Formation of metal-anion arrays within layered perovskite hosts. Preparation of a series of new metastable transition-metal oxyhalides, (MCl)LaNb(2)O(7) (M = Cr,Mn, Fe,Co)

A new series of transition-metal oxyhalides (MCl)LaNb(2)O(7) (M = Cr, Mn, Fe, Co) have been prepared by a simple topochemical route. Layered perovskite hosts (ALaNb(2)O(7), A = Li, Na, K or Rb) were reacted with the corresponding anhydrous metal halides under mild reaction conditions (<400 degrees C). The compounds were examined by X-ray powder diffraction; the series appears to be isostructural with (CuCl)LaNb(2)O(7), and the layer spacings, with the exception of M = Co, follow the trend expected from transition-metal cationic radii. Thermal analysis with differential scanning calorimetry (DSC) shows the materials to be metastable where all four compounds decompose exothermically above 690 degrees C.     

Adhesion hysteresis in dynamic atomic force microscopy

The effects of adhesion hysteresis in the dynamic‐dissipation curves measured in amplitude‐modulation atomic force microscopy are discussed. Hysteresis in the interaction forces is shown to modify the dynamics of the cantilever leading to different power dissipation curves in the repulsive and attractive regimes. Experimental results together with numerical simulations show that power dissipation, as measured in force microscopy, is not always proportional to the energy dissipated in the tip–sample interaction process. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Carbon-13 NMR characterisation of carboxyl derivatives of 1-ureidopyrroles

1-Ureido-5-methyl-2,3-dicarbethoxypyrrole under acidic conditions afforded different partially hydrolyzed or decarboxylated products. It has been possible to characterize two isomeric monoethyl esters of dicarboxylic acids of 1-ureidopyrroles by proton gated decoupled carbon-13 nmr spectra on the basis of multiplicities of the carbonyl carbons resonances.     

Zur Reaktionsweise von Diphenylcyclopropenon mit β-Carbonyl-enolaten. I. Einsatz von Acetylaceton,Acetessigsäure-methylester, 2-Äthoxycarbonyl-cyclododecanon und Malonsäure-dimethylester

Reaction of Diphenylcyclopropenone with β-Carbonyl-enolates. I. Use of Acetylacetone, Methyl Acetoacetate, 2-Ethoxycarbonyl-cyclododecanone and Dimethyl Malonate The reaction of the sodium salts of acetylacetone ( 6 ), methyl acetoacetate (7) , 2-ethoxycarbonyl-cyclododecanone (8) , dimethyl malonate (19) and its methyl derivative 20 with diphenylcyclopropenone ( 5 ) in dimethylformamide at room temperature led to the unsaturated γ-lactones 14, 15, 17, 22 and 36 . In the case of dimethyl malonate ( 19 ), the halfester 21 , the acyl-malonic ester 24 and the indenone-malonic ester 23 were also isolated. Several intermediates and the final products were characterised by reactions and spectroscopically. A general mechanism is discussed for the addition of cyclo-propenones ( 1 ) to the enolate salts of β-dicarbonyl compounds 4 involving the bicyclic lactone-enolates 18 and 32 as intermediates. The products formed via 18 and 32 are considered to be the result of an attack of one of the oxygen atoms of the β-carbonyl-enolate anion ( 4 ), the product 24 , on the other hand, of the attack of the α-carbon atom of 4 ; in both cases the attack is on the carbonyl C-atom of 5 .     

Oxidative coupling of 17beta-estradiol: inventory of oligomer products and configuration assignment of atropoisomeric c4-linked biphenyl-type dimers and trimers

The oxidation chemistry of 17beta-estradiol (1) is of central relevance to the nongenomic effects of estrogens and offers valuable prospects in the search for novel steroidal scaffolds of academic and industrial interest. Herein, we report the results of a detailed investigation into the nature of the oligomer products formed by phenolic oxidation of 1. Of the oxidants tested, the peroxidase/H2O2 system proved to be the most effective in inducing conversion of 1 to a complex mixture of oligomer species. Repeated chromatographic fractionation followed by extensive 2D NMR and mass spectrometric analysis allowed identification of a series of phenolic coupling products comprising, besides the C2-symmetric dimers 2 and 3, a 2,4' dimer (4), two O-linked dimers (5, 6), and the novel trimers 7-9. All 4-linked biphenyl-type oligomers, i.e., 3 and 7-9, occurred as couples of atropoisomers, reflecting steric hindrance at biphenyl linkages. For all atropoisomers, absolute configuration was established by the exciton chirality method and the interconversion energy was determined by dynamic NMR. These results provide the first systematic inventory of oxidative coupling products of 1 and lay the foundation for future studies aimed to develop novel estrogen derivatives based on oligomeric scaffolds.     

Co-digestion of agricultural and industrial wastes

The efficiency of anaerobic digestion process is dependent on the type and composition of the material to be digested. This work examines the co-digestion of corn silage, beet pulp silage, carrot residues, and cheese whey in different configurations together with a glycerin fraction — the waste product of transestrification of oils (biodiesel production) in a 25 L bioreactor operated mesophically in a quasi-continuous mode. Co-digestion of corn silage with carrot residues appeared to be more effective than that with cheese whey resulting in the gas production rate equal to 5.9 L L⁻¹ d⁻¹ and 1.4 L L⁻¹ d⁻¹, respectively. The performed experiments showed that a combination of three substrates: corn silage, cheese whey, and glycerin fraction resulted in the highest methane content equal to 61 % and the biogas production rate of 1.8 L L⁻¹ d⁻¹.     

On double sine and cosine transforms,Lipschitz and Zygmund classes

We consider complex-valued functions f ∈ L 1 (R+2),where R +:= [0,∞),and prove sufficient conditions under which the double sine Fourier transform f ss and the double cosine Fourier transform f cc belong to one of the two-dimensional Lipschitz classes Lip(α,β) for some 0 α,β≤ 1;or to one of the Zygmund classes Zyg(α,β) for some 0 α,β≤ 2.These sufficient conditions are best possible in the sense that they are also necessary for nonnegative-valued functions f ∈ L 1 (R+2).