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51.
52.
Thomas E. Albrecht-Schmitt David E. Hobart Dayan Páez-Hernández Cristian Celis-Barros 《International journal of quantum chemistry》2020,120(15):e26254
Experimental studies on the speciation of berkelium in carbonate media have shown that complexation of berkelium(III) by carbonate results in spontaneous oxidation to berkelium(IV) and that multiple species can be present in solution. We studied two proposed structures present in solution based on theoretical comparisons with spectroscopic data previously reported for Bk(IV) carbonate solutions. The multiconfigurational character of the ground and low-lying excited states in both complexes is demonstrated to result from the strong spin-orbit coupling. Although bonding in Bk(IV) carbonate and carbonate-hydroxide complexes is dominated by strong Coulombic forces, the presence of non-negligible covalent character is supported by ligand-field theory, natural localized orbitals, topological studies of the electron density, and energy transition state natural orbitals for chemical valence. Bond orders based on natural localized molecular orbitals show that Bk OH bonds possess enhanced orbital overlap, which is reflected in the bond strength. This is also observed in the decomposition of the orbital interaction energy into individual deformation density pairs. 相似文献
53.
Jiajia Ma Felix Schfers Constantin Daniliuc Klaus Bergander Cristian A. Strassert Frank Glorius 《Angewandte Chemie (International ed. in English)》2020,59(24):9639-9645
Lanthanide photocatalysts are much less investigated in synthetic chemistry than rare and expensive late transition metals. We herein introduce GdIII photocatalysis of a highly regioselective, intermolecular [2+2] photocycloaddition/ring‐expansion sequence with indoles, which could provide divergent access to cyclopenta[b]indoles and indolines. A simple and commercially available Gd(OTf)3 salt is sufficient for this visible‐violet‐light‐induced transformation. The reaction proceeds either through a transient or start‐to‐end dearomatization cascade and shows excellent regioselectivity (usually >95:5 r.r.), broad scope (59 examples), good functional group tolerance and facile scale‐up under mild, direct visible‐light‐excitation conditions. Mechanistic investigations reveal that direct excitation of the Gd(OTf)3/indole mixture gives an excited state intermediate, which undergoes the subsequent [2+2] cycloaddition and cyclobutane‐expansion cascade. 相似文献
54.
Kathrin Brmmel Sarah Maskri Ivan Maisuls Christian Paul Konken Marius Rieke Zoltan Peth Cristian A. Strassert Oliver Koch Albrecht Schwab Bernhard Wünsch 《Angewandte Chemie (International ed. in English)》2020,59(21):8277-8284
Small‐molecule probes for the in vitro imaging of KCa3.1 channel‐expressing cells were developed. Senicapoc, showing high affinity and selectivity for the KCa3.1 channels, was chosen as the targeting component. BODIPY dyes 15 – 20 were synthesized and connected by a CuI‐catalyzed azide–alkyne [3+2]cycloaddition with propargyl ether senicapoc derivative 8 , yielding fluorescently labeled ligands 21 – 26 . The dimethylpyrrole‐based imaging probes 25 and 26 allow staining of KCa3.1 channels in NSCLC cells. The specificity was shown by removing the punctate staining pattern by pre‐incubation with senicapoc. The density of KCa3.1 channels detected with 25 and by immunostaining was identical. The punctate structure of the labeled channels could also be observed in living cells. Molecular modeling showed binding of the senicapoc‐targeting component towards the binding site within the ion channel and orientation of the linker with the dye along the inner surface of the ion channel. 相似文献
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Natalia Calonghi Carla Boga Patrizia Nitti Dario Telese Silvia Bordoni Giovanna Farruggia Fioretta Asaro Martina Grandi Chiara Zalambani Gabriele Micheletti 《Molecules (Basel, Switzerland)》2022,27(8)
A series of regioisomers of the hydroxystearic acid (HSA) was prepared, and the effect of the position of the hydroxyl group along the chain on a panel of human cancer cell lines was investigated. Among the various regioisomers, those carrying the hydroxyl at positions 5, 7, and 9 had growth inhibitor activity against various human tumor cell lines, including CaCo-2, HT29, HeLa, MCF7, PC3, and NLF cells. 10-HSA and 11-HSA showed a very weak effect. 8-HSA did not show inhibitory activity in all cell lines. The biological role of 7-HSA and 9-HSA is widely recognized, while little is known about the effects of 5-HSA. Therefore, the biological effects of 5-HSA in HeLa, HT29, MCF7, and NLF cell lines were investigated using the Livecyte’s ptychography technology, which allows correlating changes in proliferation, motility, and morphology as a function of treatment at the same time. 5-HSA not only reduces cell proliferation but also induces changes in cell displacement, directionality, and speed. It is important to characterize the biological effects of 5-HSA, this molecule being an important component of fatty acyl esters of hydroxy fatty acids (FAHFA), a class of endogenous mammalian lipids with noticeable anti-diabetic and anti-inflammatory effects. 相似文献
58.
Mihai Răducă Cristian D. Ene Sorana Ionescu Mihaela Florea 《Journal of Coordination Chemistry》2019,72(8):1222-1237
Abstract1-D coordination polymers, 1∞[Zn(fl)2]·2EtOH and 1∞[Zn(fl)2]·2MeOH, and a dinuclear complex, [{Zn(fl)2}2(dienpip)]·4H2O·4EtOH (dienpip?= N,N′-bis(2-aminoethyl)piperazine), were obtained using Zn(II) ions and fluorescein anions (fl). Thermal analysis shows stability of the polymers after solvent removal up to more than 400?°C. Crystallization solvent molecules were removed under reduced pressure with the preservation of the polymeric structure, 1∞[Zn(fl)2]. Desolvated crystals were exposed to I2 vapors and the crystal structure determination by X-ray diffraction confirmed the presence of I2 molecules in the channels generated in crystals by the metal-organic framework. The iodine content, evaluated by X-ray diffraction, corresponds to the overall formula 1∞[Zn(fl)2]·0.3I2. The optical properties of the coordination polymers and the dinuclear complex have been investigated. 相似文献
59.
The Ram–Yip formula for Macdonald polynomials (at t = 0) provides a statistic which we call charge. In types A and C it can be defined on tensor products of Kashiwara–Nakashima single column crystals. In this paper we prove that the charge is equal to the (negative of the) energy function on affine crystals. The algorithm for computing charge is much simpler and can be more efficiently computed than the recursive definition of energy in terms of the combinatorial R-matrix. 相似文献
60.
Manuel Delgado Cristian Morales-Rodrigo Antonio Suárez J. Ignacio Tello 《Nonlinear Analysis: Real World Applications》2010,11(5):3884-3902
This paper deals with a nonlinear system of parabolic–elliptic type with a logistic source term and coupled boundary conditions related to pattern formation. We prove the existence of a unique positive global in time classical solution. We also analyze the associated stationary problem. Moreover it is proved, under the assumption of sufficiently strong logistic damping, that there is only one nonzero homogeneous equilibrium, and all the solutions to the nonstationary problem tend to this steady state for large times. 相似文献