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61.
Regioselectivity and stereoselectivity of nucleophilic addition to glycal and imino‐glycal vinyl epoxides and their carba analogs: a rationalization based on HSAB theory and MEP
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62.
A Combined Experimental and Theoretical Study on the Formation of Ag Filaments on β‐Ag2MoO4 Induced by Electron Irradiation
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Juan Andrés Mateus M. Ferrer Lourdes Gracia Armando Beltran Valeria M. Longo Guilherme H. Cruvinel Ricardo L. Tranquilin Elson Longo 《Particle & Particle Systems Characterization》2015,32(6):646-651
A combined experimental and theoretical study is presented to understand the novel observed nucleation and early evolution of Ag filaments on β‐Ag2MoO4 crystals, driven by an accelerated electron beam from an electronic microscope under high vacuum. The growth process, chemical composition, and the element distribution in these filaments are analyzed in depth at the nanoscale level using field‐emission scanning electron microscopy (FE‐SEM) and transmission electron microscopy (TEM) with energy‐dispersive spectroscopy (EDS) characterization. To complement experimental results, chemical stability, structural and electronic aspects have been studied systematically using first‐principles electronic structure theory within a quantum theory of atoms in molecules (QTAIM) framework. The Ag nucleation and formation on β‐Ag2MoO4 are a result of structural and electronic changes of the AgO4 tetrahedral cluster as a constituent building block of β‐Ag2MoO4, consistent with Ag metallic formation. The formation of Ag filament transforms the β‐Ag2MoO4 semiconductor from n‐ to p‐type concomitant with the appearance of Ag defects. 相似文献
63.
Probing the CH⋅⋅⋅π Weak Hydrogen Bond in Anesthetic Binding: The Sevoflurane–Benzene Cluster
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![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Nathan A. Seifert Dr. Daniel P. Zaleski Dr. Cristóbal Pérez Dr. Justin L. Neill Prof. Brooks H. Pate Montserrat Vallejo‐López Prof. Alberto Lesarri Dr. Emilio J. Cocinero Prof. Fernando Castaño Prof. Isabelle Kleiner 《Angewandte Chemie (International ed. in English)》2014,53(12):3210-3213
Cooperativity between weak hydrogen bonds can be revealed in molecular clusters isolated in the gas phase. Here we examine the structure, internal dynamics, and origin of the weak intermolecular forces between sevoflurane and a benzene molecule, using multi‐isotopic broadband rotational spectra. This heterodimer is held together by a primary C? H???π hydrogen bond, assisted by multiple weak C? H???F interactions. The multiple nonbonding forces hinder the internal rotation of benzene around the isopropyl C? H bond in sevoflurane, producing detectable quantum tunneling effects in the rotational spectrum. 相似文献
64.
Valeria Mantella Michal Strach Kilian Frank James R. Pankhurst Dragos Stoian Chethana Gadiyar Bert Nickel Raffaella Buonsanti 《Angewandte Chemie (International ed. in English)》2020,59(28):11627-11633
The classical nucleation theory (CNT) is the most common theoretical framework used to explain particle formation. However, nucleation is a complex process with reaction pathways which are often not covered by the CNT. Herein, we study the formation mechanism of copper nanospheres using in situ X‐ray absorption and scattering measurements. We reveal that their nucleation involves coordination polymer lamellae as pre‐nucleation structures occupying a local minimum in the reaction energy landscape. Having learned this, we achieved a superior monodispersity for Cu nanospheres of different sizes. This report exemplifies the importance of developing a more realistic picture of the mechanism involved in the formation of inorganic nanoparticles to develop a rational approach to their synthesis. 相似文献
65.
Johanne Heitmann Solheim Boris Zimmermann Valeria Tafintseva Simona Dzurendov Volha Shapaval Achim Kohler 《Molecules (Basel, Switzerland)》2022,27(6)
Extended multiplicative signal correction (EMSC) is a widely used preprocessing technique in infrared spectroscopy. EMSC is a model-based method favored for its flexibility and versatility. The model can be extended by adding constituent spectra to explicitly model-known analytes or interferents. This paper addresses the use of constituent spectra and demonstrates common pitfalls. It clarifies the difference between analyte and interferent spectra, and the importance of orthogonality between model spectra. Different normalization approaches are discussed, and the importance of weighting in the EMSC is demonstrated. The paper illustrates how constituent analyte spectra can be estimated, and how they can be used to extract additional information from spectral features. It is shown that the EMSC parameters can be used in both regression tasks and segmentation tasks. 相似文献
66.
Valeria Avataneo Alice Palermiti Amedeo De Nicol Jessica Cusato Gloria Giussani Andrea Calcagno Antonio DAvolio 《Molecules (Basel, Switzerland)》2022,27(3)
Vitamin D (VD) is a calcium- and phosphate-controlling hormone used to treat bone disorders; yet, several other effects are progressively emerging. VD deficiency is highly prevalent worldwide, with suboptimal exposure to sunlight listed among the leading causes: oral supplementation with either cholecalciferol or calcitriol is used. However, there is a scarcity of clinical studies investigating how quickly VD concentrations can increase after supplementation. In this pilot study, the commercial supplement ImmuD3 (by Erboristeria Magentina®) was chosen as the source of VD and 2000 IU/day was administered for one month to 21 healthy volunteers that had not taken any other VD supplements in the previous 30 days. Plasma VD levels were measured through liquid chromatography coupled to tandem mass spectrometry after 7, 14, and 28 days of supplementation. We found that 95% of the participants had insufficient VD levels at baseline (<30 ng/mL; median 23.72 ng/mL; IQR 18.10–26.15), but after 28 days of supplementation, this percentage dropped to 62% (median 28.35 ng/mL; IQR 25.78–35.20). The median increase in VD level was 3.09 ng/mL (IQR 1.60–5.68) after 7 days and 8.85 ng/mL (IQR 2.85–13.97F) after 28 days. This study suggests the need for continuing VD supplementation and for measuring target level attainment. 相似文献
67.
This paper presents a finite-strain, multi-scale constitutive model for semi-crystalline polymers, accounting explicitly for the current state and evolution of the underlying crystallographic, lamellar and morphological texture. Specifically, a semi-crystalline polymer is modeled as a two-scale composite, assumed to be, at the larger length scale, an aggregate of randomly distributed grains that, at the smaller length scale, are made up of alternating layers of an amorphous and a crystalline phase. The model incorporates finite elasticity for the amorphous phase and crystallographic hardening for the crystalline phase. The instantaneous effective response of this composite is determined by means of multi-scale homogenization methods, consisting in the use of a “linear comparison composite” (LCC) with the same internal structure as the actual nonlinear composite, with local properties that are optimally chosen via suitably designed variational principles. The effective properties of the resulting two-scale LCC are obtained through a “sequential” homogenization procedure, involving the exact solution for the effective behavior of the lamellar grains and a self-consistent estimate for the aggregate. The latter results are also used to establish evolution laws for the appropriate internal variables in the material. The predictions of the model for the macroscopic response and texture evolution in high-density polyethylene are confronted with available experimental results and compared with those of earlier models. 相似文献
68.
69.
Roberta Sanna Davide Sanna Valeria Alzari Daniele Nuvoli Sergio Scognamillo Massimo Piccinini Massimo Lazzari Emilia Gioffredi Giulio Malucelli Alberto Mariani 《Journal of polymer science. Part A, Polymer chemistry》2012,50(19):4110-4118
Thermoresponsive poly(N‐vinylcaprolactam) nanocomposite hydrogels containing graphene were successfully prepared by frontal polymerization. High concentration of graphene (5.0 mg/mL) was obtained by direct graphite sonication in the self‐same liquid monomer, thus avoiding any chemical manipulation and obtaining “real” graphene as nanofiller instead of one of its more or less oxidized derivative, which is what generally reported in published reports. Furthermore, the corresponding nanocomposites were obtained without using any solvent to be eventually removed. The materials were fully characterized by RAMAN, SEM, and TEM, and their swelling behavior and rheological properties were investigated. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
70.
Carmen FestaSimona De Marino Valentina SepeMaria Valeria D’Auria Giuseppe BifulcoRosa Andrés Maria Carmen TerencioMiguel Payá Cécile DebitusAngela Zampella 《Tetrahedron》2011,67(40):7780-7786
Two new cyclopeptides, perthamides E and F were isolated from the polar extracts of the sponge Theonella swinhoei. The new structures, featuring an unprecedented β-amino acid unit (AHMOA), were determined by interpretation of NMR and MS data. The absolute configuration of the AHMOA residue was proposed on the basis of quantum chemical calculation of NMR chemical shifts. Perthamides were proved to inhibit TNF-α and IL-8 release in primary human keratinocytes cells and therefore could represent potentially leads for the treatment of psoriasis. 相似文献