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51.
Tonson Abraham 《Monatshefte für Chemie / Chemical Monthly》1982,113(11):1275-1282
When dibenzo[b,f]-1-azapentalene dianion (3) was allowed to react with either iron (III) chloride or ethylene bromide, a one-electron transfer from3 took place readily to give the radical anion11. Further electron transfer from11 did not occur presumably due to the antiaromatic character of dibenzo[b,f]-1-azapentalene (1) that would have resulted. The radical anion11 underwent further transformation by hydrogen abstraction from the solvent to give 5,10-dihydroindeno[1,2-b]indole (2) and by dimerization to themeso and (R,S) isomers of 5,5,10,10-tetrahydro-10,10-biindeno[1,2-b]indole (4 a and4 b) respectively.
Elektronentransfer von Dibenzo[b,f]-1-azapentalen-Dianion: Ein Versuch zur Synthese von Dibenzo[b,f]-1-azapentalen
Zusammenfassung Die Reaktion von Dibenzo[b,f]-1-azapentalen-Dianion (3) mit Eisen (III) oder Ethylenbromid ergab einen Ein-Elektronentransfer zum Radikalanion11. Ein weiterer Elektronentransfer fand nicht statt, vermutlich wegen des antiaromatischen Charakters von Dibenzo[b,f]-1-azapentalen (1), das dabei entstehen müßte. Das Radikalanion11 ergab unter Wasserstoffentzug aus dem Lösungsmittel 5,10-Dihydroindeno[1,2-b]indol (2), das weiter zummeso- bzw. (R,S)-5,5,10,10-tetrahydro-10,10-biindeno[1,2-b]indol (4 a bzw.4 b) dimerisierte.相似文献
52.
53.
Heidar Raissi Effat Moshfeghi Abraham F. Jalbout Mohammad Saeid Hosseini Mustapha Fazli 《International journal of quantum chemistry》2007,107(9):1835-1845
The molecular structure and intramolecular hydrogen bond energy of 32 conformers of 4‐methylamino‐3‐penten‐2‐one were investigated at MP2 and B3LYP levels of theory using the standard 6–31G** basis set and AIM analyses. Furthermore, calculations for all the possible conformations of 4‐methylamino‐3‐penten‐2‐one in water solution were also carried out at B3LYP/6–31G** level of theory. The calculated geometrical parameters and conformational analyses in gas phase and water solution show that the ketoamine conformers of this compound are more stable than the other conformers (i.e., enolimine and ketoimine). This stability is mainly due to the formation of a strong N? H···O intramolecular hydrogen bond, which is assisted by π‐electrons resonance. Hydrogen bond energies for all conformers of 4‐methylamino‐3‐penten‐2‐one were obtained from the related rotamers method. The nature of intramolecular hydrogen bond existing within 4‐methylamino‐3‐penten‐2‐one has been investigated by means of the Bader theory of atoms in molecules, which is based on topological properties of the electron density. The results of these calculations support the results which obtained by related rotamers method. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
54.
Givens RS Timberlake GT Conrad PG Yousef AL Weber JF Amslinger S 《Photochemistry and photobiology》2003,78(1):23-29
On the basis of the earlier examples of diazopyruvoyl (DAP) groups reported by Lawton for covalent binding and cross-linking of proteins and oligopeptides and our recent demonstration that a coumaryl diazopyruvamide was used to label Type-I collagen, we have extended our investigations to the synthesis and cross-linking capabilities of a bis-DAP polyethylene glycol to cross-link Type-I collagen. The new photoactivated cross-linking agent, N,N'-bis(3-diazopyruvoyl)-2,2'-(ethylenedioxy)bis(ethylamine) (DPD, 2), has been designed and synthesized specifically to "weld" collagenous tissues by cross-linking Type-I collagen. A working model for the photochemical welding studies of collagenous tissues was developed using gelatin strips (gel strips) composed of denatured Type-I collagen. Gel strips are transparent to near-UV and visible light, uniform in thickness, and have reproducible composition. Furthermore, the availability of nucleophilic amine sites in gel strips was demonstrated by reaction with o-phthalaldehyde, producing a fluorescent derivative of the protein. Gel strips were coated with a solution of DPD in chloroform 7 irradiated at 320-390 nm, and the resulting bonded gel strips were tested for the strength of the weld. The welds were generally brittle and had average tensile strengths that exceeded 100 N/cm2. Welds were not formed in the absence of light or DPD. Scanning electron microscopy studies revealed a pockmarked surface from severed welds. Welds of rabbit Achilles tendon were also obtained using the tethered diazopyruvamide. These welds were much weaker, having an average tensile strength of 11.95 N/cm2 for DPD-2,2'-ethylenedioxy(bis)ethylamine comonomers in the cross-linking reaction. In both studies the welds obtained by this method were significantly stronger than the controls. 相似文献
55.
Olivier Mentre Anne-Claire Dhaussy Francis Abraham Hugo Steinfink 《Journal of solid state chemistry》1998,140(2):120
The solid solution Sr2−xPbxV3O9, 0≤x≤2, was prepared by solid state reactions and characterized by X-ray diffraction, IR spectroscopy, and magnetic susceptibility measurements. Single crystals of the pure strontium phase and mixed Sr/Pb compounds were prepared by high temperature treatment of the respective powder compositions. Pb2V3O9crystals could only be obtained by the electrochemical reduction of molten PbV2O6. These crystals were always twinned. The previously reported crystal structure of Sr2V3O9was confirmed. It was refined toR=0.050,Rw=0.057, in space group C2/c,a=7.555(1) Å,b=16.275(2) Å,c=6.948(1) Å,β=119.78(1)°. The single crystal structural studies of the Sr1.02Pb0.98V3O9and Sr0.67Pb1.33V3O9members of the series show that the introduction of lead gives rise to a progressively complicated splitting of Sr2+/Pb2+and the tetrahedral vanadium ion crystallographic sites. As a consequence the vanadium framework distorts and beyond the Sr0.5Pb1.5V3O9composition the crystal symmetry becomes triclinic. This distortion is ascribed to the stereochemical effect of the 6s2lone pair of Pb2+. The crystallographic parameters of Pb2V3O9area=7.598(1) Å,b=16.393(3) Å,c=6.972(2) Å,α=91.38(1)°,β=119.35(1)°,γ=90.47(1)°. Pb2V3O9exhibits a more complex IR spectrum than the monoclinic phases. Despite the similarity between the triclinic and monoclinic phases the magnetic susceptibilities indicate differences in the coupling between V4+ions at low temperatures. 相似文献
56.
Substitution of Pb for Bi in the recently characterized mixed-valence lead-platinum oxide PbPt2O4 was attempted and a Pb1−xBixPt2O4 solid solution was obtained for 0≤x≤0.3. Powder X-ray diffraction study showed that all substituted compounds crystallize with similar triclinic unit cell and PbPt2O4 lattice parameters. The structural model of Pb0.7Bi0.3Pt2O4 was refined from powder X-ray diffraction data using the Rietveld method and the results indicate the same crystal structure than PbPt2O4 with one mixed Pb/Bi atomic site. Neutron diffraction realized on the two limit compositions of the solid solution (x=0 and 0.3) allowed to confirm the PbPt2O4 and Pb0.7Bi0.3Pt2O4 stoichiometries. Mean oxidation degree of Pt atoms in the [PtO4] infinite chains decreases from +3 for PbPt2O4 to +2.7 for Pb0.7Bi0.3Pt2O4. Conductivity measurements show a metallic behavior for all the compositions except the limit composition x=0.3 for which a semiconducting behavior appears. 相似文献
57.
Protein crystallization conditions are usually identified by empirical screening methods because of the complexity of the process, such as the existence of nonequilibrium phases and the different crystal forms that may result from changes in solution conditions. Here the crystallization of a model protein is studied using computer simulation. The model consists of spheres that have both an isotropic interaction of short range and anisotropic interactions between patch-antipatch pairs. The free energy of a protein crystal is calculated using expanded ensemble simulations of the Einstein crystal, and NpT-Monte Carlo simulations with histogram reweighting are used to determine the fluid-solid coexistence. The histogram reweighting method is also used to trace out the complete coexistence curve, including multiple crystal phases, with varying reduced temperature, which corresponds to changing solution conditions. At a patch-antipatch interaction strength five times that of the isotropic interaction, the protein molecules form a stable simple cubic structure near room temperature, whereas an orientationally disordered face-centered-cubic structure is favored at higher temperatures. The anisotropic attractions also lead to a weak first-order transition between orientationally disordered and ordered face-centered-cubic structures at low temperature, although this transition is metastable. A complete phase diagram, including a fluid phase, three solid phases, and two triple points, is found for the six-patch protein model. A 12-patch protein model, consistent with the face-centered-cubic structure, leads to greater thermodynamic stability of the ordered phase. Metastable liquid-liquid phase equilibria for isotropic models with varying attraction tails are also predicted from Gibbs ensemble simulations. 相似文献
58.
The three-dimensional structure of a complex tubular uranyl phosphonate, (UO(2))(3)(HO(3)PC(6)H(5))(2)(O(3)PC(6)H(5))(2).H(2)O, was determined ab initio from laboratory X-ray powder diffraction data and refined by the Rietveld method. The crystals belong to the space group P2(1)2(1)2(1), with a = 17.1966(2) ?, b = 7.2125(2) ?, c = 27.8282(4) ?, and Z = 4. The structure consists of three independent uranium atoms, among which two are seven-coordinated and the third is eight-coordinated. These metal atoms are connected by four different phosphonate groups to form a one-dimensional channel structure along the b axis. The phenyl groups are arranged on the outer periphery of the channels, and their stacking forces keep the channels intact in the lattice. The determination of this structure which contains 50 non-hydrogen atoms in the asymmetric unit, from conventional X-ray powder data, represents significant progress in the application of powder techniques to structure solution of complex inorganic compounds, including organometallic compounds. 相似文献
59.
Yan-Ping Yuan De-Yuan Kong Abraham Clearfield 《Journal of solid state chemistry》2005,178(6):2030-2035
The first organically templated 3d-4f mixed metal sulfates, [H2en]2{La2M(SO4)6(H2O)2} (M=Co 1, Ni 2) have been synthesized and structurally determined from non-merohedrally twinned crystals. The two compounds are isostructural and their structures feature a three-dimensional anionic network formed by the lanthanum(III) and nickel(II) ions bridged by sulfate anions. The La(III) ions in both compounds are 10-coordinated by four sulfate anions in bidentate chelating fashion, and two sulfate anions in a unidentate fashion. The transition metal(II) ion is octahedrally coordinated by six oxygens from four sulfate anions and two aqua ligands. The doubly protonated enthylenediamine cations are located at the tunnels formed by 8-membered rings (four La and four sulfate anions). 相似文献
60.
The composition of cellulose, hemicellulose, starch, lignin, pectin, protein, and total lipid content in the selected cellulosic
wastes-tapioca (Manihot esculenta) stem, leaf, petiole, and water hyacinth (Eichhornia crassipes) were determined. The effectiveness of various physical and chemical pretreatments on the enzymatic digestibility of these
wastes were identified. In general, chemical pretreatments were more effective than physical pretreatments. The efficiency
of the pretreatment was checked by subjecting these wastes to enzymatic saccharification after the pretreatments. 相似文献