Minor cacospongionolide derivatives from the sponge Fasciospongia cavernosa

Together with the known cacospongionolide, three new related sesterterpenes have been isolated from the sponge Fasciospongia cavernosa, collected from the Northern Adriatic Sea. The structures of the new compounds were proposed on the basis of spectroscopic data.     

New sesterterpenes from Madagascan Lendenfeldia sponges

A new furanoterpene designated dehydrofurodendin and nine scalarane sesterterpenes of which four are new, were isolated from two different species of Madagascan sponges of the genus Lendenfeldia, both of which seem to be yet undescribed. The structure of the compounds was elucidated by interpretation of 1D and 2D NMR data. Dehydrofurodendin was found to be a potent inhibitor of HIV-1 RT. Several of the isolated scalaranes exhibited cyctotoxicity against several human tumor cells.     

Biotransformation of resveratrol: synthesis of trans-dehydrodimers catalyzed by laccases from Myceliophtora thermophyla and from Trametes pubescens

Laccases from different sources have been used, for the first time, for the selective oxidation of the stilbenic phytoalexin trans-resveratrol (3,5,4′-trihydroxystilbene, 1a) on a preparative scale. Specifically, the enzymes from Myceliophtora thermophyla and from Trametes pubescens gave the dehydrodimer 2a in 31 and 18% isolated yields, respectively. These results compare favorably with the reported data for the chemically catalyzed dimerization of 1a (18% yields). The antioxidant properties of 2a have also been investigated.     

Two new luffarin derivatives from the Adriatic Sea sponge Fasciospongia cavernosa

Together with the known luffarin V and 6Z-luffarin V, two new sesterterpenes (1a and 2), related to luffarins have been isolated from the sponge Fasciospongia cavernosa, collected in the Northern Adriatic Sea. The structures of the new compounds were proposed on the basis of spectroscopic data. The absolute stereochemistry of compound 1a was determined by application of Mosher's method.     

Structure and “oxidation behavior” of W24O70, a new member of the {103} CS series of tungsten oxides

Reduced tungsten trioxide crystals WO_3?x, formed by vapor transport from a preparation with bulk composition WO_?2.90, have been studied by X-ray diffraction and electron microscopy. A single-crystal X-ray investigation showed the existence of the ordered {103} CS-structure W₂₄O₇₀, a new member of the homologous series W_nO_3n?2. Electron diffraction patterns of crystal fragments, with a few exceptions, showed the presence of the W₂₄O₇₀ phase (composition WO_2.917). Lattice images, however, indicated a fairly ordered {103} CS-phase, W₂₄O₇₀, intergrown with slabs of WO₃ giving gross compositions of the examined crystals in the range WO_2.93WO_2.96. The wide WO₃ slabs were probably formed by an oxidation process during the preparation.     

Sesterterpene metabolites from the sponge Hyatella intestinalis

The sponge Hyatella intestinalis from the Gulf of California contains the new scalarane-related sesterterpenes hyatelones A-C and hyatolides A-B, together with the new scalaranes hyatolides C-E, hyatelactam, 12-O-deacetyl-19-epi-scalarin and the new norscalarane 12-O-deacetylnorscalaral B. The structures of the new metabolites have been established by spectroscopic analysis of the natural products and, in some instances, of their acetyl derivatives. The new compounds hyatelone A, 19,20-di-O-acetylhyatelone B, hyatolide A, 20-O-acetylhyatolide C, hyatelactam, and 12-O-deacetylnorscalaral B have shown activity as growth inhibitors of several tumor cell lines.     

Cytotoxic sesterterpenes, 6-epi-ophiobolin G and 6-epi-ophiobolin N, from marine derived fungus Emericella variecolor GF10

Two new sesterterpenes, 6-epi-ophiobolin G (1) and 6-epi-ophiobolin N (3), and six known ophiobolins were isolated from the extracts of the fungus, Emericella variecolor GF10, which was separated from marine sediment. The planar structures of the new compounds were deduced from analysis of the 2D NMR spectra, and the stereochemistry was determined by extensive examination of the NOESY spectrum. Additionally, the configuration of the C-6 proton in ophiobolin G (2) was revised from α to β, and the unsolved stereochemistry of ophiobolin H (4) was determined by its physicochemical evidence and the chemical correlation with ophiobolin K (8). Ophiobolin K (8) showed cytotoxic activity against various tumor cell lines, including adriamycin-resistant mouse leukemia cells (P388), with IC₅₀ of 0.27-0.65 μM.     

Novel rare-earth-containing manganites Ba4REMn3O12 (RE=Ce, Pr) with 12R structure

Novel rare-earth-containing manganites, Ba₄REMn₃O₁₂ (RE=Ce, Pr), with 12R structure, have been prepared by solid-state reaction. Although the phases are formed at 950°C, to obtain single-phase samples high temperatures (up to 1300°C) and long synthesis periods are needed.Their structure is built up from chains of BO₆ face-sharing and corner-sharing octahedra running along the c-axis giving a quasi-one-dimensional oxide. Every polyhedral column consists of (Mn₃O₁₂) units of three face-sharing octahedra, both ends connected by the three terminal oxygen atoms to three different (REO₆) octahedra. Mixed occupation of the three octahedral positions in the structure, (Mn(1), Mn(2) and Re), was not found. Vacancies are not observed, neither in the cationic sublattice nor in the oxygen one. Thus, as in all the other 1-D manganites, the oxidation state of manganese ions seems to be four, as the rare-earth valence is. High-resolution electron microscopy suggests the eventual existence of ordered polytypes for different compositions, which could be stabilized by adjusting the thermodynamic conditions.     

On the conformational characteristics of the O,O,O-trimethyl selenophosphate molecule

Spectroscopic and theoretical studies were carried out for O,O,O-trimethyl selenophosphate molecule. DFT structural and vibrational calculations were performed at 6-311++G^∗∗ level. Ar/matrix-FTIR spectra were recorded. A coexistence of different conformers with C₃ and C₁ symmetries was detected at different temperatures. Spectral evidence of a lower energy C_s conformer was found. These conclusions are consistent with the results from DFT calculations. A tentative assignment of the features observed in the Ar/matrix-FTIR spectra is proposed.     

Transformation of 2,4-dichlorophenol by H2O2/UV-C, Fenton and photo-Fenton processes: Oxidation products and toxicity evolution

In the present study, H₂O₂/UV-C, Fenton and photo-Fenton treatment of 2,4-dichlorophenol was compared in terms of oxidation products and acute toxicity. The oxidation products were identified by gas chromatography-mass spectroscopy, high performance liquid chromatography and ion chromatography, whereas changes in acute toxicity were evaluated by the Vibrio fischeri luminescence inhibition assay. H₂O₂/UV-C and photo-Fenton processes ensured complete 2,4-dichlorophenolremoval, detoxification and significant mineralization. Hydroquinone and formic acid were identified as the common oxidation products of the studied advanced oxidation processes investigated. 3,5-dichloro-2-hydroxybenzaldehyde, phenol, 4-chlorophenol and 2,5-dichlorohydroquinone were identified as the additional H₂O₂/UV-C oxidation products of 2,4-dichlorophenol. Acute toxicity decreased with decreasing 2,4-dichlorophenol and increasing chloride release.     

N,N-Ethylene-bridged flavinium salts derived from l-valinol: synthesis and catalytic activity in H2O2 oxidations

Three chiral N¹,N¹⁰-ethylene-bridged flavinium salts with a stereogenic centre derived from l-valinol are prepared and investigated as oxidation catalysts. These salts efficiently catalyse chemoselective H₂O₂ oxidation of sulfides to sulfoxides and the oxidation of 3-phenylcyclobutanone to the corresponding lactone at room temperature. The flavinium salts react with hydrogen peroxide to form flavin-10a-hydroperoxide, which is the agent responsible for oxidation of the substrate.     

Smectic E,C and A free radicals

Some new paramagnetic liquid crystals are described. Their mesophases have been identified, by isomorphism with known phases, as smectic mesophases of types S_E, S_C and S_A.     

Etude cristallographique des termes n = 4,5, 5 et 6 des séries (La,Ca)nTinO3n+2, (Nd,Ca)nTinO3n+2 et Can(Ti,Nb)nO3n+2

The homologous phases corresponding to the formula A_nB_nO_3n+2 observed in the systems: La₂Ti₂O₇CaTiO₃, Nd₂Ti₂O₇CaTiO₃ and Ca₂Nb₂O₇CaTiO₃, have a structure derived from the structure of perovskite by periodic crystallographic shears, which delimitate n octahedra thick sheets. In the [0 1 0]1 direction, the sheets are following each other with two types of arrangement.Crystals of terms n = 4,5, 5 and 6 were investigated by X-ray diffraction. According to the type of arrangement of the sheets, the phases studied have either an orthorhombic symmetry or a monoclinic symmetry, this last one giving rise to merohedral twins.     

Synthesis of homologously pure bacteriochlorophyll-e and f analogues from BChls-c/d via transformation of the 7-methyl to formyl group and self-aggregation of synthetic zinc methyl bacteriopheophorbides-c/d/e/f in non-polar organic solvent

Homologously pure methyl bacteriopheophorbides-e and f (BPhes-e/f_M) were prepared from modification of naturally occurring bacteriochlorophylls-c and d (BChls-c/d), respectively, by transformation of the methyl to formyl group at the 7-position. The absolute configuration of the 1-hydroxyethyl group at the 3-position of (Zn-)BPhes-e/f_M was determined from comparison with structurally known BChl-c/d epimers. Visible spectra of synthetic (Zn-)BPhe-c/d/e/f_M showed that the 7¹-oxidation and the 8²/12¹/20-methylation affected Soret, Q_x and Q_y bands of both the monomeric (in a polar organic solvent) and oligomeric species (in a non-polar solvent).     

New synthesis of N-substituted benz[g]isoquinoline-3,5,10(2H)-triones

Various N-substituted benz[g]isoquinoline-3,5,10(2H)-triones 7 were prepared starting from vitamin K₃ (menadione) 9. The key steps involve substitution of a benzylic bromide by a primary amine and intramolecular condensation across the ester moiety of a (3-bromomethyl-naphth-2-yl)acetate 8 followed by oxidation with cerium(IV) ammonium nitrate (CAN) and spontaneous dehydrogenation, resulting in the title compounds 7. A selection of the synthesised new compounds was tested in vitro against Mycobacterium tuberculosis.     

1,9-Bis(N,N-dimethylaminomethyl)dipyrromethanes in the synthesis of porphyrins bearing one or two meso substituents

A synthesis of 5,15-disubstituted zinc-porphyrins has been developed that employs condensation of a 1,9-bis(N,N-dimethylaminomethyl)dipyrromethane+a dipyrromethane in refluxing ethanol containing zinc acetate followed by oxidation with DDQ. The N,N-dimethylaminomethylation of the dipyrromethane was achieved via Eschenmoser's reagent (N,N-dimethylmethyleneammonium iodide) in CH₂Cl₂ at room temperature. The synthesis is compatible with diverse substituents (e.g., alkyl, aryl, ester, acetal) and enables rapid synthesis of trans-AB-, A₂-, and A-porphyrins. The synthesis of >40 zinc porphyrins has been surveyed; 13 zinc porphyrins were isolated in yields of 5-20% without detectable scrambling.     

Identification of in vivo nitrosylated phytochelatins in Arabidopsis thaliana cells by liquid chromatography-direct electrospray-linear ion trap-mass spectrometry

Reversed-phase liquid chromatography (RPLC) and electrospray (ESI)-linear ion trap (LIT) mass spectrometry was applied to the direct characterization of in vivo S-nitrosylated (SNO) phytochelatins (PCs) expressed in cadmium-stressed Arabidopsis thaliana cells. Cys-nitrosylation is under discussion as in vivo redox-based post-translational modification of proteins and peptides in plants in which the –NO group is involved as signal molecule in different biological functions. The gas-phase ion chemistry of in vivo and in vitro generated SNO-PC_s was compared with the aim of evaluating NO binding stability and improving MS knowledge about peptide nitrosation. Using RPLC separation and ESI-LIT-MS, mono-nitrosylated PCs were identified in in vivo cadmium treated A. thaliana cells without derivatization. The in vivo binding of the NO group to PC₂, PC₃ and PC₄ resulted to occur selectively on only one cystein residue. The fragmentation pathway energies of the in vitro GSNO-generated NO-PCs with respect to the in vivo NO-PCs were investigated, suggesting the presence of a different internal stability for these molecules. By carrying out MS² experiments on these quasi-symmetric peptides, the different stability degree of the NO group was demonstrated to be correlated with the PC chain length. In addition, the data obtained highlight a putative role of the adjacent Glu/Cys motif in the gas-phase stability of the NO-containing molecule.     

Synthesis, Mo-valence state, thermal stability and thermoelectric properties of SrMoO3−xNx (x>1) oxynitride perovskites

Oxynitrides of the general composition SrMoO_3−xN_x (x>1) were synthesized by thermal ammonolysis of crystalline SrMoO₄. According to neutron and X-ray diffraction experiments, the materials crystallize in the cubic perovskite structure (space group Pm3¯m). X-ray absorption spectroscopy (XAS) shows evidence of local distortions of the Mo(O,N)₆ octahedra. The oxidation states of Mo determined by X-ray absorption near edge structure (XANES) spectroscopy are slightly lower than that calculated from the oxygen/nitrogen(O/N) content. The disagreement arises from the higher covalence of the Mo-N bonding when compared to the Mo-O bonding (“chemical shift”). The electrical transport properties of the samples are strongly different from SrMoO₃. It was found that the conductivity of the samples decreases with increasing nitrogen content. The Seebeck coefficient values are up to three times higher than those of SrMoO₃.     

Concise synthesis of two trisaccharides related to the saponin isolated from Centratherum anthelminticum

Chemical synthesis of two trisaccharides related to the saponin isolated from Centratherum anthelminticum is reported. Stereoselective, high-yielding glycosylation strategies were developed using H₂SO₄ immobilized on silica for activation of trichloroacetimidate donors, or in conjunction with N-iodosuccinimide for activation of a thioglycoside. A late stage TEMPO-mediated oxidation was performed for the formation of the required uronic acid moiety.     

An in situ oxidation route to fabricate graphene nanoplate-metal oxide composites

We report our studies on an improved soft chemical route to directly fabricate graphene nanoplate-metal oxide (Ag₂O, Co₃O₄, Cu₂O and ZnO) composites from the in situ oxidation of graphene nanoplates. By virtue of H⁺ from hydrolysis of the metal nitrate aqueous solution and NO₃⁻, only a small amount of functional groups were introduced, acting as anchor sites and consequently forming the graphene nanoplate-metal oxide composites. The main advantages of this approach are that it does not require cumbersome oxidation of graphite in advance and no need to reduce the composites due to the lower oxidation degree. The microstructures of as-obtained metal oxides on graphene nanoplates can be dramatically controlled by changing the reaction parameters, opening up the possibility for processing the optical and electrochemical properties of the graphene-based nanocomposites.