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

The isomerization of aliphatic amine radical cations via intermediate [cyclopropane-NH3]+• 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 ß- and/or γ-carbon atoms isomerize via transient complexes of NH3 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. Isomerization via complex intermediates is a major reaction pathway when the internal energy of the amine radical cation is less than that required for simple CC-bond cleavage. Complexes of unsubstituted or monosubstituted ionized cyclopropanes rarely contribute to the isomerization reactions. Secondary and tertiary amine radical cations do not undergo isomerization via cyclopropane intermediates, whereas aliphatic ether radical cations do.

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, [Mn9O4(Me-sao)6(L)3(MeO)3(MeOH)3]Cl (1; Me-saoH2 = methylsalicylaldoxime, HL = lipoic acid) is reported. Compound 1 crystallizes in the orthorhombic P212121 space group and consists of a metallic skeleton describing a defect super-tetrahedron missing one vertex. The chirality of the [MnIII 9] core originates from the directional bridging of the Me-sao2- ligands via the -N-O- oximate moieties, which define a clockwise (1ΔΔ) or counter-clockwise (1ΛΛ) rotation in both the upper [MnIII 3] and lower [MnIII 6] subunits. Structural integrity and retention of chirality upon dissolution and upon deposition on (a) gold nanoparticles, 1@AuNPs, (b) transparent Au(111) surfaces, 1ΛΛ@t-Au(111); 1ΔΔ@t-Au(111), and (c) epitaxial Au(111) on mica surfaces, 1@e-Au(111), was confirmed by CD and IR spectroscopies, mass spectrometry, TEM, XPS, XAS, and AFM. Magnetic susceptibility and magnetization measurements demonstrate the simultaneous retention of SMM behaviour and optical activity, from the solid state, via dissolution, to the surface deposited species.

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

Six novel one-dimensional chloro-bridged ReIVCuII complexes of formula {[Cu(L)4][ReCl6]}n, 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 ReIV and CuII ions. Theoretical calculations reveal the coupling to be primarily ferromagnetic, increasing in magnitude as the bridging angle becomes smaller and the bond lengths shorten.

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 ReIV chemistry leads to the isolation of a family of complexes of general formula (NBu4)2[(ReX5)2(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. That is, the spin-polarization mechanism present dictates that odd and even numbers of atoms favour ferromagnetic (F) and antiferromagnetic (AF) exchange interactions, respectively. Hence, while the pyz ligand in 1 and 2 mediates AF coupling, the pym and triz ligands in 3 and 4 promote F interactions.

Hexahalorhenate(iv) salts of metal oxazolidine nitroxides.

Eight coordination compounds of formulae [FeII(L˙)2][ReIVCl6] (1a), [FeII(L˙)2][ReIVBr6] (1b), [CoII(L˙)2][ReIVCl6]·CH3CN (2a), [CoII(L˙)2][ReIVBr6] (2b), [NiII(L˙)(CH3CN)3][ReIVCl6]·CH3CN (3a), [NiII(L˙)(CH3CN)3][ReIVBr6]·3CH3CN (3b), [CuII(L˙)2][ReIVCl6] (4a) and [CuII(L˙)2][ReIVBr6] (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 [MII(L˙)2]2+ 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)). Microanalysis and IR spectroscopy on 3a(dried) and 3b(dried) suggest that the dried samples are best formulated as [NiII(L˙)(H2O)3][ReIVX6], where X = Cl (3a(dried)) and Br (3b(dried)). All forms of 3a and 3b exhibit cationic metal-radical ferromagnetic interactions resulting in S = 3/2 ground states. In addition, 3a(dried) exhibits spin-canting behaviour with an ordering temperature of 2.7 K, an open hysteresis loop with a coercive field Hc = 580 Oe, and a remanent magnetisation Mr = 0.21µB, resulting in a canting angle of ∼1.8°. In contrast, 3b(dried) shows no spin-canting behaviour; a maximum in χMvs. T at T = 3 K suggesting long-range antiferromagnetic ordering. 3a(solvated) and 3b(solvated) show no indication of long-range magnetic ordering, unlike 4a and 4b where anomalies are evident in the low-temperature magnetic susceptibility measurements.

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.

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. METHODS: We have therefore compared the sensitivity of four methods currently used in animal models to assess kidney injury induced by aminoglycoside antibiotics by applying them to the analysis of urine from male rats treated with low doses of gentamicin. RESULTS: Excretion of phospholipids was significantly increased in contrast to excretion of N-acetyl-beta-glucosaminidase (NAG), neutrophil gelatinase-associated lipocalin (NGAL) and protein. Assessment of phospholipiduria thus is the more sensitive noninvasive way to monitor initial renal injury induced by aminoglycoside antibiotics. A protocol is given for the serial analysis of urinary phospholipids allowing a considerable number of determinations to be carried out in the course of 2-3 days. DISCUSSION: It is well known that all four considered methods do detect kidney damage induced in rats by high gentamicin doses far above doses used in clinics. The present investigation shows that only the analysis of the urinary phospholipids will detect damage induced by low doses of gentamicin. The method is relevant for animal model studies but will require considerable and innovative development for use in clinics.

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. Here we have synthesized a number of NAPE analogues with variation in the phosphoester structure. The NAPE analogues as well as selected phospholipids and beta-lactamase substrates were tested as potential modifiers of cloned human NAPE-PLD in an enzyme assay involving a (14)C-labeled diether-NAPE substrate. One hit was identified, namely 1,2-dihexanoyl-glycero-N-(3-(tetradecanoylamino)propyl)phosphoramidate (AHP-71B) which showed inhibitory activity and may serve as template for further structure-activity developments. Furthermore, it was found that NAPE-PLD was activated by phosphatidylethanolamine and inhibited by the beta-lactamase substrate nitrocefin.