Metallocene‐based functionalized polyolefins as compatibilizers in polyolefin nanocomposites

This article reports a study of some functionalized polyolefins evaluated as compatibilizers in polyethylene nanocomposites. The functionalized polymers were prepared by direct metallocene‐mediated copolymerizations of ethylene and a functional comonomer. The prepared nanocomposites were evaluated for mechanical and barrier property enhancement. A good combination of mechanical and barrier properties was obtained with the metallocene‐based functionalized polyethylene. The toughness–stiffness balance was better than or comparable to that achieved with conventional functionalized polymers such as maleic anhydride grafted polyethylene. The results also indicated that these metallocene‐based functionalized polyolefins, when used as compatibilizers, could have relatively higher molar masses and lower functionality than those of conventional post‐reactor‐modified compatibilizers, and so the drawbacks associated with the latter could be avoided. Their inherent properties could also further improve the final nanocomposite properties. This was attributed to the more homogeneous nature of metallocene‐catalyzed polymers in comparison with post‐reactor‐modified products. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1094–1100, 2004     

Mannans as stabilizers of oil-in-water beverage emulsions

The stabilizing effect of spruce galactoglucomannan (GGM) on a model beverage emulsion system was studied and compared to that of guar gum and locust bean gum galactomannans, konjac glucomannan, and corn arabinoxylan. In addition, guar gum was enzymatically modified in order to examine the effect of the degree of polymerization and the degree of substitution of galactomannans on emulsion stability. Use of GGM increased the turbidity of emulsions both immediately after preparation and after storage of up to 14 days at room temperature. GGM emulsions had higher turbidity than the emulsions containing other mannans. The initial turbidity increased with increasing GGM content, but after 14 days storage at room temperature, the turbidity was the highest for GGM/oil ratio of 0.10:1 when ethanol-precipitated GGM was used. Increasing the storage temperature to +45 °C led to rapid emulsion breakdown, but a decrease in storage temperature increased emulsion stability after 14 days. Confocal microscopy showed that the average particle size in the bottom part of GGM emulsions stored for 14 days was smaller than 1 μm. A low degree of polymerization and a high degree of substitution of the modified galactomannans were associated with a decrease in emulsion turbidity.     

Synthesis of charge transporting block copolymers containing 2,7-dimethoxycarbazole units for light emitting device

The block copolymers consisting of 2,7-dimethoxycarbazole- and oxadiazole-containing segments as hole and electron transporting units, respectively, were synthesized by NMRP manner. OLED devices were fabricated using block copolymer, random copolymer, and polymer blend for matrix of the emitting layer with Ir(ppy)₃ as a phosphorescent dopant in order to investigate morphological effect on the performance. From the finding that the block copolymer system overwhelmed the others in EQE, we assumed that a morphology with dimethoxycarbazole units assembled to the surface of PEDOT:PSS played a considerable role for effective recombination of charges as well as sufficient charge injection into the emitting layer.     

Ante- and perinatal factors and child characteristics predicting parenting experience among formerly infertile couples during the child's first year: A controlled study.

In this prospective controlled study, the authors examined (a) parenting experiences among couples with successful assisted reproduction treatment (ART; n = 367) and fertile spontaneously conceiving controls (n = 371) and (b) the impact of ante- and perinatal factors and child characteristics on parenting experiences. The results show that positive mothering experiences increased more during the 1st year of parenting and were generally higher among ART mothers than control mothers. No differences were found between ART fathers and controls in their fathering experience. Unpleasant birth experiences, low birth weight, and difficulty soothing the child were associated with high levels of parental stress in the control group, but this was not so among the ART parents. Psychosocial interventions in maternal care should take into account the various meanings that couples give to the history of infertility and conception and ante- and perinatal experiences. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Development of coincidence transmission electron microscope. III. Incorporation with gamma-type imaging energy filter

We have developed a new analytical transmission electron microscope (TEM), called coincidence TEM, which, in principle, enables observation of elemental mapping images at a high signal-to-noise ratio. We have previously reported the successful observation of an elemental mapping image of a specimen, but over a very long period of time (168 h). To solve this inefficiency, we installed a gamma-type imaging energy filter in the coincidence TEM to remove the no-loss electrons, which are mainly transmitted electrons. This has enabled the intensity of the background signals in the coincidence measurement to be markedly reduced. The coincidence TEM with a gamma-type imaging energy filter allows the coincidence image to be observed in 3 h, thus, the measurement time is shortened by two orders of magnitude. Moreover, the use of a silicon drift detector (SDD) will shorten the measurement time.     

Electropolymerization of N-methylanthranilic acid and spectroelectrochemical characterization of the formed film

The electropolymerization of N-methylanthranilic acid (NMAA) is reported in this paper. The monomer is substituted both at ortho- and N-position and, to the best of our knowledge, it has not been previously electropolymerized. Electropolymerization of NMAA was done on glassy carbon and optically transparent (indium) tin oxide electrodes. The obtained films, which are probably of an oligomeric nature (oligoNMMA), were characterized with cyclic voltammetry (CV), in situ UV–vis and Raman spectroscopy, ex situ FTIR spectroscopy and scanning electron microscopy (SEM).Our results show that NMAA can be electropolymerized as thin films in 1.0 M HClO₄, but the oxidation and reduction peak currents in the CVs indicate that the formed oligoNMAA films are thinner than poly(N-methylaniline) or poly(N-butylaniline) films prepared under similar conditions. The CV and UV–vis measurements confirm that oligoNMAA have three oxidation states like suggested in the redox scheme of substituted polyanilines. The Raman spectra of oligoNMAA also verify that more quinoid units are formed at higher potentials in accordance with the redox scheme. The ex situ FTIR measurement proves that covalently attached carboxylic acid groups are present in the film structure and attached to the oligoNMAA backbone.     

BET Inhibition Upregulates SIRT1 and Alleviates Inflammatory Responses

Control of histone acetylation is a part of the epigenetic mechanism that regulates gene expression and chromatin architecture. The members of the bromodomain and extra terminal domain (BET) protein family are a group of epigenetic readers that recognize histone acetylation, whereas histone deacetyl‐ ases such as sirtuin 1 (SIRT1) function as epigenetic erasers. We observed that BET inhibition by the specific inhibitor JQ1 upregulated SIRT1 expression and activated SIRT1. Moreover, we observed that BET inhibition functionally reversed the pro‐inflammatory effect of SIRT1 inhibition in a cellular lung disease model. SIRT1 activation is desirable in many age‐related, metabolic and inflammatory diseases; our results suggest that BET protein inhibition would be beneficial in treatment of those conditions. Most importantly, our findings demonstrate a novel mechanism of SIRT1 activation by inhibition of the BET proteins.     

Planar‐Chiral Cyclopentadienyl‐Ruthenium‐Catalyzed Regio‐ and Enantioselective Asymmetric Allylic Alkylation of Silyl Enolates under Unusually Mild Conditions

We report the asymmetric allylic alkylation of allylic chlorides with silyl enolates as a carbon nucleophile using a planar‐chiral cyclopentadienyl‐ruthenium (Cp′Ru) catalyst. The reaction proceeds under unusually mild conditions to give the desired branched products with complete regioselectivity and high enantioselectivity, and reactive functional groups, such as aldehyde, can be tolerated. In this reaction system, Cp′Ru plays an important role in activating both silyl enolate and allylic chloride.

     

Noninvasive optical imaging of the subarachnoid space and cerebrospinal fluid pathways based on near-infrared fluorescence

The authors have developed a noninvasive optical method to image the subarachnoid space and cerebrospinal fluid pathways in vivo based on the near-infrared fluorescence of indocyanine green (ICG). The ICG was bound to purified lipoproteins (ICG-lipoprotein) and injected into the subarachnoid space of neonatal and adult rats. The ICG fluorescence was detected by a cooled charge-coupled device camera. After injection of ICG-lipoprotein into the cerebral subarachnoid space of the neonatal rat, ICG fluorescence was clearly detected at the injection site through the skull and skin. The ICG fluorescence was observed in the cerebellum and the lumbar spinal cord 1 and 8 hours postinjection, respectively. After injection of ICG-lipoprotein into the lumbar spinal subarachnoid space of an adult rat, ICG fluorescence was observed from the injection site to the thoracic levels along the spinal subarachnoid space. In addition, with the rat's head tilted downward, ICG fluorescence had extended to the cerebral subarachnoid space by 1 hour postinjection. The ICG fluorescence imaging of the cerebral subarachnoid space demonstrated an increase in fluorescence intensity around the lambdoid suture and the forebrain. On dissection of the rat brain the former location was identified as the supracerebellar cistern and the latter as the olfactory cistern. The results of this study are the first to demonstrate that an optical technique is applicable to imaging of the subarachnoid space and cerebrospinal fluid pathways in vivo. In addition, ICG-lipoprotein provides a sensitive optical tracer for imaging extravascular biological structures. Finally, ICG fluorescence imaging does not require an intricate imaging system because ICG is localized near the surface of the body.