Stereoselective synthesis of 2,3-epoxy alcohols mediated by a remote sulfinyl group

The influence of the sulfinyl group as a chiral auxiliary in the stereoselective addition of oxiranyllithiums to (S)-2-p-tolylsulfinylbenzaldehyde has been studied. All reactions evolve with retention of configuration at the starting lithiated carbon. Completely stereoselective additions have been observed when configurations at sulfur and the lithiated carbon are different (matched pair), whereas variable dr's values (ranging between 52:48 and >99:<1%) when they are identical (mismatched pair).     

Doubly diastereoselective conjugate addition of enantiopure lithium amides to enantiopure N-enoyl oxazolidin-2-ones: a mechanistic probe

The doubly diastereoselective conjugate addition of the antipodes of lithium N-benzyl-N-(α-methylbenzyl)amide to a range of enantiopure N-enoyl oxazolidin-2-ones has been used as a mechanistic probe to determine that the reactive conformation is the anti-s-cis form. The β-amino carbonyl products resulting from these conjugate addition reactions are useful templates for further elaboration into an α,β,α-pseudotripeptide.     

Poly(ε-caprolactone) modified by functional groups: Preparation and chemical–physical investigation

Functionalization of polymers is a particular relevant approach in the field of biodegradable polymers, where modifications are often required to allow these materials to replace more conventional, not biodegradable polymers in a wider range of applications. This article will report on functionalization of poly(ε-caprolactone) with unsaturated monomers bearing either anhydride groups (PCL-g-(MA-GMA)) or tertiary amines (PCL-g-DMAEA), obtained through radical grafting in a Brabender mixer. Crystallization kinetics parameters have been determined with several techniques (rheology, optical microscopy and differential scanning calorimetry) and the results obtained are in good agreement. It was observed that the crystallization rate significantly increases in the case of the modified polymers.     

Liquid-crystalline rigid-core semiconductor oligothiophenes: influence of molecular structure on phase behaviour and thin-film properties

The design, synthesis and properties of liquid-crystalline semiconducting oligothiophenes containing dithienothiophene (DTT), benzothiadiazole (BTZ) and carbazole (CBZ) rigid cores are described. The effect of molecular structure (shape, size and substitution) on their thermal behaviour and electrical properties has been investigated. Polarised optical microscopy (POM) and differential scanning calorimetry (DSC) analyses have revealed highly ordered smectic mesophases for most of the newly synthesised compounds. X-ray diffraction (XRD) studies performed at various temperatures have shown that the smectic order is retained in the crystalline state upon cooling across the transition temperature, affording cast films with a more favourable morphology for FET applications.     

Solvent Extraction: Structure of the Liquid–Liquid Interface Containing a Diamide Ligand

Knowledge of the (supra)molecular structure of an interface that contains amphiphilic ligand molecules is necessary for a full understanding of ion transfer during solvent extraction. Even if molecular dynamics already yield some insight in the molecular configurations in solution, hardly any experimental data giving access to distributions of both extractant molecules and ions at the liquid–liquid interface exist. Here, the combined application of X‐ray and neutron reflectivity measurements represents a key milestone in the deduction of the interfacial structure and potential with respect to two different lipophilic ligands. Indeed, we show for the first time that hard trivalent cations can be repelled or attracted by the extractant‐enriched interface according to the nature of the ligand.     

Design of a functional membrane protein by engineering a heme-binding site in glycophorin A

We have designed a functional model membrane protein by engineering a bis-Histidine heme-binding site into a natural membrane protein, glycophorin A (GpA), structurally characterized by the dimerization of a single transmembrane helix. Out of the 32 residues comprising the transmembrane helix of GpA, five amino acids were mutated; the resulting protein, ME1, has been characterized in dodecyl phosphocholin (DPC) micelles by UV-vis, CD spectroscopy, gel electrophoresis, and analytical ultracentrifugation. ME1 binds heme with sub-micromolar affinity and maintains the highly helical secondary structure and dimeric oligomerization state of GpA. The ME1-Heme complex exhibits a redox potential of -128 +/- 2 mV vs SHE, indicating that the heme resides in a hydrophobic environment and is well shielded from the aqueous phase. Moreover, ME1 catalyzes the hydrogen peroxide dependent oxidation of organic substrates such as TMB (2,2',5,5'-tetramethyl-benzidine). This protein may provide a useful framework to investigate how the protein matrix tunes the cofactor properties in membrane proteins.     

Bioadhesive properties of a polyaminoacidic hydrogel: evaluation by ATR FT-IR spectroscopy

The bioadhesive properties of a novel chemical hydrogel based on a polymer of protein-like structure, have been investigated by using ATR FT-IR spectroscopy. In particular, the copolymer PHG obtained by partial derivatization of PHEA with GMA was chemically crosslinked by UV irradiation at 313 nm. Crosslinked PHG was treated with water to obtain a swelled sample, named PHG-UV gel, that was brought into contact with a phosphate buffer/citric acid solution at pH 7.0 in the absence or in the presence of mucin at various concentrations (0.01, 0.1 and 1 wt.-%). Preliminary dynamic swelling studies have evidenced the occurrence of an interaction between the PHG-UV gel and the glycoprotein. This result was confirmed by ATR FT-IR measurements. A diffusion model using a solution of Ficks' second law was employed to determine the diffusion coefficient of water into PHG-UV gel as a consequence of adsorption and/or interdiffusion which occur at the PHG-UV gel/mucin solution interface. Experimental results suggest a potential use of PHG-UV gel to prepare bioadhesive devices.     

Certification of nitrate in spinach powder reference material SPIN-1 by high-precision isotope dilution GC–MS

A high-precision exact-matching quadruple isotope dilution method (ID⁴MS) was employed for the quantitation of nitrate in an air-dried spinach powder Certified Reference Material (CRM). The analyte was extracted in hot water following addition of ¹⁵NO\({}_{3}^{-}\) internal standard. The blend was then treated with sulfamic acid to remove nitrite and with triethyloxonium tetrafluoroborate to promote aqueous conversion of nitrate into volatile EtONO₂. The derivative was analyzed by headspace GC–MS with 3-min elution time. The method performance was validated with a series of tests which demonstrated adequate selectivity and ruggedness. This method supported the development of novel SPIN-1 CRM giving a modest contribution to its uncertainty (u_char = 0.85%). With respect to previous attempts, the SPIN-1 was proven stable, homogeneous (u_hom = 0.44%), and suitable for spinach monitoring under EU regulations. On dried basis, the nitrate content of SPIN-1 was found to be 22.53 ± 0.43 mg/g (U_c = 1.9%, k = 2). The material was also used in an inter-laboratory study where four laboratories employed a total of ten measurement methods.

SPIN-1 Certified Reference Material for nitrate in spinach powder