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991.
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Ariel Carreño-Montero Luis A. Maldonado María Isabel Chávez Simón Hernández-Ortega Guillermo Delgado 《Tetrahedron letters》2019,60(48):151282
The synthesis of ethyl (2′-hydroxy-4′,5′-methylendioxophenyl)acetate, a fragment of the antihyperglycemic natural coumarin subcoriacin, is reported. We found an expeditious route to the title compound in five steps. Final metal catalyzed acid ethanolysis of the vinylic 1,1-methylthio methylsulfoxide derivative afforded the required aryl acetic ester, but in the absence of metal catalyst, an unexpected Pummerer rearrangement produced the 2,3-dimethylthiofuran derivative as the major product. This last result provides an alternative entry to 2,3-dimethlythiobenzofurans. 相似文献
994.
Elías-Zúñiga Alex Palacios-Pineda Luis Manuel Olvera-Trejo Daniel Martínez-Romero Oscar 《Nonlinear dynamics》2020,102(3):1239-1270
Nonlinear Dynamics - In this paper, the dynamics response of a finite extensibility nonlinear elastic (FENE) absorber attached to a nonlinear primary system is investigated by writing the modal... 相似文献
995.
996.
New Perspectives for Old Clusters: Anderson–Evans Anions as Building Blocks of Large Polyoxometalate Frameworks in a Series of Heterometallic 3 d–4 f Species
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Dr. Beñat Artetxe Dr. Santiago Reinoso Dr. Leire San Felices Prof. Luis Lezama Prof. Juan M. Gutiérrez‐Zorrilla Dr. Cristian Vicent Fadi Haso Prof. Tianbo Liu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(13):4616-4625
A series of nine [Sb7W36O133Ln3M2(OAc)(H2O)8]17? heterometallic anions ( Ln3M2 ; Ln=La–Gd, M=Co; Ln=Ce, M=Ni and Zn) have been obtained by reacting 3 d metal disubstituted Krebs‐type tungstoantimonates(III) with early lanthanides. Their unique tetrameric structure contains a novel {MW9O33} capping unit formed by a planar {MW6O24} fragment to which three {WO2} groups are condensed to form a tungstate skeleton identical to that of a hypothetical trilacunary derivative of the ?‐Keggin cluster. It is shown, for the first time, that classical Anderson–Evans {MW6O24} anions can act as building blocks to construct purely inorganic large frameworks. Unprecedented reactivity in the outer ring of these disk‐shaped species is also revealed. The Ln3M2 anions possess chirality owing to a {Sb4O4} cluster being encapsulated in left‐ or right‐handed orientations. Their ability to self‐associate in blackberry‐type vesicles in solution has been assessed for the Ce3Co2 derivative. 相似文献
997.
Luis Gutiérrez-Arzaluz David Ignacio Ramírez-Palma Lillian G. Ramírez-Palma Prof. Dr. José Enrique Barquera-Lozada Prof. Dr. Jorge Peon Prof. Dr. Fernando Cortés-Guzmán 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(3):775-784
Copper(I) complexes (CICs) are of great interest due to their applications as redox mediators and molecular switches. CICs present drastic geometrical change in their excited states, which interferes with their luminescence properties. The photophysical process has been extensively studied by several time-resolved methods to gain an understanding of the dynamics and mechanism of the torsion, which has been explained in terms of a Jahn–Teller effect. Here, we propose an alternative explanation for the photoinduced structural change of CICs, based on electron density redistribution. After photoexcitation of a CIC (S0→S1), a metal-to-ligand charge transfer stabilizes the ligand and destabilizes the metal. A subsequent electron transfer, through an intersystem crossing process, followed by an internal conversion (S1→T2→T1), intensifies the energetic differences between the metal and ligand within the complex. The energy profile of each state is the result of the balance between metal and ligand energy changes. The loss of electrons originates an increase in the attractive potential energy within the copper basin, which is not compensated by the associated reduction of the repulsive atomic potential. To counterbalance the atomic destabilization, the valence shell of the copper center is polarized (defined by ∇2ρ(r) and ∇2Vne(r)) during the deactivation path. This polarization increases the magnitude of the intra-atomic nuclear–electron interactions within the copper atom and provokes the flattening of the structure to obtain the geometry with the maximum interaction between the charge depletions of the metal and the charge concentrations of the ligand. 相似文献
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999.
Fernando Saldaña Ignacio Barradas 《Mathematical Methods in the Applied Sciences》2020,43(3):1216-1229
Persistent infection with human papillomavirus (HPV) is the main cause of cervical cancer. Current HPV vaccines protect against both HPV-16 and -18, which are known to cause approximately 70% of cervical cancer cases worldwide. These vaccines have shown to be highly effective in preventing infection by their targeted types. However, there is a broad diversity of HPV types not targeted by the vaccines, and there is controversy about a possible increase in the prevalence of these non-targeted types after a vaccination program. Here, we propose a within-host metapopulation model to study the possibility of vaccine-induced type replacement for oncogenic types. It is generally believed that the theoretical possibility of type replacement strongly depends on the existence of natural type competition mechanisms. Nevertheless, our results suggest that type replacement is viable at the within-host level if the degree of cross-protection induced by the vaccine is low, even if there is no underlying competition among HPV types. Consequently, the impact of current HPV vaccines at both the immunological and epidemiological levels rely upon the level of cross-protection. 相似文献
1000.
Dr. Thais F. Abelha Dr. Graeme Morris Dr. Sandro M. Lima Dr. Luis H. C. Andrade Dr. Andrew J. McLean Prof. Cameron Alexander Dr. Jesus Calvo-Castro Dr. Callum J. McHugh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(14):3173-3180
Development of novel bioimaging materials that exhibit organelle specific accumulation continues to be at the forefront of research interests and efforts. Among the various subcellular organelles, mitochondria, which are found in the cytoplasm of eukaryotic cells, are of particular interest in relation to their vital function. To date, most molecular probes that target mitochondria utilise delocalised lipophilic cations such as triphenylphosphonium and pyridinium. However, the use of such charged motifs is known to be detrimental to the working function of the mitochondrial transmembrane potential and there remains a strong case for development of neutral mitochondrial fluorescent probes. Herein, we demonstrate for the first time the exploitation of diketopyrrolopyrrole-based chemistries for the realisation of a neutral fluorescent probe that exhibits organelle specific accumulation within the mitochondria at the nanomolar level. The synthesised probe, which bears a neutral triphenylphosphine oxide moiety, exhibits a large Stokes shift and high fluorescence quantum yield in water, both highly sought-after properties in the development of bioimaging agents. In vitro studies reveal no interference with cell metabolism when tested for the human MCF7 breast cancer cell and nanomolar subcellular organelle colocalisation with commercially available mitochondrial staining agent Mitotracker Red. In light of its novelty, neutral structure and the preferential accumulation at nanomolar concentrations we anticipate this work to be of significant interest for the increasingly larger community devoted to the realisation of neutral mitochondrial selective systems and more widely to those engaged in the rational development of superior organic architectures in the biological field. 相似文献