Mössbauer study and molecular orbital calculations on some bimetallic derivatives of ferrocene and ferricinium

We have studied by absorption Mössbauer spectroscopy, some bridged derivatives of biferrocene, unoxidized (Fe^II– Fe^II) and mono-oxidized (Fe^II – Fe^III). The mixed-valence species exhibits a quasi-delocalized behavior at the Mössbauer timescale (～ 10^?8 s), with a splitting of the lines which is interpreted in terms of a partial valence trapping. This in turn reveals intramolecular properties at variance from those of the unbridged cation. SCC-Xα MO calculations have been performed; they correctly reproduce the measured quadruple splittings and provide evidence that the HOMO of the mixed-valence complex is of \(d_{xy} ,d_{x^2 - y^2 } \) type. Some consequences on the mixed-valence properties are discussed.     

Crystal and Molecular Structure of the 4:3 Complex between Lanthanum Nitrate and Pentaethyleneglycol Dimethyl Ether

The crystal and molecular structure of [La(NO₃)₃]₄(C₁₂H₂₆O₅)₃ has been determined from low-temperature single-crystal X-ray diffraction data. The complex crystallizes in the monoclinic space group I2 with Z = 2. Lattice parameters at 150 K are a = 12.234 (6) Å, b = 11.105 (5), c = 26.613 (9), β = 90.65 (4)°. The structure was solved by Patterson and Fourier techniques and refined to a conventional R_F-value of 0.068. The compound contains three dinitrato complex cations [La(NO₃)₂C₁₂H₂₆O₆]⁺ with 10-coordinate lanthanum ions and one hexanitrato anion, [La(NO₃)₆]^3?, with a 12-coordinate La(III)-ion. One complex cation has a C₂-symmetry while the two others, which are crystallographically equivalent, have no symmetry and contain a disordered ligand molecule. The polyther adopts a ring-like conformation in all the complex moietis. The La? O(nitrate) distances lie in the ranges 2.52–2.53 and 2.49–2.62 Å, with average values of 2.53 (7) and 2.56 (6) Å, respectively, fo the species with C₂- and C₁-symmetry; the La? O(ether) bond lengths lie int he range 2.54–2.79 Å (average: 2.6 (1)) for the C₂-moiety and their mean value amounts to 2.6 (2) for the disordered species. The hexanitrate has a C₂-symmetry and the La? O distances range between 2.56 and 2.67 Å with an average value fo 2.64 (4) Å. The effective ionic radii of the 10- and 12-coordinate La(III) ions are estimated as 1.28 and 1.33 Å, respectively.     

Isomerization dynamics in homo- and heterochiral atropoisomer copper(I) diimine complexes: a 2D EXSY NMR study

Two-dimensional exchange NMR spectroscopy has been employed to study the isomerization process of copper(I) complexes formed upon complexation of Cu+ with a racemic mixture of the atropoisomer diimine benzimidazole-pyridine ligands 1-3 and evaluate the configurational stability of the pseudotetrahedral complexes [Cu(1-3)2]PF6. Racemization of the heterochiral isomers RSLambda/RSDelta proceeds through an intramolecular ligand rearrangement on a time scale of about 1.9 s(-1) for 1, 4.4 s(-1) for 2, and 0.3 s(-1) for 3 in CD2Cl2 at room temperature. The intramolecular Lambda/Delta isomerizations in the homochiral diastereoisomers RRDelta/SSLambda and RRLambda/SSDelta of [Cu(1)2]PF6 proceed at room temperature on a time scale of about 0.6 s(-1) for the conversion of RRDelta/SSLambda into RRLambda/SSDelta and 13 s(-1) for the conversion of RRLambda/SSDelta into RRDelta/SSLambda. The kinetics of these intramolecular exchange processes were found to be sensitive to the stabilizing interligand pi-stacking interactions that develop within the [Cu(1-3)2]+ structure and to the bulkiness of the benzimidazole aryl substituents. The kinetics of racemization in the heterochiral RSLambda/RSDelta isomers of [Cu(3)2]PF6 with the bulky cumyl-derived ligand were 1 order of magnitude lower than in [Cu(2)2]PF6 with the tolyl-based ligand. Slower intermolecular ligand exchanges between all the isomers have also been shown to occur at ambient temperature in CD2Cl2 through complete ligand dissociation. Free energies at 298 K varying between 66.7 and 74.4 kJ.mol(-1) and entropies varying between -26.4 and 28.3 J.K(-1).mol(-1) were determined for the intramolecular Lambda/Delta isomerizations. For the intermolecular ligand exchanges free energies at 298 K varying between 55.6 and 62.5 kJ.mol(-1) and entropies varying between -97.9 and -74.5 J.K(-1).mol(-1) were measured.     

Optimized simultaneous determination of several elements in human intestinal Caco-2 TC7 cells by inductively coupled plasma-mass spectrometry after closed vessel microwave digestion

A rapid procedure, based on closed vessels microwave digestion and inductively coupled plasma-mass spectrometry (ICP-MS), was evaluated to ascertain the effect of chronic exposure to cadmium on intracellular accumulation of minor and essential trace elements in cultured epithelial cells (Caco-2 TC7). For all measurements, the method of external calibration was used and 3 elements (Be, Sc, In) were selected as internal standards. Optimization procedures are discussed and results are presented for the total determination of 9 key analytes (Na, Mg, Ca, Cr, Mn, Cu, Zn, Mo, and Cd) in certified reference materials (CRMs) and 20 samples of Caco-2 TC7 cells long-term exposed to Cd. The performance characteristics of the analytical system were evaluated by calibration and linearity, limits of detection and quantitation, accuracy with spiking, trueness and repeatability with available CRMs. As a complement to the ICP-MS determinations, both available CRMs and cell samples were analyzed either by electro thermal- or flame atomic absorption spectrometry. The results were in good agreement with the ICP-MS results.     

Thermal growth of organic supramolecular crystals with screw dislocations

We report here a simple pathway to thermally assemble acene-based molecules into large crystals without modification of their chemical structures. Differential scanning calorimetry was used to characterize properly thermal events occurring during successive heating and cooling processes. More interestingly, observations by means of polarized light microscopy (POM) revealed that a spontaneous formation of screw dislocations within crystals during the isothermal treatment triggered a structural reorganization by forming large and well-defined spiral architectures. After this reorganization, new crystals showed an excellent ordering in both vertical and horizontal directions. Due to the richness in pi-electrons of acene-based molecules, we expect this work of importance to organic electronics, especially in the design of new molecular building blocks and investigation of their assembly into sophisticated supramolecular structures.     

A Total,Asymmetric Synthesis of 2-Deoxy-L-fucose from Furan

Abstract

The Diels-Alder adduct (+)?1 of furan to 1-cyanovinyl (1′S)-campha-nate was converted to methyl 3,5-O-diacetyl-2,6-deoxy-β-L-lyxo-hexofurano-side ((+)?12), a protected form of 2-deoxy-L-fucose, in 8 steps and 16.6% overall yield.     

Coupled structural and magnetic properties of ferric fluoride nanostructures: Part II,a Monte Carlo–Heisenberg study

We present a numerical study of the magnetic structure of nanostructured iron fluoride, using the Monte Carlo Metropolis simulated annealing technique and a classical Heisenberg Hamiltonian with superexchange angle dependent interactions. The parameters are adjusted on experimental results, and the atomic structure and topology taken from a previous atomistic model of grain boundaries in the same system. We find perfect antiferromagnetic crystalline grains and a disordered magnetic configuration (speromagnetic) at the grain boundary, in agreement with experimental features. Both the lowest magnetic energy and the rate of magnetic frustration are found to be dependent on the relative disorientation of crystalline grains, i.e. on the cationic topology. We conclude on possible extensions of the model.     

Chiral Diels–Alder reaction between cyclopentadiene and nitroso derivatives: thermal isomerisation/racemisation of the adducts

Cyclopentadiene nitroso adducts 1a and ent-1a were synthesised in good yields and good enantiomeric excess from chiral chloro-nitroso derivatives 4 and 5 in the d-mannose and d-ribose series, respectively. The thermal racemisation of these adducts occurred below room temperature. Some other chiral Diels–Alder nitroso adducts were prepared in the d-mandelic, l-prolinol and d-O-methylprolinol series and their thermal isomerisation was specified according to the N-substitution. A simple synthesis of the chiral amido-cyclopentenol (+)-2b, an important precursor for biological interesting compounds, is presented from ent-1a.     

Local and global modes of drug action in biochemical networks

Background  

It is becoming increasingly accepted that a shift is needed from the traditional target-based approach of drug development towards an integrated perspective of drug action in biochemical systems. To make this change possible, the interaction networks connecting drug targets to all components of biological systems must be identified and characterized.