Synthesis and structure of a dinuclear gold(II) complex with terminal fluoride ligands

The potential for reductive elimination of fluorine from dinuclear gold(II) for catalysis has prompted our efforts to synthesize a dinuclear gold(II) fluoride complex. This has been achieved with bis(2,6-dimethylphenyl)formamidinate bridging ligands. In order to obtain this product, it was necessary first to synthesize the corresponding dinuclear gold(II) nitrate, which reacts readily with KF in a metathesis reaction. The nitrate complex and fluoride complexes have been structurally characterized. The Au-Au distance in the dinuclear fluoride, 2.595 ?, is longer than the distance found in the analogous chloride complex, 2.567 ?. This result is consistent with the presence of a fluoride "π electron effect" on the filled Au 5d orbitals. The Raman spectrum shows an Au-Au stretch at 206 cm(-1), which agrees with Woodruff's rules and the density functional theory computational model used for modeling the complex.     

Examining epistemic beliefs across conceptual and procedural knowledge in statistics

The purpose of this paper was to examine whether students’ epistemic beliefs differed as a function of variations in procedural versus conceptual knowledge in statistics. Students completed Hofer’s (Contem Edu Psychol 25:378–405, 2000) Discipline-Focused Epistemological Beliefs Questionnaire five times over the course of a semester. Differences were explored between students’ initial beliefs about statistics knowledge and their specific beliefs about conceptual knowledge and procedural knowledge in statistics. Results revealed differences across these contexts; students’ beliefs differed between procedural versus conceptual knowledge. Moreover, students’ initial beliefs about statistics knowledge were more similar to their beliefs about conceptual knowledge rather than procedural knowledge. Finally, regression analyses revealed that students’ beliefs about the justification of knowledge, attainability of truth and source of knowledge were significant predictors of examination performance, depending on the examination. These results have important theoretical, methodological and pedagogical implications.     

Detection of pulse trains in the electrically stimulated cochlea: effects of cochlear health

Perception of electrical stimuli varies widely across users of cochlear implants and across stimulation sites in individual users. It is commonly assumed that the ability of subjects to detect and discriminate electrical signals is dependent, in part, on conditions in the implanted cochlea, but evidence supporting that hypothesis is sparse. The objective of this study was to define specific relationships between the survival of tissues near the implanted electrodes and the functional responses to electrical stimulation of those electrodes. Psychophysical and neurophysiological procedures were used to assess stimulus detection as a function of pulse rate under the various degrees of cochlear pathology. Cochlear morphology, assessed post-mortem, ranged from near-normal numbers of hair cells, peripheral processes and spiral ganglion cells, to complete absence of hair cells and peripheral processes and small numbers of surviving spiral ganglion cells. The psychophysical and neurophysiological studies indicated that slopes and levels of the threshold versus pulse rate functions reflected multipulse integration throughout the 200 ms pulse train with an additional contribution of interactions between adjacent pulses at high pulse rates. The amount of multipulse integration was correlated with the health of the implanted cochlea with implications for perception of more complex prosthetic stimuli.     

In Vitro Reconstitution Reveals a Central Role for the N-Oxygenase PvfB in (Dihydro)pyrazine-N-oxide and Valdiazen Biosynthesis

The Pseudomonas virulence factor (pvf) operon is essential for the biosynthesis of two very different natural product scaffolds: the (dihydro)pyrazine-N-oxides and the diazeniumdiolate, valdiazen. PvfB is a member of the non-heme diiron N-oxygenase enzyme family that commonly convert anilines to their nitroaromatic counterparts. In contrast, we show that PvfB catalyzes N-oxygenation of the α-amine of valine, first to the hydroxylamine and then the nitroso, while linked to the carrier protein of PvfC. PvfB modification of PvfC-tethered valine was observed directly by protein NMR spectroscopy, establishing the intermediacy of the hydroxylamine. This work reveals a central role for PvfB in the biosynthesis of (dihydro)pyrazine-N-oxides and valdiazen.     

Evaluating the biological potential of some new cobalt (II) complexes with acrylate and benzimidazole derivatives

This paper presents the synthesis, physico‐chemical and biological properties of four new coordination compounds with mixed ligands: acrylate ion (acr) and benzimidazole/benzimidazole derivatives with the general formula [Co(L) ₂ (acr) ₂ ]·nH ₂ O [ (1) L: benzimidazole (HBzIm), n: 0.5; (2) L: 2‐methylbenzimidazole (2‐MeBzIm), n: 0.5; (3) L: 5‐methylbenzimidazole (5‐MeBzIm), n: 0; (4) L: 5,6‐dimethylbenzimidazole (5,6‐Me₂BzIm), n: 0]. Their chemical formulae were achieved correlating the chemical analysis with mass spectrometry data, the ligands coordination modes were assigned by Fourier transform‐infrared measurements, and the trigonal bipyramidal geometry of cobalt ion in complexes was assigned by data correlation of UV–Vis‐NIR spectra and magnetic moments measurements. Single‐crystal X‐ray diffraction reveals a mononuclear structure with a pentacoordinated cobalt (II) ion, connected to two acrylato coordinated in different modes and two unidentate 5,6‐dimethylbenzimidazole ligands for compound (4) . The biological tests were performed against several microbial strains, the cytotoxicity was evaluated on HCT8 cellular lines and the cell cycle analysis was performed on HT29 cellular lines. Microbiological assays indicated that Co (II) complexes present a very good to good activity against Candida albicans 1760, Enterococcus faecium E5, Bacillus subtilis ATCC 6683 and Escherichia coli ATCC 25922. Predictive pharmacokinetic (ADME), toxicity and drug‐likeness profiles were evaluated for Co (II) complexes. Our results highlight that Co (II) complexes depicted in the present study are suitable to be used as efficient pharmacological agents.     

Investigation of multiaxis molecular motion by off-magic angle spinning deuteron NMR

The relatively new deuteron NMR method of off-axis-magic angle spinning (OMAS) has been extended and used to investigate multiaxis rotational jump motion. Floquet theory is developed for simulating deuteron OMAS spectra with multisite jumps at different rates about noncoincident axes, and efficient procedures are presented for computing the sideband line shapes. It is demonstrated experimentally that reproducible adjustment of the angle between the rotor axis and the static magnetic field is feasible with precision approaching +/- 0.01 degrees. This leads to the reintroduction of a scaled, first-order quadrupole coupling that defines a new kinetic window and makes deuteron OMAS much more sensitive than ordinary magic angle spinning to motion on the kilohertz time scale. Temperature-dependent deuteron OMAS line shapes of octanoic acid/urea-d4 inclusion compound have been recorded and fitted, using least-squares procedures, to provide rates of rotation about both CN and CO bonds. The Arrhenius activation parameters for rotation about CN bonds, Ea = 60.4+/-2.4 kJ/mol and ln(A) = 24.9+/-0.3, agree well with previous values determined by selective inversion experiments. However, OMAS yields Ea = 26.3+/-0.4 kJ/mole and ln(A) = 24.9+/-0.3 for whole-body rotation about the CO bond axis in contrast to previous analysis of static quadrupole echo (QE) line shapes which gave Ea = 22.3+/-0.3 kJ/mole and ln(A) = 24.8+/-0.6 for the same sample. The underlying homogeneous linewidths of OMAS spectra are much smaller than those of QE spectra, and this provides higher precision and less systematic error in the determination of rates.     

Convergent synthesis of isomeric pairs of metallocene-containing polyether macrocycles

A general method for rapid construction of metallocene-based hosts is described. Treatment of polyether bridged bis(diphenylacetylenes) with a source of cyclopentadienyl cobalt at high temperature leads, via macrocyclization and capture of the intermediate cyclobutadiene, to macrocyclic systems tethered to an integral metallocene platform. Equal yields of the two possible structural isomers, the products of parallel or antiparallel cycloaddition of the precursor, are obtained. A combination of X-ray crystallography and NMR is employed to assign structures to the individual isomers and to assess the strength of lithium ion binding by the individual macrocycles.     

Internal standard signal suppression by co-eluting analyte in isotope dilution LC-ESI-MS

The suppression of the internal standard by increasing concentrations of the co-eluting analyte in calibration series and plasma samples analysed by LC-ESI-MS was studied using the isotope dilution technique. A series of three analyte/deuterated analyte pairs including fexofenadine/d6-fexofenadine, dapsone/d4-dapsone and peudoephedrine/d3-ephedrine were investigated. Suppression of the internal standard signal was noticed in extracted plasma samples containing fexofenadine and d6-fexofenadine as internal standard, as well as in solvent based calibration solutions of the three pair of compounds noted above during LC-ESI-MS analysis at flow rates greater than 100 microL min(-1). This signal suppression effect was described by invoking Enke's model of electrospray ion generation. This model suggests that signal suppression can be ascribed to the competition between ionic species for charged surface sites present on the generated droplets during the electrospray process. The slopes of the calibration curves of the three analytes were close to unity (fexofenadien/d6-fexofenadine 0.964 +/- 0.008, pseudoephedrine/d3-ephedrine 1.02 +/- 0.080 and dapsone/d4-dapsone 0.905 +/- 0.048) as predicted by the model, indicating that quantitation should not be affected by the variation in the peak area of the internal standard.     

Sensitized Photochemical CO2 Reduction by Hetero-Pacman Compounds Linking a ReI Tricarbonyl with a Porphyrin Unit

The hetero-Pacman architecture places two different metal coordination sites in close proximity, which can support efficient energy and/or electron transfer and allow for cooperative activation of small molecules. Here, the synthesis of dyads consisting of a porphyrin unit as photosensitizer and a rhenium unit as catalytically active site, which are held together by the rigid xanthene backbone, is presented. Mononuclear [(NN)Re(CO)₃(Cl)] complexes for CO₂ reduction in which NN represents a bidentate diimine ligand (e.g., bipyridine or phenanthroline) lack light absorption in the visible region, resulting in poor photocatalysis upon illumination with visible light. To improve their visible-light absorption, we have focused on the incorporation of a strongly absorbing free base or zinc porphyrin unit. Resulting photocatalytic experiments showed a strong dependence of the catalytic performance on both the type of photosensitizer and the excitation wavelengths. Most notably, the intramolecular hetero-Pacman system containing a zinc porphyrin unit showed much better catalytic activity in the visible region (excitation wavelengths >450 nm) than the free base porphyrin version or the corresponding mononuclear rhenium compound or an intermolecular system comprised of a 1:1 mixture of the mononuclear analogues.