Miscible blends of poly(ethylene oxide) with brush copolymers of poly(vinyl alcohol)‐graft‐poly(l‐lactide)

Even though poly(ethylene oxide) (PEO) is immiscible with both poly(l ‐lactide) (PLLA) and poly(vinyl alcohol) (PVA), this article shows a working route to obtain miscible blends based on these polymers. The miscibility of these polymers has been analyzed using the solubility parameter approach to choose the proper ratios of the constituents of the blend. Then, PVA has been grafted with l ‐lactide (LLA) through ring‐opening polymerization to obtain a poly(vinyl alcohol)‐graft‐poly(l ‐lactide) (PVA‐g‐PLLA) brush copolymer with 82 mol % LLA according to ¹H and ¹³C NMR spectroscopies. PEO has been blended with the PVA‐g‐PLLA brush copolymer and the miscibility of the system has been analyzed by DSC, FTIR, OM, and SEM. The particular architecture of the blends results in DSC traces lacking clearly distinguishable glass transitions that have been explained considering self‐concentration effects (Lodge and McLeish) and the associated concentration fluctuations. Fortunately, the FTIR analysis is conclusive regarding the miscibility and the specific interactions in these systems. Melting point depression analysis suggests that interactions of intermediate strength and PLOM and SEM reveal homogeneous morphologies for the PEO/PVA‐g‐PLLA blends. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1217–1226     

Generation of bismuthane in non-aqueous media

The generation of BiH₃ in non-aqueous media in an MHS-10 Perkin-Elmer hydride generator is studied. Optimal conditions for generation of BiH₃ inN,N-dimethylformamide, dimethylsulfoxide and formamide (concentration of NaBH₄, acidic medium, optimum volume, characteristic concentration and detection limit) are studied. The results obtained are compared with those corresponding to hydride generation in aqueous medium.     

Dopant distribution in a Tm(3+)-Yb(3+) codoped silica based glass ceramic: an infrared-laser induced upconversion study

The optically active dopant distribution in a Tm(3+)-Yb(3+) doped silica based glass ceramic sample has been investigated. A systematic analysis of the upconversion fluorescence of the Tm(3+)-Yb(3+) codoped glass and glass ceramic has been performed at room temperature. Tm(3+) and Yb(3+) single doped glass and glass ceramics have also been included in the study. Upon infrared excitation at 790 nm into the (3)H(4) level of the Tm(3+) ions a blue upconversion emission is observed, which is drastically increased in the Yb(3+) codoped samples. A rate equation model confirmed the energy transfer upconversion mechanism. Based on these results, the temporal dynamic curves of the levels involved in the upconversion process, (3)H(4), (2)F(5/2), and (1)G(4) were interpreted in the glass ceramic samples. The contribution of the optically active Tm(3+) and Yb(3+) ions in the crystalline and in the vitreous phase of the glass ceramic was distinguished and the ratio of Tm(3+) ions in the crystalline phase could be quantified for the 1 mol % Tm(3+)-2.5 mol % Yb(3+) glass ceramic. A surprising result was obtained for that concentration: the main contribution to the upconversion emission of the glass ceramic is due to Tm(3+)-Yb(3+) ions in the vitreous phase.     

A Theoretical Perspective of the Photochemical Potential in the Spectral Performance of Photovoltaic Cells

We present a novel theoretical approach to the problem of light energy conversion in thermostated semiconductor junctions. Using the classical model of a two-level atom, we deduced formulas for the spectral response and the quantum efficiency in terms of the input photons’ non-zero chemical potential. We also calculated the spectral entropy production and the global efficiency parameter in the thermodynamic limit. The heat transferred to the thermostat results in a dissipative loss that appreciably controls the spectral quantities’ behavior and, therefore, the cell’s performance. The application of the obtained formulas to data extracted from photovoltaic cells enabled us to accurately interpolate experimental data for the spectral response and the quantum efficiency of cells based on Si-, GaAs, and CdTe, among others.     

Structural changes induced on strontium barium niobate glass by femtosecond laser irradiation

Localized modification of the optical properties of erbium doped strontium barium niobate (SBN) glass has been performed using femtosecond laser irradiation. The samples, with composition SrO–BaO–Nb₂O₅–B₂O₅ and doped with 5%mol of Er³⁺, were fabricated using a melt-quenching method. The samples were irradiated with different number of pulses per spot (1–50 pulses) at two different laser fluences (2.6 and 5.6 J/cm²) by using an fs laser amplifier operating at 800 nm and generating pulses with a duration of 120 fs. Micro-luminescent microscopy, using an Ar⁺ laser as excitation source, has been used to analyze the modifications of the luminescent properties of the sample upon fs laser exposure. The emissions of the Er³⁺: ⁴I_11/2→⁴I_15/2 and ⁴I_13/2→⁴I_15/2 transitions allow appreciating the structural modifications caused by femtosecond laser exposure. The lifetimes of the levels involved in these transitions were measured inside and outside the laser irradiated region. These measurements have been compared with those obtained in bulk glass ceramic sample, which is obtained from the glass precursor by a thermal treatment in order to estimate the optimal conditions to produce nanocrystals in a localized region by ultrafast laser irradiation.     

Synthesis and biological evaluation of aromatic analogues of conduritol F, L-chiro-inositol, and dihydroconduritol F structurally related to the amaryllidaceae anticancer constituents

Pancratistatin is a potent anticancer natural product, whose clinical evaluation is hampered by the limited natural abundance and the stereochemically complex structure undermining practical chemical preparation. Fifteen aromatic analogues of conduritol F, l-chiro-inositol, and dihydroconduritol F that possess four of the six pancratistatin stereocenters have been synthesized and evaluated for anticancer activity. These compounds serve as truncated pancratistatin analogues lacking the lactam ring B, but retaining the crucial C10a-C10b bond with the correct stereochemistry. The lack of activity of these compounds provides further insight into pancratistatin's minimum structural requirements for cytotoxicity, particularly the criticality of the intact phenanthridone skeleton. Significantly, these series provide rare examples of simple aromatic conduritol and inositol analogues and, therefore, this study expands the chemistry and biology of these important classes of compounds.     

Quintessential inflation from a variable cosmological constant in a 5D vacuum

We explore an effective 4D cosmological model for the universe where the variable cosmological constant governs its evolution and the pressure remains negative along all the expansion. This model is introduced from a 5D vacuum state where the (space-like) extra coordinate is considered as noncompact. The expansion is produced by the inflaton field, which is considered as nonminimally coupled to gravity. We conclude from experimental data that the coupling of the inflaton with gravity should be weak, but variable in different epochs of the evolution of the universe.