Influence of co‐dopant in the europium reduction in SrAl2O4 host

Xerogels of strontium chlorate and aluminium chlorate doped with europium (un‐co‐doped) and co‐doped with rare earth ions (Ln = Gd, Dy, Er and Y) were prepared using the proteic sol–gel route. Synchrotron radiation was used to investigate the effect of different co‐dopants on the Eu³⁺→ Eu²⁺ reduction process during the synthesis of the samples. Samples were excited at the Eu L_III‐edge and the XANES regions were analyzed. The results suggest that some of the Eu ions can be stabilized in the divalent state and that it is difficult to completely reduce Eu³⁺ to Eu²⁺ during thermal treatment. The mechanisms of the Eu reduction processes are explained by a proposed model based on the incorporation of charge‐compensation defects.     

Bimodal Therapeutic Agents Against Glioblastoma,One of the Most Lethal Forms of Cancer

About 95 % of people diagnosed with glioblastoma die within five years. Glioblastoma is the most aggressive central nervous system tumour. It is necessary to make progress in the glioblastoma treatment so that advanced chemotherapy drugs or radiation therapy or, ideally, two-in-one hybrid systems should be implemented. Tyrosine kinase receptors–inhibitors and boron neutron capture therapy (BNCT), together, could provide a therapeutic strategy. In this work, sunitinib decorated-carborane hybrids were prepared and biologically evaluated identifying excellent antitumoral- and BNCT-agents. One of the selected hybrids was studied against glioma-cells and found to be 4 times more cytotoxic than sunitinib and 1.7 times more effective than ¹⁰B-boronophenylalanine fructose complex when the cells were irradiated with neutrons.     

The Effects of an Impurity in an Ising‐XXZ Diamond Chain on Thermal Entanglement,on Quantum Coherence,and on Quantum Teleportation

The effects of an impurity plaquette on the thermal quantum correlations measurement by the concurrence, on quantum coherence quantified by the recently proposed l₁‐norm of coherence and on quantum teleportation in a Ising‐ $XXZ$ diamond chain are discussed. Such an impurity is formed by the $XXZ$ interaction between the interstitial Heisenberg dimers and the nearest‐neighbor Ising coupling between the nodal and interstitial spins. All the interaction parameters are different from those of the rest of the chain. By tailoring them, quantum entanglement and quantum coherence can be controlled and tuned. Therefore, the quantum resources—thermal entanglement and quantum coherence—of the model exhibit a clear performance improvement in comparison to the original model without impurities. It is demonstrated that quantum teleportation can be tuned by its inclusion. Thermal teleportation is modified in a significant way as well, and a strong increase in the average fidelity is observed. The exact solution is furnished by the use of the transfer‐matrix method.     

Diselenolane-Mediated Cellular Uptake: Efficient Cytosolic Delivery of Probes,Peptides, Proteins,Artificial Metalloenzymes and Protein-Coated Quantum Dots

Cyclic oligochalcogenides are emerging as powerful tools to penetrate cells. With disulfide ring tension maximized, selenium chemistry had to be explored next to enhance speed and selectivity of dynamic covalent exchange on the way into the cytosol. We show that diseleno lipoic acid (DiSeL) delivers a variety of relevant substrates. DiSeL-driven uptake of artificial metalloenzymes enables bioorthogonal fluorophore uncaging within cells. Binding of a bicyclic peptide, phalloidin, to actin fibers evinces targeted delivery to the cytosol. Automated tracking of diffusive compared to directed motility and immobility localizes 79 % of protein-coated quantum dots (QDs) in the cytosol, with little endosomal capture (0.06 %). These results suggest that diselenolanes might act as molecular walkers along disulfide tracks in locally denatured membrane proteins, surrounded by adaptive micellar membrane defects. Miniscule and versatile, DiSeL tags are also readily available, stable, soluble, and non-toxic.     

Synthesis,characterization, density functional theory calculations,and in vitro antibacterial activity of novel transition metal complexes containing an O3-tridentate amoxicillin-based Schiff base: A silver(II) complex as alternative against Pseudomonas aeruginosa resistant to amoxicillin

Transition metal complexes containing an amoxicillin-based Schiff base (H₂L, 3 ) obtained from the condensation of amoxicillin 1 with salicylaldehyde 2 were prepared. Spectroscopic and physicochemical techniques, namely, UV–visible, Fourier-transform infrared spectroscopy, ¹H NMR, electron paramagnetic resonance, transmission electron microscopy, mass spectrometry, magnetic susceptibility, molar conductance, density functional theory (DFT) calculations, together with elemental and thermal analyses were used to characterize the synthesized complexes. Based on these studies, the general formulae [ML(H₂O)₃], where M = Mn 4 , Ni 5 , Zn 6 , and [ML(H₂O)], where M = Cu 7 , Ag 8 , were proposed for the complexes. The amoxicillin-based Schiff base ligand behaved as a dianionic O₃-tridentate chelating agent. DFT studies and magnetic and spectral data revealed octahedral geometries for Mn, Ni, and Zn atoms and distorted tetrahedral geometries for Cu(II) and Ag(II) complexes. Synthesized compounds were tested for antibacterial activity by both agar disk diffusion method and the minimum inhibitory concentration. in vitro bacterial viability revealed that complex 5 had similar antibacterial activity as 1 against Staphylococcus aureus and Staphylococcus epidermidis, whereas Pseudomonas aeruginosa, resistant to amoxicillin, was sensitive to complex 8 . The antibacterial activity of complex 8 could be attributed to its greater catalytic activity as shown by DFT calculations. Toxicity bioassay of the tested compounds showed LC₅₀ values > 1000 ppm, indicating their nontoxicity against brine shrimp nauplii (Artemia salina).     

Fractional Kirchhoff problem with critical indefinite nonlinearity

We study the existence and multiplicity of positive solutions for a family of fractional Kirchhoff equations with critical nonlinearity of the form where is a smooth bounded domain, and . Here M is the Kirchhoff coefficient and is the fractional critical Sobolev exponent. The parameter λ is positive and the is a real valued continuous function which is allowed to change sign. By using a variational approach based on the idea of Nehari manifold technique, we combine effects of a sublinear and a superlinear term to prove our main results.     

Min-Oo Conjecture for Fully Nonlinear Conformally Invariant Equations

In this paper we show rigidity results for supersolutions to fully nonlinear, elliptic, conformally invariant equations on subdomains of the standard n -sphere under suitable conditions along the boundary. We emphasize that our results do not assume concavity on the fully nonlinear equations we will work with. This proves rigidity for compact, connected, locally conformally flat manifolds (M, g) with boundary such that the eigenvalues of the Schouten tensor satisfy a fully nonlinear elliptic inequality and whose boundary is isometric to a geodesic sphere ∂D(r) , where D(r) denotes a geodesic ball of radius r ∈ (0, π/2] in , and totally umbilical with mean curvature bounded below by the mean curvature of this geodesic sphere. Under the above conditions, (M, g) must be isometric to the closed geodesic ball . As a side product, in dimension 2 our methods provide a new proof to Toponogov's theorem about rigidity of compact surfaces carrying a shortest simple geodesic. Roughly speaking, Toponogov's theorem is equivalent to a rigidity theorem for spherical caps in the hyperbolic three-space ℍ³ . In fact, we extend it to obtain rigidity for supersolutions to certain Monge-Ampère equations. © 2019 Wiley Periodicals, Inc.     

13C NMR Chemical Shifts Substituent Effects of (E)- and (Z)-N-ethyl-N-Methylamides

Carbon-13 NMR chemical shifts of a series of (E)- and (Z)-N-ethyl-N-methylamides [RC(O)NEtMe, R=H, Me, Et, i-Pr, t-Bu, CF₃, ClCH₂, Cl₂CH, Cl₃C, BrCH₂, Br₂CH, Br₃C and ICH₂] are reported. The α-carbon and carbonyl carbon chemical shifts are correlated with the empirical α-substituent effect and Charton's electrical parameter ([sgrave]_I), respectively. The N-alkyl carbon resonances were attributed mainly to the γ- and δ-effects of R.     

Theoretical developments and applications of polarization propagators

The Argentinian studies of response properties by applying polarization propagators started more than 35 years ago. It began when the research group led by Professor Ruben Contreras in Buenos Aires started to apply it to the study of NMR spectroscopic parameters on top of semiempirical methods. Novel theoretical developments and its successful early applications make that this group quickly grew up with students from different regions of Argentina. In this review, we shall expose some Argentinian developments of that formalism, including its extension to the relativistic regime and also its latest formal development, which shows how can it be derived from the more fundamental path integral formalism. The interpretative power and the analysis of different electronic effects, that influence the NMR spectroscopic parameters, will be shown with few selected examples. They include molecules with light and heavy atoms, and also hydrogen-bonded systems. Novel results and analysis of earlier and latest developments will also be given. One of the main advantages of the formalism of polarization propagators is its flexibility for being applied in both regimes, relativistic and nonrelativistic in the same manner. One can go from one to the other framework, by only scaling the velocity of light.