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61.
Maria Ana Castro Zulema D. Chaia Oscar E. Piro Fabio D. Cukiernik Eduardo E. Castellano Marcia Rusjan 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(7):m393-m395
The title compound, tetrakis(μ‐3,4,5‐triethoxybenzoato‐κ2O:O′)bis[(pyrazine‐κN)rhodium(II)](Rh—Rh), [Rh2(C13H17O5)4(C4H4N2)2], crystallizes on an inversion centre in the triclinic space group . The equatorial carboxylate ligands bridge the two RhII atoms, giving a binuclear lantern‐like structure. The pyrazine molecules occupy the two axial coordination sites. The phenyl rings are tilted by ca 10° with respect to the attached carboxylate groups. The pyrazine planes have a torsion angle of ca 19° around the Rh—N bond with respect to the plane of the nearer carboxylate group and are not coplanar with the Rh—Rh bond. 相似文献
62.
Barluenga J Ballesteros A Bernardo De La Rúa R Santamaría J Rubio E Tomás M 《Journal of the American Chemical Society》2003,125(7):1834-1842
Cyclization reactions of group 6 Fischer carbene complexes with cyclopentanone and cyclohexanone enamines are described. Enamine 3a undergoes thermal alpha,beta,beta'-annulation with alkenylcarbene complexes 1 and 2 (THF, 60 degrees C), affording semibullvalenes 5. The metalate intermediates 6, resulting from beta,beta'-annulation of the enamines 3a and 4a, were quantitatively formed by running the reaction in hexane at room temperature. Acid-promoted demetalation of 6 afforded endo-2-bicyclo[3.2.1]octen-8-ones 7 and endo/exo-2-bicyclo[3.3.1]nonen-9-ones 8 (endo/exo = 5:1). Using (S)-methoxymethylpyrrolidine-derived enamines 3b and 4b,c allowed highly enantioenriched cycloadducts endo-(+)-7 as well as endo-(-)-8 and exo-(-)-8 to be accessed. The non-heteroatom-stabilized carbene complex 10 was formed from complex 6 by Me(3)SiOTf-promoted elimination of the methoxy group, characterized by (13)C NMR, and transformed into the organic compounds 7, 7-d, and 11 as well as into bicyclo[3.2.1]octan-2,8-diones 14 and cycloheptanones 15. On the basis of this sequence, enantioenriched cycloheptanones (+)-15 were efficiently prepared in one pot from carbene complexes 2 and enamine 3b (51-55% yield, 91-96% ee). Extension of this work to simple Fischer carbene complexes 16 allowed an appropriate way to generate the nonstabilized pentacarbonyl[(phenyl(alkyl)carbene]tungsten complex 17 to be designed, for which the thermal and chemical behavior leading to compounds 18-21 is described. 相似文献
63.
Cornejo A Fraile JM García JI García-Verdugo E Gil MJ Legarreta G Luis SV Martínez-Merino V Mayoral JA 《Organic letters》2002,4(22):3927-3930
[formula: see text] A chiral pyridine-bis(oxazoline) ligand, functionalized with a vinyl group in the pyridine ring, can be polymerized with styrene and divinylbenzene to obtain supported chiral ligands. As proof of the usefulness of this supported ligands, the corresponding ruthenium complexes are catalysts for the cyclopropanation reaction of styrene with ethyl diazoacetate with up to 85% ee. 相似文献
64.
Eduardo Prez-Cordero Rosanna Buigas Nancy Brady Luis Echegoyen Claudia Arana Jean-Marie Lehn 《Helvetica chimica acta》1994,77(5):1222-1228
Reductive electrocrystallization at a constant current density (11.0–11.5 μA/cm2) of millimolar solutions of [M(bpy)3](PF6)2, where M = Fe, Ru, or Os, and bpy = 2,2′-bipyridine in acetonitrile containing 0.1M Bu4NPF6 results in the formation of dark crystals on the Pt cathode. The crystals grow as long, thin, and shiny needles having a hexagonal cross section of 0.1–0.5 mm in diameter. Combustion microanalyses results are consistent with the composition for [Fe(bpy)3], [Ru(bpy)3], and [Os(bpy)3]. In addition, the chromophores are conserved, as confirmed by recording both the electronic and the 1H-NMR spectra after reoxidation of the electrocrystals in humid air. The spectra are identical to those for authentic samples of [Fe(bpy)3]2+, [Ru(bpy)3]2+, and [Os(bpy)3]2+. A ratio of 2.0 ± 0.1 e?/molecule is observed upon completion of the controlled potential electrolysis of a solution of [M(bpy)3]2+, which results in the precipitation of a dark solid and the almost complete fading of the color of the original solution. Unexpectedly, the crystals do not exhibit an ESR signal. These data indicate the formation of novel materials, crystalline [Fe(bpy)3], [Ru(bpy)3], and [Os(bpy)3]. 相似文献
65.
Arelí Durón-Castellanos Vanesa Zazueta-Novoa Hortencia Silva-Jiménez Yolanda Alvarado-Caudillo Eduardo Peña Cabrera Roberto Zazueta-Sandoval 《Applied biochemistry and biotechnology》2005,121(1-3):279-288
Different soluble NAD+-dependent alcohol dehydrogenase (ADH) isozymes were detected in cell-free homogenates from aerobically grown mycelia of YR-1
strain of Mucor circinelloides isolated from petroleumcontaminated soil samples. Depending on the carbon source present in the growth media, multiple NAD+-dependent ADHs were detected when hexadecane or decane was used as the sole carbon source in the culture media. ADH activities
from aerobically or anaerobically grown mycelium or yeast cells, respectively, were detected when growth medium with glucose
added was the sole carbon source; the enzyme activity exhibited optimum pH for the oxidation of different alcohols (methanol,
ethanol, and hexadecanol) similar to that of the corresponding aldehyde (≈7.0). Zymogram analysis conducted with partially
purified fractions of extracts from aerobic mycelium or anaerobic yeast cells of the YR-1 strain grown in glucose as the sole
carbon source indicated the presence of a single NAD+-dependent ADH enzyme in each case, and the activity level was higher in the yeast cells. ADH enzyme from mycelium grown in
different carbon sources showed high activity using ethanol as substrate, although higher activity was displayed when the
cells were grown in hexadecane as the sole carbon source. Zymogram analysis with these extracts showed that this particular
strain of M. circinelloides has four different isozymes with ADH activity and, interestingly, one of them, ADH4, was identified also as phenanthrene-diol-dehydrogenase,
an enzyme that possibly participates in the aromatic hydrocarbon biodegradation pathway. 相似文献
66.
Reaction of a (237)Np(V) stock solution in the presence of oxalic acid, calcium chloride, and sodium hydroxide under hydrothermal conditions produces single crystals of a neptunium(V) oxalate, Na(2)NpO(2)(C(2)O(4))OH.H(2)O. The structure consists of one-dimensional chains running down the a axis and is the first example of a neptunium(V) oxalate compound containing hydroxide anions. 相似文献
67.
Hsu FF Turk J Shi Y Groisman EA 《Journal of the American Society for Mass Spectrometry》2004,15(1):1-11
Acylphosphatidylglycerol (Acyl-PG), a polar lipid class containing three fatty acyl groups, was isolated from Salmonella bacteria and characterized by tandem quadrupole and quadrupole ion-trap mass spectrometric methods with electrospray ionization. The structural characterization of the acyl-PG with various acyl groups (A-B/C-PG, where A not equal B not equal C) is based on the findings that the carboxylate anions (R(x)CO(2)(-)) arising from sn-2 (R(2)CO(2)(-)) is more abundant than that arising from sn-3' (R(3')CO(2)(-)), which is much more abundant than that arising from sn-1 (R(1)CO(2)(-)). This information provides a simple method for determination of the fatty acyl moieties and their positions in the molecule. The structural identification of the molecule can also be achieved by the findings that the fragment ion reflecting the ketene loss at sn-2 is more prominent than that reflecting the acid loss (i.e., [M - H - R'(2)CH=CO](-) > [M - H - R(2)CO(2)H](-)), while the ion arising from acid loss at sn-1 or sn-3' is, respectively, more abundant than the corresponding ketene loss (i.e., [M - H - R(1)CO(2)H](-) > [M - H - R'(1)CH=CO](-); [M - H - R(3')CO(2)H](-) > [M - H -R'(3')CH=CO](-)). The identity of the acyl moiety at sn-3' can be confirmed by an acyl-glycerophosphate anion observed in the product-ion spectrum obtained with a triple-stage quadrupole (TSQ) instrument, but not in that obtained with an ion-trap mass spectrometer (ITMS). However, the MS(2)-spectrum obtained with an ITMS is featured by the ion series that abundances of [M - H - R'(2)CH=CO - R(3)CO(2)H - 74](-) > [M - H - R'(2)CH=CO - R(1)CO(2)H - 74](-) z.Gt; [M - H - R'(1(or 3'))CH=CO - R(3'(or 1))CO(2)H - 74](-). This information also facilitates structural elucidation of the acyl-PG subclass that contains various acyl substituents. Structural identifications of molecular species having two identical fatty acyl substituents at sn-1, sn-2, or sn-3' or consisting of more than one isomeric structures are also demonstrated. The identities of the minor isomeric species in the molecules can be revealed by the aforementioned structural information arising from the various ion series combined. 相似文献
68.
The effects of addition of alkanols (ethanol, n-hexanol, and 3-ethyl-3-pentanol) on the micropolarity and microviscosity of the head group region in reverse micelles of AOT-heptane-water have been investigated by fluorescence probing methods (ANS fluorescence yield and TMADPH fluorescence anisotropy), complemented by the use of the solvatochromic probe E(T)(30) in absorption spectroscopy. For all the alkanols considered, ANS fluorescence in AOT reverse micelles (at W=3) is quenched by additive incorporation, being the effect elicited almost independent of the alkanol chain length and topology. As sensed by the E(T)(30) parameter, the micropolarity of the micelle surface increases, remains unmodified, and decreases upon addition of ethanol, 3-ethyl-3-pentanol, and hexanol, respectively. While ethanol barely modifies the fluorescence anisotropy of TMADPH, 3-ethyl-3-pentanol and n-hexanol addition strongly decrease it. The similarity of the tendencies of ANS data to TMADPH anisotropies and the differences between ANS data and E(T)(30) values would indicate that, at least for 3-ethyl-3-pentanol and n-hexanol, microviscosity, rather than micropolarity, must be considered to interpret the effect of the alkanols upon the fluorescent behavior of ANS. 相似文献
69.
Andrs Zelcer Zulema D. Chaia Fabio D. Cukiernik Oscar E. Piro Eduardo E. Castellano 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(3):m144-m146
The title compound, catena‐poly[[tetrakis(μ‐decanoato‐κ2O:O′)diruthenium(II,III)(Ru—Ru)]‐μ‐octanesulfonato‐κ2O:O′], [Ru2(C10H19O2)4(C8H17O3S)], is an octanesulfonate derivative of the mixed‐valence complex diruthenium tetradecanoate. The equatorial carboxylate ligands are bidentate, bridging two Ru atoms to form a dinuclear structure. Each of the two independent dinuclear metal complexes in the asymmetric unit is located at an inversion centre. The octanesulfonate anion bridges the two dinuclear units through axial coordination. The alkyl chains of the carboxylate and sulfonate ligands are arranged in a parallel manner. The global structure can be seen as infinite chains of polar moieties separated by a double layer of non‐polar alkyl groups, without interdigitation of the alkyl chains. 相似文献
70.
Fontana José D. Almeida Eduardo R. A. Baron Madalena Guimaraes Manoel F. Deschamps Francisco C. Schwartsmann Gllberto Cervi Armando C. Zanette Flávio Vilegas Janete LanÇas Fernando M. 《Applied biochemistry and biotechnology》1994,(1):295-313
The acetogenins are strongly bioactive natural compounds present in the bark, roots, leaves, and seeds of manyAnnonaceae plants. They are modified fatty acids and their cytotoxicities have been determined for different biological models including
the in vitro growth inhibition of several human cancer cell lines.
Very low acetogenin yield (< 0.1 g%) has been found previously in native phytobiomass, and we have now investigated the nonpredatory
exploitation of the seeds as acetogenin sources characterizing the seed triacylglycerols (dominant fraction; > 90% of the
whole lipid extracts) as potential valuable by-products. 相似文献