Iodocyclization versus diiodination in the reaction of 3-alkynyl-4-methoxycoumarins with iodine: synthesis of 3-iodofuro[2,3-b]chromones

The reaction of 3-alkynyl-4-methoxycoumarins with molecular iodine in chlorinated solvents allows access to 3-iodofurochromones in good to excellent yields as the result of a iodocyclization-demethylation process. Competitive diiodination of the coumarin acetylene moiety could be eliminated by simply performing the reactions in refluxing 1,2-dichloroethane, owing to the thermal instability of the resulting (E)-1,2-diiodoethenylcoumarins.     

A thienoquinoxaline and a styryl-quinoxaline as new fluorescent probes for amyloid-β fibrils

Simple and easy to prepare quinoxaline derivatives proved able to stain amyloid fibers such as aggregated lysozyme and Aβ(1-40)-peptide by a fluorescence “turn on” mechanism. Thienoquinoxaline 1 allowed the detection of lysozyme and Aβ(1-40) fibers at λ = 555 and 532 nm, respectively, with excitation at λ = 450 nm. Styryl-quinoxaline 2 stained lysozyme and Aβ(1-40) fibers with fluorescence at λ = 579 and 567 nm, respectively, upon excitation at λ = 453 nm. The apparent K_d values for Aβ(1-40) fibers were 77 and 294 nM for 1 and 2, respectively. The sensitivity of the aggregates detection assay with these new dyes was higher than that of thioflavin T. Considering their unique fluorescence properties compared to other dyes reported in the field, they can be considered as additional staining tools for the detection and studies of peptide/protein aggregation.     

Full discretization of some reaction diffusion equation with blow up

This paper aims at the development of numerical schemes for nonlinear reaction diffusion problems with a convection that blows up in a finite time. A full discretization of this problem that preserves the blow — up property is presented as well as a numerical simulation. Efficiency of the method is derived via a numerical comparison with a classical scheme based on the Runge Kutta scheme.     

Self-organization of porphyrin units induced by magnetic field during sol-gel polymerization

The use of a magnetic field as a controlling factor during the hydrolysis-polycondensation of porphyrin precursors substituted by Si(OR)(3) groups, induces a self-organization of porphyrin moieties due to the stacking of these units in the hybrid material and this study also confirms the effect of the magnetic field in the nano- and micrometric organization during the kinetically controlled polycondensation process.     

Small-angle neutron and X-ray scattering from amphiphilic stimuli-responsive diamond-type bicontinuous cubic phase

The structural evolution of a diamond-type bicontinuous lipid cubic phase upon application of thermal and chemical (hydration agent) stimuli is investigated by means of small-angle neutron (SANS) and X-ray scattering (SAXS). The soft-matter cubic architecture responds by dramatic swelling (DLarge cubic structure) upon incorporation of a hydration-enhancing guest component (octyl glucoside) at low and ambient temperatures, the aqueous channel diameter increasing twice to approximately 7 nm. DLarge appears to be built up from an assembly of cubosomic domains, which may coexist with an amphiphilic lamellae domain at low temperatures. The chemical stimulus concentration can be selected as to tune the hydration of the nanochannels in the DLarge phase and its transformation into a DNormal phase at temperatures above the body temperature. Two-dimensional SANS images recorded upon heating scan reveal growth of spontaneously oriented domains of single-crystal cubic nature. Phase separation and squeezing out the guest-hydrating agent from the higher-curvature regions of the amphiphilic bilayer suggest a possible mechanism for the established transformations. The order-order structural transition, cubic DLarge-cubic DNormal, is found to be reversible upon cooling. The obtained results put forward a structure-based concept for release of encapsulated guest molecules from stimuli-responsive and self-regulated cubosomic nanocarriers.     

Lower semicontinuity of the attractor for a singularly perturbed hyperbolic equation

For a smooth, bounded domain R, n 3, and a real, positive parameter, we consider the hyperbolic equationu _tt +u _t –u=–f(u) –g in with Dirichlet boundary conditions. Under certain conditions onf, this equation has a global attractorA inH ₀ ¹ () ×L ²(). For=0, the parabolic equation also has a global attractor which can be naturally embedded into a compact setA ₀ inH ₀ ¹ () ×L ²(). If all of the equilibrium points of the parabolic equation are hyperbolic, it is shown that the setsA are lower semicontinuous at=0. Moreover, we give an estimate of the symmetric distance betweenA ₀ andA .     

Super‐Elastic Air/Water Interfacial Films Self‐Assembled from Soluble Surfactants

We show that water‐soluble monosodic salts of F‐alkyl phosphates C_nF_2n+1(CH₂)₂OP(O)(OH)₂, with n=8 and 10 (F8H2Phos and F10H2Phos) form Gibbs films with exceptionally high dilational viscoelastic modules E that reach ～900 mN m^?1 in the condensed phases. These E values are up to one order of magnitude larger than those recorded for phospholipid, protein and polymer films commonly considered as highly viscoelastic. F8H2Phos.1Na undergoes a transition between a liquid‐expanded and a liquid‐condensed phase. In the case of F10H2Phos.1Na, a transition occurs between a gas phase of surface domains, in which the molecules are densely packed, and a liquid‐condensed phase.     

New Trimethoxybenzamides and Trimethoxyphenylureas Derived from Dimethylcarbazole as Cytotoxic Agents. Part I

A convenient synthesis of novel functionalized 1,4‐dimethylcarbazole derivatives containing 3,4,5‐trimethoxybenzamido‐ureido or N‐(3,4,5‐trimethoxyphenyl)ureido group starting from their corresponding indole derivatives is reported. Three derivatives prepared ( 5g , 6c , and 6g ) were active against leukemia cell lines HL60. Both 5g and 6g showed potent antiproliferative activity against KB cell lines, likely associated with the inhibition of tubulin polymerization.     

Dinitrogen Activation Upon Reduction of a Triiron(II) Complex

Reaction of a trinuclear iron(II) complex, Fe₃Br₃ L ( 1 ), with KC₈ under N₂ leads to dinitrogen activation products ( 2 ) from which Fe₃(NH)₃ L ( 2‐1 ; L is a cyclophane bridged by three β‐diketiminate arms) was characterized by X‐ray crystallography. ¹H NMR spectra of the protonolysis product of 2 synthesized under ¹⁴N₂ and ¹⁵N₂ confirm atmospheric N₂ reduction, and ammonia is detected by the indophenol assay (yield ～30 %). IR and Mössbauer spectroscopy, and elemental analysis on 2 and 2‐1 as well as the tri(amido)triiron(II) 3 and tri(methoxo)triiron 4 congeners support our assignment of the reduction product as containing protonated N‐atom bridges.     

Direct synthesis of novel amphiphilic cyclodextrin

A novel amphiphilic cyclodextrin derivative was obtained by controlled esterification of lauric acid chloride on the primary face of the native β-cyclodextrin in a one step synthesis. The characterization of the substitution degree and isomer structure was performed by mass and NMR spectroscopies. A specific purification procedure by sublimation was developed in order to eliminate the excess of lauric acid molecules in the reaction product. The sublimation efficiency was assessed by differential scanning calorimetry (DSC) in quantifying the remaining fatty acid. In this way the duration of the sublimation process could be optimized.