Synthesis of NMP/RAFT inifers and preparation of block copolymers

Two different initiator/transfer agents (inifers) containing an alkoxyamine and a dithiobenzoate were synthetized and used to trigger out either reversible addition‐fragmentation chain transfer (RAFT) polymerization or nitroxide‐mediated polymerization (NMP). α‐Dithiobenzoate‐ω‐alkoxyamine‐difunctional polymers were produced in both cases which were subsequently used as precursors in the formation of block copolymers. This synthetic approach was applied to N‐isopropylacrylamide (NIPAM) or polyethylene oxide methacrylate (EOMA) to form α,ω‐heterodifunctional homopolymers via RAFT at 60°C which were chain extended with styrene by activating the alkoxyamine moiety at 120°C. Under such temperature conditions, it is proposed that a tandem NMP/RAFT polymerization is initiated producing a simultaneous growth of polystyrene blocks at both chain‐ends. Self‐assembled nanostructures of these amphiphilic block copolymers were evidenced by scanning electron microscopy. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Inverse colloidal crystal membranes for hydrophobic interaction membrane chromatography

A collaborative study on the robustness and portability of a capillary electrophoresis‐mass spectrometry method for peptide mapping was performed by an international team, consisting of 13 independent laboratories from academia and industry. All participants used the same batch of samples, reagents and coated capillaries to run their assays, whereas they utilized the capillary electrophoresis‐mass spectrometry equipment available in their laboratories. The equipment used varied in model, type and instrument manufacturer. Furthermore, different types of sheath‐flow capillary electrophoresis–mass spectrometry interfaces were used. Migration time, peak height and peak area of ten representative target peptides of trypsin‐digested bovine serum albumin were determined by every laboratory on two consecutive days. The data were critically evaluated to identify outliers and final values for means, repeatability (precision within a laboratory) and reproducibility (precision between laboratories) were established. For relative migration time the repeatability was between 0.05 and 0.18% RSD and the reproducibility between 0.14 and 1.3% RSD. For relative peak area repeatability and reproducibility values obtained were 3–12 and 9–29% RSD, respectively. These results demonstrate that capillary electrophoresis‐mass spectrometry is robust enough to allow a method transfer across multiple laboratories and should promote a more widespread use of peptide mapping and other capillary electrophoresis‐mass spectrometry applications in biopharmaceutical analysis and related fields.     

Photooxidation of Tryptophan Leading to 2‐Aminoacetophenone – A Possible Reason for the Untypical Aging Off‐flavor in Wine

2‐Aminoacetophenone (AAP) was recognized as the key compound for the so‐called untypical aging off‐flavor (UTA) in Vitis vinifera wines. In this study, it was shown that AAP can be formed by photooxidation of free and protein‐bound tryptophan (TRP) in combination with a subsequent storage in model wine. Solutions of TRP and lysozyme were exposed to artificial sunlight both in the presence and in the absence of the photosensitizer riboflavin. Aliquots of the irradiation batches were stored in model wine solutions containing tartaric acid, sulfite and ethanol in different combinations. AAP formation could be identified from both free and bound (lysozyme) TRP, while free TRP resulted in higher yields. The presence of riboflavin during irradiation generally favored the AAP formation. AAP formation increased with increasing irradiation times, but AAP was not detectable, if TRP was directly incubated in model wine. Not only the irradiation time but also the storage time of model wines favored the formation of AAP. Concerning the model wine composition, it became evident that the presence of tartaric acid resulted in the highest AAP formation during storage.     

Divergent synthetic approach to 6'-modified α-GalCer analogues

A synthetic approach is presented for the synthesis of galacturonic acid and D-fucosyl modified KRN7000. The approach allows for late-stage functionalisation of both the sugar 6'-OH and the sphingosine amino groups, which enables convenient synthesis of promising 6'-modified KRN7000 analogues.     

Ruthenium-catalyzed oxidative synthesis of 2-pyridones through C-H/N-H bond functionalizations

An inexpensive ruthenium catalyst enabled oxidative annulations of alkynes by acrylamides with ample scope, which allowed for the preparation of 2-pyridones employing various electron-rich and electron-deficient acrylamides as well as (di)aryl- and (di)alkyl-substituted alkynes.     

Synthesis, spectral, thermal and magnetic studies of Mn(II), Ni(II) and Cu(II) complexes with some benzopyran-4-one Schiff bases

The Schiff bases of N(2)O(2) dibasic ligands, H(2)La and H(2)Lb are prepared by the condensation of ethylenediamine (a) and trimethylenediamine (b) with 6-formyl-7-hydroxy-5-methoxy-2-methylbenzopyran-4-one. Also tetra basic ligands, H(4)La and H(4)Lb are prepared by the condensation of aliphatic amines (a) and (b) with 6-formyl-5,7-dihydroxy-2-methylbenzopyran-4-one. New complexes of H(4)La and H(4)Lb with metal ions Mn(II), Ni(II) and Cu(II) are synthesized, in addition Mn(II) complexes with ligands H(2)La and H(2)Lb are also synthesized. Elemental and thermal analyses, infrared, ultraviolet-visible as well as conductivity and magnetic susceptibility measurements are used to elucidate the structure of the newly prepared metal complexes. The structures of copper(II) complexes are also assigned based upon ESR spectra study. All the complexes separated with the stoichiometric ratio (1:1) (M:L) except Mn-H(4)La and Mn-H(4)Lb with (2:1) (M:L) molar ratio. In metal chelates of the type 1:1 (M:L), the Schiff bases behave as a dinegative N(2)O(2) tetradentate ligands. Moreover in 2:1 (M:L) complexes, the Schiff base molecules act as mono negative bidentate ligand and binuclear complex is then formed. The Schiff bases were assayed by the disc diffusion method for antibacterial activity against Staphylococcus aureus and Escherichia coli. The antifungal activity of the Schiff bases was also evaluated against the fungi Aspergillus flavus and Candida albicans.