Medicinal Organometallic Chemistry: Designing Metal Arene Complexes as Anticancer Agents

The field of medicinal inorganic chemistry is rapidly advancing. In particular organometallic complexes have much potential as therapeutic and diagnostic agents. The carbon‐bound and other ligands allow the thermodynamic and kinetic reactivity of the metal ion to be controlled and also provide a scaffold for functionalization. The establishment of structure–activity relationships and elucidation of the speciation of complexes under conditions relevant to drug testing and formulation are crucial for the further development of promising medicinal applications of organometallic complexes. Specific examples involving the design of ruthenium and osmium arene complexes as anticancer agents are discussed.     

Genetically Encoded Bioluminescent Indicator for ERK2 Dimer in Living Cells

In this study, a genetically encoded bioluminescent indicator for ERK2 dimer was developed with the split Renilla luciferase complementation method, in which the formation of ERK2 dimer induces a spontaneous emission of bioluminescence in living cells. In response to extracellular stimuli, such as epidermal growth factor (EGF) or 17β‐estradiol (E2), extracellular signal‐regulated kinase 2 (ERK2) is phosphorylated by its upstream kinase MEK, and also phosphorylates its substrates in various regions of the cell, including the nucleus. Phosphorylated ERK2 is led to form its dimer, thereby transporting itself into the nucleus. We demonstrated with the indicator that stimulation with EGF or E2 induces the formation of ERK2 dimer in living MCF‐7 cells. The dynamics of this dimer formation was examined and discussed.     

Weak Attractive Ligand–Polymer and Related Interactions in Catalysis and Reactivity: Impact,Applications, and Modeling

The notion of weak attractive ligand–polymer interactions is introduced, and its potential application, importance, and conceptual links with “cooperative” ligand–substrate interactions are discussed. Synthetic models of weak attractive ligand–polymer interactions are described, in which intramolecular weak C? H???F? C interactions (the existence of which remains contentious) have been detected by NMR spectroscopy and neutron and X‐ray diffraction experiments. These C? H???F? C interactions carry important implications for the design of catalysts for olefin polymerization, because they provide support for the practical feasibility of ortho‐F???H_β ligand–polymer contacts proposed for living Group 4 fluorinated phenoxyimine catalysts. The notion of weak attractive noncovalent interactions between an “active” ligand and the growing polymer chain is a novel concept in polyolefin catalysis.     

Untersuchungen über Papaverin

Ohne Zusammenfassung     

Prädikatives und funktionales Denken in der Wahrscheinlichkeitsrechnung

In order to emphasize functional thinking in mathematical education, arguments are brought forward for an early and frequent use of tree diagrams in teaching stochastics. Since set and tree diagrams can be regarded as two sides of the same matter, Bayes’ theorem, which is strongly associated with predicative set diagrams, need not be dealt with explicitly any longer. Set diagrams are replaced by tree diagrams that are labelled in detail and by tree inversion as a functional instrument of dealing with conditioned probabilities. This technique is demonstrated by three typical problems in the context of conditioned probability. Finally, two letters by Pascal to Fermat are analysed in order to illustrate that predicative and functional approaches were already pursued in the early stages of probability calculus in the 17^th century.     

Synthesis of poly(ethylene oxide) with pending 2,2,6,6‐tetramethylpiperidine‐1‐oxyl groups and its further initiation of the grafting polymerization of styrene

A new stratagem for the synthesis of amphiphilic graft copolymers of hydrophilic poly(ethylene oxide) as the main chain and hydrophobic polystyrene as the side chains is suggested. A poly(ethylene oxide) with pending 2,2,6,6‐tetramethylpiperidine‐1‐oxyls [poly(4‐glycidyloxy‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl‐co‐ethylene oxide)] was first prepared by the anionic ring‐opening copolymerization of ethylene oxide and 4‐glycidyloxy‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl, and then the graft copolymerization of styrene was completed with benzoyl peroxide as the initiator in the presence of poly(4‐glycidyloxy‐2,2,6,6‐tetramethylpiperidine‐1‐oxyl‐co‐ethylene oxide). The polymerization of styrene was under control, and comblike, amphiphilic poly(ethylene oxide)‐g‐polystyrene was obtained. The copolymer and its intermediates were characterized with size exclusion chromatography, ¹H NMR, and electron spin resonance in detail. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3836–3842, 2006     

Determination of 17 kinds of banned organochlorine pesticides in water by activated carbon fiber-solid phase microextraction coupled with GC-MS.

Activated carbon fiber (ACF) as extraction fiber for solid-phase microextraction (SPME) and its application for the analysis of banned organochlorine pesticides (OCPs) were investigated. Firstly, ACF was activated by different concentration of zinc chloride, which indicated that ACF activated by 60% zinc chloride had a reasonable specific surface area, pore volume and pore distribution. Secondly, the parameters for the ACF-SPME procedure, the adsorption and desorption conditions, were also optimized when coupled with gas chromatography-mass spectrometry (GC-MS). Thirdly, the ACF-SPME was used to analyze 17 kinds of OCPs in water. The linearity of most pesticides was found to be between 0.2 and 50 microg/l with GC-MS under the selected ion monitoring (SIM) acquisition mode. The limits of detection (LOD) at the sub microg/l were obtained. The work demonstrated here shows that ACF is a promising alternative for the SPME procedure.     

4-Amino-imidazole durchThorpe-Cyclisierung

The alkylation of arylaminomethylenecyanamides1 or cyano-imidothiocarbamates2 with -halogen carbonyl compounds followed by base catalysed cyclization yields substituted 4-amino-imidazoles4. Imidazo[4,5-d]pyrimidones5, 6 and imidazo[4,5-b]pyridines7 can be obtained from4.