Enzymatic desaturation of fatty acids: delta11 desaturase activity on cyclopropane acid probes

The formation of methylenecyclopropanes by enzymatic desaturation of 11-cyclopropylundecanoic acid (1) and its disubstituted derivatives cis- and trans-3-5 has been investigated using the Delta(11) desaturase of Spodoptera littoralis as model enzyme. Gas chromatography coupled to mass spectrometry analyses of methanolyzed lipidic extracts from tissues incubated with each probe revealed that all the cyclopropyl fatty acids were transformed into the corresponding 11-cyclopropylidene acids, except for compound trans-5 (5b), which was not desaturated at C11. The formation of methylenecyclopropane 9 as the only reaction product from 1 indicates that a potential radical intermediate is too short-lived to allow rearrangement reactions. Information on the Delta(11) desaturase substrate binding domain is provided considering the cyclopropyl probes 3-5 as conformationally restricted analogues of the straight-chain substrates.     

Influence of the chain stiffness on the thermodynamics of a Gō-type model for protein folding

The relative importance of local and long range interactions in the characteristics of the protein folding process has long been a matter of controversy. Computer simulations based on Gō-type models have been widely used to study this topic, but without much agreement on which type of interactions is more relevant for the foldability of a protein. In this work, the authors also employ a topology-based potential and simulation model to analyze the influence of local and long range interactions on the thermodynamics of the folding transition. The former are mainly used to control the degree of flexibility (or stiffness) of the chain, mostly appreciable in the unfolded (noncompact) state. Our results show the different effects that local and nonlocal interactions have on the entropy and the energy of the system. This implies that a balance between both types of interactions is required, so that a free energy barrier exists between the native and the denatured states. The variations in the contribution of both types of interactions have also a direct effect on the stability of the chain conformations, including the possible appearance of thermodynamic folding intermediates.     

Unsaturated,biobased polyesters and their cross‐linking via radical copolymerization

Biobased, unsaturated polyesters derived from isosorbide, maleic anhydride, and succinic acid were synthesized and characterized. The presence of maleic anhydride units in the structure of the polyesters allowed converting them into cured coatings by radical copolymerization with crosslinking agents such as 2‐hydroxyethyl methacrylate, N‐vinyl‐2‐pyrrolidinone, acrylic acid or methacrylamide. The investigated polyesters were obtained via bulk polycondensation, catalyzed by titanium(IV) n‐butoxide. 2D NMR and MALDI‐Tof‐MS spectroscopy proved that this polymerization resulted in isomerization of maleic acid units into fumaric ones and in the formation of slightly branched structures by the reaction of isosorbide (end) groups with main chain unsaturated bonds. Moreover, some double bonds proved to have reacted with the condensation by‐product water. The resulting polyesters displayed the expected correlation between variables such as molecular weight and content of unsaturated bonds and their T_g values. Since the thermal properties of the obtained polyesters were appropriate for coating applications, the polymers were crosslinked with unsaturated monomers by radical copolymerization. The crosslinking process was studied using FTIR spectroscopy and by measurements of the soluble part of the cured coatings. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2885–2895, 2010     

Asymmetric Synthesis of Fluorinated Isoindolinones through Palladium‐Catalyzed Carbonylative Amination of Enantioenriched Benzylic Carbamates

The asymmetric synthesis of fluorinated isoindolinones has been achieved by a palladium‐catalyzed aminocarbonylation reaction of the corresponding α‐fluoroalkyl o‐iodobenzylamines. A base‐mediated anti β‐hydride elimination process was suggested to explain the partial erosion of the optical purity observed in some cases. This mechanistic rationale enabled the minimization of this partial racemization by fine‐tuning the pK_a of the base.     

Leak testing of carbon–tin nanocomposites by thermal analysis methods

Electrode materials consisted of tin nanograins encapsulated in different origin carbon buffer matrix (starch or water soluble polymer) were obtained in a simple and inexpensive process. The tin precursor was synthesized using modified reverse nanoemulsion technique (w/o) and then coated by a source of carbon. The composites precursors were pyrolysed, affording formation of C/Sn anode materials. The resulting samples were investigated by powder X-ray diffraction studies in order to verify the structure and calculate crystallites sizes. The morphology of the nanocomposites was characterized by low-temperature nitrogen adsorption method (N₂-BET). Thermal analysis measurements (EGA-TG/DTG/DTA and DSC) allowed determining optimal conditions of preparation process and estimating carbon content in the obtained anode materials. Thermogravimetric studies also proved to be highly useful in establishing the leak behaviour of C/Sn nanocomposites. The electrochemical performance of the nanopowders was examined by charge–discharge tests in R2032-type coin cell. The thermal analysis results as well as low-temperature nitrogen adsorption data indicated that the origin of carbon precursor has major impact on morphology and leak behaviour of the obtained carbon buffer matrix. The electrochemical tests showed that better tightness of carbon–tin nanocomposites resulted in higher gravimetric capacity and better cell performance.     

Potentiometric Studies on the Equilibria of Flufenamic Acid in Aqueous Solutions and in Two-phase Organic Solvent + Water Systems

In this paper, the flufenamic acid equilibria in aqueous solution and in two-phase organic solvent + aqueous solution are described and presented. The dissociation constants K _a1 and K _a2 were determined in MDM + water mixtures. The Yashuda-Shedlovsky extrapolation procedure has been used to obtain the values of K _a1 and K _a2 in aqueous solutions. The distribution ratio D was measured in the toluene + water system over a wide range of pH by the shaking flask method. Based on the results of potentiometric titrations in two-phase organic solvent (benzene, ethylbenzene, toluene, carbon tetrachloride, chloroform, chlorobenzene, and bromobenzene) + aqueous systems, and using models of single and multistep equilibria, the values of distribution constants K _D and dimerization constants K _dim were calculated. The influences of polarity of the applied solvents and pH of the aqueous phase, on the speciation of the particular forms of flufenamic acid in both phases, were demonstrated.     

Binuclear zinc(II) complexes with the anti-inflammatory compounds salicylaldehyde semicarbazone and salicylaldehyde-4-chlorobenzoyl hydrazone (H2LASSBio-1064)

Complexes [Zn₂(HL¹)₂(CH₃COO)₂] (1) and [Zn₂(L²)₂] (2) were synthesized with salicylaldehyde semicarbazone (H₂L¹) and salicylaldehyde-4-chlorobenzoyl hydrazone (H₂LASSBio-1064, H₂L²), respectively. The crystal structure of (1) was determined. Upon recrystallization of previously prepared [Zn₂(HL²)₂(Cl)₂] (3) in 1:9 DMSO:acetone crystals of [Zn₂(L²)₂(H₂O)₂]·[Zn₂(L²)₂(DMSO)₄] (3a) were obtained. The crystal structure of 3a was also determined. All crystal structures revealed the presence of phenoxo-bridged binuclear zinc(II) complexes.