4,4′-Substituted biphenyl coronands. Preparation of a new selective fluorescent sensor for mercury salts

Six new 4,4′-substituted biphenyl coronands have been prepared. The ligands containing dimethylamino groups in the biphenyl moiety have been used in transition metal cations’ complexation and one of them (3) has demonstrated to be a selective fluorescent sensor for mercury. Stoichiometries of the formed complexes and complexation constants have been determined by titration experiments. In addition, the extractant ability of some ligands has also been studied. Finally, the electrochemical properties of some of these ligands are also described.     

Self-assembly of a tetranuclear Ni4 cluster with an S = 4 ground state: the first 3d metal cluster bearing a mu4-eta2:eta2-O,O carbonate ligand

Reaction of nickel(II) acetate with H(3)L (2-(5-bromo-2-hydroxyphenyl)-1,3-bis[4-(5-bromo-2-hydroxyphenyl)-3-azabut-3-enyl]-1,3-imidazolidine) yields [Ni(2)L(OAc)(H(2)O)(2)].3MeCN.2H(2)O (1.3MeCN.2H(2)O), crystallographically characterized. 1 is unstable in solution for a long time and hydrolyzes to give [Ni(2)L(o-OC(6)H(3)BrCHO)(H(2)O)].2.25MeCN.H(2)O (2.2.25MeCN.H(2)O). In addition, 1 uptakes CO(2) from air in a basic methanol/acetonitrile solution, yielding [[Ni(2)L(MeOH)](2)(CO(3))].1.5MeOH.MeCN.H(2)O (3.1.5MeOH.MeCN.H(2)O). The X-ray characterization of 3 reveals that it is a tetranuclear nickel cluster, which can be considered as the result of a self-assembly process from two dinuclear [Ni(2)L](+) blocks, joined by a mu(4)-eta(2):eta(2)-O,O carbonate ligand. The coordination mode of the carbonate anion is highly unusual and, to the best of our knowledge, it has not been described thus far for first-row transition metal complexes or magnetically studied until now. Magnetic characterization of 1 and 3 shows net intramolecular ferromagnetic coupling between the metal atoms in both cases, with S = 2 and S = 4 ground states for 1 and 3, respectively.     

{Fe(3CNpy)2[Cu(3CNpy)(mu-CN)2]2}: a one-dimensional cyanide-based spin-crossover coordination polymer

A novel one-dimensional coordination polymer made up of Fe(II), 3-cyanopyridine (3CNpy), and the singular in situ formed [Cu(I)(3CNpy)(CN)2]- anionic bridge has been synthesized. This compound undergoes a spin-crossover behavior according to its magnetic and calorimetric properties. The crystal structure of the title compound has been studied in the high- and low-spin states and correlated with the character of the spin conversion. Evidence for intense spin-state-dependent Cu....Cu interactions between the chains is also reported.     

Suzuki-Miyaura cross-coupling reactions of aryl tellurides with potassium aryltrifluoroborate salts

[reaction: see text] Palladium(0)-catalyzed cross-coupling between potassium aryltrifluoroborate salts and aryl tellurides proceeds readily to afford the desired biaryls in good to excellent yield. The reaction seems to be unaffected by the presence of electron-withdrawing or electron-donating substituents in both the potassium aryltrifluoroborate salts and aryl tellurides partners. Biaryls containing a variety of functional groups can be prepared. A chemoselectivity study was also carried out using aryl tellurides bearing halogen atoms in the same compound. In addition, this new version of the Suzuki-Miyaura cross-coupling reaction was monitored by electrospray ionization mass spectrometry where some reaction intermediates were detected and analyzed.     

Regiospecific synthesis of 4-alkoxy and 4-amino substituted 2-trifluoromethyl pyrroles

A simple and regiospecific synthesis of 4-alkoxy(amino)-2-trifluoromethyl pyrroles from 5-azido-4-alkoxy(amino)-1,1,1-trifluoro-pent-3-en-2-ones by an aza-Wittig cyclization of aminophosphoranes is described. The structures of the pyrroles and their synthetic intermediates were supported by NMR and HRMS analysis.     

Er, Yb Doped Yttrium Based Nanosized Phosphors: Particle Size, “Host Lattice” and Doping Ion Concentration Effects on Upconversion Efficiency

The upconverter phosphors studied herein have different percentages of Er³⁺ and Yb³⁺ as doping ions in different Y³⁺ matrixes (Y₂O₃, Y₂O₂S), and were prepared from different precursors (polymeric resin, oxalate, basic carbonate) and method (combustion). Upconversion emission spectra were recorded at 298 K for all the doped samples in the visible region, for efficiency and Green/Red emission relative intensity comparisons. Therefore, an investigation of the influence of the doping ion concentration, particle size and host lattice on the upconversion process is provided in view of the UPT (Upconverting phosphor technology application). On the basis of the results, it was possible to evaluate the best combination for a specific assay, considering whether it is advantageous to have the greatest contribution from the green or red emissions, or from both in comparable intensities.     

Use of Fluorescence Probes for Detection of Reactive Nitrogen Species: A Review

The biological and toxicological effects that have been attributed to reactive nitrogen species (RNS) are increasingly stirring the scientific inquisitiveness about the molecular mechanisms involved. However, RNS present some characteristics that complicate their detection, namely their short lifetime and the normal presence of a variety of endogenous compounds capable of reacting with these reactive species, when the studies are performed in biological matrices. The development of methodologies capable of circumvent these difficulties is thus of fundamental importance. Fluorescence probes are particularly important due to their high sensibility and usefulness in temporal and spatial monitoring of RNS, particularly in microanalysis conditions in biological media akin to cells or tissues. In the present review is given an account of the fluorescence probes that have been used for detection of nitric oxide (^⋅NO), peroxynitrite anion (ONOO⁻), as well as of some of its derivatives in biological and nonbiological media.     

Cytotoxicity and physico-chemical evaluation of acetylated and pegylated cellulose nanocrystals

The high hydrophilicity of cellulose nanocrystals (CNC) may result in poor dispersion in some matrices and solvents. So in this work, two different methodologies were used to reduce the hydrophilicity of CNC. In the first methodology, CNC were acetylated (CNC-Ac) in a mixture of acetic and hydrochloric acid, and in the second methodology, polyethylene glycol (PEG) was adsorbed onto CNC surface (CNC-PEG) under stirring in aqueous solution. CNC obtained by both methods were characterized by transmission electron microscopy (TEM), infrared spectroscopy (FTIR), X-ray diffraction (XRD), dynamic light scattering (DLS), zeta potential, and thermogravimetric analysis (TGA). Images of TEM showed that the intrinsic morphology of cellulose was preserved after both treatments. FTIR confirmed acetylation reaction by the presence of a new band at 1732 cm^?1 (acetate groups) and the consumption of OH groups. XRD showed a reduction in the crystallinity index for both applied methodologies. DLS showed reduced stability in water for CNC-Ac and CNC-PEG. Values of zeta potential changed after acetylation, from ??45 mV (CNC) to ??1 mV (CNC-Ac), and after adsorption of PEG, to ??26.7 mV (CNC-PEG). TGA showed a reduction in the thermal stability after both treatments and a change in the main degradation behavior for CNC-PEG. MTT assays showed that both proposed functionalizations induce cell proliferation, being even more evident for acetylation because, in addition to viability increase with time, it increased with the sample concentration.     

Entanglement generation through the interplay of harmonic driving and interaction in coupled superconducting qubits

We study the manipulation of quantum entanglement by periodic external fields. As an entanglement measure we compute numerically the concurrence of two coupled superconducting qubits both driven by a dc + ac external control parameter. We show that when the driving term of the Hamiltonian commutes with the qubit–qubit interaction term, it is possible to create or destroy entanglement in a controlled way by tuning the system at or near multiphoton resonances. On the other hand, when the driving does not commute with the qubit–qubit interaction, the control and generation of entanglement induced by the driving field is more robust and extended in parameter space, beyond the multiphoton resonances.     

Extreme Value Laws for Dynamical Systems with Countable Extremal Sets

We consider stationary stochastic processes arising from dynamical systems by evaluating a given observable along the orbits of the system. We focus on the extremal behaviour of the process, which is related to the entrance in certain regions of the phase space, which correspond to neighbourhoods of the maximal set \(\mathcal M\), i.e.,the set of points where the observable is maximised. The main novelty here is the fact that we consider that the set \(\mathcal M\) may have a countable number of points, which are associated by belonging to the orbit of a certain point, and may have accumulation points. In order to prove the existence of distributional limits and study the intensity of clustering, given by the Extremal Index, we generalise the conditions previously introduced in Freitas (Adv Math 231(5): 2626–2665, 2012, Stoch Process Appl 125(4): 1653–1687, 2015).