Molecular multifunctionality preservation upon surface deposition for a chiral single-molecule magnet.

The synthesis and characterization of a chiral, enneanuclear Mn(iii)-based, Single-Molecule Magnet, [MnO(Me-sao)(L)(MeO)(MeOH)]Cl (; Me-saoH = methylsalicylaldoxime, HL = lipoic acid) is reported. Compound crystallizes in the orthorhombic 222 space group and consists of a metallic skeleton describing a defect super-tetrahedron missing one vertex. The chirality of the [Mn ] core originates from the directional bridging of the Me-sao ligands the -N-O- oximate moieties, which define a clockwise () or counter-clockwise () rotation in both the upper [Mn ] and lower [Mn ] subunits.

Possible Intermediacy of Cyclopropane Complexes in the Isomerization of Aliphatic Amine Radical Cations.

The isomerization of aliphatic amine radical cations via intermediate [cyclopropane-NH] and [cyclopropane-amine] ion-neutral complexes was studied experimentally with double-focusing mass spectrometers and computationally with composite ab initio methods. The results examine and extend Audier's suggestion that primary amine radical cations with alkyl substituents at the β- and/or γ-carbon atoms isomerize via transient complexes of NH and alkyl cyclopropanes; these are formed by ring closure of the easily accessible γ-distonic isomers. Ionized amines with substituents at the α-carbon may react analogously when trialkyl cyclopropane complexes can be formed.

Magneto-structural correlations in dirhenium(iv) complexes possessing magnetic pathways with even or odd numbers of atoms.

The employment of pyrazine (pyz), pyrimidine (pym) and s-triazine (triz) ligands in Re chemistry leads to the isolation of a family of complexes of general formula (NBu)[(ReX)(μ-L)] (L = pyz, X = Cl (1) or Br (2); L = pym, X = Br (3); L = triz, X = Br (4)). 1-4 are dinuclear compounds where two pentahalorhenium(iv) fragments are connected by bidentate pyz, pym and triz ligands. Variable-temperature magnetic measurements, in combination with detailed theoretical studies, uncover the underlying magneto-structural correlation whereby the nature of the exchange between the metal ions is dictated by the number of intervening atoms.

Magneto-structural correlations in a family of ReCu chains based on the hexachlororhenate(iv) metalloligand.

Six novel one-dimensional chloro-bridged ReCu complexes of formula {[Cu(L)][ReCl]}, where L = imidazole (Imi, 1), 1-methylimidazole (Meim, 2), 1-vinylimidazole (Vim, 3), 1-butylimidazole (Buim, 4), 1-vinyl-1,2,4-triazole (Vtri, 5) and N,N'-dimethylformamide (DMF, 6) are characterised structurally, magnetically and theoretically. The structures exhibit significant differences in Cu-Cl bond lengths and Re-Cl-Cu bridging angles, resulting in large differences in the nature and magnitude of magnetic exchange interactions between the Re and Cu ions. Theoretical calculations reveal the coupling to be primarily ferromagnetic, increasing in magnitude as the bridging angle becomes smaller and the bond lengths shorten.

Hexahalorhenate(iv) salts of metal oxazolidine nitroxides.

Eight coordination compounds of formulae [Fe(L˙)][ReCl] (1a), [Fe(L˙)][ReBr] (1b), [Co(L˙)][ReCl]·CHCN (2a), [Co(L˙)][ReBr] (2b), [Ni(L˙)(CHCN)][ReCl]·CHCN (3a), [Ni(L˙)(CHCN)][ReBr]·3CHCN (3b), [Cu(L˙)][ReCl] (4a) and [Cu(L˙)][ReBr] (4b), where L˙ is the aminoxyl radical chelating ligand, 4,4'-dimethyl-2,2'-di(2-pyridyl)oxazolidine-N-oxide, have been synthesised. Structural and magnetic studies reveal metal-radical intramolecular antiferromagnetic interactions in the [M(L˙)] cations in the iron, cobalt and copper based compounds (1a, 1b, 2a, 2b, 4a and 4b) with the central metal ion low-spin in the case of iron (1a and 1b) and a gradual, cobalt based, spin-crossover transition present in 2a and 2b. The nickel based compounds, 3a and 3b, were analysed in the dried form (3a(dried) and 3b(dried)) and directly in acetonitrile (3a(solvated) and 3b(solvated)).

Isomerization of metastable amine radical cations by dissociation-recombination.

The metastable molecular ions of primary aliphatic amines branched at C2 can isomerize by cleavage-recombination, thereby facilitating fragmentation reactions that require less energy than simple cleavage of the initial molecular ion. This process complements the reactions described by Audier to account for the conspicuous absence of the conventional a-cleavage among the major fragmentation reactions of the metastable molecular ions of primary amines.

Fulleropyrrolidine end-capped molecular wires for molecular electronics--synthesis, spectroscopic, electrochemical, and theoretical characterization.

In continuation of previous studies showing promising metal-molecule contact properties a variety of C(60) end-capped "molecular wires" for molecular electronics were prepared by variants of the Prato 1,3-dipolar cycloaddition reaction. Either benzene or fluorene was chosen as the central wire, and synthetic protocols for derivatives terminated with one or two fullero[c]pyrrolidine "electrode anchoring" groups were developed. An aryl-substituted aziridine could in some cases be employed directly as the azomethine ylide precursor for the Prato reaction without the need of having an electron-withdrawing ester group present.

Effect of synthetic and natural phospholipids on N-acylphosphatidylethanolamine-hydrolyzing phospholipase D activity.

N-Acylethanolamines (NAEs) constitute a family of endogenous bioactive lipids that includes arachidonoylethanolamide (anandamide), palmitoylethanolamide (PEA) and oleoylethanolamide (OEA). These lipids are formed from their respective N-acylated ethanolamine phospholipid (NAPE) precursor by the action of a phospholipase D enzyme (NAPE-PLD). Anandamide, OEA, and PEA are all bioactive lipids that may influence, amongst others: neuroinflammation, food intake, and oocyte implantation.

Assessing low-dose gentamicin-induced kidney injury in rats by analysis of urine.

Introduction: Gentamicin is an important aminoglycoside antibiotic used in clinics to combat infections from especially gram negative bacteria. A frequent side-effect of aminoglycoside antibiotics is a kidney injury consisting of necrosis of proximal tubular cells. It is important both in clinics and in research directed to eliminate or ameliorate this side-effect that a method is available for detection of injury at an early stage.