Modulating Electronic Coupling Using O- and S-donor Linkers

Structures of compounds having two dimolybdenum units Mo2(DAniF)3+ (DAniF = N,N'-di-p-anisylformamidinate) connected by unsubstituted oxamidate (1) and dithiooxamidate (2) linkers are isomorphous, and the cores of the molecules are planar because of two intramolecular hydrogen bonds within the linkers. Molecular mechanics calculations show a barrier of rotation along the C-C bond of approximately 10 kcal x mol(-1), which suggests that planar conformations are also expected in solution. Changing the two oxygen atoms in the linker of 1 to sulfur atoms results in a significant enhancement of the electronic coupling between the dimetal units (Delta(E1/2) = 204 mV for 1 and 407 mV for 2). The electronic spectrum of 2 shows an intense low energy (600 nm) metal-to-ligand charge transfer (MLCT) band, whereas that for 1 shows only a weak absorption band at 460 nm. DFT calculations on models 1' and 2', in which the anisyl groups were replaced by hydrogen atoms, show that the energy of the pi* orbital of the linker is much lower for 2'. This allows dpi-ddelta interactions from the electrons in the delta orbitals of the Mo2 unit to the sulfur atom that in turn facilitates an electron hopping pathway.     

Hierarchical Functionalized Polymeric‐Ceramic Coatings on Mg‐Ca Alloys for Biodegradable Implant Applications

Magnesium‐based implants present several advantages for clinical applications, in particular due to their biocompatibility and degradability. However, degradation products can affect negatively the cell activity. In this work, a combined coating strategy to control the implant degradation and cell regulation processes is evaluated, including plasma electrolytic oxidation (PEO) that produces a 13 µm‐thick Ca, P, and Si containing ceramic coating with surface porosity, and breath figures (BF) approach that produces a porous polymeric poly(ε‐caprolactone) surface. The degradation of PCL‐PEO‐coated Mg hierarchical scaffold can be tailored to promote cell adhesion and proliferation into the porous structure. As a result, cell culture can colonize the inner PEO‐ceramic coating structure where higher amount of bioelements are present. The Mg/PEO/PCL/BF scaffolds exhibit equally good or better premyoblast cell adhesion and proliferation compared with Ti CP control. The biological behavior of this new hierarchical functionalized scaffold can improve the implantation success in bone and cardiovascular clinical applications.     

Studies on Immobilization and Partial Characterization of Lipases from Wheat Seeds (<Emphasis Type="Italic">Triticum aestivum</Emphasis>)

The objective of this study was to provide some features on immobilization and partial characterization of lipases from wheat seeds. The optimum pH and temperature were found to be 5.5 and 32–37 °C, respectively. The stability of the concentrated enzymatic extract to high temperatures (25, 35, 45, and 55 °C) showed that the incubation of the extract at 55 °C led to its complete inactivation. The concentrated enzymatic extract kept 90% of its hydrolytic and esterification activities until 70 and 40 days of storage at 4 °C, respectively. The extract presented higher hydrolytic specificity to substrates of medium and long chains and higher esterification affinity to fatty acids of short and medium chains and alcohols with two and three carbon atoms. After the immobilization process using activated coal and sodium alginate as supports, an enhancement of about threefold in lipase activity was observed. The development of the present work permitted us to point out some characteristics of lipases from wheat seeds necessary for the proposition of new future industrial applications for this important biocatalyst.     

Increasing the solubility of strong reducing agents containing Mo(2)(4+) units and alkyl-substituted guanidinate ligands

Six very soluble paddlewheel compounds containing Mo(2)(n+) units, n = 4, 5, 6, and two alkyl-substituted bicyclic guanidinate ligands have been synthesized. The quadruply bonded complexes with n = 4, Mo(2)(TMhpp)(4) and Mo(2)(TEhpp)(4), (TMhpp = the anion of 3,3,9,9-tetramethyl-1,5,7-triazabicyclo[4.4.0]dec-4-ene and TEhpp = the anion of 3,3,9,9-tetraethyl-1,5,7-triazabicyclo[4.4.0]dec-4-ene) are easily oxidized. The electrode potentials in THF are -1.08 and -1.17 V vs. Ag/AgCl, respectively, for the Mo(2)(5+/4+) couple. These potentials are in accord with the low ionization potentials for the quadruply bonded compounds. Because of the high solubility of the Mo(2)(4+) compounds in most common organic solvents they are attractive candidates for use as strong reducing agents in homogeneous systems.     

Towards Controlled Graft Polymerization of Poly[styrene‐co‐(maleic anhydride)] on Functionalized Silica Mediated by Oxoaminium Bromide Salt. Facile Synthetic Pathway Using Nitroxide Chemistry

A TEMPO bromide salt is used to functionalize a silica surface with nitroxyl moieties. The functionalization reaction takes place in 48 h under mild conditions. In a second step, grafts of styrene‐maleic anhydride copolymer are grown from the functionalized silica surface by heating it in the presence of the monomers. FT‐IR and TGA analysis show that the silica was first functionalized with nitroxide moieties, and then that grafts of styrene‐maleic anhydride grew from the functionalized silica surface. A reaction mechanism is proposed in order to explain the findings. The results suggest that the oxoaminium salts are good candidates for the functionalization and grafting of surfaces that contain hydroxy groups and for the generation of hybrid materials with improved properties.

     

Polymeric Gene Carriers Bearing Pendant β‐Cyclodextrin: The Relevance of Glycoside Permethylation on the “In Vitro” Cell Response

The incorporation of cyclodextrins (CDs) to nonviral cationic polymer vectors is very attractive due to recent studies that report a clear improvement of their cytocompatibility and transfection efficiency. However, a systematic study on the influence of the CD derivatization is still lacking. In this work, the relevance of β‐CD permethylation has been addressed by preparing and evaluating two series of copolymers of the cationic N‐ethyl pyrrolidine methacrylamide (EPA) and styrenic units bearing pendant hydroxylated and permethylated β‐CDs (HCDSt and MeCDSt, respectively). For both cell lines, CDs permethylation shows a strong influence on plasmid DNA complexation, “in vitro” cytocompatibility and transfection efficiency of the resulting copolymers over two murine cell lines. While the incorporation of the hydroxylated CD moiety increased the cytotoxicity of the copolymers in comparison with their homopolycationic counterpart, the permethylated copolymers have shown full cytocompatibility as well as superior transfection efficiency than the controls. This behavior has been related to the different chemical nature of both units and tentatively to a different distribution of units along the polymeric chains. Cellular internalization analysis with fluorescent copo­lymers supports this behavior.

     

1,1',3,3',6,6',8,8'-Octachloro-9,9'-bifluorenylidene and perchloro-9,9'-bifluorenylidene,two exceedingly twisted ethylenes

The syntheses of 1,1',3,3',6,6',8,8'-octachloro-9,9'-bifluorenylidene (1), its precursors, and the byproduct 3,3',5,5'-tetrachloro-4-(trichloromethyl)biphenyl (5) are described. Accurate structural X-ray data on 1 and on perchloro-9,9'-bifluorenylidene (2) are reported and discussed. Because of chlorine overcrowding, the dihedral angles between their two identical fluorenylidene moieties are abnormally large, the central-ethylene twist angles being 55 and 66 degrees, respectively. Significant out-of-plane carbon-chlorine bond bending is likewise exhibited. Their ESR spectra and magnetic measurements prove that they are singlet species. The exceptionally large bathochromic displacements of their UV-vis absorption spectrum with respect to that of their parent hydrocarbon are mainly attributed to bond bending and molecular warping.     

Proventriculus of Cephalotes ants: A structural and comparative analysis

The use of optic microscopy and scanning electron microscopy propitiated the comparative examination of the structure of the proventriculus bulb of Cephalotes atratus, Cephalotes clypeatus and Cephalotes pusillus. This portion of the digestive tract possesses highly sclerotized projections which act in the selection of victuals. This structure is of importance to phylogeny studies and thus was compared with others known species of ants in a dendrogram adapted from Eisner (1957). We did not detect differences among the three studied species in the nature of histochemistry and ultra morphology.     

Shallow Water equations for Non-Newtonian fluids

The purpose of this paper is to provide a consistent thin layer theory for some Non-Newtonian fluids that are incompressible and flowing down an inclined plane under the effect of gravity. We shall provide a better understanding of the derivation of Shallow Water models in the case of power-law fluids and Bingham fluids. The method is based on asymptotic expansions of solutions of the Cauchy Momentum equations in the Shallow Water scaling and in the neighbourhood of steady solutions so that we can close the average equations on the fluid height h and the total discharge rate q. Such a method has been first introduced in the case of Newtonian fluids where the computations are proved to be rigorous (Vila, in preparation [20]; Bresch and Noble, 2007 [9]) whereas the more complex case of arbitrary topography has been treated formally (Boutounet et al., 2008 [5]). The well posedness of the free surface Cauchy Momentum equations for these Non-Newtonian fluids is still an open problem: the computations carried out here are only formal.     

An Expedient Method for the Umpolung Coupling of Enols with Heteronucleophiles**

In this paper, we present an unprecedented and general umpolung protocol that allows the functionalization of silyl enol ethers and of 1,3-dicarbonyl compounds with a large range of heteroatom nucleophiles, including carboxylic acids, alcohols, primary and secondary amines, azide, thiols, and also anionic carbamates derived from CO₂. The scope of the reaction also extends to carbon-based nucleophiles. The reaction relies on the use of 1-bromo-3,3-dimethyl-1,3-dihydro-1λ³[d][1,2]iodaoxole, which provides a key α-brominated carbonyl intermediate. The reaction mechanism has been studied experimentally and by DFT, and we propose formation of an unusual enolonium intermediate with a halogen-bonded bromide.