C18 tetraynoic fatty acids and essential oil composition of Mkilua fragrans

The fatty acids 17,18-dihydroxyoctadeca-9,11,13,15-tetraynoic acid (mkiluaynoic acid A) and 18-hydroxyoctadeca-9,11,13,15-tetraynoic acid (mkiluaynoic acid B), 5,7,3',4'-tetrahydroxyflavanol, 3,4-dihydroxybenzoic acid and a mixture of stearic and oleic acids were isolated from fruits and stem barks of Mkilua fragrans (Annonaceae). Mkiluaynoic acid A exhibited antifungal activity against Candida albicans comparable with that of the standard antifungal agent Ketoconazole. Structural determination was achieved by analysis of spectroscopic data. The flower stalks yielded essential oils that mainly consisted of sesquiterpenoids as revealed by GC-MS analysis, whereby 14 sesquiterpenes and four other compounds were identified.     

Screening of protein-ligand interactions using dynamic protein-affinity chromatography solid-phase extraction-liquid chromatography-mass spectrometry

A novel methodology is shown enabling the screening of mixtures of compounds for their affinity to a receptor protein. The system presented, dynamic protein-affinity chromatography solid-phase extraction (DPAC-SPE), overcomes the limitations of the existing methods by performing an incubation of the His-tagged protein with a mixture of possible ligands, which are still in their native conditions. This is followed by a fully automated affinity trapping step, coupled on-line to an LC-MS system in order to detect and identify the bound ligands. The system has been optimized using a commercially available on-line SPE system, using the estrogen receptor alpha (ERalpha) as model protein. A representative range of ligands with sub-nanomolar to millimolar affinities has been identified successfully from a mixture. The weakest binder that can be identified is norethindrone (approximately K(d)=0.1-1mM). The same setup also provides the possibilities to measure EC50 curves of both weak and strong binders.     

Critical sets in parametric optimization

We deal with one-parameter families of optimization problems in finite dimensions. The constraints are both of equality and inequality type. The concept of a generalized critical point (g.c. point) is introduced. In particular, every local minimum, Kuhn-Tucker point, and point of Fritz John type is a g.c. point. Under fairly weak (even generic) conditions we study the set consisting of all g.c. points. Due to the parameter, the set is pieced together from one-dimensional manifolds. The points of can be divided into five (characteristic) types. The subset of nondegenerate critical points (first type) is open and dense in (nondegenerate means: strict complementarity, nondegeneracy of the corresponding quadratic form and linear independence of the gradients of binding constraints). A nondegenerate critical point is completely characterized by means of four indices. The change of these indices along is presented. Finally, the Kuhn-Tucker subset of is studied in more detail, in particular in connection with the (failure of the) Mangasarian-Fromowitz constraint qualification.     

Photoresponsive Formation of an Intermolecular Minimal G‐Quadruplex Motif

The ability of three different bifunctional azobenzene linkers to enable the photoreversible formation of a defined intermolecular two‐tetrad G‐quadruplex upon UV/Vis irradiation was investigated. Circular dichroism and NMR spectroscopic data showed the formation of G‐quadruplexes with K⁺ ions at room temperature in all three cases with the corresponding azobenzene linker in an E conformation. However, only the para–para‐substituted azobenzene derivative enables photoswitching between a nonpolymorphic, stacked, tetramolecular G‐quadruplex and an unstructured state after E–Z isomerization.     

MobileMath: exploring mathematics outside the classroom

Computer games seem to have a potential for engaging students in meaningful learning, inside as well as outside of school. With the growing availability of mobile handheld technology (HHT), a number of location-based games for handheld mobile phones with GPS have been designed for educational use. The exploitation of this potential for engaging students into meaningful learning, however, so far remains unexplored. In an explorative design research, we investigated whether a location-based game with HHT provides opportunities for engaging in mathematical activities through the design of a geometry game called MobileMath. Its usability and opportunities for learning were tested in a pilot on three different secondary schools with 60 12–14-year-old students. Data were gathered by means of participatory observation, online storage of game data, an online survey and interviews with students and teachers. The results suggest that students were highly motivated, and enjoyed playing the game. Students indicated they learned to use the GPS, to read a map and to construct quadrilaterals. The study suggests learning opportunities that MobileMath provides and that need further investigation.     

Evaluation of clean-up agents for total petroleum hydrocarbon analysis in biota and sediments

Petroleum hydrocarbons (oil) are common environmental contaminants. For risk assessment purposes, their concentrations in environmental matrixes, such as biota and soils/sediments are frequently determined by solvent extraction and subsequent analysis with gas chromatography (GC) equipped with flame ionization detection (FID) or mass spectrometry (MS). Because the total GC detector response is labeled as total petroleum hydrocarbon (TPH) concentration and matrix compounds (lipids, organic matter) will contribute to this response, proper extract clean-up is crucial. Still, the choice for a specific clean-up material during open column chromatography often seems arbitrary, since no comparative study on clean-up agents for TPH analysis is available. Here, such a study is described and it is demonstrated that none of the commonly used agents fulfills the requirements of complete matrix compound removal and TPH recovery. A novel column filled with (top-down) 1 g of 33% (w/w) 1 M NaOH-impregnated and 2.2 g of 7% (w/w) H₂SO₄-impregnated silica gel is recommended for cleaning-up biota extracts, as it fully removes extracted lipids and yields acceptable TPH recoveries of around 90%, based on a certified oil reference standard. For sediment extracts, most columns tested resulted in a negligibly low contribution of matrix compounds to the overall detector response, but 5% deactivated Florisil or 10% deactivated aluminum oxide are preferable, because these materials yield the highest (∼95%) TPH recoveries.