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排序方式: 共有73条查询结果,搜索用时 16 毫秒
1.
On the basis of Altona's empirical generalization of the Karplus equation, an expression of 3JH,H as function of pseudorotation parameters for five-membered rings, was deduced. The resulting equation was parametrized by means of molecular mechanics calculations for tetrahydrofuran and tetrahydrothiophene. Estimation of 3JH,H for the full pseudorotational itinerary was made. From the best fit between calculated and measured 3JH,H values the preferred conformation of those rings may be established. The procedure was applied for the conformational analysis of 4-thiohexofuranose derivatives, having and β,
-galacto and D- manno, and -
-talo configurations. 相似文献
2.
Gilbert Dana Feiga Weisbuch Brigitte Lo Cicero Jean-Michel Drancourt Jacqueline Mercier 《Tetrahedron》1985,41(7):1241-1249
We show that the four studied 4-hydrindenones (with or without a methyl substituant at C3 or C7a) give by hydrogenation on Raney nickel or on Pd/C, in various solvants, the cis 4-hydrindanones, by a kinetically controlled process. During the hydrogenation, the double bond can migrate only in the positions conjugated to the carbonyl group.In contrast, when the carbonyle is protected as a dioxolanne, the double bond is free to migrate around the five membered ring. In spite of this mobility the optical purity of the saturated dioxolannes formed is high. In the case of the (+)3-methyl Δ3(3a) 4-hydrindenone, the enantiomeric hydrindanones obtained by direct hydrogenation or with isomerization of the double bond are not the same. Therefore, the optical purity of the product is low, but its value allows an estimation of the relative importance of the two reaction pathways. 相似文献
3.
Lamellar crystalline calcium phenylphosphonate, as anhydrous Ca(HO3PC6H5)2 and hydrated Ca(HO3PC6H5)2·2H2O compounds, were used as hosts for intercalation of polar n-alkylmonoamine molecules of the general formula CH3(CH2)nNH2 (n=0–4, 7) in water or 1,2-dichloroethane. An increase in the interlayer distance was observed. The exothermic enthalpic values for intercalation increased with the number of carbon atoms and with increasing concentration of the amines. The intercalation followed by a titration procedure in the solid/liquid interface with Ca(HO3PC6H5)2·2H2O and Ca(HO3PC6H5)2 gave the enthalpy/number of carbons correlations: ΔintH=−(1.74±0.43)–(1.30±0.13)nc and ΔintH=−(4.15±0.15)–(1.07±0.03)nc, for water and 1,2-dichloroethane, respectively. A similar correlation ΔintH=−(4.27±0.80)–(1.85±0.21)nc was obtained in water by using the ampoule breaking procedure for Ca(HO3PC6H5)2·2H2O. The increase in exothermic enthalpic values with the increase in n-aliphatic carbon atoms is more pronounced for the anhydrous compound and also when using the ampoule breaking procedure. The Gibbs free energies are negative. Positive entropic values favor intercalation in these systems. 相似文献
4.
The interaction of water with Si- and C- terminated beta-SiC(001) surfaces was investigated by means of ab initio molecular dynamics simulations. Irrespective of coverage, varied from 1/4 to 1 monolayer, we found that water dissociates on the Si-terminated surface, substantially modifying the clean surface reconstruction, while the C-terminated surface is nonreactive and hydrophobic. Based on our results, we propose that STM images and photoemission experiments may detect specific changes induced by water on both the structural and electronic properties of SiC(001) surfaces. 相似文献
5.
Massimo Bietti Alessandra Calcagni Daniel Oscar Cicero Roberto Martella Michela Salamone 《Tetrahedron letters》2010,51(31):4129-1537
A product study on the reactivity of a 1,1-diarylalkoxyl radical bearing 2,2-diphenylcyclopropyl groups in the para-positions has been carried out. The exclusive formation of a product deriving from cyclopropyl ring-opening has been observed, indicating that 1,1-diarylalkoxyl radicals exist in equilibrium with a bridged 1-oxaspiro[2,5]octadienyl radical. This represents the first experimental evidence in support of the stepwise nature of the O-neophyl rearrangement of 1,1-diarylalkoxyl radicals. 相似文献
6.
7.
In every infinite-dimensional vector space we build a complete, non-locally convex linear Hausdorff topology under the prescribed
condition that it shall be compatible with a bounded algebraic structure for the space, that is, it admits a bounded Hamel
basis whose coefficient linear functionals are continuous. As a byproduct, we obtain the existence of non-locally convex topologies
having the approximate and fixed point property as prescribed conditions. The obstruction of bounded Hamel bases by complete
vector topologies on linear space of countable dimension is also discussed. 相似文献
8.
Greta Petrella Camilla Montesano Sara Lentini Giorgia Ciufolini Domitilla Vanni Roberto Speziale Andrea Salonia Francesco Montorsi Vincenzo Summa Riccardo Vago Laura Orsatti Edith Monteagudo Daniel Oscar Cicero 《Molecules (Basel, Switzerland)》2021,26(14)
A new strategy that takes advantage of the synergism between NMR and UHPLC–HRMS yields accurate concentrations of a high number of compounds in biofluids to delineate a personalized metabolic profile (SYNHMET). Metabolite identification and quantification by this method result in a higher accuracy compared to the use of the two techniques separately, even in urine, one of the most challenging biofluids to characterize due to its complexity and variability. We quantified a total of 165 metabolites in the urine of healthy subjects, patients with chronic cystitis, and patients with bladder cancer, with a minimum number of missing values. This result was achieved without the use of analytical standards and calibration curves. A patient’s personalized profile can be mapped out from the final dataset’s concentrations by comparing them with known normal ranges. This detailed picture has potential applications in clinical practice to monitor a patient’s health status and disease progression. 相似文献
9.
Dr. Oscar Francesconi Federico Cicero Prof. Dr. Cristina Nativi Dr. Stefano Roelens 《Chemphyschem》2020,21(3):257-262
The choice between adaptive and preorganized architectures, or of the most effective hydrogen bonding groups to be selected, are dilemmas that supramolecular chemists must address in designing synthetic receptors for such a challenging guest as carbohydrates. In this paper, structurally related architectures featuring two alternative hydrogen bonding motifs were compared to ascertain the structural and functional origin of their binding differences and the advantages that can be expected in monosaccharide recognition. A set of structurally related macrocyclic receptors were prepared, and their binding properties were measured by NMR and ITC techniques in chloroform vs a common saccharidic target, namely, the β-octyl glycoside of D-glucose. Results showed that the diaminocarbazolic motif, recently reported as the constituting unit of highly effective receptors for saccharides in water, is a superior hydrogen bonding motif compared to the previously described diaminopyrrolic motif, which was successfully employed in molecular recognition of carbohydrates in polar organic solvents, due to intrinsic structural and functional factors, rather than to hydrophobic contributions. In addition, the occurrence of a rare example of a thermodynamic template effect exerted by the beta-glucoside has been ascertained, enhancing the synthesis outcome of the otherwise low yielding preparation of the described macrocyclic receptors. 相似文献
10.
Andrea Salvo Nicola Cicero Rossella Vadalà Antonio Francesco Mottese Daniel Bua Domenico Mallamace 《Natural product research》2016,30(6):657-664
Toxic and essential metals content was determined by inductively coupled plasma mass spectrometry in commercial sea urchins samples from the Mediterranean Sea and Pacific Ocean. Results show that Chilean samples have the highest values of Cd, As, Ni, Cr and V; Spanish samples have the maximum Hg content while Sicilian samples have the lowest content of toxic metals. The toxic metal traces were compared with the limits of European Community (EC) No. 1881/2006 for bivalve molluscs. All samples exceed Pb and Cd limit levels; regarding Hg levels, only Sicilian and Sardinian samples have Hg content below the EC limits. The dietary intake of toxic and essential elements was evaluated for an adult. Furthermore, our study highlights a correlation between the toxic elements content and the marine environmental conditions of the places of origin even though only the generic FAO fishing area is specified. 相似文献