Survey of the Chemical Defence Potential of Diatoms: Screening of Fifty Species for α,β,γ,δ-unsaturated aldehydes

In recent years a negative influence of diatom-derived ,,,-unsaturated aldehydes (PUA) on the reproductive success of copepods and invertebrates has been suggested. Since adverse chemical properties of diatoms would question the traditional view of the marine food web, this defense mechanism has been investigated in detail, but the PUA-release by test organisms has only been determined in a few cases. The observed effects were nevertheless frequently discussed from a general point of view often leading to contradictory conclusions. We have examined the PUA-production of 50 diatom species (71 isolates) in order to provide a basis for the interpretation of laboratory and field results on the influence of diatom food on the reproductive success of their consumers. PUA-production is species and strain dependent. Thirty-six percent of the investigated species (38% of the cultivated isolates) release ,,,-unsaturated aldehydes upon cell disruption in concentrations from 0.01 to 9.8 fmol per cell. Thalassiosira rotula and Thalassiosira pacifica, major spring-bloom forming diatoms isolated from Roscoff (Bretagne, English Channel, France) and Puget Sound (Washington, USA) were among the PUA-producing strains.     

Organic phase PPO biosensor based on hydrophilic films of electropolymerized polypyrrole

We described herein, the construction of an organic phase enzyme electrode (OPEE) via polyphenol oxidase (PPO) entrapment within a hydrophilic polypyrrole film electrogenerated from on a new bispyrrolic derivative (1) containing a long hydrophilic spacer. The so-called “adsorption step procedure” was adopted for the preparation of the organic phase PPO biosensor. The amperometric detection of catechol was carried out in anhydrous chloroform at −0.2 V versus Ag/AgCl. The electroanalytical parameters of the biosensor strongly depend on its configuration and on the hydration state of the enzyme matrix. The best sensitivity obtained for catechol in chloroform was 15.6 mA M⁻¹ cm⁻².     

Adsorption of a weakly charged polymer on an oppositely charged colloidal particle: Monte Carlo simulations investigation

Monte Carlo simulations were used to investigate the conformational and electrical properties of isolated weak polyelectrolytes in the presence of an oppositely charged particle. Titrations curves were calculated to get an insight into the role of pH on the degree of ionization and conformation of isolated chains. The effect of ionic concentration and polyelectrolyte length on the titration curves was also investigated. The complex formation between the isolated polyelectrolyte and the oppositely charged particle was considered at different pH and ionic concentration values. The adsorption/desorption limit was calculated and the effect of the polyelectrolyte adsorption on the titration curves investigated. In particular, it was demonstrated that the presence of an oppositely charged particle clearly increases the degree of ionization of the weak polyelectrolyte and that ionic concentration plays a subtle role by increasing/reducing both the attractive energy between the polyelectrolyte and the particle and the polyelectrolyte degree of ionization.     

A triple spin-labeling strategy coupled with DEER analysis to detect DNA modifications and enzymatic repair

In a spin: Spin-labeled oligonucleotides produced by click chemistry can be studied by EPR, by using a DEER sequence. This was used to test a complex triple-labeling strategy with damaged DNA. Extensive and accurate analysis of DNA structure and enzymatic repair processes were performed after digestion by EndoIV. Modified DNA structures and DNA-protein interactions can now be readily studied.     

Leakage radiation microscopy of surface plasmons launched by a nanodiamond-based tip

Leakage-radiation microscopy of a thin gold film demonstrates the ability of an ensemble of fluorescent diamond nanoparticles attached onto the apex of an optical tip to serve as an efficient near-field surface-plasmon polariton launcher. The implementation of the nanodiamond-based tip in a near-field scanning optical microscope will allow for an accurate control on the launching position, thereby opening the way to scanning plasmonics.     

Characterization of multi-walled carbon nanotube electrodes functionalized by electropolymerized tris(pyrrole-ether bipyridine) ruthenium (II)

We synthesized new electropolymerizable [Ru(bpy)_nL_m](PF₆)₂ (L = 4,4 bis(3-pyrrol-1-ylpropyloxy)bipyridyl) derivatives. The introduction of electron donating ether groups in the bipyridine ligand induced a negative shift of the Ru(III)/(II) redox couple. The electrochemical behavior of complex Ru1 (n = 2, m = 1) and complex Ru2 (n = 0, m = 3) were compared using platinum and Multi-Walled Carbon Nanotube (MWCNT) electrode. Higher polymerization yields and surface concentrations were obtained at MWCNT electrodes. Furthermore, MWCNT electrodes increase polymer permeability and decrease the charge trapping phenomenon involved in the oxidation and reduction of the polypyrrolic skeleton of the Ru(II) functionalized polymers.     

Nickel Nanoparticles Supported on Silica of Low Surface Area. Hydrogen Chemisorption and TPD and Catalytic Properties

Nickel metal nanoparticles supported on silica of low surface area (15 m² g^-1) were prepared by reduction of nickel acetate by hydrazine in aqueous medium. Their gas-phase stability and surface properties depended on thermal pre-treatment under H₂ or air atmosphere. Small nickel particles (<10 nm), in oxidized or reduced state, are strongly resistant to reductive or oxidative treatment respectively. For H₂-treated catalysts, H₂ chemisorption and TPD results suggested the occurrence of spillover hydrogen between the metal nickel phase and silica. For air then H₂ treated catalysts, hydrogen spillover seemed to involve the NiO phase. The activity of the catalysts in gas-phase benzene hydrogenation also depended on the thermal pre-treatment. Pre-calcined then reduced catalysts exhibited higher TOFs than non pre-calcined catalysts, suggesting that the presence of NiO phase may have influenced the hydrogenation process.     

New dendrimer-peptide host-guest complexes: towards dendrimers as peptide carriers

Adamantyl urea and adamantyl thiourea modified poly(propylene imine) dendrimers act as hosts for N-terminal tert-butoxycarbonyl (Boc)-protected peptides and form chloroform-soluble complexes. Investigations with NMR spectroscopy show that the peptide is bound to the dendrimer by ionic interactions between the dendrimer outer shell tertiary amines and the C-terminal carboxylic acid of the peptide, and also through host-urea to peptide-amide hydrogen bonding. The hydrogen-bonding nature of the peptide-dendrimer interactions was further confirmed by using Fourier transform IR spectroscopy, for which the NH- and CO-stretch signals of the peptide amide moieties shift towards lower wavenumbers upon complexation with the dendrimer. Spatial analysis of the complexes with NOESY spectroscopy generally shows close proximity of the N-terminal Boc group of the peptide to the peripheral adamantyl groups on the dendrimer host. The influence of side-chain motif on interactions with the host is analyzed by using seven different N-Boc-protected tripeptides as guests for the dendrimer. Downfield shifts of up to 1.3 ppm were observed for the guest amide NH-proton signals. These shifts decreased with increasing 'bulkiness' of the amino acid side chains. Despite this, the dendrimer was capable of making multiple peptide-dendrimer complexes when presented with a library of seven peptides. The different peptides were all present in the host, which did not show specific preferences, and could be released under mild acidic conditions. These results show the general nature of the peptide-dendrimer interactions in the formation of either single- or multiple-peptide-dendrimer complexes.     

Synthesis and characterization of (co)polymers containing a phosphonate function for use in dental composites

Novel monomers 1a, 1b, in which a phosphonate function is incorporated in both aromatic rings, were synthesized from the addition reaction of tetraisopropyl [2,2′-disulfanyl-5,5′-thiodiphenyl]-1,1′-diphosphonate and diisopropyl (2-sulfanylphenyl)-1-phosphonate with the glycidylmethacrylate. Free radical homo- and copolymerizations of phosphonate monomers containing methacrylate groups were first carried out in bulk and in THF solution. They offered (co)polymers for potential use in dental resins, in high yields and moderate to high inherent viscosities. The components and structure of the (co)polymers were confirmed by FTIR, SEC, ¹H, ³¹P NMR spectra.

Thermal analysis by using differential scanning calorimetry indicated an amorphous structure of the (co)polymers obtained by polymerization in solution. Upon UV-radiation the composite resins have been synthesized by cross-linking reaction.     

Pyrene-adamantane-β-cyclodextrin: An efficient host–guest system for the biofunctionalization of SWCNT electrodes

The design of nanostructured biological architectures based on host–guest interactions between β-cyclodextrin and adamantane was investigated on SWCNT coatings using glucose oxidase (GOX) as biomolecule model. β-Cyclodextrin tagged GOX was immobilized on adamantane functionalized carbon nanotubes, deposited on platinum electrodes. Different functionalization techniques to attach “pyrene adamantane” on nanotubes were studied and compared in terms of the performances of the subsequently constructed glucose biosensors. The best results were obtained by dipping the nanotube deposit into a pyrene-adamantane solution followed by electropolymerization of the adsorbed pyrene monolayer. The constructed biosensor exhibited a good linear response toward glucose concentrations between 2 × 10⁻⁷ M and 1.6 × 10⁻³ M. The maximum current density and glucose sensitivity were 154.9 μA cm⁻² and 14.4 mA M⁻¹ cm⁻², respectively.