Biomimetic Interaction between FeII and O2: Effect of the Second Coordination Sphere on O2 Binding to FeII Complexes: Evidence of Coordination at the Metal Centre by a Dissociative Mechanism in the Formation of μ‐Oxo Diferric Complexes

We report that the formation of μ‐oxo diferric compounds from O₂ and FeCl₂ complexes within the tris(2‐pyridylmethyl)amine series (N. K. Thallaj et al. Chem. Eur. J., 2008 , 14, 6742–6753) involves coordination of O₂ to the metal centre and that this reaction occurs following initial dissociation of the bound equatorial chloride anion. We also report evidence of the formation of a reduced form of dioxygen by an inner‐sphere mechanism, thus leading to modification of the ligand. The solid‐state structures of [FeCl₂L] complexes (L¹=mono(α‐pivalamidopyridylmethyl)bis(2‐pyridylmethyl)amine, L²=mono(α‐pivalesteropyridylmethyl)bis(2‐pyridylmethyl)amine, L³=bis(α‐pivalamidopyridylmethyl)mono(2‐pyridylmethyl)amine are described, and spectroscopic data support the structural retention in solution. In [FeCl₂L³], the two amide hydrogen atoms stabilise the equatorial chloride anion in such a way that its exchange by a weak ligand is impossible: [FeCl₂L³] is perfectly oxygen‐stable. In [FeCl₂L²], the equatorial chloride anion is completely free to move and coordination of O₂ can take place. The reaction product with [FeCl₂L²] is a μ‐oxo diferric complex in which the ester function has been transformed into a phenol group. This conversion can be seen as a hydrolysis reaction in basic medium, hence supporting the initial formation of a reduced form of dioxygen in the medium. Complex [FeCl₂L¹] exhibits a very weak reactivity with O₂, in line with a semistabilised equatorial chloride counteranion.     

Variation du champ seuil avec une tension uniaxiale dans FeCl2 A 4,2°K

In FeCl₂, at low temperature, the Fe²⁺ ions present an antiferromagnetic order characterised by an easy magnetization axis perpendicular to the ion-containing planes. There exists a value h_s of a magnetic field parallel to the axis, which transforms the system from an antiferromagnetic order into a saturated paramagnetic order. There we present the variations of h_s at 4·2°K as well as the deformations of the sample, when we impose upon it a strain parallel to the axis without allowing its lateral dilatation. These results, when added to those already obtained with χ_i in similar experiments enable us to determine the variations of the crystalline anisotropy and anti-ferromagnetic exchange (between Fe²⁺ ions belonging to two consecutive planes) in terms of the deformations. Our results concerning h_s are different from the ones obtained when exerting a hydrostatic strain. We compare the two cases by using the relations between elastic constants of FeCl₂ obtained at 300°K and recorded in the Appendix.     

2,4,4,6-Tetrabromo-2,5-cyclohexadienone (TABCO), N-Bromosuccinimide (NBS) and Bromine as Efficient Catalysts for Dithioacetalization and Oxathioacetalization of Carbonyl Compounds and Transdithioacetalization Reactions

The use of 2,4,4,6-tetrabromo-2,5-cyclohexadienone (TABCO), N-bromosuccinimide (NBS), and bromine as efficient catalysts for conversion of carbonyl compounds to their cyclic and acyclic dithioacetals and 1,3-oxathiolanes under mild reaction conditions are described. These catalysts are also used for efficient transdithioacetalization of acetals, diacetals, ketals, acylals, enamines, hydrazones, and oximes with high yields in the presence of thiols.     

Al Kα and Cu Kα1 excited XPS of vanadium oxide and VF3 powders: Measurement of the V 1s – KLL Auger parameters

Al Kα (hν = 1486.6 eV) excited XPS shows that powder samples of V₂O₃, V₂O₅ and VF₃ are surface contaminated and that the V₂O₃ can be cleaned by heating in vacuum at 400 °C. The greater sampling depth of Cu Kα₁ (hν = 8047.8 eV) excited XPS allows measurement of the bulk V 1s – KL₂L₃ Auger parameters (APs) for these materials. The APs of VF₃ and V₂O₅, relative to V metal, fall into the range of values expected for metal fluorides and oxides with non-local final state core-hole screening, whereas the AP of V₂O₃ is significantly closer to that of V metal. We ascribe this to a greater final state valence orbital occupation following photionisation in V₂O₃, part of which results from metal-like screening.     

Quantum deficits and correlations of two superconducting charge qubits

Motivated by recent experiments [Y.A. Pashkin, T. Yamamoto, O. Astafiev, Y. Nakamura, D.V. Averin, J.S. Tsai, Nature 421 (2003) 823] that show coherent oscillations of two superconducting qubits system, we consider a system of two charge qubits coupled to a common stripline microwave resonator. We discuss the separable and entangled behavior as well as the quantum and classical information deficits. Numerical computation of these quantities is performed for several regimes. We find that for less entangled states the partner can extract much more information by means of classical communication and local operations.     

Numerical Investigation of Magnetic Nanoparticles Distribution Inside a Cylindrical Porous Tumor Considering the Influences of Interstitial Fluid Flow

A numerical simulation of interstitial fluid flow and blood flow and diffusion of magnetic nanoparticles (MNPs) are developed, based on the governing equations for the fluid flow, i.e., the continuity and momentum and mass diffusion equations, to a tissue containing two-dimensional cylindrical tumor. The tumor is assumed to be rigid porous media with a necrotic core, interstitial fluid and two capillaries with arterial pressure input and venous pressure output. Blood flow through the capillaries and interstitial fluid flow in tumor tissues are carried by extended Poiseuille’s law and Darcy’s law, respectively. Transvascular flows are also described using Starling’s law. MNPs diffuse by interstitial fluid flow in tumor. The finite difference method has been used to simulate interstitial fluid pressure and velocity, blood pressure and velocity and diffusion of MNPs injected inside a biological tissue during magnetic fluid hyperthermia (MFH). Results show that the interstitial pressure has a maximum value at the center of the tumor and decreases toward the first capillary. The reduction continues between two capillaries, and interstitial pressure finally decreases in direction of the tumor perimeter. This study also shows that decreasing in intercapillary distance may cause a decrease in interstitial pressure. Furthermore, multi-site injection of nanoparticles has better effect on MFH.     

Rapid determination of lysine in biological samples by isocratic liquid chromatography.

A simple, rapid, and sensitive method was developed for detection and quantitation of lysine (Lys) in various biological samples by isocratic liquid chromatography (LC). Samples containing Lys and other amino acids were derivatized with 9-fluorenylmethyl chloroformate (FMOC-CI). The mobile phase used for isocratic elution was 50 mmol/L sodium acetate buffer (pH 4.20)-acetonitrile (43 + 57, v/v). Lys was detected with a UV detector at 265 nm. The derivatized Lys eluted from a LiChrospher 100 RP-18 (150 x 4.0 mm id) column at a retention time of 5.6 min. The limit of detection was 0.73 mumol/L (signal-to-noise [S/N] ratio, 3:1), and the limit of quantitation was 2.37 mumol/L (S/N ratio, 10:1). Lys recoveries from fortified biological samples were > 97.5%. Average Lys contents found in rumen fluid samples collected before the morning feeding and at 2.0, 4.0, and 6.0 h after feeding were 4.26, 3.34, 3.58, and 3.82 mumol/L, respectively. The hydrolysate of a sample of mixed rumen microorganisms collected before the morning feeding was determined to contain 1.372 mumol/mg microbial nitrogen in the form of Lys. The Lys concentrations of human plasma, goat plasma, human urine, and goat urine were 140.0, 102.0, 58.0, and 32.0 mumol/L, respectively.     

Synthesis of 4‐Hydroxy‐3‐(2‐arylimidazo[1,2‐a]pyridin‐3‐yl)quinolin‐2(1H)‐ones in the Presence of DABCO as an Efficient Organocatalyst

The one‐pot, three‐component, synthesis of a new series of 4‐hydroxy‐3‐(2‐arylimidazo[1,2‐a]pyridin‐3‐yl)quinolin‐2(1H)‐ones in the presence of DABCO as a catalyst has been achieved using aryl glyoxal monohydrates, quinoline‐2,4(1H,3H)‐dione, and 2‐aminopyridine in H₂O/EtOH under reflux conditions. The cheapness of organocatalyst, simple workup, operational simplicity, regioselectivity, and high yields are some advantages of this protocol.     

2-Aminophenyl diphenylphosphinite as an easily accessible ligand for heterogeneous palladium-catalyzed Suzuki-Miyaura reaction in water in the absence of any organic co-solvent

In this article, we have introduced application of 2-aminophenyl diphenylphosphinite as an easily accessible ligand for heterogeneous palladium-catalyzed Suzuki-Miyaura reaction in water in the absence of any organic co-solvent. By using 2-aminophenyl diphenylphosphinite as a ligand and Pd(OAc)₂ as the pre-catalyst, structurally different aryl halides (I, Br, Cl) were reacted efficiently with phenylboronic acid in water to produce their corresponding biphenyl products in good to excellent yields under heterogeneous conditions. The catalyst is recyclable and was recycled for seven runs for the reaction of bromobenzene with phenylboronic acid without appreciable loss of its catalytic activity.     

A water-stable lanthanide metal-organic framework for fluorimetric detection of ferric ions and tryptophan

Microchimica Acta - The preparation of a highly water stable and porous lanthanide metal-organic framework (MOF) nanoparticles (denoted SUMOF-7II; SU refers to Stockholm University) is described....