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91.
Bibiana Alejandra Yez‐Martínez Gabriel Luna‐Brcenas Eduardo Vivaldo‐Lima 《Macromolecular theory and simulations》2009,18(3):171-194
Complete parameter sensitivity analyses using the numerical fractionation technique are presented for the cases of homopolymerization with chain transfer to polymer and termination by combination. Also, using reported values for the kinetic rate constants associated with the linear and non‐linear homopolymerizations of styrene, vinyl acetate, methyl methacrylate and butyl acrylate, overall molecular weight distributions and averages of the MWD were calculated using the NFT. Good agreement with the expected behavior, with MMA and STY not gelling while BA and VAc do, was obtained. It is concluded that the NFT produces coherent and reliable performance for known polymerization systems, whether linear or non‐linear.
92.
Luciano Zunino Alejandra Figliola Benjamin M. Tabak Darío G. Prez Mario Garavaglia Osvaldo A. Rosso 《Chaos, solitons, and fractals》2009,41(5):2331-2340
We study the multifractal nature of daily price and volatility returns of Latin-American stock markets employing the multifractal detrended fluctuation analysis. Comparing with the results obtained for a developed country (US) we conclude that the multifractality degree is higher for emerging markets. Moreover, we propose a stock market inefficiency ranking by considering the multifractality degree as a measure of inefficiency. Finally, we analyze the sources of multifractality quantifying the contributions of two factors, the long-range correlations of the time series and the broad fat-tail distributions. We find that the multifractal structure of Latin-American market indices can be mainly attributed to the latter. 相似文献
93.
Alejandra?Londono-Calderon Daniel?Bahena Miguel?Jose-YacamanEmail author 《Journal of nanoparticle research》2017,19(6):219
Synthetic methods to obtain hollow-like systems based on galvanic reaction are of wide importance due to the simplicity and efficiency of the method, yet due to fast and spontaneous reduction, the reaction for platinum-based structures is usually not well controlled. Systematic studies over the evolution of the galvanization process are still important in order to determine key feature on the structural transformation. On this paper, electron microscopy techniques were used to correlate the crystallinity of Ag/Pt nanoboxes of 78 nm in size with low and high-index facets surfaces from Ag nanocubes template. It was observed that 1.6 μmol addition of platinum precursor is enough to produce Ag/Pt nanoboxes. However, the crystallinity of the walls was tune from single crystal to polycrystalline by increasing the amount of platinum. More importantly, electron tomography reconstructions allow us to identify the concavities sides on the polycrystalline double-layer porous sample. Platinum content and nanostructure has been also associated to the optical properties were an extinction of the absorption band is observed after the solid template has been fully transformed to a nanobox. The final Ag/Pt porous/hollow nanoboxes with concave sides were tested on a model reaction for the reduction of 4-ntp to 4-amp. 相似文献
94.
Jesse Murillo Rina Bhowmick Katie L. M. Harriman Alejandra Gomez-Torres Joshua Wright Robert W. Meulenberg Pere Mir Alejandro Metta-Magaa Muralee Murugesu Bess Vlaisavljevich Skye Fortier 《Chemical science》2021,12(40):13360
Addition of [UI2(THF)3(μ-OMe)]2·THF (2·THF) to THF solutions containing 6 equiv. of K[C14H10] generates the heteroleptic dimeric complexes [K(18-crown-6)(THF)2]2[U(η6-C14H10)(η4-C14H10)(μ-OMe)]2·4THF (118C6·4THF) and {[K(THF)3][U(η6-C14H10)(η4-C14H10)(μ-OMe)]}2 (1THF) upon crystallization of the products in THF in the presence or absence of 18-crown-6, respectively. Both 118C6·4THF and 1THF are thermally stable in the solid-state at room temperature; however, after crystallization, they become insoluble in THF or DME solutions and instead gradually decompose upon standing. X-ray diffraction analysis reveals 118C6·4THF and 1THF to be structurally similar, possessing uranium centres sandwiched between bent anthracenide ligands of mixed tetrahapto and hexahapto ligation modes. Yet, the two complexes are distinguished by the close contact potassium-arenide ion pairing that is seen in 1THF but absent in 118C6·4THF, which is observed to have a significant effect on the electronic characteristics of the two complexes. Structural analysis, SQUID magnetometry data, XANES spectral characterization, and computational analyses are generally consistent with U(iv) formal assignments for the metal centres in both 118C6·4THF and 1THF, though noticeable differences are detected between the two species. For instance, the effective magnetic moment of 1THF (3.74 μB) is significantly lower than that of 118C6·4THF (4.40 μB) at 300 K. Furthermore, the XANES data shows the U LIII-edge absorption energy for 1THF to be 0.9 eV higher than that of 118C6·4THF, suggestive of more oxidized metal centres in the former. Of note, CASSCF calculations on the model complex {[U(η6-C14H10)(η4-C14H10)(μ-OMe)]2}2− (1*) shows highly polarized uranium–arenide interactions defined by π-type bonds where the metal contributions are primarily comprised by the 6d-orbitals (7.3 ± 0.6%) with minor participation from the 5f-orbitals (1.5 ± 0.5%). These unique complexes provide new insights into actinide–arenide bonding interactions and show the sensitivity of the electronic structures of the uranium atoms to coordination sphere effects.Use of Chatt metal-arene protocols with uranium leads to the synthesis of the first well-characterized, unsupported actinide–arenide sandwich complexes. The electronic structures of the actinide centres show a key sensitivity to ion pairing effects. 相似文献
95.
Martín A. Lerma-Herrera Lidia Beiza-Granados Alejandra Ochoa-Zarzosa Joel E. Lpez-Meza Pedro Navarro-Santos Rafael Herrera-Bucio Judit Avia-Verduzco Hugo A. García-Gutirrez 《Molecules (Basel, Switzerland)》2022,27(12)
Different ethnomedicinal studies have investigated the relationship between various phytochemicals as well as organic extracts and their bioactive aspects. Studies on biological effects are attributed to secondary metabolites such as alkaloids, phenolic compounds, and terpenes. Since there have been no reviews in the literature on the traditional, phytochemical, and ethnomedicinal uses of the genus Aristolochia so far, this article systematically reviews 141 published studies that analyze the associations between secondary metabolites present in organic extracts and their beneficial effects. Most studies found associations between individual secondary metabolites and beneficial effects such as anticancer activity, antibacterial, antioxidant activity, snake anti-venom and anti-inflammatory activity. The aim of this review was to analyze studies carried out in the period 2005–2021 to update the existing knowledge on different species of the genus Aristolochia for ethnomedicinal uses, as well as pharmacological aspects and therapeutic uses. 相似文献
96.
Didem P. Aykas Alejandra Urtubia Kevin Wong Luju Ren Claudia Lpez-Lira Luis E. Rodriguez-Saona 《Molecules (Basel, Switzerland)》2022,27(4)
Current assays for acrylamide screening rely heavily on LC-MS/MS or GC-MS, techniques that are not suitable to support point of manufacturing verification because it can take several weeks to receive results from a laboratory. A portable sensor that can detect acrylamide levels in real-time would enable in-house testing to safeguard both the safety of the consumer and the economic security of the agricultural supplier. Our objective was to develop a rapid, accurate, and real-time screening technique to detect the acrylamide content in par-fried frozen French fries based on a portable infrared device. Par-fried French fries (n = 70) were manufactured at times ranging from 1 to 5.5 min at 180 °C to yield a wide range of acrylamide levels. Spectra of samples were collected using a portable FT-IR device operating from 4000 to 700 cm−1. Acrylamide was extracted using QuEChERS and quantified using uHPLC-MS/MS. Predictive algorithms were generated using partial least squares regression (PLSR). Acrylamide levels in French fries ranged from 52.0 to 812.8 µg/kg. The best performance of the prediction algorithms required transformation of the acrylamide levels using a logarithm function with models giving a coefficient of correlation (Rcv) of 0.93 and RPD as 3.8, which means the mid-IR model can be used for process control applications. Our data corroborate the potential of portable infrared devices for acrylamide screening of high-risk foods. 相似文献
97.
98.
Reactions of 4-methylphenyl 4-nitrophenyl carbonate (MPNPC) and 4-chlorophenyl 4-nitrophenyl carbonate (ClPNPC) with a series of quinuclidines (QUIN) and the latter carbonate with a series of secondary alicyclic amines (SAA) are subjected to a kinetic investigation in 44 wt % ethanol-water, at 25.0 degrees C and an ionic strength of 0.2 M. The reactions were followed spectrophotometrically at 330 or 400 nm (4-nitrophenol or 4-nitrophenoxide anion appearance, respectively). Under excess amine, pseudo-first-order rate coefficients (k(obsd)) are found. For all these reactions, plots of k(obsd) vs free amine concentration at constant pH are linear, the slope (k(N)) being independent of pH. The Br?nsted-type plots (log k(N) vs pK(a) of the conjugate acids of the amines) for the reactions of the series of QUIN with MPNPC and ClPNPC are linear with slopes (beta(N)) 0.88 and 0.87, respectively, which are explained by a stepwise process where breakdown of a zwitterionic tetrahedral intermediate (T(+/-)) to products is rate limiting. The Br?nsted-type plot for the reactions of the series of SAA with ClPNPC is biphasic with slopes beta(1) = 0.2 (high pK(a) region) and beta(2) = 0.9 (low pK(a) region) and a curvature center at pK(a)(0) = 10.6. This plot is in accordance with a stepwise mechanism through T(+/-) and a change in the rate-determining step, from T(+/-) breakdown to T(+/-) formation as the basicity of the SAA increases. Two conclusions arise from these results: (i) QUIN are better leaving groups from T(+/-) than isobasic SAA, and (ii) the non-leaving group effect on k(N) for these reactions is small, since beta(nlg) ranges from -0.2 to - 0.3. From these values, it is deduced that ClPNPC is ca. 70% more reactive than MPNPC toward SAA and QUIN, when expulsion of the leaving group from T(+/-) is the rate determining step. 相似文献
99.
Recent results on blends containing star polymers have revived the interest on the interaction parameters of structures that contain junctions between chains, a matter which can be connected with the earlier studies on the influence of crosslinks on the interaction parameters of polymer networks and gels. Here, we review results on crosslinked networks and star polymer solutions together with the more recent work on star polymer blends. The review covers swelling and elastic deformation of gels, differential vapour sorption between crosslinked and uncrosslinked polymers, osmotic equilibrium of gels and of star polymer solutions, and neutron scattering of polymer blends containing star polymers. In the systems reviewed, the interaction parameters of stars and networks differ from those of linear chains, and the difference is attributed mainly to entropic effects. 相似文献
100.
Dr. Tuan-Anh Phan Dr. Nicola Armaroli Dr. Alejandra Saavedra Moncada Dr. Elisa Bandini Dr. Béatrice Delavaux-Nicot Dr. Jean-François Nierengarten Prof. Dominique Armspach 《Angewandte Chemie (International ed. in English)》2023,62(6):e202214638
A β-cyclodextrin-based diphosphane with metal-confining properties was efficiently synthesized thanks to an unprecedented Smiles-like rearrangement of diphenyl-(2-phosphanylphenyl)phosphane in the presence of excess n-BuLi. The cis-chelating bidentate ligand is capable of forming very stable heteroleptic [Cu(NN)(PP)]+ complexes in which a metal-bound diimine ligand (bpy, phen, or mmp) is located within the cyclodextrin cavity. As a result of ligand encapsulation, flattening of the metal tetrahedral geometry in the excited state is disfavored, thereby resulting in enhanced luminescent properties. 相似文献