A complete TSDC description of molecular mobilities in polylactide/starch blends from local to normal modes: Effect of composition,moisture, and crystallinity

Thermally stimulated depolarization current is applied to study the dielectric relaxations coexisting from 80 to 380 K in the PLLA/starch, immiscible biodegradable blend system. The relaxation parameters are determined for chain mobilities at different ranges, whether in the amorphous or cold‐crystallized state for PLLA, and totally amorphous one for starch as demonstrated by wide‐angle X‐ray scattering experiments. The PLLA crystallization is favored by the presence of starch, in both the crystallinity degree reached and the crystallization time. The effect of moisture is followed for both the local modes and the segmental mobilities, where a bimodal relaxation for starch sweeps the temperature range, thus evidencing the heterogeneities existing in the starch disordered phase. The moisture plasticization effect is estimated and shows differences in the water absorption in starch either neat or as a minority component. The onset of the segmental mobility in PLLA is independent of composition or crystallinity, but the large intensity decrease observed when PLLA cold‐crystallizes evidences the simultaneous formation of a rigid amorphous fraction and the crystallites. The normal relaxation mode is recorded in amorphous PLLA whether neat or blended, which again demonstrates the absence of interactions among the blend components. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 680–691     

A novel fiber-packed column for on-line preconcentration and speciation analysis of chromium in drinking water with flame atomic absorption spectrometry

A novel on-line preconcentration and determination system based on a fiber-packed column was developed for speciation analysis of Cr in drinking water samples prior to its determination by flame atomic absorption spectrometry (FAAS). All variables involved in the development of the preconcentration method including, pH, eluent type, sample and eluent flow rates, interfering effects, etc., were studied in order to achieve the best analytical performance. A preconcentration factor of 32 was obtained for Cr(VI) and Cr(III). The levels of Cr(III) species were calculated by difference of total Cr and Cr(VI) levels. Total Cr was determined after oxidation of Cr(III) to Cr(VI) with hydrogen peroxide. The calibration graph was linear with a correlation coefficient of 0.999 at levels near the detection limit and up to at least 50 μg L⁻¹. The relative standard deviation (R.S.D.) was 4.3% (C = 5 μg L⁻¹ Cr(VI), n = 10, sample volume = 25 mL). The limit of detection (LOD) for both Cr(III) and Cr(VI) species was 0.3 μg L⁻¹. Verification of the accuracy was carried out by the analysis of a standard reference material (NIST SRM 1643e “Trace elements in natural water”). The method was successfully applied to the determination of Cr(III) and Cr(VI) species in drinking water samples.     

Enantioselective Synthesis of All‐Carbon Quaternary Stereogenic Centers via Copper‐Catalyzed Asymmetric Allylic Alkylation of (Z)‐Allyl Bromides with Organolithium Reagents

A copper/phosphoramidite catalyzed asymmetric allylic alkylation of Z trisubstituted allyl bromides with organolithium reagents is reported. The reaction affords all‐carbon quaternary stereogenic centers in high yields and very good regio‐ and enantioselectivity. This systematic study illustrates the crucial role of the olefin geometry of the allyl substrate on the outcome of the reaction and provides a viable alternative to access these important structural motifs.     

Individual exponential stability for linear skew-products semiflows over a semiflow

Periodica Mathematica Hungarica - In this paper we consider individual stability for linear skew-product semiflows over semiflows by using the standard Perron’s method. To our knowledge, in...     

Synthesis and characterization of tungstophosphoric acid-modified mesoporous sponge-like TUD-1 materials

Mesoporous sponge-like siliceous materials (TUD-1) were synthesized using TEOS (tetraethylorthosilicate) as a precursor of silica and TEA (triethanolamine) as a mesostructure-directing agent. Different TEOS/TEA molar ratios and hydrotreatment times were used, and their influence on the textural and morphological properties of the solids was evaluated. They were characterized by transmission electron microscopy (TEM), X-ray diffraction, and N₂ adsorption/desorption isotherm analysis. By changing the TEOS/TEA molar ratio, micro-mesoporous and mesoporous (with a narrow or wide pore size distribution) materials were obtained. The increment of hydrotreatment times increased the average pore size of TUD-1 and significantly reduced the specific surface area. TEM images showed that the solids were formed by agglomerates of rather spherical particles whose size increased with the increment of the TEA amount used. The structure and morphology of TUD-1 solids modified with tungstophosphoric acid (TPA) were similar to those of the mesoporous silica used as support. Their diffraction patterns did not display any of the characteristic peaks of TPA or its more common hydrates, suggesting that TPA was well dispersed on the support as a noncrystalline phase. In addition, the characterization of all the solids impregnated with TPA by FT-IR and ³¹P NMR indicated the presence of undegraded [PW₁₂O₄₀]^3? and [H_3?XPW₁₂O₄₀]^X? species interacting electrostatically with the ≡Si–OH₂⁺ groups, and by potentiometric titration it was estimated that the solids presented very strong acid sites. The TUD-1 solids modified with TPA gave excellent yield in the solvent-free synthesis of 2,4,5-triphenyl-1H-imidazole, without formation of by-products resulting from competitive reactions or decomposition products. In summary, they are good candidates to be used in multicomponent reactions catalyzed by acids.

Open image in new window

     

Group decision-making based on heterogeneous preference relations with self-confidence

Preference relations are very useful to express decision makers’ preferences over alternatives in the process of group decision-making. However, the multiple self-confidence levels are not considered in existing preference relations. In this study, we define the preference relation with self-confidence by taking multiple self-confidence levels into consideration, and we call it the preference relation with self-confidence. Furthermore, we present a two-stage linear programming model for estimating the collective preference vector for the group decision-making based on heterogeneous preference relations with self-confidence. Finally, numerical examples are used to illustrate the two-stage linear programming model, and a comparative analysis is carried out to show how self-confidence levels influence on the group decision-making results.     

The meso Helix: Symmetry and Symmetry‐Breaking in Dynamic Oligourea Foldamers with Reversible Hydrogen‐Bond Polarity

Oligoureas (up to n=6) of meso cyclohexane‐1,2‐diamine were synthesized by chain extension with an enzymatically desymmetrized monomer 2 . Despite being achiral, the meso oligomers adopt chiral canonical 2.5‐helical conformations, the equally populated enantiomeric screw‐sense conformers of which are in slow exchange on the NMR timescale, with a barrier to screw‐sense inversion of about 70 kJ mol^?1. Screw‐sense inversion in these helical foldamers is coupled with cyclohexane ring‐flipping, and results in a reversal of the directionality of the hydrogen bonding in the helix. The termini of the meso oligomers are enantiotopic, and desymmetrized analogues of the oligoureas with differentially and enantioselectively protected termini display moderate screw‐sense preferences. A screw‐sense preference may furthermore be induced in the achiral, meso oligoureas by formation of a 1:1 hydrogen‐bonded complex with the carboxylate anion of Boc‐d ‐proline. The meso oligoureas are the first examples of hydrogen‐bonded foldamers with reversible hydrogen‐bond directionality.     

Semi-Slant Submanifolds of a Sasakian Manifold

We define and study both bi-slant and semi-slant submanifolds of an almost contact metric manifold and, in particular, of a Sasakian manifold. We prove a characterization theorem for semi-slant submanifolds and we obtain integrability conditions for the distributions which are involved in the definition of such submanifolds. We also study an interesting particular class of semi-slant submanifolds.     

Enantiospecific synthesis of the phospholipase A2 inhibitor (-)-cinatrin B

The first enantiospecific synthesis of phospholipase A2 (PLA2) inhibitor (-)-cinatrin B (2) from the D-arabinose derivative 9 is described. The spirolactone system was formed by an Ireland-Claisen rearrangement of the allyl ester 8 followed by hydrolysis and stereoselective iodolactonization. The stereoselectivity of the rearrangement was controlled by the asymmetry in the allylic alcohol fragment. Ester (S)-8 gave the desired rearrangement product 7 and the epimer 13 in high yield as a 73:27 ratio, respectively. The final stereocenter at C2 was introduced via a chelation-controlled addition of the Grignard reagent derived from trimethylsilylacetylene to alpha-hydroxy ketone 6. Transformation of the terminal alkyne into the methyl ester 21 followed by acetal hydrolysis and selective lactol oxidation afforded cinatrin B methyl ester (22). Base hydrolysis and acid-induced relactonization then gave (-)-cinatrin B (2).     

Rapid determination of methyl tert-butyl ether using dynamic headspace/ion mobility spectrometry

Using an original, experimental set-up named dynamic headspace/IMS (DHS/IMS), ppb levels of methyl tert-butyl ether (MTBE), a gasoline additive and environmental pollutant, were determined in drinking and ground water. A portable IMS (Bruker, Raid-1 model) was connected to the outlet of a Drechsel bottle containing 100 ml of water-based sample. Automatically activated to sample air, the IMS built-in pump was used to produce a continuous and gentle air flow bubbling through the water-based sample. This allowed volatile MTBE to be isolated and transferred into the Drechsel headspace and then into the IMS. Analyses of reference solutions and real samples resulted in MTBE detection limits of 20 ppb, calibration curves in the 20-200 ppb range, and relative standard deviations of 4.7 and 8.4%, respectively, for inter- and intra-day reproducibility tests. Detection limits were further improved to 0.5 ppb by means of a Tenax trap cooled with liquid nitrogen, placed between the sample bottle and the IMS. Overall, DHS/IMS could well become a simple and cost-effective tool for rapid and on-line analysis of volatile organic compounds in water.