Dye‐Doped Polyhedral Oligomeric Silsesquioxane (POSS)‐Modified Polymeric Matrices for Highly Efficient and Photostable Solid‐State Lasers

Here, the design, synthesis, and characterization of laser nanomaterials based on dye‐doped methyl methacrylate (MMA) crosslinked with octa(propyl‐methacrylate) polyhedral oligomeric silsesquioxane (8MMAPOSS) is reported in relation to their composition and structure. The influence of the silicon content on the laser action of the dye pyrromethene 567 (PM567) is analyzed in a systematic way by increasing the weight proportion of POSS from 1 to 50%. The influence of the inorganic network structure is studied by replacing the 8MMAPOSS comonomer by both the monofunctionalized heptaisobutyl‐methacryl‐POSS (1MMAPOSS), which defines the nanostructured linear network with the POSS cages appearing as pendant groups of the polymeric chains, and also by a new 8‐hydrogenated POSS incorporated as additive to the polymeric matrices. The new materials exhibit enhanced thermal, optical, and mechanical properties with respect to the pure organic polymers. The organization of the molecular units in these nanomaterials is studied through a structural analysis by solid‐state NMR. The domain size of the dispersed phase assures a homogeneous distribution of POSS into the polymer, thus, a continuous phase corresponding to the organic matrix incorporates these nanometer‐sized POSS crosslinkers at a molecular level, in agreement with the transparency of the samples. The silicon–oxygen core framework has to be covalently bonded into the polymer backbone instead of being a simple additive and both the silica content and crosslinked degree exhibit a critical influence on the laser action.     

HPLC-DAD-ESI/MS identification of anthocyanins in Dioscorea trifida L. yam tubers (purple sachapapa)

The coloured tubers of purple sachapapa (Dioscorea trifida L.), a common crop in the subtropical and tropical regions, were analysed to characterise their anthocyanin composition. High-performance liquid chromatography-diode array detection-mass spectrometry (HPLC-DAD-ESI/MS) allowed the detection of 12 anthocyanin pigments. The compounds identified were derived from peonidin (Pn), cyanidin (Cy), and pelargonidin (Pg) aglycones, most of them showing the same substitution pattern, anthocyanin 3-acylglucoside-5-glucoside, where the acyl residue consisted of a hydroxycinnamic acid (i.e., ferulic or p-coumaric acid). The main anthocyanin found was peonidin 3-O-p-coumaroylglucoside-5-O-glucoside.     

Proanthocyanidin metabolites associated with dietary fibre from in vitro colonic fermentation and proanthocyanidin metabolites in human plasma

Proanthocyanidins (PAs) or condensed tannins, a major group of dietary polyphenols, are oligomers and polymers of flavan‐3‐ol and flavan‐3, 4‐diols widely distributed in plant foods. Most literature data on PAs' metabolic fate deal with PAs that can be extracted from the food matrix by aqueous‐organic solvents ( extractable proanthocyanidins). However, there are no data on colonic fermentation of non‐extractable proanthocyanidins (NEPAs), which arrive almost intact to the colon, mostly associated to dietary fibre (DF). The aim of the present work was to examine colonic fermentation of NEPAs associated with DF, using a model of in vitro small intestine digestion and colonic fermentation. Two NEPA‐rich materials obtained from carob pod (Ceratonia siliqua L. proanthocyanidin) and red grapes (grape antioxidant dietary fibre) were used as test samples. The colonic fermentation of these two products released hydroxyphenylacetic acid, hydroxyphenylvaleric acid and two isomers of hydroxyphenylpropionic acid, detected by HPLC‐ESI‐MS/MS. Differences between the two products indicate that DF may enhance the yield of metabolites. In addition, the main NEPA metabolite in human plasma was 3,4‐dihydroxyphenyl acetic acid. The presence in human plasma of the same metabolites as were detected after in vitro colonic fermentation of NEPAs suggests that dietary NEPAs would undergo colonic fermentation releasing absorbable metabolites with potential healthy effects.     

Extracts of Mexican Oregano (<Emphasis Type="Italic">Lippia berlandieri</Emphasis> Schauer) with Antioxidant and Antimicrobial Activity

Antimicrobial activity of fractions obtained from Mexican oregano (Lippia berlandieri Schauer) chloroform extract was tested by growth inhibition against Escherichia coli, Staphylococcus aureus and Bacillus cereus, and antioxidant capacity was tested by inhibition of linoleic acid oxidation. Fractions were obtained by differences in polarity or structure (phenolic and non-phenolic fraction). Gram-positive organisms were more susceptible to Mexican oregano extracts. Fraction 3 (by polarity) and phenolic fractions I, II, III, IV and V were the extracts with higher antimicrobial activity. The non-phenolic fraction had effect against B. cereus. Polarity fraction 5 and phenolic Fraction II had a high antioxidant capacity; a 0.08% concentration of fraction 5 had a similar effect as butylated hydroxytoluene at 0.01% concentration. Fractions of Mexican oregano with different polarity and functional groups had antioxidant and antimicrobial activity and can be used in a variety of applications.     

Aggregation of Alcohols Ethoxylates in n-Heptane

The solubility and aggregation process of polyethoxylated non-ionic surfactants, of general formula C _i H_2i+1–(O–CH₂–CH₂) _j –OH with i = 6, 8, 10 and j = 3–6 (C _i EO _j ), in heptane were studied. The aggregation of C _i EO _j surfactants in heptane was investigated by using methylene blue (MB) as an absorption probe. In solutions of MB in the presence of these surfactants in heptane, at concentrations larger than the re-dissolution concentration, the UV bands associated to free MB (A ₁) and MB–EO complex (A ₂) were detected. The ratio of these intensities A ₂/A ₁, was used to study the kinetics of the complex formation in pure surfactant. The value of A ₂/A ₁ depends on the surfactant structure and the media wherein MB is dissolved, being larger in the pure surfactant than in heptane solutions. These results are explained in terms of solvent effect and aggregate structures on the complex formation.

Synthesis,characterization and compared reactivity of asymmetrical ansa-metallocenes

Rac and meso ansa-zirconocenes [Zr{1-Me₂Si(3-R-(η⁵-C₉H₅))(3-R′-(η⁵-C₉H₅))}Cl₂] (R = Et, R′ = H; R = Pr, R′ = H; and R = Et, R′ = Pr) 4–9 have been prepared by the reaction of ZrCl₄ with the corresponding dilithiated derivatives from the ligands {1-Me₂Si(3-R-(η⁵-C₉H₅))(3-R′-(η⁵-C₉H₅))} (R = Et, R′ = H 1; R = Pr, R′ = H 2; and R = Et, R′ = Pr 3) in diethyl ether/toluene at ?78 °C. The molecular structure of rac [Zr{1-Me₂Si(3-Et-(η⁵-C₉H₅))(3-Pr-(η⁵-C₉H₅))}Cl₂] 8 has been determined by single crystal X-ray diffraction studies, which show a pseudotetrahedral environment formed by the two chlorine ligands and two η⁵-coordinated indenyl ligands. The activity in homogeneous and heterogeneous polymerization is compared and discussed.     

Natural Brazilian Amazonic (Curauá) Fibers Modified with Polyaniline Nanoparticles

The surface of natural Brazilian amazonic fibers (curauá, Ananas erectifolius) was modified with polyaniline nanoparticles, through in situ preparation of polyaniline nanoparticles in presence of the curauá fibers. This allowed for a significant increase in the electrical conductivity of the fibers (≈2 500 times). As the electrical resistivity of the modified fibers is a function of the applied external pressure, the produced composites can be used as a cheap pressure‐sensing material. The modified materials were also characterized by FT‐IR, XPS and SAXS, and the obtained results were used to explain some of the observed characteristics of the materials.

     

Effects of vinyltrimethoxy silane on mechanical properties and morphology of polypropylene‐woodflour composites

The effects of composition and interface modification on the tensile properties and the impact resistance of different woodflour/polypropylene composites (WPC) were studied. The woodflour was treated with vinyltrimethoxy silane as a coupling agent, and its effect on the WPC properties was examined. In addition, the tensile data were fitted with several semiempirical models to clarify the mechanical behavior of the composites. The Pukánszky parameters obtained from the fit of the tensile strength data revealed that the distribution of the filler was more homogeneous in the composites containing silane and that interaction between components was improved. The impact strength was maximal for the composites containing 30% of silane‐treated woodflour. Morphological analysis by SEM revealed that the woodflour tended to form agglomerates when present in relatively high amounts in the formulations. For the silane‐treated composites, the dispersion of the filler into the polypropylene (PP) matrix improved, although surface treatment blocked the inclusion of PP into the wood cells. This probably decreased the elastic moduli, even when the filler‐matrix interaction was improved. The beneficial effects of the coupling agent on the WPC properties were greater in the materials containing a relatively low amount of filler (up to 30%); the effectiveness of 0.5% and 1% organosilane were very similar, demonstrating the effectiveness of the coupling agent. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

Blue pigments based on CoxZn1−xAl2O4 spinels synthesized by the polymeric precursor method

The Co_xZn_1?xAl₂O₄ system (x = 0; 0.1; 0.3; 0.5; 0.7; 0.9 and 1) was synthesized by the polymeric precursor method and characterized by the techniques XRD, TG-DTA, IR, UV–vis and colorimetry. The XRD patterns displayed the characteristic peaks of the spinel structure and a good crystallinity. The DTA curves showed an exothermic peak corresponding to the enthalpy of the transition taking place at about 700 °C. The infrared spectra displayed vibrations at about 650, 550, 540, 520, 500, 490 cm^?1, which were ascribed to the spinel structure. The UV–vis spectra presented three bands at 550, 580 and 620 nm attributed to the Co²⁺ spin transitions in tetrahedral sites. The colorimetric data point out the formation of blue pigments, corresponding to highly negative values of b¹. The lightness, coordinate L¹, increases with the heat treatment temperature. These facts reveal that Co_xZn_1?xAl₂O₄ is a promising system that can be employed to obtain ceramic blue pigments.     

Flexible design‐planning of supply chain networks

Nowadays market competition is essentially associated to supply chain (SC) improvement. Therefore, the locus of value creation has shifted to the chain network. The strategic decision of determining the optimal SC network structure plays a vital role in the later optimization of SC operations. This work focuses on the design and retrofit of SCs. Traditional approaches available in literature addressing this problem usually utilize as departing point a rigid predefined network structure which may restrict the opportunities of adding business value. Instead, a novel flexible formulation approach which translates a recipe representation to the SC environment is proposed to solve the challenging design‐planning problem of SC networks. The resulting mixed integer linear programming model is aimed to achieve the best NPV as key performance metric. The potential of the presented approach is highlighted through illustrative examples of increasing complexity, where results of traditional rigid approaches and those offered by the flexible framework are compared. The implications of exploiting this potential flexibility to improve the SC performance are highlighted and are the subject of our further research work. © 2009 American Institute of Chemical Engineers AIChE J, 2009