Facile formation of molybdenum(VI) monooxo aryloxides MoO(OAr)4-nCln from molybdenum dioxo dichloride

Molybdenum monooxo compoundsMoO(OAr)4-nCln (n=0-2, Ar=2,6-Me2C6H3 or 2,6-i-Pr2C6H3) have been synthesized starting from the dioxo precursor MoO2Cl2. The complexes are characterized spectroscopically and by X-ray diffraction. The formation mechanism likely involves phenol precoordination followed by addition across the Mo=O bond.     

A charge-transfer-induced spin transition in the discrete cyanide-bridged complex [[Co(tmphen)2]3[Fe(CN)6]2

A charge-transfer-induced spin transition (CTIST) is observed in the discrete cyanide-bridged complex, {[Co(tmphen)2]3[Fe(CN)6]2}. Single-crystal X-ray diffraction, 57Fe M?ssbauer spectroscopy, and magnetic susceptibility were used collectively to describe the oxidation states of the Co and Fe ions in this cluster as a function of temperature. This pentanuclear complex represents the first example of a CTIST at the discrete molecular level.     

Synthesis of 2,6-bridged piperazine-3-ones by N-acyliminium ion chemistry

Several 2-substituted and 2,5-disubstituted piperazine-3,6-diones were synthesized starting from readily available alpha-amino acids. After activation of a lactam carbonyl via introduction of a methoxycarbonyl group onto nitrogen, this carbonyl was selectively reduced. Treatment of the resulting urethane with protic acid generated the corresponding N-acyliminium ion, which was trapped by a nucleophilic C2-side chain to provide 2,6-bridged piperazine-3-ones. Several aromatic, heteroaromatic, and nonaromatic side chains were used as pi-nucleophiles. In addition, the effect of the presence of a C5-methyl group on the stereochemical outcome of the cyclization was examined.     

Beyond Schmittel and Myers-Saito cyclizations: rearrangements of 4-heteroatom-1,2-hexa-diene-5-ynes

The thermal rearrangements of 4-heteroatom-1,2-hexadiene-5-ynes (2) were studied at the BLYP/6-311+G//BLYP/6-31G level of theory. Cyclization of 2 to heteroatom-containing cyclopentadienyl structures (6) competes with the Claisen-type rearrangement to acyclic, allenic structures. Cyclizations to cyclobutene (4)- and cyclohexadiene (8)-derived heterocycles are not feasible as a result of high reaction barriers and lower-lying alternative pathways. [structure: see text]     

Dioscorealides and dioscoreanone,novel cytotoxic naphthofuranoxepins,and 1,4-phenanthraquinone from Dioscorea membranacea Pierre

[structure: see text] Commonly used among ingredients in Thai traditional anticancer preparations, the rhizome of Dioscorea membranacea Pierre was found potently cytotoxic and possibly contributed to such a therapeutic effect. Bioassay-guided isolation resulted in two novel cytotoxic naphthofuranoxepins, dioscorealides A (1) and B (2), and a new 1,4-phenanthraquinone, dioscoreanone (3). The structure determination, achieved mainly by means of NMR and CD spectral and X-ray crystallographic analyses, and cytotoxicity are discussed here.     

Nanofoaming in the surface of biopolymers by femtosecond pulsed laser irradiation

In this work, the nanostructuring induced in femtosecond (fs) laser irradiation of biopolymers is examined in self-standing films of collagen and gelatine. Irradiation by single 90 fs pulses at 800, 400 and 266 nm is shown to result in the formation of a modified layer with submicrometric size structures. The size and uniformity of the observed features are strongly dependent on irradiation wavelength and on the characteristics of the biopolymer (water content and mechanical strength). Examination of the films by laser induced fluorescence serves to assess the chemical modifications induced by laser irradiation, revealing changes in the emission bands assigned to the aromatic amino acid tyrosine and its degradation products. The results are discussed in the framework of a mechanism involving the generation of large free-electron densities, through multiphoton and avalanche ionization, which determine the temperature and stress distribution in the irradiated volume.     

Separation and Preconcentration by Dispersive Liquid�CLiquid Microextraction Procedure: Recent Applications

Dispersive liquid?Cliquid microextraction (DLLME) is a relatively novel miniaturized sample pre-treatment technique. DLLME has been applied for the analysis of a large variety of organic compounds and metal ions in different samples. This paper reviews the more recent applications of this procedure for sample preparation.     

Surface free energy of films of alkali-treated cellulose microfibrils from banana rachis

Cellulose microfibrils extracted by various alkaline treatments of vascular bundles from banana rachis were used to elaborate films. The films were comparatively studied to determine changes in polarity induced by various treatments. Atomic force microscopy was used to characterize the surface morphology of the films and transmission electron microscopy was employed to characterize the microfibrils used to elaborate the films. Contact angles were measured to determine surface free energy (SFE) and thermogravimetric analyses were carried out to determine changes in composition of the films. The results showed that the films of cellulose microfibrils prepared by the peroxide alkaline (PA) and peroxide alkaline-hydrochloric acid (PA-HCl) treatments had lower content of non-cellulosic constituents like xylose and had lower SFE than films of microfibrils treated with KOH-5. Furthermore, specimens treated with the most concentrated KOH solution (18 wt%) and sodium chloride presented the highest SFE and polar component.