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81.
Franco FernándezXerardo Garc?&#x;a-Mera José Enrique Rodr?&#x;guez-BorgesMar?&#x;a Luisa C. Vale 《Tetrahedron letters》2003,44(3):431-433
The recently reported compound (+)-(1R,endo)-2-benzonorbornenol (2) proved to be an efficient chiral auxiliary in the asymmetric aza-Diels-Alder reaction between cyclopentadiene and the N-benzyl imine of its glyoxylate, which afforded a virtually all-exo mixture of cycloaducts with a 1S:1R diastereomeric ratio of 63:37. 相似文献
82.
Aschi M Lucente G Mazza F Mollica A Morera E Nalli M Paglialunga Paradisi M 《Organic & biomolecular chemistry》2003,1(11):1980-1988
The conformational study of a new group of synthetic peptides containing 4-amino-1,2-dithiolane-4-carboxylic acid (Adt), a cysteine-related achiral residue, has been carried out through a joint application of computational and experimental methodologies. Molecular Dynamics simulations clearly suggest the tendency of this molecule to adopt a gamma-turn conformation in vacuum and help in analyzing the complex and crucial conformational behaviour of the dithiolane ring which appears to preferentially adopt a C(S)-like structure. Electronic structure calculations carried out in solution using the Density Functional Theory also indicate the preservation of the gamma-like folding in apolar solvents and the helix-like one in more polar solvents. A comparison with the achiral 1-aminocycloalkane-1-carboxylic acid (Ac5c) has been carried out using the same computational tools. NMR and IR data on dipeptide derivatives containing the Adt or Ac5c residue show that in chloroform solution all the models prefer a gamma-turn structure, centered at the cyclic residue, stabilized by an intramolecular H-bond, whereas in a more polar solvent, i.e. dimethyl sulfoxide, this folding is not maintained. The experimental conformational studies, extended to N-Boc protected tripeptides, clearly indicate the remarkable tendency of both the five-membered C(alpha)-tetrasubstituted cyclic amino acids Adt and Ac5c to induce the gamma-turn structure also in models able to adopt the beta-bend conformation. 相似文献
83.
The synthesis of imidazo [1,2-c] quinazoline was effected by manganese dioxide oxidation of the 5,6-dihydroimidazo [1,2-c] quinazoline which was prepared by treatment of 2-(o-nitro-phenyl)-1-hydroxyimidazole-3-oxide with zinc powder and formic acid. The synthesis of some methyl derivatives of this ring system are also described. Structural assignments for all of the products were made from spectral data. 相似文献
84.
Andrade Eiroa A Vázquez Blanco E López Mahía P Muniategui Lorenzo S Prada Rodríguez D 《The Analyst》2000,125(7):1321-1326
Two spectrofluorimetric methods, second-derivative constant-energy synchronous luminescence (SDCESL) and constant-wavelength synchronous luminescence (CWSL) in combination with multiple linear regression (MLR), for the quantification of benzo[a]pyrene (BaP) at sub-ng mL-1 levels, in the presence of benzo[b]fluoranthene (BbFt), benzo[k]fluoranthene (BkFt), benzo[ghi]perylene (BghiP) and indeno[1,2,3-cd]pyrene (IP), were developed and compared in detail. SDCESL presents lower limits of detection and quantification than CWSL/MLR and also gives more exact and precise results for levels close to the quantification limit. For BaP, SDCESL achieved quantification limits of 0.019 ng mL-1 in river waters and 0.007 ng mL-1 in drinking waters. This work offers a sensitive, precise, accurate, rapid, simple and economic methodology for monitoring BaP in waters for public consumption, meeting all the requirements of the EC Directive 98/83/CE that fixes the maximum admissible limit for this polycyclic aromatic hydrocarbon in drinking waters at of 0.010 ng mL-1. 相似文献
85.
Alejandro R. Engelmann Mario A. Natiello Mikael Hghede Erik Engdahl Erkki Brndas 《International journal of quantum chemistry》1987,31(5):841-845
In the present article we show how the bound states of the Coulomb potential may be associated with resonances that occur when this potential is perturbed by a barrier potential. The main idea is to trace the bound states on successive switching on of the barrier perturbation. It is found that those bound states that are localized inside the barrier are highly sensitive to variation with respect to the barrier height, whereas those that are localized outside are less sensitive. However, there are certain intervals for the barrier height when the role of being “a state localized inside the barrier” is shifted from one bound state to another. The result can be pictured as a “relay race,” where the “deliveries of the baton” are carried out over corresponding avoided crossings. The baton is ultimately handed over to a shape-type resonance state. 相似文献
86.
Neira-Carrillo A Yazdani-Pedram M Retuert J Diaz-Dosque M Gallois S Arias JL 《Journal of colloid and interface science》2005,286(1):134-141
The biopolymer chitosan was chemically modified by grafting polyacrylamide or polyacrylic acid in a homogeneous aqueous phase using potassium persulfate (KPS) as redox initiator system in the presence of N,N-methylene-bis-acrylamide as a crosslinking agent. The influence of the grafted chitosan on calcium salts crystallization in vitro was studied using the sitting-drop method. By using polyacrylamide grafted chitosan as substrate, rosette-like CaSO4 crystals were observed. This was originated by the presence of sulfate coming from the initiator KPS. By comparing crystallization on pure chitosan and on grafted chitosan, a dramatic influence of the grafted polymer on the crystalline habit of both salts was observed. Substrates prepared by combining sulfate with chitosan or sulfate with polyacrylamide did not produce similar CaSO4 morphologies. Moreover, small spheres or donut-shaped CaCO3 crystals on polyacrylic acid grafted chitosan were generated. The particular morphology of CaCO3 crystals depends also on other synthetic parameters such as the molecular weight of the chitosan sample and the KPS concentration. 相似文献
87.
Gancitano P Ciriminna R Testa ML Fidalgo A Ilharco LM Pagliaro M 《Organic & biomolecular chemistry》2005,3(13):2389-2392
Valuable organic compounds such as alpha-hydroxy acids are easily synthesised with relevant selectivity enhancement using a sol-gel hydrophobized nanostructured silica matrix doped with the organocatalyst TEMPO: A materials science based synthetic route which cannot be achieved via classical homogeneous synthesis. 相似文献
88.
Mass spectrometric identification and characterization of steroids using electrospray ionization and tandem mass spectrometry has advantages in drug testing and doping control analysis attributable to limitations of gas chromatography followed by electron ionization mass spectrometry. Steroids with an androstadiene-17beta-ol-3-one nucleus and double bonds located either at C-1 and C-4, C-4 and C-9, or C-4 and C-6 were used to determine characteristic fragmentation pathways. Diagnostic dissociation routes are proposed using deuterium labeling, MS3 experiments, and analyses of structurally closely related compounds. Steroids such as boldenone (androst-1,4-diene-17beta-ol-3-one) produced characteristic product ions at m/z 121, 135, and 147. Compounds with double bonds at C-4 and C-9 generated abundant product ions at m/z 145 and 147. Conjugated double bonds at C-4 and C-6 gave rise to an intense and characteristic signal at m/z 133. Stereochemical differentiation between 5alpha- and 5beta-isomers of androstan-17beta-ol-3-ones was possible because of significant differences in relative abundance of product ions generated by elimination of acetone from alpha,beta-saturated 3-keto steroids. 相似文献
89.
90.
Miguel A. Bañares Amador Angoso Juan L. Manzano Emilio Rodríguez 《Transition Metal Chemistry》1987,12(2):149-152
Summary Cobalt(II) chlorocomplexes with empirical formulae (bnH2)2CoCl6·2H2O (1) and (bnH2)2CoCl6 (2), where bnH
2
2+
represents the diprotonated species of putrescine (1,4-butanediamine), were prepared.The visible spectra in the solid state and measurement of the magnetic moments permit the assignation of an octahedral geometry for cobalt in (1) and a tetrahedral geometry for (2). 相似文献