Nanoscale coordination polymers exhibiting luminescence properties and NMR relaxivity

This article presents the first example of ultra-small (3-4 nm) magneto-luminescent cyano-bridged coordination polymer nanoparticles Ln0.33(3+)Gdx3+/[Mo(CN)8]3- (Ln=Eu (x=0.34), Tb (x=0.35)) enwrapped by a natural biocompatible polymer chitosan. The aqueous colloidal solutions of these nanoparticles present a luminescence characteristic of the corresponding lanthanides (5D0→7F0-4 (Eu3+) or the 5D4→7F6-2 (Tb3+)) under UV excitation and a green luminescence of the chitosan shell under excitation in the visible region. Magnetic Resonance Imaging (MRI) efficiency, i.e. the nuclear relaxivity, measurements performed for Ln0.33(3+)Gdx3+/[Mo(CN)8]3- nanoparticles show r1p and r2p relaxivities slightly higher than or comparable to the ones of the commercial paramagnetic compounds Gd-DTPA? or Omniscan? indicating that our samples may potentially be considered as a positive contrast agent for MRI. The in vitro studies performed on these nanoparticles show that they maybe internalized into human cancer and normal cells and well detected by fluorescence at the single cell level. They present high stability even at low pH and lack of cytotoxicity both in human cancer and normal cells.     

Evidence for Diffusion-Controlled Hydrocarbon Selectivities in the Fischer�CTropsch Synthesis Over Cobalt Supported on Ordered Mesoporous Silica

A series of four cobalt-based catalysts (two of which promoted with ruthenium) supported on SiO₂ or SBA-15 were prepared and tested in the Fischer?CTropsch synthesis at industrially relevant process conditions (483 K, 20 bar, H₂/CO ratio = 2.1, pellet size: 53?C90 ??m). The catalysts were characterized by N₂-adsorption, X-ray diffraction (XRD), temperature-programmed reduction (TPR), H₂-chemisorption and transmission electron microscopy (TEM). Ru as promoter enhanced the activity but not the selectivity to long-chain hydrocarbons ( $ {\text{S}}_{{{\text{C}}_{ 5+ } }} $ ). The $ {\text{S}}_{{{\text{C}}_{ 5+ } }} $ values of the SBA-supported catalysts were very low, especially at low conversion levels (i.e. low water partial pressure), suggesting that CO diffusion limitation increased the H₂/CO ratio inside the 1-dimensional (1-D) porous network. A superimposition of the selectivity results on the correlations found in our recent study, derived for Co-based catalysts supported on ??-Al₂O₃, ??-Al₂O₃ and TiO₂ free from diffusion limitations, was made. While the SiO₂-supported catalysts with a 3-D porous structure followed the correlations, the SBA-catalysts deviated significantly at low conversions, giving a further indication that the selectivity results of these catalysts were affected by CO diffusion limitations. Hence, it may be concluded that the kinetically significant diffusion distances (i.e. those long enough to cause an intrapore H₂/CO ratio higher than that of the bulk gas phase) are probably much shorter for 1-D porous networks than for conventional 3-D supports. This is explained by a significantly lower effective diffusivity in 1-D porous networks. The potential of using the correlations between non-ASF distributed hydrocarbons and C₅₊, to give insight on the occurrence of diffusion limitations, was confirmed by superimposing data from the literature that were anticipated to be influenced by CO diffusion limitations.     

Viscoelastic,thermo-mechanical and environmental properties of composites based on polypropylene/poly(lactic acid) blend and copper modified nanoclay

Poly(lactic acid) (PLA)/polypropylene (PP) blends composites were prepared by incorporating 3 wt.% of copper modified montmorillonite (MMT-Cu²⁺), obtained using cation exchange in a CuSO₄ solution, and 10 wt.% of polypropylene-graft-maleic anhydride (PP-g-MA) as a compatibilizer then varying the PLA content until 50 wt.%. These materials were subjected to several investigations such as X-rays diffraction, dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and tensile and environmental tests. The DMTA analysis showed that the glassy PLA high stiffness and the PP crystalline phase compensate the decrease in the storage modulus occurring during the PP and PLA glass transitions, respectively. The variations of tan δ revealed no changes on the PP and PLA phases glass transitions temperatures which indicate the immiscibility of the two polymers, as supported by DSC analysis. Blends composites SEM micrographs stated the immiscibility of the system resulting in the poor adhesion of the PLA droplets to the PP matrix. Also, the blends composites exhibited intermediate tensile properties between those of PP and PLA. The incorporation of MMT-Cu²⁺ to the (50/50) PP/PLA blend accentuated its aptitude to water absorption and ensured an efficient antimicrobial activity over a satisfactorily long period of around six months.     

A Microfluidic Ion Pump for In Vivo Drug Delivery

Implantable devices offer an alternative to systemic delivery of drugs for the treatment of neurological disorders. A microfluidic ion pump (µFIP), capable of delivering a drug without the solvent through electrophoresis, is developed. The device is characterized in vitro by delivering γ‐amino butyric acid to a target solution, and demonstrates low‐voltage operation, high drug‐delivery capacity, and high ON/OFF ratio. It is also demonstrated that the device is suitable for cortical delivery in vivo by manipulating the local ion concentration in an animal model and altering neural behavior. These results show that µFIPs represent a significant step forward toward the development of implantable drug‐delivery systems.     

Ce-promoted Co/Al2O3 catalysts for Fischer–Tropsch synthesis

The effect of ceria promotion on the performance of Co/Al₂O₃ catalyst was evaluated in a high pressure fixed bed reactor for Fischer–Tropsch (FT) synthesis at close industrial conditions. Ce–Al₂O₃ supports with a molar ratio of Al/Ce = 8 were prepared by two different methods: one by co-precipitation of cerium and aluminum precursors in water-in-oil microemulsion and the other one by aqueous impregnation of cerium nitrate on commercial alumina. These supports, together with the unmodified alumina carrier, were used to prepare four cobalt-based catalysts. These catalysts were characterized by XRD, SEM, EDX, TEM, N₂ adsorption/desorption, TPR and chemisorption techniques. The results show that the presence of CeO₂ on the surface of the support favors the reducibility of cobalt oxides with a shift down in reduction temperature of about 70 °C. The catalytic evaluation of the catalysts revealed that cerium addition by impregnation increases the activity and selectivity to C₅₊ catalyst in FTS. The catalyst synthetized by microemulsion show lower catalytic performance. Nevertheless, the catalytic property of this material can be improved by increasing the crystalline micro-domains size of CeO₂.     

The influence of ripening stage and cultivation system on the total antioxidant activity and total phenolic compounds of yellow passion fruit pulp

BACKGROUND: This work aimed to investigate the influence of both ripening stage and cultivation system on the total phenolic compounds (TPC) and total antioxidant activity (TAA) of passion fruit pulp. TPC extraction was optimized using a 2³ central composed design. The variables were fruit pulp volume, methanol volume and extraction solution volume. TPC was determined using the Folin–Ciocalteu reaction, and TAA using the ABTS radical reaction. RESULTS: The conditions to extract TPC were 2 mL passion fruit pulp and 9 mL extraction solution containing 40% methanol:water (v/v). TPC values increased in the passion fruit pulp during ripening for both cultivation systems, ranging from 281.8 to 361.9 mg gallic acid L^?1 (P?0.05) for the organic pulp and from 291.0 to 338.6 mg gallic acid L^?1 (P?0.05) for the conventional pulp. CONCLUSION: TPC values increased during ripening for both organic and conventional passion fruit. The same was true for TAA values for conventional passion fruit. For organic passion fruit, however, TAA values were highest at the initial ripening stages. These results suggest that antioxidant compounds exert strong influence on the initial ripening stages for organic passion fruit, when TPC still did not reach its maximum level. Copyright © 2012 Society of Chemical Industry     

Bioaccumulation and trophic magnification of short- and medium-chain chlorinated paraffins in food webs from Lake Ontario and Lake Michigan

Chlorinated paraffins (CPs) are complex mixtures of chlorinated alkanes used in a myriad of industrial applications as flame retardant plasticizers and additives. In this study, the distribution and bioaccumulation/biomagnification of short-chain CPs (C10-C13, SCCPs) and medium-chain CPs (C14-C17, MCCPs) were investigated in samples collected between 1999 and 2004 from Lake Ontario and northern Lake Michigan. Total (sigma) SCCPs and sigmaMCCPs concentrations in water from Lake Ontario were 1190 pg/L and 0.9 pg/L (data from 2004 only), respectively. CPs were also detected in invertebrates and fish from both lakes. SCCP predominated in organisms from Lake Michigan with the highest mean concentrations found in lake trout [Salvelinus namaycush, 123 +/- 35 ng/g wet weight (ww)]. In Lake Ontario, MCCPs predominated in most species with the highest levels detected in slimy sculpin (Cottus cognatus, 108 ng/g ww) and rainbow smelt (Osmerus mordax, 109 ng/g ww). Bioaccumulation and biomagnification of CPs was evaluated on an isomer basis (i.e., C10H17Cl5, C10H16Cl6, etc). Log bioaccumulation factors for lake trout (lipid based) ranged from 4.1 to 7.0 for SCCPs and 6.3 to 6.8 for MCCPs. SCCPs and MCCPs were found to biomagnify between prey and predators from both lakes with highest values observed for Diporeia-sculpin (Lake Ontario, C15Cl9 = 43; Lake Michigan, C10Cl5 = 26). Trophic magnification factors for the invertebrates-forage fish-lake trout food webs ranged from 0.41 to 2.4 for SCCPs and from 0.06 to 0.36 for MCCPs. Given the prominence of CPs, particularly in lake waters and in lower food web organisms, further investigation is needed to evaluate the magnitude of their distribution and accumulation/magnification in the Great Lakes environment.     

Aging of polyethylene pipes transporting drinking water disinfected by chlorine dioxide. Part II—Lifetime prediction

This article deals with the failure of polyethylene pipes transporting chlorine dioxide (DOC) disinfected water under pressures of few bars. Accelerated aging tries made at 20 or 40°C show that the antioxidant is rapidly consumed in a superficial layer until a depth of about 1.2 mm. Carbonyl groups appear in a sharper layer of few hundreds micrometers. Natural aging results at various places, for various times up to about 30 years, reveal also a superficial attack with a depth of the order of 1.2 mm. An antioxidant loss by migration, in the whole sample thickness, is also observable. The shape of antioxidant concentration profiles indicates that the crossing of interfaces controls partially the whole migration kinetics. Failures, with brittle cracking, were observed in natural aging, after exposure times of the order of 5–15 years, i.e., far before the expected lifetime (50 years). A kinetic model has been elaborated to predict the time to failure. It is based on a chemical unit, which models the radical processes induced by DOC, and a mechanical unit based on an empirical creep law and a failure criterion depending of the molar mass calculated by the chemical unit. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Disulfide Bond Substitution by Directed Evolution in an Engineered Binding Protein

Breaking ties : The antitumour protein, neocarzinostatin (NCS), is one of the few drug‐carrying proteins used in human therapeutics. However, the presence of disulfide bonds limits this protein's potential development for many applications. This study describes a generic directed‐evolution approach starting from NCS‐3.24 (shown in the figure complexed with two testosterone molecules) to engineer stable disulfide‐free NCS variants suitable for a variety of purposes, including intracellular applications.

     

Expository multimedia comprehension in E-learning: Presentation format,verbal ability and working memory capacity

Most of the studies establishing factors affecting digital text and multimedia comprehension have been conducted in controlled conditions. The present study sought to test and extend the modality and seductive details effects, and the role of verbal ability and working memory capacity, to a remote, self-paced, E-learning scenario. Two hundred and thirteen first-year undergraduates read or watched videos about scientific expository content in three formats: digital text (written expository texts, navigated in seven screens), presentation video (audio explanation, with written keywords), and presentation video with dynamic decorative images (audio explanation, written keywords, and dynamic decorative and irrelevant images). In a face-to-face session, they completed working memory and verbal ability tests. Comprehension performance was similar for the three conditions. For the multimedia videos with dynamic decorative irrelevant images, comprehension depended on working memory capacity. Verbal ability was relevant for both expository text and videos.