Tuning the biomimetic performances of 4-hydroxyproline-containing cyclic peptoids.

Five new cyclic peptoids containing (2S,4R)-4-hydroxyproline (Hyp) residues have been designed and synthesized using a mixed "submonomer/monomer" approach. Alkali metal cation affinities and ion transport activities were assessed by experimental (NMR and HPTS assay in liposomes) and computational methods. Easy functionalization of hydroxyproline residues afforded a bouquet of cyclic oligomers showing correlation between ion transport abilities and cytotoxic activities on selected human cancer cell lines.

Conformational isomerism in cyclic peptoids and its specification.

Most of the structural studies made on the secondary structure of peptoids describe their geometric attributes in terms of the classic Ramachandran plot (based on the local analysis of ω, ψ, χ, φ dihedral angles). However, little intuitive understanding is available from internal coordinates when stereochemistry is involved. In this contribution we list all the conformationally stable cyclic peptoids reported up to the year 2017 and propose a simple method to define their geometric arrangement in terms of planar chirality. Evidence of conformational isomerism (due to the long average time of single bond rotation) and conformational chirality (induced by the absence of roto-reflection axes) in this promising class of synthetic macrocycles is provided by NMR spectroscopy (using Pirkle's alcohol as chiral solvating agent) and careful evaluation of X-ray crystallographic studies. The full understanding of the oligomeric macrocycles' structural properties and the clear framing of their conformational isomerism in a proper conceptual scheme is fundamental for future application of peptoids in asymmetric synthesis, chiral recognition and supramolecular chemistry.

Synthesis and complexing properties of cyclic benzylopeptoids - a new family of extended macrocyclic peptoids.

An efficient protocol for the solid-phase synthesis of six members of a new class of extended macrocyclic peptoids (based on ortho-, meta- and para-N-(methoxyethyl)aminomethyl phenylacetyl units) is described. Theoretical (DFT) and experimental (NMR) studies on the free and Na+-complexed cyclic trimers (3-5) and tetramers (6-8) demonstrate that annulation of the rigidified peptoids can generate new hosts with the ability to sequestrate one or two sodium cations with the affinities and stoichiometries defined by the macrocycle morphology. Ion transport studies have been also performed in order to better appreciate the factors promoting transmembrane cation translocation.

Electrocatalysts for methanol oxidation based on platinum/carbon nanofibers nanocomposite.

New carbon nanomaterials, i.e., carbon nanotubes and nanofibers, with special physico-chemical properties, are recently studied as support for methanol oxidation reaction electrocatalysts replacing the most widely used carbon black. Particularly, carbon fibrous structures with high surface area and available open edges are thought to be promising. Platelet type carbon nanofibers, which have the graphene layers oriented perpendicularly to the fiber axis, exhibit a high ratio of edge to basal atoms. Different types of carbon nanofibers (tubular and platelet) were grown by plasma enhanced chemical vapour deposition on carbon paper substrates. The process was controlled and optimised in term of growth pressure and temperature. Carbon nanofibers were characterised by high resolution scanning electron microscopy and X-ray photoelectron spectroscopy to assess the morphological properties. Then carbon nanofibers of both morphologies were used as substrates for Pt electrodeposition. High resolution scanning electron microscopy images showed that the Pt nanoparticles distribution was well controlled and the particles size went down to few nanometers. Pt/carbon nanofibers nanocomposites were tested as electrocatalysts for methanol oxidation reaction. Cyclic voltammetry in H2SO4 revealed a catalyst with a high surface area. Cyclic voltammetry in presence of methanol indicated a high electrochemical activity for methanol oxidation reaction and a good long time stability compared to a carbon black supported Pt catalyst.

Synthesis, structures, and properties of nine-, twelve-, and eighteen-membered N-benzyloxyethyl cyclic alpha-peptoids.

N-Benzyloxyethyl cyclic alpha-peptoids of various size were prepared and their conformational features were investigated by means of computational, spectroscopic, and X-ray crystallographic studies.

Total synthesis of bioactive peptides and depsipeptides from marine opisthobranch molluscs.

This chapter covers the synthetic aspects of both linear or cyclic peptides and depsipeptides isolated from opisthobranch molluscs. In many cases, synthetic effort not only determined the absolute stereostructure of these compounds but also made it possible to supply sufficient amounts for the evaluation of pharmacological activities. A summary of the synthetic work associated with each compound is reported after a short description of its natural source and biological properties. Discussion in the text concentrates on key reactions and synthetic efficiency.

Comparative investigation of the surface properties of commercial titanium dental implants. Part I: chemical composition.

The surfaces of five commercially available titanium implants (Brånemark Nobel Biocare, 3i ICE, 3i OSSEOTITE, ITI-TPS, and ITI-SLA) were compared by scanning electron microscopy, X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectroscopy. All five implant types were screw-shaped and fabricated from commercially pure (cp) titanium, but their surface properties differed both as regards surface morphology and surface chemical composition. The macro- and microstructure of the implant surfaces were investigated by scanning electron microscopy. The surfaces chemical composition was determined using the surface-sensitive analytical techniques of X-ray photoelectron spectroscopy and time-of-flight secondary ion spectrometry. Surface topographies were found to reflect the type of mechanical/chemical fabrication procedures applied by the manufacturers. The titanium oxide (passive) layer thickness was similar (5-6 nm) and typical for oxide films grown at or near room temperature. A variety of elements and chemical compounds not related to the metal composition were found on some implant types. They ranged from inorganic material such as sodium chloride to specific organic compounds believed to be due to contamination during fabrication or storage. The experimental findings are believed to make a contribution to a better understanding of the interplay between industrial fabrication procedure and physico-chemical implant surface properties.

Xanthones and flavonoids from Leiothrix curvifolia and Leiothrix flavescens.

8-Carboxymethyl-1,6-dihydroxy-3,5-dimethoxyxanthone, 8-carboxymethyl-1,5,6-trihydroxy-3-methoxyxanthone and 8-carboxymethyl-1,3,5,6-tetrahydroxyxanthone were isolated from the capitula of Leiothrix curvifolia and Leiothrix flavescens and characterized by spectroscopic methods, mainly 1D and 2D NMR experiments, as well as by electrospray mass spectrometry. Eight known flavonoids were also isolated and they were identified by 1D and 2D NMR experiments and comparison with literature data.

Alfalfa (Medicago sativa L.) flavonoids. 1. Apigenin and luteolin glycosides from aerial parts.

Nine flavones and adenosine have been identified in aerial parts of alfalfa, and their structures were established by spectral (FABMS and NMR) techniques. Five of the identified compounds, including apigenin 7-O-[beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranosyl]-4'-O-beta-D-glucuronopyranoside, apigenin 7-O-[2-O-feruloyl-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranosyl]-4'-O-beta-D-glucuronopyranoside, apigenin 7-O-[2-O-feruloyl-[beta-D-glucuronopyranosyl(1-->3)]-O-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranoside], apigenin 7-O-[2-O-p-coumaroyl-[beta-D-glucuronopyranosyl(1-->3)]-O-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranoside], and luteolin 7-O-[2-O-feruloyl-beta-D-glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranosyl]-4'-O-beta-D-glucuronopyranoside, have not been reported before in the plant kingdom. Additionally, five known compounds, including apigenin 7-O-beta-D-glucuronopyranoside, apigenin 4'-O-beta-D-glucuronopyranoside, apigenin 7-O-[beta-D- glucuronopyranosyl(1-->2)-O-beta-D-glucuronopyranoside], luteolin 7-O-beta-D-glucuronopyranoside, and adenosine, were identified.

Chemical synthesis of cross-linked purine nucleosides.

[reaction: see text] An efficient route to all of the possible cross-linked 2'-deoxypurines 1-3 has been developed by means of the Pd-mediated C-N bond formation in the key step. Utilizing this protocol, the synthesis of the first unnatural protected purine trimeric adduct 4 has been accomplished.

Starfish saponins, Part 53. A reinvestigation of the polar steroids from the starfish Oreaster reticulatus: isolation of sixteen steroidal oligoglycosides and six polyhydroxysteroids.

A reinvestigation of the starfish Oreaster reticulatus has led to the isolation of sixteen steroidal oligoglycosides and six polyhydroxysteroids. One steroidal monoglycoside has been identified as asterosaponin-1 [5], previously isolated from the same organism, and one pentaglycoside steroidal sulfate has been identified with the known ophidianoside F [1], previously isolated from starfish species of the family Ophidiasteridae. The novel pentaglycoside steroidal sulfates reticulatosides A [3] and B [4] represent the second examples of asterosaponins containing the 5 alpha-cholesta-9(11)-en-3 beta,6 alpha,20,22-tetraol aglycone. Of the remaining new steroidal oligoglycosides, the majority are characterized by the common (24S)-5 alpha-cholesta-3 beta,6 alpha,8,15 alpha,24-pentaol aglycone, with some having a sulfate group at C-6, and differing in the sugar moiety. Compounds 11, 12, 15, and 16 represent major departures from the more common structural features encountered in steroidal glycosides from starfish with the presence in 11 and 12 of a rare 5-O-methylgalactofuranosyl unit and in 15 and 16 of a 3-O-methyl-2-O-sulfate-xylopyranosyl unit. The latter was shown by nmr data combined with molecular dynamics calculations to exist in an 8:2 equilibrium mixture of the 1C4 and 4C1 conformations.

Microbial transformation of isoprenoid systems by means of fungi of Zoophthora genus--microbial transformation of compounds with alpha-campholenic system by means of fungus Zoophthora (Neopandora) sp.

Unsaturated ketones (4 and 10) and epoxides (2-3 and 8-9) were the main products of biotransformation performed by means of Zoophthora (Neopandora) phyllobii. Enantiospecificity of both reactions leading to these compounds strongly depends on the distance of reacting fragment of molecule from the chiral center at C-1'.

Starfish saponins, 52. Chemical constituents from the starfish Echinaster brasiliensis.

This paper reports an analysis of the chemical constituents from the Caribbean starfish Echinaster brasiliensis collected at Grand Bahama Island. This species is completely devoid of cyclic steroidal glycosides, previously isolated from two species of the genus Echinaster in place of the more common penta- and hexa-glycoside steroidal sulfates ("asterosaponins"). Two typical "asterosaponins" and ten glycosides of polyhydroxysteroids were instead isolated in relatively large amounts from E. brasiliensis. The asterosaponins include the known marthasteroside A1 [1] and the new brasiliensoside [2], while the glycosides of polyhydroxysteroids include seven new compounds (six monoglycosides and one diglycoside). The known echinasteroside A, previously found in Echinaster sepositus and in the related Henricia laeviuscula (both belonging to the family Echinasteridae), and laeviusculosides C and I from H. laeviuscula were also isolated. Most of the glycosides from E. brasiliensis are 3-O-beta-xylopyranosides of delta 4-3 beta,6 beta,8,15 alpha,16 beta pentahydroxysteroid aglycones, having different side chains and sometimes a sulfate group at C-15, structural features which are typical of steroidal glycosides from starfishes of the family Echinasteridae. Continuing the analysis of the constituents of E. brasiliensis, we have also isolated a series of anthraquinones, known animal pigments found only in echinoderms and particularly in Crinoidea and in the Echinasteridae family of Asteroidea.