Titanium complexes bearing carbamato ligands as catalytic precursors for propylene polymerization reactions

This report describes propylene polymerization reactions with titanium complexes bearing carbamato ligands, Ti(O₂CNMe₂)Cl₂ ( I ) and Ti(O₂CR₂)₄ [R₂ = NMe₂ ( II ), NEt₂ ( III ) and ( IV )]. Combinations of these complexes and MAO form catalysts for the synthesis of atactic polypropylene, as confirmed by FT‐IR, DSC and ¹³C NMR analysis. Effects of main reaction parameters on the catalyst activity were studied including the type of complex, solvent, temperature, and the [Al]/[Ti] molar ratio. The highest activity was observed when chlorobenzene was used as a solvent and AlMe₃‐depleted MAO was employed as a cocatalyst. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4095–4102     

Sensitive detection of hydroxymethylcytosine levels in normal and neoplastic cells and tissues

A new sensitive analytical method using capillary electrophoresis with laser induced fluorescence (CE‐LIF) was applied for the simultaneous detection of DNA methylation and hydroxymethylation levels in human cancers of different origin. DNA hydroxymethylation, measured as 5‐hydroxymethylcytosine (5hmC) levels, was decreased in gliomas with mutation in the isocitrate dehydrogenase 1 (IDH1) gene when compared to IDH1‐wildtype gliomas. Independent from IDH1 mutation, 5hmC levels were decreased in lung carcinomas when compared to normal lung tissue. Reduced DNA hydroxymethylation was also observed upon dedifferentiation in cultured murine embryonic fibroblasts. Our data show that reduced DNA hydroxymethylation is related to cellular dedifferentiation and can be detected in various types of cancers, independent from the IDH1 mutation status. Quantitative determination of altered 5hmC levels may therefore have potential as a biomarker linked to cellular differentiation and tumorigenesis.     

Aromatic hydrocarbons, carbocyclic ligands spanning several oxidation states in both Main Group and transition elements. Recent advances with early transition d elements

In this paper some synthetic procedures to obtain (η⁶-arene)metal derivatives are reviewed. The metal-atom-arene-vapor co-condensation technique is the most appropriate to generate complexes of polycyclic aromatic hydrocarbons or heterocycles. As far as the aluminium halide-mediated synthesis is concerned, two classes of reaction are observed. When AlX₃ is used with a metal halide in the presence of an aromatic hydrocarbon in the absence of any reducing agent, AlX₃ can function as a dehalogenating agent, to give ionic compounds of general formula [M(η⁶-arene)n](AlX₄)_m, or it can add across the M---X bond with formation of M(μ-X)_nAlX_4−n systems. In both cases the metal displays its typical oxidation state. However, the use of AlX₃ in combination with aluminium (the Fischer-Hafner reducing system) affords ionic or covalent low-oxidation-state metal(η⁶-arene) complexes. Attention is focused on our most recent results concerning the synthesis, properties and reactivity of η⁶-arene derivatives of Group 4 and 5 elements, showing, inter alia, the first example of a tetraarylborate anion behaving as a 12-electron donor to one metal atom and low-valent η⁶-arene compounds as useful reagents in the inorganic and coordination chemistry of the corresponding metal in nonaqueous systems.     

Structure and cytotoxicity of phidianidines A and B: first finding of 1,2,4-oxadiazole system in a marine natural product

Two indole alkaloids, phidianidines A (1) and B (2), exhibiting an uncommon 1,2,4-oxadiazole ring linked to the indole system, have been isolated from the marine opisthobranch mollusk Phidiana militaris. The structures of the two metabolites have been elucidated by spectroscopic techniques. Phidianidines exhibit high cytotoxicity against tumor and nontumor mammalian cell lines in in vitro assays.     

Identification of protein surfaces by NMR measurements with a pramagnetic Gd(III) chelate.

Gd-diethylenetriamine pentaacetic acid-bismethylamide, Gd(DTPA-BMA), is shown to be a reagent suitable for the identification of protein surfaces. Compared to the conventionally used spin-label TEMPOL, Gd(DTPA-BMA) is a stronger relaxation agent, requiring lesser concentrations to achieve the same paramagnetic relaxation enhancement of solvent-exposed protein protons. It is also less hydrophobic and therefore less prone to specific binding to proteins. Relaxation enhancements predicted by a second-sphere interaction model correlated with experimental data recorded with ubiquitin, while the correlation with corresponding data recorded with TEMPOL was poor.     

One-Pot,Fluoride-Promoted Wittig Reaction

A one-pot, fluoride-promoted Wittig reaction was developed. The reactions of ethyl α-bromoacetate with aliphatic, aromatic, and heteroaromatic aldehydes in the presence of tri-n-butylphosphine and tetrabutylammonium fluoride produced α,β-unsaturated esters in good to excellent yields and E-stereoselectivity. Under the same conditions, reactions of ethyl α-bromopropionate, α-bromo acetonitrile, and α-bromoacetophenone with aliphatic and aromatic aldehydes in the presence of tri-n-butylphosphine and tetrabutylammonium fluoride produced the expected α,β-unsaturated derivatives in good E-stereoselectivity. The protocol was extended to semistabilized ylides and applied to the synthesis of some combretastatin analogs.