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421.
[reaction: see text] An original TiCl(4)/t-BuNH(2)-mediated hydroamination/annulation domino reaction of delta-keto-acetylenes is described. The synthesis of pyrrolo[1,2-a]indole-2-carbaldehydes, starting from 2-carbonyl-1-propargyl-1H-indoles runs under mild reaction conditions. A conceivable mechanism is also discussed. TiCl(4) has proved to be an effective multiactivity reagent: catalyst/Lewis acid/water scavenger. Some unpublished 2-carbonyl-1-propargyl-1H-indoles are prepared by means of Suzuki- and Negishi-type reactions. 相似文献
422.
Influence of astaxanthin, zeaxanthin and lutein on DNA damage and repair in UVA-irradiated cells 总被引:5,自引:0,他引:5
Santocono M Zurria M Berrettini M Fedeli D Falcioni G 《Journal of photochemistry and photobiology. B, Biology》2006,85(3):205-215
In order to gain more knowledge about the antioxidant role of the predominant carotenoids (lutein and zeaxanthin) of the human retina, this study investigated their antioxidant activity and capacity. Astaxanthin was also studied, because its structure is very close to that of lutein and zeaxanthin. The antioxidant activity of these molecules was evaluated using chemiluminescence techniques, with lucigenin and luminol as chemiluminogenic probes for the superoxide radical and hydrogen peroxide, respectively. It was found that all three carotenoids have similar superoxide-scavenging activity. The effect on the reduction of H(2)O(2)-luminol chemiluminescence was present in the following order, zeaxanthin>astaxanthinlutein. Possible antioxidant capacity of these three compounds was sought using a biological system consisting of SK.N.SH human neuroblastoma and rat trachea epithelial cells subjected to oxidative stress from exposure to UVA radiation. In particular, we determined whether these compounds were capable of minimizing DNA damage and influencing the kinetics of DNA repair. DNA damage was assessed using the Comet assay, a rapid and sensitive single-cell gel electrophoresis technique used to detect primary DNA damage in individual cells. Neuroblastoma cells appeared more resistant to oxidative irradiation insult. The presence of carotenoids reduced DNA damage when rat epithelial cells were exposed to UVA radiation for 2min. A different result was obtained in experiments performed on neuroblastoma cells; in this case, the presence of carotenoid during UVA exposition increased the damage. The addition of carotenoids to epithelial cells after 2min of UVA exposition did not seem to improve the kinetics of DNA repair; on the contrary, zeaxanthin (after 60' incubation) and lutein (after 180' incubation) showed a genotoxic effect. The addition of carotenoids to neuroblastoma cells after 30' UVA exposition positively influences the kinetics of DNA repair in the first 15min of incubation. At longer exposition times, while the behaviour measured was not constant, a genotoxic effect was not observed. The data from this study provide additional information on the antioxidant and pro-oxidant activities of the predominant macular pigment carotenoids of the human retina. 相似文献
423.
The synthesis of chiral 3-aryl-1-alkynes 3 via cross-coupling of 3-alkyl- and 3,3-dialkyl-1-bromo-1,2-dienes 1 and arylbromocuprates (RCuBr)MgBr.LiBr 2 was examined. With phenylcopper reagents and its para-substituted derivatives, as well as with 2-naphthyl cuprates, the reaction gave compounds 3 with high regioselectivity and good yields on the chemically pure product. On the contrary, when ortho-substituted phenyl reagents and 1-naphthyl cuprates were used, the regioselectivity of the process was very dependent upon the steric requirements of the alkyl substituents on the bromoallenic substrate. When the steric bulk was increased, remarkable quantities of isomeric arylallenes 4 were also observed in the reaction mixtures. The high 1,3-anti stereoselectivity of the coupling process allowed us to obtain enantiomerically enriched 3-aryl-1-alkynes from optically active allenic substrates, thus indicating a simple pathway toward the synthesis of quaternary stereogenic centers characterized by an aryl group. A possible cross-coupling mechanism was also suggested to explain the regio- and stereochemical data. For the preparation of omega-functionalized 3-phenyl-1-alkynes, the reaction of 1-bromo-3-phenylpropadiene with Knochel reagents RCu(CN)ZnCl.2LiCl was also studied; this reaction led to the acetylenic compounds in high yields mainly when the R group (also omega-functionalized) on the copper reagent was primary. 相似文献
424.
In this paper we present the theory of implicit Riordan arrays, that is, Riordan arrays which require the application of the Lagrange Inversion Formula to be dealt with. We show several examples in which our approach gives explicit results, both in finding closed expressions for sums and, especially, in solving classes of combinatorial sum inversions. 相似文献
425.
Donatella Capitani Noemi Proietti Marco Gobbino Luigi Soroldoni Umberto Casellato Massimo Valentini Elisabetta Rosina 《Analytical and bioanalytical chemistry》2009,395(7):2245-2253
An integrated study of microclimate monitoring, IR thermography (IRT), gravimetric tests and portable unilateral nuclear magnetic
resonance (NMR) was applied in the framework of planning emergency intervention on a very deteriorated wall painting in San
Rocco church, Cornaredo (Milan, Italy). The IRT investigation supported by gravimetric tests showed that the worst damage,
due to water infiltration, was localized on the wall painting of the northern wall. Unilateral NMR, a new non-destructive
technique which measures the hydrogen signal of the moisture and that was applied directly to the wall, allowed a detailed
map of the distribution of the moisture in the plaster underlying the wall panting to be obtained. With a proper calibration
of the integral of the recorded signal with suitable specimens, each area of the map corresponded to an accurate amount of
moisture. IRT, gravimetric tests and unilateral NMR applied to investigate the northern wall painting showed the presence
of two wet areas separated by a dry area. The moisture found in the lower area was ascribed to the occurrence of rising damp
at the bottom of the wall due to the slope of the garden soil towards the northern exterior. The moisture found in the upper
area was ascribed to condensation phenomena associated with the presence of a considerable amount of soluble, hygroscopic
salts. In the framework of this integrated study, IRT investigation and gravimetric methods validated portable unilateral
NMR as a new analytical tool for measuring in situ and without any sampling of the distribution and amount of moisture in
wall paintings. 相似文献
426.
Carina Sinclér Delfino Michel Nicolau Youssef Fábio Barbosa De Souza Rodivan Braz Míriam Lacalle Turbino 《Optik》2012,123(3):263-267
The objective of this study was to compare the microhardness of two resin composites (microhybrid and nanoparticles). Light activation was performed with argon ion laser 1.56 J (L) and halogen light 2.6 J (H) was used as control. Measurements were taken on the irradiated surfaces and those opposite them, at thicknesses of 1, 2 and 3 mm. To evaluate the quality of polymerization, the percentages of maximum hardness were calculated (PMH). For statistical analysis the ANOVA and Tukey tests were used (p ≤ 0.05). To microhybrid was shown that the hardness with laser was inferior to the hardness achieved with halogen light, for both the 1 mm and 2 mm. The nanoparticles polymerized with laser, presented lower hardness even on the irradiated surface, than the same surface light activated with halogen light. The microhybrid attained a minimum PMH of 80% up to the thickness of 2 mm with halogen light, and with laser, only up to 1 mm. The nanoparticles attained a minimum PMH of 80% up to 3 mm thickness with halogen light and with laser this minimum was not obtained at any thickness. Based on these results, it could be concluded that light activation with argon ion laser is contra-indicated for the studied nanoparticles. 相似文献
427.
Annalisa Vigorito Camilla Calabrese Assimo Maris Donatella Loru Isabel Pea M. Eugenia Sanz Sonia Melandri 《Molecules (Basel, Switzerland)》2022,27(9)
Benzenesulfonamides are a class of molecules of extreme interest in the biochemical field because many of them are active against a variety of diseases. In this work, the pharmacophoric group benzensulfonamide, its derivatives para-toluensulfonamide and ortho-toluensulfonamide, and the bioactive molecule sulfanilamide, were investigated using rotational spectroscopy to determine their conformations and the influence of different substituents on their structures. For all species, the hyperfine structure due to the 14N atom was analyzed, and this provided crucial information for the unambiguous identification of the observed conformation of all molecules. In addition, for ortho-toluensulfonamide, the vibration–rotation hyperfine structure related to the methyl torsion was analyzed, and the methyl group rotation barrier was determined. For benzensulfonamide, partial rS and r0 structures were established from the experimental rotational constants of the parent and two deuterated isotopic species. In all compounds except ortho-toluensulfonamide, the amino group of the sulfonamide group lies perpendicular to the benzene plane with the aminic hydrogens eclipsing the oxygen atoms. In ortho-toluensulfonamide, where weak attractive interactions occur between the nitrogen lone pair and the methyl hydrogen atoms, the amino group lies in a gauche orientation, retaining the eclipsed configuration with respect to the SO2 frame. A comparison of the geometrical arrangements found in the PDB database allowed us to understand that the bioactive conformations are different from those found in isolated conditions. The conformations within the receptor are reached with an energy cost, which is balanced by the interactions established in the receptor. 相似文献
428.
429.
Valeria DAnnibale Donatella Fracassi Paolo Marracino Guglielmo DInzeo Marco DAbramo 《Molecules (Basel, Switzerland)》2022,27(19)
Here we present a theoretical-computational study dealing with the evaluation of the pKa of the Cysteine residues in Thioredoxin (TRX) and in its complex with the Thioredoxin-interacting protein (TXNIP). The free energy differences between the anionic and neutral form of the Cysteine 32 and 35 have been evaluated by means of the Perturbed Matrix Method with classical perturbations due to both the environment and an exogenous electric field as provided by Molecular Dynamics (MD) simulations. The evaluation of the free energies allowed us to show that the effect of the perturbing terms is to lower the pKa of Cysteine 32 and Cysteine 35 with respect to the free amino-acid. On the other hand, in the complex TRX-TXNIP, our data show an enhanced stabilization of the neutral reduced form of Cys 35. These results suggest that external electric stimuli higher than 0.02 V/nm can modulate the Cysteine pKa, which can be connected to the tight regulation of the TRX acting as an antioxidant agent. 相似文献
430.
Lucia De Rosa Donatella Diana Domenica Capasso Rachele Stefania Rossella Di Stasi Roberto Fattorusso Luca Domenico DAndrea 《Molecules (Basel, Switzerland)》2022,27(20)
The N-capping region of an α-helix is a short N-terminal amino acid stretch that contributes to nucleate and stabilize the helical structure. In the VEGF mimetic helical peptide QK, the N-capping region was previously demonstrated to be a key factor of QK helical folding. In this paper, we explored the effect of the chiral inversion of the N-capping sequence on QK folding, performing conformational analysis in solution by circular dichroism and NMR spectroscopy. The effect of such a modification on QK stability in serum and the proliferative effect were also evaluated. 相似文献