An Expedient Method for the Umpolung Coupling of Enols with Heteronucleophiles**

In this paper, we present an unprecedented and general umpolung protocol that allows the functionalization of silyl enol ethers and of 1,3-dicarbonyl compounds with a large range of heteroatom nucleophiles, including carboxylic acids, alcohols, primary and secondary amines, azide, thiols, and also anionic carbamates derived from CO₂. The scope of the reaction also extends to carbon-based nucleophiles. The reaction relies on the use of 1-bromo-3,3-dimethyl-1,3-dihydro-1λ³[d][1,2]iodaoxole, which provides a key α-brominated carbonyl intermediate. The reaction mechanism has been studied experimentally and by DFT, and we propose formation of an unusual enolonium intermediate with a halogen-bonded bromide.     

Zinc Oxide Nanoparticles and Zinc Sulfate Impact Physiological Parameters and Boosts Lipid Peroxidation in Soil Grown Coriander Plants (Coriandrum sativum)

The objective of this study was to determine the oxidative stress and the physiological and antioxidant responses of coriander plants (Coriandrum sativum) grown for 58 days in soil with zinc oxide nanoparticles (ZnO NPs) and zinc sulfate (ZnSO₄) at concentrations of 0, 100, 200, 300, and 400 mg of Zn/kg of soil. The results revealed that all Zn compounds increased the total chlorophyll content (CHLt) by at least 45%, compared to the control group; however, with 400 mg/kg of ZnSO₄, chlorophyll accumulation decreased by 34.6%. Zn determination by induction-plasma-coupled atomic emission spectrometry (ICP–AES) showed that Zn absorption in roots and shoots occurred in plants exposed to ZnSO₄ at all concentrations, which resulted in high levels of hydrogen peroxide (H₂O₂) and malondialdehyde (MDA). Only at 400 mg/kg of ZnSO₄, a 78.6% decrease in the MDA levels was observed. According to the results, the ZnSO₄ treatments were more effective than the ZnO NPs to increase the antioxidant activity of catalase (CAT), ascorbate peroxidase (APX), and peroxidases (POD). The results corroborate that phytotoxicity was higher in plants subjected to ZnSO₄ compared to treatments with ZnO NPs, which suggests that the toxicity was due to Zn accumulation in the tissues by absorbing dissolved Zn⁺⁺ ions.     

Black hole entropy quantization

Ever since the pioneering works of Bekenstein and Hawking, black hole entropy has been known to have a quantum origin. Furthermore, it has long been argued by Bekenstein that entropy should be quantized in discrete (equidistant) steps given its identification with horizon area in (semi-)classical general relativity and the properties of area as an adiabatic invariant. This lead to the suggestion that the black hole area should also be quantized in equidistant steps to account for the discrete black hole entropy. Here we shall show that loop quantum gravity, in which area is not quantized in equidistant steps, can nevertheless be consistent with Bekenstein's equidistant entropy proposal in a subtle way. For that we perform a detailed analysis of the number of microstates compatible with a given area and show consistency with the Bekenstein framework when an oscillatory behavior in the entropy-area relation is properly interpreted.     

Electron microscopy characterization of nanostructured carbon obtained from chlorination of metallocenes and metal carbides

In this work we report some new well-defined carbon nanostructures produced by direct chlorination of metallocenes (ferrocene and cobaltocene) and NbC, at temperatures from 100 to 900 degrees C. Thus, amorphous carbon nanotubes with variable dimensions depending on reaction temperature were produced from ferrocene. When cobaltocene is the carbon precursor the main product are solid amorphous nanospheres. The high refractory metal carbide NbC as carbon source favours the growth of nanospherical cabbage-like particles with a higher degree of graphene sheets order. Besides, NbC crystallites encapsulated in an amorphous carbon shell were also found at lower temperatures (T< or =700 degrees C).     

The turnpike property in finite-dimensional nonlinear optimal control

Turnpike properties have been established long time ago in finite-dimensional optimal control problems arising in econometry. They refer to the fact that, under quite general assumptions, the optimal solutions of a given optimal control problem settled in large time consist approximately of three pieces, the first and the last of which being transient short-time arcs, and the middle piece being a long-time arc staying exponentially close to the optimal steady-state solution of an associated static optimal control problem. We provide in this paper a general version of a turnpike theorem, valuable for nonlinear dynamics without any specific assumption, and for very general terminal conditions. Not only the optimal trajectory is shown to remain exponentially close to a steady-state, but also the corresponding adjoint vector of the Pontryagin maximum principle. The exponential closedness is quantified with the use of appropriate normal forms of Riccati equations. We show then how the property on the adjoint vector can be adequately used in order to initialize successfully a numerical direct method, or a shooting method. In particular, we provide an appropriate variant of the usual shooting method in which we initialize the adjoint vector, not at the initial time, but at the middle of the trajectory.     

First passage percolation and escape strategies

Consider first passage percolation on with passage times given by i.i.d. random variables with common distribution F. Let be the time from u to v for a path π and the minimal time among all paths from u to v. We ask whether or not there exist points and a semi‐infinite path such that for all n. Necessary and sufficient conditions on F are given for this to occur. When the support of F is unbounded, we also obtain results on the number of edges with large passage time used by geodesics. © 2014 Wiley Periodicals, Inc. Random Struct. Alg., 47, 414–423, 2015     

Molecular Recognition of Nucleotides in Water by Scorpiand‐Type Receptors Based on Nucleobase Discrimination

The detection of nucleotides is of crucial importance because they are the basic building blocks of nucleic acids. Scorpiand‐based polyamine receptors functionalized with pyridine or anthracene units are able to form stable complexes with nucleotides in water, based on coulombic, π–π stacking, and hydrogen‐bonding interactions. This behavior has been rationalized by means of an exploration with NMR spectroscopy and DFT calculations. Binding constants were determined by potentiometry. Fluorescence spectroscopy studies have revealed the potential of these receptors as sensors to effectively and selectively distinguish guanosine‐5′‐triphosphate (GTP) from adenosine‐5′‐triphosphate (ATP).     

Two C3‐Symmetric Dy3III Complexes with Triple Di‐μ‐methoxo‐μ‐phenoxo Bridges,Magnetic Ground State,and Single‐Molecule Magnetic Behavior

Two series of isostructural C₃‐symmetric Ln₃ complexes Ln₃ ? [BPh₄] and Ln₃ ? 0.33[Ln(NO₃)₆] (in which Ln^III=Gd and Dy) have been prepared from an amino‐bis(phenol) ligand. X‐ray studies reveal that Ln^III ions are connected by one μ₂‐phenoxo and two μ₃‐methoxo bridges, thus leading to a hexagonal bipyramidal Ln₃O₅ bridging core in which Ln^III ions exhibit a biaugmented trigonal‐prismatic geometry. Magnetic susceptibility studies and ab initio complete active space self‐consistent field (CASSCF) calculations indicate that the magnetic coupling between the Dy^III ions, which possess a high axial anisotropy in the ground state, is very weakly antiferromagnetic and mainly dipolar in nature. To reduce the electronic repulsion from the coordinating oxygen atom with the shortest Dy?O distance, the local magnetic moments are oriented almost perpendicular to the Dy₃ plane, thus leading to a paramagnetic ground state. CASSCF plus restricted active space state interaction (RASSI) calculations also show that the ground and first excited state of the Dy^III ions are separated by approximately 150 and 177 cm^?1, for Dy₃ ? [BPh₄] and Dy₃ ? 0.33[Dy(NO₃)₆], respectively. As expected for these large energy gaps, Dy₃ ? [BPh₄] and Dy₃ ? 0.33[Dy(NO₃)₆] exhibit, under zero direct‐current (dc) field, thermally activated slow relaxation of the magnetization, which overlap with a quantum tunneling relaxation process. Under an applied H_dc field of 1000 Oe, Dy₃ ? [BPh₄] exhibits two thermally activated processes with U_eff values of 34.7 and 19.5 cm^?1, whereas Dy₃ ? 0.33[Dy(NO₃)₆] shows only one activated process with U_eff=19.5 cm^?1.