X-ray Crystal Structures of Some Arene Oxides

Using a recently disclosed modification to the dimethyldioxirane method we have synthesized four arene monooxides and one trioxide in good to excellent yield. The X-ray crystal structures have been determined for all of these compounds. In the case of the chrysene trioxide the X-ray determination reveals that the structure is bent out of the plane.     

Manganese(III) complexes of bis(hydroxyphenyl)dipyrromethenes are potent orally active peroxynitrite scavengers

We report a new series of biscyclohexano-fused Mn(III) complexes of bis(hydroxyphenyl)dipyrromethenes, 4a-c, as potent and orally active peroxynitrite scavengers. Complexes 4a-c are shown to reduce peroxynitrite through a two-electron mechanism, thereby forming the corresponding Mn(V)O species, which were characterized by UV, NMR, and LC-MS methods. Mn(III) complex 4b and its strained BODIPY analogue 9b were analyzed by X-ray crystallography. Finally, complex 4a is shown to be an orally active and potent analgesic in a model carrageenan-induced hyperalgesia known to be driven by the overproduction of peroxynitrite.     

New iron(II) α-iminopyridine complexes and their catalytic activity in the oxidation of activated methylene groups and secondary alcohols to ketones

A set of iron(II) complexes of the general formula [Fe(OTf)(2)L(2)] was synthesized in 32 to 78% isolated yields, where L represents a bidentate α-iminopyridine ligand. Four of the iron complexes were characterized structurally, revealing a rich coordination chemistry, because the coordination geometry of the iron complexes strongly depends on the substitution pattern exhibited by the ligands L. The catalytic activity of the new complexes was demonstrated in the oxidation of cyclohexane, activated methylene groups and secondary alcohols to the corresponding ketones utilizing H(2)O(2) and t-BuOOH as the oxidants. The oxidation of activated methylene groups and secondary alcohols to the corresponding ketones with t-BuOOH gave isolated yields between 22 and 91% (4 h, room temperature, 3% catalyst load). The influence of the structure of the ligand on the activity of the corresponding metal complex is also reported. Furthermore, UV-vis experiments were performed which provided evidence for the formation of an [Fe-O-O-t-Bu] intermediate.     

Synthesis and In Vitro Antimicrobial SAR of Benzyl and Phenyl Guanidine and Aminoguanidine Hydrazone Derivatives

A series of benzyl, phenyl guanidine, and aminoguandine hydrazone derivatives was designed and in vitro antibacterial activities against two different bacterial strains (Staphylococcus aureus and Escherichia coli) were determined. Several compounds showed potent inhibitory activity against the bacterial strains evaluated, with minimal inhibitory concentration (MIC) values in the low µg/mL range. Of all guanidine derivatives, 3-[2-chloro-3-(trifluoromethyl)]-benzyloxy derivative 9m showed the best potency with MICs of 0.5 µg/mL (S. aureus) and 1 µg/mL (E. coli), respectively. Several aminoguanidine hydrazone derivatives also showed good overall activity. Compounds 10a, 10j, and 10r–s displayed MICs of 4 µg/mL against both S. aureus and E. coli. In the aminoguanidine hydrazone series, 3-(4-trifluoromethyl)-benzyloxy derivative 10d showed the best potency against S. aureus (MIC 1 µg/mL) but was far less active against E. coli (MIC 16 µg/mL). Compound 9m and the para-substituted derivative 9v also showed promising results against two strains of methicillin-resistant Staphylococcus aureus (MRSA). These results provide new and potent structural leads for further antibiotic optimisation strategies.     

Itinerant electron metamagnetism and magnetocaloric effect in Dy(Co,Si)2

Itinerant electron metamagnetism in Dy(Co_1-xSi_x)₂ compounds was studied in the light of a recent theoretical model based on magnetovolume effect and spin fluctuations. The nature of the magnetic transition in these compounds was analyzed within the framework of this model. The magnetocaloric effect in these compounds has been calculated and correlated with the strength of itinerant electron metamagnetism. The domain wall pinning effect was found to be dominant at low temperatures.     

Novel electron transfer mechanism in lithium alanate reduction of benzylic halides

Occurrence of a new electron transfer mechanism in the LiAlH₄ reduction of 9-chloromethylanthrancene, diphenylchloromethane and 9-bromofluorene is demonstrated. Alanate anion serves as a source of electrons and hydrogen atoms.     

Über die Verformung der Röntgenabsorptionskanten in Metallen und Legierungen durch Gitterleerstellen

In order to account for the distortion in the shape of x-ray absorption edges in some metals and alloys, a mechanism involving lattice vacancies is proposed. It is shown that an atom near a lattice vacancy will be under the influence of an electrical field resulting from the asymmetric surroundings. The magnitude of this field is found to be large enough to produce a Stark-splitting in the exciton orbit of the absorbing atom. The distortion appearing as a kink on the slope of the absorption curve is shown to be a consequence of this splitting.     

Forbidden transition LIINII in the spectrum of gadolinium-64

Using a 40 cm curved mica crystal spectrograph of the transmission type, the L spectrum of gadolinium has been investigated. The forbidden transition L_IIN_II at λ = 1618.9 X.U. has been reported for the first time.     

X-ray energy levels: Deviations between experimental and theoretical values

Energy values ofK, L _II andL _III levels calculated by the relativistic self consistent field method have been used to compute the energies ofKα _{1, 2} lines. These values deviate considerably from the experimental values due to Bearden and Burr. The deviations are discussed and given an empirical fit.