Glycoside and peptide clustering around the octasilsesquioxane scaffold via photoinduced free-radical thiol-ene coupling. The observation of a striking glycoside cluster effect

Two series of multivalent octasilsesquioxane glyco- and peptido-conjugates were synthesized using the photoinduced free-radical thiol-ene coupling (TEC). The first series was obtained by coupling C-glycosylpropyl thiols and cysteine containing peptides with the known octavinyl octasilsesquioxane while the second series was obtained by reacting glycosyl thiols with a new octasilsesquioxane derivative displaying eight PEGylated chains functionalized with terminal allyl groups. The evaluation of the binding properties of mannoside and glucoside clusters toward Concanavalin A by Enzyme-Linked Lectin Assay (ELLA) revealed a modest glycoside cluster effect. On the other hand, the PEGylated POSS-based glycocluster featuring eight N-acetyl-glucosamine residues showed high affinity toward Wheat Germ Agglutinin to give a measured IC(50) at 3 nM. The calculated relative potency per number of sugar unit (rp/n) was superior to a value of 10(6), thus revealing the occurrence of a striking glycoside cluster effect.     

Allergen microarrays on high-sensitivity silicon slides

We have recently introduced a silicon substrate for high-sensitivity microarrays, coated with a functional polymer named copoly(DMA-NAS-MAPS). The silicon dioxide thickness has been optimized to produce a fluorescence intensification due to the optical constructive interference between the incident and reflected lights of the fluorescent radiation. The polymeric coating efficiently suppresses aspecific interaction, making the low background a distinctive feature of these slides. Here, we used the new silicon microarray substrate for allergy diagnosis, in the detection of specific IgE in serum samples of subjects with sensitizations to inhalant allergens. We compared the performance of silicon versus glass substrates. Reproducibility data were measured. Moreover, receiver-operating characteristic (ROC) curves were plotted to discriminate between the allergy and no allergy status in 30 well-characterized serum samples. We found that reproducibility of the microarray on glass supports was not different from available data on allergen arrays, whereas the reproducibility on the silicon substrate was consistently better than on glass. Moreover, silicon significantly enhanced the performance of the allergen microarray as compared to glass in accurately identifying allergic patients spanning a wide range of specific IgE titers to the considered allergens.     

Free-radical hydrothiolation of glycals: a thiol-ene-based synthesis of S-disaccharides

A method for the synthesis of a new family of 1-deoxy S-disaccharides has been established via free-radical hydrothiolation of glycals by sugar thiols (thiol-ene coupling). The photoinduced coupling between four tri-O-acetyl-d-glycals and three different sugar thiols reveals that the reaction efficiency and stereoselectivity are highly dependent on the stereochemistry of the OAc groups at C3 and C4 of the glycal.     

Riboswitches Based on Kissing Complexes for the Detection of Small Ligands

Biosensors derived from aptamers were designed for which folding into a hairpin shape is triggered by binding of the cognate ligand. These aptamers (termed aptaswitches) thus switch between folded and unfolded states in the presence and absence of the ligand, respectively. The apical loop of the folded aptaswitch is recognized by a second hairpin called the aptakiss through loop–loop or kissing interactions, whereas the aptakiss does not bind the unfolded aptaswitch. Therefore, the formation of a kissing complex signals the presence of the ligand. Aptaswitches were designed that enable the detection of GTP and adenosine in a specific and quantitative manner by surface plasmon resonance when using a grafted aptakiss or in solution by anisotropy measurement with a fluorescently labeled aptakiss. This approach is generic and can potentially be extended to the detection of any molecule for which hairpin aptamers have been identified, as long as the apical loop is not involved in ligand binding.     

Indirect proof: what is specific to this way of proving?

The study presented in this paper is part of a wide research project concerning indirect proofs. Starting from the notion of mathematical theorem as the unity of a statement, a proof and a theory, a structural analysis of indirect proofs has been carried out. Such analysis leads to the production of a model to be used in the observation, analysis and interpretation of cognitive and didactical issues related to indirect proofs and indirect argumentations. Through the analysis of exemplar protocols, the paper discusses cognitive processes, outlining cognitive and didactical aspects of students’ difficulties with this way of proving.     

The control of the growth of Pt clusters in solution: A way to prepare Pt particles of tailored size

The growth of Pt particles in mesitylene-solvated metal atoms, obtained by metal vapour synthesis (MVS), has been followed at two temperatures (−40 and 25 °C) by NMR DOSY technique. The addition of 1,3-divinyltetramethyldisiloxane (DVS) at different time allows to quench the growth process and to make the resulting thermally stable solutions suitable for the evaluation of the Pt particles size at that moment. These solutions can be conveniently used to prepare supported Pt systems containing Pt particles of tailored size.     

Time-resolved reflectance at null source-detector separation: improving contrast and resolution in diffuse optical imaging

We propose a novel approach to imaging in diffusive media based on time-resolved reflectance measurements at null source-detector separation. This approach yields better spatial resolution and contrast as compared to the classical approach, which typically employs a separation of 20-40 mm. Results are obtained by an analytical perturbation approach to diffusion theory and on Monte Carlo simulations. Practical implementation with state-of-the-art technology and performance of a complementary approach based on the use of small but not null source-detector separation are also discussed.