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91.
Jansat S Gómez M Philippot K Muller G Guiu E Claver C Castillón S Chaudret B 《Journal of the American Chemical Society》2004,126(6):1592-1593
Palladium nanoparticles (4 nm, fcc) were prepared through decomposition of [Pd2(dba)3] by H2 in the presence of a chiral xylofuranoside diphosphite. These particles catalyze the allylic alkylation of rac-3-acetoxy-1,3-diphenyl-1-propene with dimethyl malonate leading to an almost total conversion of the (R) enantiomer and almost no reaction with the (S). This gives rise to 97% ee for the alkylation product and a kinetic resolution of the substrate recovered with ca. 90% ee. This behavior was compared to that of a molecular catalyst at various dilutions, and the differences between the two systems are discussed. This is the first colloidal system shown to display such a high enantioselectivity besides the well-known Pt/cinchonidine system. 相似文献
92.
Guernelli S Fontana A Noto R Spinelli D Turco Liveri ML 《Journal of colloid and interface science》2012,370(1):67-72
The pH-induced swelling of poly(2-vinylpyridine) microgel particles was studied using dynamic light scattering. The increase in particle diameter with decreasing pH was modeled using a well-established thermodynamic model for microgel swelling. The Maxwell construction was applied to extend the model and yield a prediction for a pH-responsive microgel across the entire pH range. The model predicts a first order phase transition for polymer-solvent combinations with a Flory interaction parameter, χ, greater than a critical value χ(c). The modified theory compared favorably to the dynamic light scattering data for the hydrodynamic diameter of microgel particles based on 2-vinylpyridine at different pH values. In particular, the swelling transition is both predicted theoretically and observed experimentally to occur at a pH lower than the pK(a) of the polymer. 相似文献
93.
Evaluation of volatile chlorinated hydrocarbons distribution along depth profiles in the Ross Sea, Antarctica 总被引:1,自引:0,他引:1
The presence and the distribution along depth profiles of volatile chlorinated hydrocarbons (VCHCs) were evaluated in seawater samples collected in the Ross Sea (Southern Ocean, Antarctica) during the 2002-2003 Italian expedition. Sampling areas were located where the Circumpolar Deep Water interacts with the shelf waters that supply the Ross Sea.The VCHCs investigated were: 1,1,1-trichloroethane (C2H3Cl3), tetrachloromethane (CCl4), trichloroethylene (C2HCl3), tetrachloroethylene (C2Cl4). The analytical procedure consisted of a liquid-liquid extraction carried out with n-hexane directly in Antarctica, followed by gas chromatographic analysis with electron capture detection carried out in Italy.Concentration levels for the VCHCs analysed ranged from digits to hundreds of ng/L according to the station, depth and substance considered. Important differences in concentration levels between the three stations near the Ross Ice Shelf and the two stations located in the Cape Adare area were observed. In particular the stations situated in the Cape Adare zone, at certain depths, showed a thermal inversion due to the mixing of the Circumpolar Deep Water with the waters generated inside the Ross Sea Basin. The lowest concentration levels were recorded at this temperature increase. 相似文献
94.
Studies focusing on different groups of students show that the prevalence of vocal symptoms and voice disorder vary depending on the study populations. A previous study of vocal symptoms and voice disorders among teacher students has shown that 20% of the students studying to become teachers in comprehensive schools and upper secondary schools reported frequently occurring vocal symptoms, ie, two symptoms or more occurring weekly or more often during the past year, and that most of these students had an organic voice disorder. This raised the question of whether other university students would also report similar, frequently occurring vocal symptoms. A questionnaire was distributed to 220 students of several faculties at the University of Turku, Finland. The results were compared with the results of a study of vocal symptoms reported by 175 students studying to become teachers. This comparison showed that students in general reported frequently occurring vocal symptoms, whereas the students studying to become teachers reported a greater number of frequently occurring symptoms than did other students at the university. 相似文献
95.
96.
Angle-resolved photoelectron spectroscopy of randomly oriented 3-hydroxytetrahydrofuran enantiomers.
Anna Giardini Daniele Catone Stefano Stranges Mauro Satta Mario Tacconi Susanna Piccirillo Stefano Turchini Nicola Zema Giorgio Contini Tommaso Prosperi Pietro Decleva Devis Di Tommaso Giovanna Fronzoni Mauro Stener Antonello Filippi Maurizio Speranza 《Chemphyschem》2005,6(6):1164-1168
Circular dichroism in the angular distribution of valence photoelectrons emitted from randomly oriented 3-hydroxytetrahydrofuran enantiomers (ThS and ThR) has been observed in gas-phase experiments using circularly polarized vacuum ultraviolet (VUV) light. The measured dichroism for both ThS and ThR, acquired at the single magic angle theta=234.73 degrees and at photon energies of 22, 19, 16, and 14 eV, points to an asymmetric forward-backward scattering of the photoelectrons from their highest occupied molecular orbitals (HOMO) HOMO-1 and HOMO-2, of up to 5%, depending on the photon energy. The asymmetry reverses on exchange of either the helicity of the radiation or the configuration of Th. The photoionization dichroic D parameters of ThS and ThR have been measured and their values discussed in the light of LCAO B-spline density functional theory (DFT) predictions. While an acceptable agreement is found between the dichroic parameter measured and calculated at the highest photon energy for the HOMO and HOMO-2 orbitals of Th, a significant discrepancy is observed for the HOMO-1 state which is attributed to the floppiness of Th, in particular to the comparatively large sensitivity of the size and shape of its HOMO-1 on nuclear vibrational motion. 相似文献
97.
Francesca Peccati Marta Díaz-Caballero Susanna Navarro Luis Rodríguez-Santiago Salvador Ventura Mariona Sodupe 《Chemical science》2020,11(48):13143
This article provides the computational prediction of the atomistic architectures resulting from self-assembly of the polar heptapeptide sequences NYNYNYN, SYSYSYS and GYGYGYG. Using a combination of molecular dynamics and a newly developed tool for non-covalent interaction analysis, we uncover the properties of a new class of bionanomaterials, including hydrogen-bonded polar zippers, and the relationship between peptide composition, fibril geometry and weak interaction networks. Our results, corroborated by experimental observations, provide the basis for the rational design of prion-inspired nanomaterials.This article provides the computational prediction of the atomistic architectures resulting from self-assembly of the polar heptapeptide sequences NYNYNYN, SYSYSYS and GYGYGYG. 相似文献
98.
Herold S 《Inorganic chemistry》2004,43(13):3783-3785
It has been suggested that nitrosyliron(II)hemoglobin may represent a form of stabilized NO. and may be responsible for NO. delivery in the peripheral circulation. In this work, we show that NO. can be released from nitrosyliron(II)hemoglobin through reaction with peroxynitrite. Outer-sphere oxidation of the iron center generates nitrosyliron(III)hemoglobin, from which NO. dissociates at a rate of ca. 1 s(-1). The second-order rate constant for the reaction of peroxynitrite with nitrosyliron(II)hemoglobin is (6.1 +/- 0.3) x 10(3) M(-1) s(-1) (at pH 7.2 and 20 degrees C). In the presence of 1.2 mM CO(2), the rather large value of the second-order rate constant, (5.3 +/- 0.2) x 10(4) M(-1) s(-1) (at pH 7.2 and 20 degrees C), indicates that this reaction may take place in vivo. The reactive nitrogen species generated from this reaction, N(2)O(3) and/or NO(2), may lead to protein modifications, such as nitration of tyrosine and/or tryptophan residues and nitrosation of cysteine residues. 相似文献
99.
Beatrice Bargagna Lidia Ciccone Susanna Nencetti M. Amlia Santos Sílvia Chaves Caterina Camodeca Elisabetta Orlandini 《Molecules (Basel, Switzerland)》2021,26(19)
Alzheimer’s disease (AD) is a severe multifactorial neurodegenerative disorder characterized by a progressive loss of neurons in the brain. Despite research efforts, the pathogenesis and mechanism of AD progression are not yet completely understood. There are only a few symptomatic drugs approved for the treatment of AD. The multifactorial character of AD suggests that it is important to develop molecules able to target the numerous pathological mechanisms associated with the disease. Thus, in the context of the worldwide recognized interest of multifunctional ligand therapy, we report herein the synthesis, characterization, physicochemical and biological evaluation of a set of five (1a–e) new ferulic acid-based hybrid compounds, namely feroyl-benzyloxyamidic derivatives enclosing different substituent groups, as potential anti-Alzheimer’s disease agents. These hybrids can keep both the radical scavenging activity and metal chelation capacity of the naturally occurring ferulic acid scaffold, presenting also good/mild capacity for inhibition of self-Aβ aggregation and fairly good inhibition of Cu-induced Aβ aggregation. The predicted pharmacokinetic properties point towards good absorption, comparable to known oral drugs. 相似文献