Exploring the Phase-Selective,Green, Hydrothermal Synthesis of Upconverting Doped Sodium Yttrium Fluoride: Effects of Temperature,Time, and Precursors

The aim of this work was i) to develop a hydrothermal, low-temperature synthesis protocol affording the upconverting hexagonal phase NaYF₄ with suitable dopants while adhering to the “green chemistry” standards and ii) to explore the effect that different parameters have on the products. In optimizing the synthesis protocol, short reaction times and low temperatures (below 150 °C) were considered. Yb³⁺ and Er³⁺ ions were chosen as dopants for the NaYF₄ material. Within the context of the second goal, parameters including nature of the precursors, treatment temperature, and treatment time were investigated to afford a pure hexagonal crystalline phase, both in the doped and undoped materials. To fully explore the synthesis results, the prepared materials were characterized from a structural (XRD), compositional (XPS, ICP-MS), and morphological (SEM) point of view. The upconverting properties of the compounds were confirmed by photoluminescence measurements.     

Parton distributions and new physics searches: the Drell–Yan forward–backward asymmetry as a case study

We present the first unquenched lattice-QCD calculation of the form factors for the decay \(B\rightarrow D^*\ell \nu \) at nonzero recoil. Our analysis includes 15 MILC ensembles with \(N_f=2+1\) flavors of asqtad sea quarks, with a strange quark mass close to its physical mass. The lattice spacings range from \(a\approx 0.15\) fm down to 0.045 fm, while the ratio between the light- and the strange-quark masses ranges from 0.05 to 0.4. The valence b and c quarks are treated using the Wilson-clover action with the Fermilab interpretation, whereas the light sector employs asqtad staggered fermions. We extrapolate our results to the physical point in the continuum limit using rooted staggered heavy-light meson chiral perturbation theory. Then we apply a model-independent parametrization to extend the form factors to the full kinematic range. With this parametrization we perform a joint lattice-QCD/experiment fit using several experimental datasets to determine the CKM matrix element \(|V_{cb}|\). We obtain \(\left| V_{cb}\right| = (38.40 \pm 0.68_{\text {th}} \pm 0.34_{\text {exp}} \pm 0.18_{\text {EM}})\times 10^{-3}\). The first error is theoretical, the second comes from experiment and the last one includes electromagnetic and electroweak uncertainties, with an overall \(\chi ^2\text {/dof} = 126/84\), which illustrates the tensions between the experimental data sets, and between theory and experiment. This result is in agreement with previous exclusive determinations, but the tension with the inclusive determination remains. Finally, we integrate the differential decay rate obtained solely from lattice data to predict \(R(D^*) = 0.265 \pm 0.013\), which confirms the current tension between theory and experiment.

     

Applications of dynamic combinatorial chemistry for the determination of effective molarity

A new strategy for determining thermodynamic effective molarities (EM) for macrocylisation reactions using dynamic combinatorial chemistry under dilute conditions is presented. At low concentrations, below the critical value, Dynamic Libraries (DLs) of bifunctional building blocks contain only cyclic species, so it is not possible to quantify the equilibria between linear and cyclic species. However, addition of a monofunctional chain stopper can be used to promote the formation of linear oligomers allowing measurement of EM for all cyclic species present in the DL. The effectiveness of this approach was demonstrated for DLs generated from mixtures of 1,3-diimine calix[4]arenes, linear diaminoalkanes and monoaminoalkanes. For macrocycles deriving from one bifunctional calixarene and one diamine, there is an alternating pattern of EM values with the number of methylene units in the diamine: odd numbers give significantly higher EMs than even numbers. For odd numbers of methylene units, the alkyl chain can adopt an extended all anti conformation, whereas for even numbers of methylene units, gauche conformations are required for cyclisation, and the associated strain reduces EM. The value of EM for the five-carbon linker indicates that this macrocycle is a strainless ring.     

Single‐Walled Carbon Nanotubes in Highly Viscous Media: A Comparison between the Dispersive Agents [BMIM][BF4], L121, and Triton X‐100

Dispersions of single‐walled carbon nanotubes (SWNTs) have been prepared by using the room‐temperature ionic liquid [BMIM][BF₄] (1‐butyl‐3‐methylimidazolium tetrafluoroborate), the triblock copolymer Pluronic L121 [poly(ethylene oxide)₅‐poly(propylene oxide)₆₈‐poly(ethylene oxide)₅] and the non‐ionic surfactant Triton X‐100 (TX100) in the pure state. The size of the SWNTs aggregates and the dispersion degree in the three viscous systems depend on the sonication time, as highlighted by UV/Vis/NIR spectroscopy and optical microscopy analysis. A nonlinear increase in conductivity can be observed as a function of the SWNTs loading, as suggested by electrochemical impedance spectroscopy. The generation of a three‐dimensional network of SWNTs showing a viscoelastic gel‐like behavior above a critical percolation concentration has been found at 25 °C in all the investigated systems by oscillatory rheology measurements.     

Ferroxidase Activity in Eukaryotic Ferritin is Controlled by Accessory‐Iron‐Binding Sites in the Catalytic Cavity

Ferritins are iron‐storage nanocage proteins that catalyze the oxidation of Fe²⁺ to Fe³⁺ at ferroxidase sites. By a combination of structural and spectroscopic techniques, Asp140, together with previously identified Glu57 and Glu136, is demonstrated to be an essential residue to promote the iron oxidation at the ferroxidase site. However, the presence of these three carboxylate moieties in close proximity to the catalytic centers is not essential to achieve binding of the Fe²⁺ substrate to the diferric ferroxidase sites with the same coordination geometries as in the wild‐type cages.     

Electrically Switchable Magnetic Molecules: Inducing a Magnetic Coupling by Means of an External Electric Field in a Mixed‐Valence Polyoxovanadate Cluster

Herein we evaluate the influence of an electric field on the coupling of two delocalized electrons in the mixed‐valence polyoxometalate (POM) [GeV₁₄O₄₀]^8? (in short V₁₄) by using both a t‐J model Hamiltonian and DFT calculations. In absence of an electric field the compound is paramagnetic, because the two electrons are localized on different parts of the POM. When an electric field is applied, an abrupt change of the magnetic coupling between the two delocalized electrons can be induced. Indeed, the field forces the two electrons to localize on nearest‐neighbors metal centers, leading to a very strong antiferromagnetic coupling. Both theoretical approaches have led to similar results, emphasizing that the sharp spin transition induced by the electric field in the V₁₄ system is a robust phenomenon, intramolecular in nature, and barely influenced by small changes on the external structure.     

Thioetherphenolate group 4 metal complexes in the ring opening polymerization of rac‐β‐Butyrolactone

Group 4 complexes 1 – 3 [ 1 = (t‐BuOS)₂Ti(O‐i‐Pr)₂; 2 = (t‐BuOS)₂Zr(O‐t‐Bu)₂; 3 = (t‐BuOS)₂Hf(O‐t‐Bu)₂] supported by two phenolate bidentate ligands (t‐BuOS‐H = 4,6‐di‐tert‐butyl‐2‐phenylsulfanylphenol) promote the well‐controlled ring opening polymerization of rac‐β‐butyrolactone. In presence of isopropanol, low dispersities and molecular weights proportional to the equivalents of isopropanol are achieved. Moreover, the zirconium complex is effective in the copolymerization of rac‐β‐butyrolactone with rac‐lactide. The 13 C nuclear magnetic resonance analysis revealed that the obtained copolymers have a tapered diblock microstructure consisting of an initial block composed of lactide sequences and a terminal block composed of butyrolactone sequences. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3132–3139