A new convenient synthesis of N-acyl-2-(dimethoxyphosphoryl)glycinates

Easily accessible N-acyl-2-triphenylphosphonioglycinate tetrafluoroborates react smoothly with trimethylphosphite in the presence of methyltriphenylphosphonium iodide to give N-acyl-2-(dimethoxyphosphoryl)glycinates in good or very good yields. The dimethoxyphosphorylglycinates may be isolated by column chromatography, or used directly for the Wadsworth-Emmons synthesis of α,β-dehydro-α-amino acids in a one-pot procedure without purification.     

Mixed Azines of Naloxone with Dihydromorphinone Derivatives

The mixed azines 4 and 5 were prepared by reaction of naloxazone ( 2 ) with either oxymorphone ( 6 ) or 14-O-methyloxymorphone ( 7 ) and tested in vitro using opioid receptor binding assays and in vivo using the AcOH-writhing test in mice. Compound 4 was found to be a partial agonist, while compound 5 was a potent opioid agonist with higher potency than morphine.     

High-performance liquid chromatographic determination of Levetiracetam in human plasma: comparison of different sample clean-up procedures

An accurate and precise high-performance liquid chromatographic method using diode array detection for the determination of the novel antiepileptic, Levetiracetam, has been developed. Three clean-up procedures for the analysis of Levetiracetam in human plasma were implemented and evaluated, namely solid-phase extraction, deproteinization by addition of organic solvents and formation of insoluble salts. Adenosine was used as the internal standard for all three sample pretreatment procedures. Among the several cartridges used for solid-phase extraction, the hydrophilic-lypophilic balance (Oasis) HLB) phase provides the best extraction yield of Levetiracetam, together with high precision. With the two other clean-up procedures involving plasma deproteinization by addition of methanol or zinc sulphate, lower sensitivity and precision of the assays were obtained. However, they are cheaper and faster when compared with the solid-phase extraction procedure.     

Aqueous dispersions of single-wall and multiwall carbon nanotubes with designed amphiphilic polycations

Poor solubility of single-walled and multiwalled carbon nanotubes (NTs) in water and organic solvents presents a considerable challenge for their purification and applications. Macromolecules can be convenient solubilizing agents for NTs and a structural element of composite materials for them. Several block copolymers with different chemical functionalities of the side groups were tested for the preparation of aqueous NT dispersions. Poly(N-cetyl-4-vinylpyridinium bromide-co-N-ethyl-4-vinylpyridinium bromide-co-4-vinylpyridine) was found to form exceptionally stable NT dispersions. It is suggested that the efficiency of macromolecular dispersion agents for NT solubilization correlates with the topological and electronic similarity of polymer-NT and NT-NT interactions in the nanotube bundles. Raman spectroscopy and atomic force and transmission electron microcopies data indicate that the polycations are wrapped around NTs forming a uniform coating 1.0-1.5 nm thick. The ability to wind around the NT originates in the hydrophobic attraction of the polymer backbone to the graphene surface and topological matching. Tetraalkylammonium functional groups in the side chains of the macromolecule create a cloud of positive charge around NTs, which makes them hydrophilic. The prepared dispersions could facilitate the processing of the nanotubes into composites with high nanotube loading for electronic materials and sensing. Positive charge on their surface is particularly important for biological and biomedical applications because it strengthens interactions with negatively charged cell membranes. A high degree of spontaneous bundle separation afforded by the polymer coating can also be beneficial for NT sorting.     

Determination of cadmium in mixtures with metal ions

A method for the determination of cadmium microamounts in mixtures with metallic ions withE _1/2 near toE _1/2 of cadmium is discussed. For higher selectivity cadmium was extracted in the form of the pyridin-thiocyanate complexes prior to polarography.

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Bestimmung von Cadmium(II) neben anderen Metallionen

Zusammenfassung Es wird eine polarographische Methode zur Bestimmung von Cd(II) neben anderen Metallionen mitE _1/2 naheE _1/2(Cd) diskutiert. Zur Erhöhung der Selektivität und Genauigkeit wird eine Pyridin-Thiocyanat-Extraktion vorgeschalten.

     

Synthesis of N-heterocyclic carbene precursors bearing biphenyl units and their use in ruthenium-catalyzed ring-opening metathesis polymerization

A range of new imidazolium and imidazolinium chlorides bearing biphenyl units on their nitrogen atoms was synthesized. They differed by the electron-withdrawing or -donating nature and the steric bulk of the substituents on their aromatic rings. These various N-heterocyclic carbene (NHC) precursors were combined with the [RuCl₂(p-cymene)]₂ dimer and potassium tert-butoxide to generate the corresponding ruthenium-arene complexes [RuCl₂(p-cymene)(NHC)] in situ. The catalytic activity of these species was investigated in the photoinduced ring-opening metathesis polymerization (ROMP) of cyclooctene. The results obtained confirmed the necessity of blocking the ortho-positions of the phenyl rings in the vicinity of the metal center in order to attain high catalytic efficiencies. They also showed that changing the steric and electronic properties of the substituents on the remote phenyl rings of the biphenyl units had no significant influence on the outcome of the polymerization.     

Characterization of low-energy chlorophylls in the PSI-LHCI supercomplex from Chlamydomonas reinhardtii. A site-selective fluorescence study

Almost all photosystem I (PSI) complexes from oxygenic photosynthetic organisms contain chlorophylls that absorb at longer wavelength than that of the primary electron donor P700. We demonstrate here that the low-energy pool of chlorophylls in the PSI-LHCI complex from the green alga Chlamydomonas reinhardtii, containing five to six pigments, is significantly blue-shifted (A(max) at 700 nm at 4 K) compared to that in the PSI core preparations from several species of cyanobacteria and in PSI-LHCI particles from higher plants. This makes them almost isoenergetic with the primary donor. However, they keep the other characteristic features of "red" chlorophylls: clear spectral separation from the bulk chlorophylls, big Stokes shift revealing pronounced electron-phonon coupling, and large homogeneous and inhomogeneous broadening of approximately 170 and approximately 310 cm(-1), respectively.     

Bioavailability, bioaccumulation and tolerance of chromium: consequences in the food chain of freshwater ecosystems

Many abiotic and biotic factors can influence the partitioning equilibrium of heavy metals, thus influencing metal impact on aquatic environments. Unicellular algal species release soluble organic substances able to complex metals. In our laboratory a Cr-tolerant strain was selected and isolated from a wild type strain of Scenedesmus acutus. The exudates released by the two strains counteracted the growth inhibition caused by Cr(VI) and the exudates of the Cr-tolerant strain were more effective. On the contrary, the exudates did not reduce chromium toxicity to the cladoceran Daphnia magna. The reduction of chromium effect on algae seems the consequence of an algae-specific interaction among Cr(VI), exudates and algal cells. Chromium uptake resulted to be energy-dependent since bioaccumulation rate in subdued light condition was lower than at high light intensity. The effect of Cr(VI) on algae changed depending on metabolism of the cells and in particular it seemed to be related to the bioaccumulation rate. Tolerance in the selected strain could not be ascribed to a lower uptake of chromium. The difference in sensitivity to chromium between the two strains was exploited to evaluate if tolerance acquired by algae could have consequences for Daphnia. After treatment with Cr(VI), the two strains of S. acutus were used as food source for D. magna. The results indicate that chromium is accumulated by algae in a form not available for daphnids and that Cr tolerance acquired by the algae can be of some advantage to the consumer organism.     

Gallium metal mediated allylation of carbonyl compounds and imines under solvent-free conditions

Gallium metal is effective in mediating the allylation of various carbonyl compounds and imines under solvent-free conditions, with the application of sonic energy, affording the corresponding homoallylic alcohols and amines. The imines themselves were also prepared under solventless conditions in high yield, thereby establishing a two-step solvent-free synthesis of homoallylic amines. In comparison, indium metal produced a mixture of the desired homoallylic secondary amine and the bis-allylated species via an iminium ion intermediate.