The [4Fe-4S](2+) cluster in reconstituted biotin synthase binds S-adenosyl-L-methionine

The combination of resonance Raman, electron paramagnetic resonance and M?ssbauer spectroscopies has been used to investigate the effect of S-adenosyl-l-methionine (SAM) on the spectroscopic properties of the [4Fe-4S]2+ cluster in biotin synthase. The results indicate that SAM interacts directly at a unique iron site of the [4Fe-4S]2+ cluster in BioB and support the hypothesis of a common inner-sphere mechanism for the reductive cleavage of SAM in the radical SAM family of Fe-S enzymes.     

An electrochemically synthesized sulfonated polyaniline layer for positive charge carrier injection improvement in conjugated polymer devices

We report the use of sulfonated polyaniline, SPAN, as a positive charge transporting layer in organic electronic devices, demonstrating that it can be used to significantly improve injection into conjugated polymers. The introduction of an intermediate SPAN layer improves device rectification, even when low-work-function anode materials such as tin oxide are used.     

Dissolution of copper foil in aqueous solution ofpH=2

The specific dissolution rate, expressed in mol cm^–2s^–1, and time-variation of the rest potential of copper foil in an aerated aqueous solution ofpH = 2.0 were measured.

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Die Auflösbarkeit von Kupfer-Folie in wäriger Lösung von pH 2 (Kurze Mitteilung)

Zusammenfassung Es wurde die spezifische Auflösungsgeschwindigkeit (in mol cm^–2s^–1) und die zeitliche Veränderung des Restpotentials von Kupfer-Folie in einer belüfteten wäßrigen Lösung von pH 2,0 gemessen.

     

Electrocatalytic reduction of ROOH by iron porphyrins

Electrocatalytic reduction of a series of chemical oxidants of different power (tert-butyl hydroperoxide, potassium peroxomonosulfate, peracetic acid, and m-chloroperbenzoic acid) at iron-porphyrin-modified graphite electrodes is studied in buffered aqueous solutions by rotating disk and ring-disk voltammetry. Both ferric and ferrous porphyrins are catalytically active. Turnover of ferric catalysts is slower than that of the ferrous analogues and involves competing catalytic reduction and disproportionation. The kinetic data are consistent with reactant binding being the rate-determining step in catalysis by Fe(III). In catalysis by Fe(II), the turnover is controlled by the first electron transfer. The covalently linked proximal imidazole ligand is found to be crucial for achieving the Fe(III) catalysis.     

Liquid chromatography of cardiac glycosides

Summary LC was used for the separation of several cardiac glycosides with water-alcohol eluents on a silanised silica column. The influence of temperature and composition of the eluent on the retention time, the retention volumes of the glycosides, the selectivity and the capacity factor of the column were studied. Higher temperature and a higher ethanol content in the eluent reduce the retention time, the selectivity and the capacity factor but the efficiency of the column increases. The best separation of six glycosides studied was obtained at 50°C, the ethanol content in the eluent being about 30%.     

Quantitative determination of acetylsalicylic acid and acetaminophen in tablets by FT-Raman spectroscopy

A procedure for quantitative determination of acetylsalicylic acid and acetaminophen in pharmaceuticals by PLS (partial least squares) and PCR (principal component regression) treatment of FT (Fourier transform)-Raman spectroscopic data is proposed. The proposed method was tested on powdered samples. Three chemometric models were built: the first, for samples consisting of an active substance diluted by lactose, starch and talc; the second, in which a simple inorganic salt was applied as an internal standard and additions were not taken into account; and the third, in which a model was constructed for a commercial pharmaceutical, where all constituents of the tablet were known. By utilising selected spectral ranges and by changing the chemometric conditions it is possible to carry out fast and precise analysis of the active component content in medicines on the basis of the simplified chemometric models. The proposed method was tested on five commercial tablets. The results were compared with data obtained by intensity ratio and pharmacopoeial methods. To appraise the quality of the models, the relative standard error of predictions (RSEPs) were calculated for calibration and prediction data sets. These were 0.7-2.0% and 0.8-2.3%, respectively, for the different PLS models. Application of these models to the Raman spectra of commercial tablets containing acetylsalicylic acid gave RSEP values of 1.3-2.0% and a mean accuracy of 1.2-1.7% with a standard deviation of 0.6-1.2%.     

Effect of mechanical activation on the catalytic, physical and chemical properties of copper oxide

Mechano-chemical activation of copper oxide powders leads to structural disordering of the near-surface layers of particles and, thus, to considerable variations in the catalytic properties of copper oxide.

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Increased structural complexity leads to higher activity: peptides as efficient and versatile catalysts for asymmetric aldol reactions

[reaction: see text] Peptides containing a secondary amine and a carboxylic acid in a specific orientation to each other are presented as highly efficient catalysts for asymmetric aldol reactions: (1) their activity is considerably higher compared to that of proline, and (2) the enantioselectivity of the peptidic catalysts can be changed from (R)- to (S)-selectivity by simple modifications of the secondary structure.     

Coordination de la phosphine organo-fer [CpFeIIC6Me5CH2PPh2]+ au RhI et proprietes spectroscopiques,electrochimiques et catalytiques des complexes heterobinucleaires FeII-RhI

The reactions between the phosphine-organoiron [CpFe^II-η⁶-C₆Me₅CH₂PPh₂]⁺ PF₆^? (1) and [RhCl(η⁴-diolefin)(μ-Cl)]₂ in CH₂Cl₂ at reflux give the new heterobinuclear air-stable crystalline complexes [CpFe^II-η⁶-C₆Me₅CH₂)P(Ph)₂Rh(η⁴-diene)Cl]PF₆,(D'*-diene=cyclooctadiene (COD): 65%, 2; trimethylfluorobenzobicyclo[2.2.2]octadiene (Me₃TFB): 48%, 3). Complexes 2 and 3 have been studied by ¹H, ¹³C and ³¹P NMR spectroscopy and they are carbonylated (CO, 1 atm). Cyclic voltammetry experiments with addition of MeOH show electron transfer Fe^IRh^I → Fe^IIRh⁰, the presence of a catalytic wave Fe^I/Fe^II and the possible formation of Rh hydrides. Under normal conditions 2 is a catalyst for hydrogenation of cyclohexene, but it is less efficient than the known mononuclear Rh¹ analogues.     

The Inverse Scattering Method and Systems of Equations qxy = F(q,qy)

Consider equations of the form where q is in general a complex vector and the function F depends nontrivially both on q and on q_y. We show that a family S of such equations can be investigated by the inverse scattering method. If an equation (*) belongs to S, the function F depends linearly on q and algebraically on q_y. We show that the family S contains a subfamily in which each equation can be obtained from the two dimensional Toda lattice equations by a Bäcklund transformation.