Dielectric Spectroscopy Analysis of Liquid Crystals Recovered from End-of-Life Liquid Crystal Displays

In the present work, the dielectric properties of recycled liquid crystals (LCs) (non-purified, purified, and doped with diamond nanoparticles at 0.05, 0.1, and 0.2 wt%) were investigated. The studied LC mixtures were obtained from industrial recycling of end-of-life LC displays presenting mainly nematic phases. Dielectric measurements were carried out at room temperature on a frequency range from 0.1 to 10⁶ Hz using an impedance analyzer. The amplitude of the oscillating voltage was fixed at 1 V using cells with homogeneous and homeotropic alignments. Results show that the dielectric anisotropy of all purified samples presents positive values and decreases after the addition of diamond nanoparticles to the LC mixtures. DC conductivity values were obtained by applying the universal law of dielectric response proposed by Jonscher. In addition, conductivity of the doped LC mixtures is lower than that of the undoped and non-purified LC.     

Effect of the Ethanol/BTC Ratio on the Methane Uptake of Mechanochemically Synthesized MOF-199

We report on a detailed textural analysis of mechanochemically synthesized MOF-199 including N₂ adsorption-desorption and CO₂ adsorption isotherms data at 77 K and 273 K (up to atmospheric pressure), respectively, and CH₄ adsorption data at 298 K (up to 35 bar). We used the isotherm adsorption data to determine the micropore volume of the MOF-199 structures, to establish their methane uptake capacity and to understand how these properties depended on the Ethanol/BTC ratio used during the synthesis. The maximum methane uptake capacity for our specimens was recorded at 130 v/v at 35 bars. These results open an avenue for a better understanding of alternative manufacturing processes of MOF structures for gas storage applications.     

Growth and Atomic-Scale Characterization of Ultrathin Silica and Germania Films: The Crucial Role of the Metal Support

The present review reports on the preparation and atomic-scale characterization of the thinnest possible films of the glass-forming materials silica and germania. To this end state-of-the-art surface science techniques, in particular scanning probe microscopy, and density functional theory calculations have been employed. The investigated films range from monolayer to bilayer coverage where both, the crystalline and the amorphous films, contain characteristic XO₄ (X=Si,Ge) building blocks. A side-by-side comparison of silica and germania monolayer, zigzag phase and bilayer films supported on Mo(112), Ru(0001), Pt(111), and Au(111) leads to a more general comprehension of the network structure of glass former materials. This allows us to understand the crucial role of the metal support for the pathway from crystalline to amorphous ultrathin film growth.     

Incorporation of β-Alanine in Cu(II) ATCUN Peptide Complexes Increases ROS Levels,DNA Cleavage and Antiproliferative Activity**

Redox-active Cu(II) complexes are able to form reactive oxygen species (ROS) in the presence of oxygen and reducing agents. Recently, Faller et al. reported that ROS generation by Cu(II) ATCUN complexes is not as high as assumed for decades. High complex stability results in silencing of the Cu(II)/Cu(I) redox cycle and therefore leads to low ROS generation. In this work, we demonstrate that an exchange of the α-amino acid Gly with the β-amino acid β-Ala at position 2 (Gly2→β-Ala2) of the ATCUN motif reinstates ROS production (^•OH and H₂O₂). Potentiometry, cyclic voltammetry, EPR spectroscopy and DFT simulations were utilized to explain the increased ROS generation of these β-Ala2-containing ATCUN complexes. We also observed enhanced oxidative cleavage activity towards plasmid DNA for β-Ala2 compared to the Gly2 complexes. Modifications with positively charged Lys residues increased the DNA affinity through electrostatic interactions as determined by UV/VIS, fluorescence, and CD spectroscopy, and consequently led to a further increase in nuclease activity. A similar trend was observed regarding the cytotoxic activity of the complexes against several human cancer cell lines where β-Ala2 peptide complexes had lower IC₅₀ values compared to Gly2. The higher cytotoxicity could be attributed to an increased cellular uptake as determined by ICP-MS measurements.     

Desorption/ionization efficiencies of triacylglycerols and phospholipids via EASI‐MS

Knowledge of the major effects governing desorption/ionization efficiency is required for the development and application of ambient mass spectrometry. Although all triacylglycerols (TAG) have the same favorable protonation and cationization sites, their desorption/ionization efficiencies can vary dramatically during easy ambient sonic‐spray ionization because of structural differences in the carbon chain. To quantify this somewhat surprising and drastic effect, we have performed a systematic investigation of desorption/ionization efficiencies as a function of unsaturation and length for TAG as well as for diacylglycerols, monoacylglycerols and several phospholipids (PL). Affinities for Na⁺ as a function of unsaturation level have also been assayed via comprehensive metadynamics calculations to understand the influence of this phenomenon on the ionization efficiency. The results suggest that dipole–dipole interactions within a carbon chain tuned by unsaturation sites govern ionization efficiency of TAG and PL. Copyright © 2014 John Wiley & Sons, Ltd.     

Polyphenolic Composition and Antioxidant Activity (ORAC,EPR and Cellular) of Different Extracts of Argylia radiata Vitroplants and Natural Roots

Plant biochemistry studies have increased in recent years due to their potential to improve human health. Argylia radiata is an extremophile plant with an interesting polyphenolic profile. However, its biomass is scarce and occasionally available. Argylia in vitro biomass was obtained from tissue culture and compared with in vivo roots regarding its polyphenolic and flavonoid content. Different solvents were used to prepare extracts from the in vitro tissue of callus and aerial plant organs and in vivo roots. UPLC-MS/MS was used to assess the chemical composition of each extract. ORAC-FL and scavenging of free radicals (DPPH and OH) methods were used to determine the antioxidant capacity of extracts. Furthermore, the biological activity of the extracts was established using the cellular antioxidant activity method. The vitroplants were a good source of polyphenols (25–68 mg GAE/100 g tissue FW), and methanol was the most efficient solvent. Eight polyphenolic compounds were identified, and their antioxidant properties were investigated by different chemical methods with EPR demonstrating its specific scavenging activity against free radicals. All extracts showed cellular dose-dependent antioxidant activity. The methanolic extract of vitroplants showed the highest cellular antioxidant activity (44.6% and 51%) at 1 and 10 µg/mL of extract, respectively. Vitroplants of A. radiata are proposed as a biotechnological product as a source of antioxidant compounds with multiple applications.     

Thermomechanical treatment of two Ecuadorian zeolite-rich tuffs and their potential usage as supplementary cementitious materials

Two Ecuadorian zeolite-rich tuffs, coded as Zeo1 (Mordenite) and Zeo2 (Clinoptilolite–Heulandite–Mordenite), were treated and used as supplementary cementitious materials (SCM) so as to study the effect of the thermal and mechanical treatments on pozzolanic reaction in mortars. The treatment was carried out by means of thermomechanical process according to a central composite-blocked cube-star experimental design. In this experimental design as independent factors the milling time (48, 60, 90, 120 and 132 min) and the heating temperatures (559, 600, 700, 800 and 841 °C) were used but keeping a constant heating time (5 h), and zeolite-rich tuffs as experimental blocks. The proportion of SCM was kept constant i.e. 15 %. On the other hand, the compressive strength, fixed lime, normalized water in hydrates and mg Ca(OH)₂ per mg Cement at 7, 28 and 45 days, as well as hydration products related to dehydration degree of the zeolitic tuffs (DOD) were used as dependent factors. In addition, Quantitative and High-temperature chamber XRD, TG-DSC, particle size distribution and SEM-EDS were also carried out. The most significant factor was calcination leading to increase in the compressive strength compared to control, but just up to 800 °C because of recrystallization. As a conclusion, a meaningful loss of crystal structure of zeolites was not observed; but instead, the treatment could only lead to removing the water in cages and voids, thus improving the reaction with Ca(OH)₂, producing more hydrates. In addition, lime was not only fixed by pozzolanic reaction, but also by carbonation.     

Abrupt Convergence and Escape Behavior for Birth and Death Chains

We link two phenomena concerning the asymptotical behavior of stochastic processes: (i) abrupt convergence or cut-off phenomenon, and (ii) the escape behavior usually associated to exit from metastability. The former is characterized by convergence at asymptotically deterministic times, while the convergence times for the latter are exponentially distributed. We compare and study both phenomena for discrete-time birth-and-death chains on ℤ with drift towards zero. In particular, this includes energy-driven evolutions with energy functions in the form of a single well. Under suitable drift hypotheses, we show that there is both an abrupt convergence towards zero and escape behavior in the other direction. Furthermore, as the evolutions are reversible, the law of the final escape trajectory coincides with the time reverse of the law of cut-off paths. Thus, for evolutions defined by one-dimensional energy wells with sufficiently steep walls, cut-off and escape behavior are related by time inversion.     

Super-exponential inflation from a dynamical foliation of a 5D vacuum state

We introduce super-exponential inflation (ω<−1) from a 5D Riemann-flat canonical metric on which we make a dynamical foliation. The resulting metric describes a super accelerated expansion for the early universe well known as super-exponential inflation that, for very large times, tends to an asymptotic de Sitter (vacuum dominated) expansion. The scalar field fluctuations are analyzed. The important result here obtained is that the spectral index for energy density fluctuations is not scale invariant, and for cosmological scales becomes ns(k<k_?)?1. However, for astrophysical scales this spectrum changes to negative values ns(k>k_?)<0.