Multisite modification of neomycin B: combined Mitsunobu and click chemistry approach

The aminoglycoside antibiotic neomycin B has been converted into several novel building blocks that can be used for the specific modification of three of the four ring systems. Under carefully controlled conditions, the Mitsunobu reaction can be used to selectively dehydrate the ido ring to give the talo epoxide. Subsequently however, under more forcing conditions, the 2-deoxy streptamine ring undergoes Mitsunobu dehydration to give an aziridine. An unusual remote neighboring group effect was observed. When the primary hydroxyl of the ribose ring was blocked, aziridine formation on the deoxystreptamine ring did not occur. Both the epoxide and epoxide-aziridine neomycin building blocks can be ring-opened with azide and subjected to "click" type chemistry with terminal alkynes to generate a series of new neomycin analogues. These reactions can all be carried out without recourse to O-protecting groups. A detailed conformational analysis by NMR revealed some unexpected conformer preferences in these systems.     

A bifurcation problem governed by the boundary condition I

We deal with positive solutions of Δu = a(x)u ^p in a bounded smooth domain subject to the boundary condition ∂u/∂v = λu, λ a parameter, p > 1. We prove that this problem has a unique positive solution if and only if 0 < λ < σ₁ where, roughly speaking, σ₁ is finite if and only if |∂Ω ∩ {a = 0}| > 0 and coincides with the first eigenvalue of an associated eigenvalue problem. Moreover, we find the limit profile of the solution as λ → σ₁. Supported by DGES and FEDER under grant BFM2001-3894 (J. García-Melián and J. Sabina) and ANPCyT PICT No. 03-05009 (J. D. Rossi). J.D. Rossi is a member of CONICET.     

Novel Copper(II) Thiodibenzoic Acid Coordination Polymers by in situ Extrusion of Sulfur from 2,2′‐Dithiodibenzoic Acid and the Unique Oxidation of Disulfide to Sulfate

Slow diffusion reaction of 2,2′‐dithiodibenzoic acid (dtdb) with CuCl₂ in the presence of N‐donor ligands results in the formation of different coordination polymers where both S–S and C–S scission and oxidation of S is observed. X‐ray diffraction analysis of [Cu(tdb)(phen)(H₂O)]₂ · 2H₂O.2DMF] ( 1 ), [Cu(tdb)(py)₂(H₂O)]₂ ( 3 ), and [Cu(tdb)(bipy)(H₂O)]₂ · 0.5H₂O ( 4 ) (tdb = thiodibenzoic acid, phen = phenanthroline, py = pyridine, bipy = 2,2′‐bipyridine) show that the metal ions are coordinated to the carboxylate oxygen atoms of the in situ generated tdb ligand in a monodenate fashion. In [Cu(phen)(SO₄)₂(H₂O)₂]_n ( 2 ) and [Cu(bipy)(SO₄)₂(H₂O)₂]_n ( 5 ), the sulfur is oxidized to sulfate ions prior to coordination with the metal. Complex 1 has a dimeric structure with π–π interactions between the phen ligands, whereas 3 and 4 form 1D polymeric chains.     

Identification of the Primary Structure of Selenium-Containing Polysaccharides Selectively Inhibiting T-Cell Proliferation

We previously described the biosynthesis, isolation, and immunosuppressive activity of the selenium-containing polysaccharide fraction isolated from the mycelial culture of Lentinula edodes. Structural studies have shown that the fraction was a protein-containing mixture of high molar mass polysaccharides α- and β-glucans. However, which of the components of the complex fraction is responsible for the immunosuppressive activity non-typical for polysaccharides of fungal origin has not been explained. In the current study, we defined four-polysaccharide components of the Se-containing polysaccharide fraction determined their primary structure and examined the effect on T- and B-cell proliferation. The isolated Se-polysaccharides, α-1,4-glucan (M_w 2.25 × 10⁶ g/mol), unbranched β-1,6-d-glucan, unbranched β-1,3-d-glucan and β-1,3-branched β-1,6-d-glucan (M_w 1.10 × 10⁵ g/mol), are not typical as components of the cell wall of L. edodes. All are biologically active, but the inhibitory effect of the isolated polysaccharides on lymphocyte proliferation was weaker, though more selective than that of the crude fraction.     

Semi-analytical method for computing effective properties in elastic composite under imperfect contact

A parallel fiber-reinforced periodic elastic composite is considered with transversely iso-tropic constituents. Fibers with circular cross section are distributed with the same periodicity along the two perpendicular directions to the fiber orientation, i.e., the periodic cell of the composite is square. The composite exhibits imperfect contact, in particular, spring type at the interface between the fiber and matrix is modeled. Effective properties of this composite for in-plane and anti-plane local problems are calculated by means of a semi-analytic method, i.e. the differential equations that described the local problems obtained by asymptotic homogenization method are solved using the finite element method. Numerical computations are implemented and comparisons with exact solutions are presented.     

Overall longitudinal shear elastic modulus of a 1–3 composite with anisotropic constituents

The overall properties of a binary elastic periodic fiber-reinforced composite, with transversely isotropic constituents in an anti-plane-strain deformation state, are studied here for a cell periodicity of square type. This analysis considers four different orientations of the axis of transverse isotropy of constituents with respect to the direction of fibers. Each case is characterized by very simple closed-form expressions for the effective coefficients, which were obtained using the asymptotic homogenization method. Local problems defined on a periodic square unit cell are solved using Weierstrassian and Natanzon’s functions and perturbation theory relative to small anisotropy. In the isotropic limit, comparison with rigorous bounds and some well-known mixing rules are made. Also, comparisons with finite element calculations show that the derived closed-form formulae provide excellent results even for large anisotropy.     

Direct synthesis of aromatic polyamides

The synthesis of aromatic polyamides, namely poly(p-phenylenetere-phthalamide) and poly(p-benzamide), via phosphorylation reaction has been thoroughly investigated. The effect of reaction temperature, concentration of monomers and reactants, type and concentration of salts, amount of the activator and its stepwise addition have been considered and the optimum reaction conditions found. The resultant synthesis of the above polymers, also in connection with the high purification techniques of all components of the reaction mixture, allowed to reach the highest molecular weights obtained so far by this synthetic way.     

The Bioactive Profile,Nutritional Value,Health Benefits and Agronomic Requirements of Cherry Silverberry (Elaeagnus multiflora Thunb.): A Review

The cherry silverberry (Elaeagnus multiflora Thunb.) is a lesser-known plant species with high nutritional and therapeutic potential. Cherry silverberry contains numerous biologically active compounds. The cherry silverberry is a shrub growing up to 3 m. Its drupe-like fruit is ellipsoidal, up to 1 cm long, and set on stems. It is red in color, juicy, and sour, and its taste resembles that of red currants. According to the literature, cherry silverberry fruit contains carbohydrates, organic acids, and amino acids, as well as vitamin C, in addition to biominerals, polyphenols, flavonoids, carotenoids, chlorophylls, and tocopherols, which contribute to its high nutritional value. New biotypes of cherry silverberry cultivated in Poland can be used for the production of functional foods and direct consumption. In China, the cherry silverberry, known as goumi, has been used as a medicinal plant and a natural remedy for cough, diarrhea, itch, foul sores, and, even, cancer. This review article summarizes the scant research findings on the nutritional and therapeutic benefits of cherry silverberry.     

Connections between different models describing imperfect interfaces in periodic fiber-reinforced composites

The paper addresses the problem of modeling of fiber reinforced composites with imperfect bonding between the matrix and the inhomogeneities. The imperfections of different kinds are usually modeled as either layered inhomogeneities or by springs of certain stiffnesses distributed along the matrix/fiber interfaces. We compare the two approaches for the case of incompressible layer between the phases and calculate effective properties of fiber reinforced composites with periodic square arrays of fibers possessing imperfect contact with the surrounding material. We identify the interval of thickness at which the interphase does not influence the effective properties and show how the imperfection effects described by different models can be expressed in terms of each other.     

Effect of Alpha-1 Antitrypsin on CFTR Levels in Primary Human Airway Epithelial Cells Grown at the Air-Liquid-Interface

The cystic fibrosis transmembrane conductance regulator (CFTR) gene is influenced by the fundamental cellular processes like epithelial differentiation/polarization, regeneration and epithelial–mesenchymal transition. Defects in CFTR protein levels and/or function lead to decreased airway surface liquid layer facilitating microbial colonization and inflammation. The SERPINA1 gene, encoding alpha1-antitrypsin (AAT) protein, is one of the genes implicated in CF, however it remains unknown whether AAT has any influence on CFTR levels. In this study we assessed CFTR protein levels in primary human lung epithelial cells grown at the air-liquid-interface (ALI) alone or pre-incubated with AAT by Western blots and immunohistochemistry. Histological analysis of ALI inserts revealed CFTR- and AAT-positive cells but no AAT-CFTR co-localization. When 0.5 mg/mL of AAT was added to apical or basolateral compartments of pro-inflammatory activated ALI cultures, CFTR levels increased relative to activated ALIs. This finding suggests that AAT is CFTR-modulating protein, albeit its effects may depend on the concentration and the route of administration. Human lung epithelial ALI cultures provide a useful tool for studies in detail how AAT or other pharmaceuticals affect the levels and activity of CFTR.