, x = 0, Cp = C(5)H(4)Me (5), C(5)HMe(4) (6), C(5)Me(5) (7); M = W, Cp = C(5)H(4)Me, x = 1 (13), x = 2 (14)] and M(2)Ir(2)(CO)(10-x)(PMe(3))(x)(eta(5)-Cp) [M = Mo, x = 0, Cp = C(5)H(4)Me (8), C(5)HMe(4) (9), C(5)Me(5) (10); M = W, Cp = C(5)H(4)Me, x = 1 (15), x = 2 (16)] have been prepared. Structural studies of 7, 10, and 13 have been undertaken; these clusters are among the most sterically encumbered, compensating by core bond lengthening and unsymmetrical carbonyl dispositions (semi-bridging, semi-face-capping). Raman spectra for 5, 8, WIr(3)(CO)(11)(eta(5)-C(5)H(4)Me) (11), and W(2)Ir(2)(CO)(10)(eta(5)-C(5)H(4)Me)(2) (12), together with the spectrum of Ir(4)(CO)(12), have been obtained, the first Raman spectra for mixed-metal clusters. Minimal mode-mixing permits correlation between A(1) frequencies and cluster core bond strength, frequencies for the A(1) breathing mode decreasing on progressive group 6 metal incorporation, and consistent with the trend in metal-metal distances [Ir-Ir < M-Ir < M-M]. Cyclic voltammetric scans for 5-15, MoIr(3)(CO)(11)(eta(5)-C(5)H(5)) (1), and Mo(2)Ir(2)(CO)(10)(eta(5)-C(5)H(5))(2) (3) have been collected. The [MIr(3)] clusters show irreversible one-electron reduction at potentials which become negative on cyclopentadienyl alkyl introduction, replacement of molybdenum by tungsten, and replacement of carbonyl by phosphine. These clusters show two irreversible one-electron oxidation processes, the easier of which tracks with the above structural modifications; a third irreversible oxidation process is accessible for the bis-phosphine cluster 14. The [M(2)Ir(2)] clusters show irreversible two-electron reduction processes; the tungsten-containing clusters and phosphine-containing clusters are again more difficult to reduce than their molybdenum-containing or carbonyl-containing analogues. These clusters show two one-electron oxidation processes, the easier of which is reversible/quasi-reversible, and the more difficult of which is irreversible; the former occur at potentials which increase on cyclopentadienyl alkyl removal, replacement of tungsten by molybdenum, and replacement of phosphine by carbonyl. The reversible one-electron oxidation of 12 has been probed by UV-vis-NIR and IR spectroelectrochemistry. The former reveals that 12(+) has a low-energy band at 8000 cm(-1), a spectrally transparent region for 12, and the latter reveals that 12(+) exists in solution with an all-terminal carbonyl geometry, in contrast to 12 for which an isomer with bridging carbonyls is apparent in solution. Approximate density functional calculations (including ZORA scalar relativistic corrections) have been undertaken on the various charge states of W(2)Ir(2)(CO)(10)(eta(5)-C(5)H(5))(2) (4). The calculations suggest that two-electron reduction is accompanied by W-W cleavage, whereas one-electron oxidation proceeds with retention of the tetrahedral core geometry. The calculations also suggest that the low-energy NIR band of 12(+) arises from a sigma(W-W) --> sigma*(W-W) transition.     

Comparison of the Structural Information on Sol-Gel Systems Provided by Pyrene Labeled Fluorescent Probes

The influence of the acid catalyst concentration on the structural evolution of a sol-gel system was studied by doping TEOS based starting solutions with two fluorescent probes: a polystyrene chain (M _n =1700) and a much shorter alkane chain (M=172), both of them labeled at both ends with 1-pyrenyl. For this purpose, each probe was incorporated in two TEOS∶H₂O∶C₂H₅OH mixtures (molar ratios 1∶4∶1), one at pH 1.2 and the other at pH 2.5 (respectively below and above the isoelectric point of silica). Very low concentrations of the probes were used (≤10⁻⁶ M), so the pyrene dimmers and excimers were formed only intramolecularly. The ratios of excimer to monomer fluorescence intensities at excitation wavelength of 360 nm (where mainly the ground state pyrene dimmers are excited) were studied as a function of time. Different evolutions of these ratios were observed, which allowed us to predict that the silica structure developsvia the formation of primary particles, even at pH values below the isoelectric point of silica, where it is not possible to directly detect their formation.     

Molybdenum(VI)-complexes with chiral N,O-ligands derived from carbohydrates: synthesis, structure and catalytic properties in asymmetric olefin epoxidation

Novel chiral 2′-pyridinyl alcohols derived from isopropylidene-protected carbohydrates are reported. They show different characteristics at the hydroxy group, but are all suitable ligands for chiral molybdenum(VI) complexes of the type MoO₂L₂ (L = chiral 2′-pyridinyl alcoholate). MoO₂(acac)₂ served as starting material in the complex syntheses. The structure of one ligand and one dioxo complex were exemplary established by X-ray crystallography. For catalytic runs in the enantioselective epoxidation catalysis trans-methylstyrene was used as model substrate, tert-butylhydroperoxide and cumolhydroperoxide, resp., as the oxidant.