Polymerization of olefins and polar monomers catalyzed by bis(imino)Ni(II)/dibutylmagnesium/alkylaluminium halide systems

[Bis(N,N′‐dimesitylimino)acenaphthene]dibromonickel ( 1 ) when activated with diethylaluminium chloride (DEAC) is a very active catalyst for ethylene homopolymerization. The activity (A_E) of 1 /100 DEAC is twenty times greater than that of 1 /100 MAO and of the same order of magnitude as 1 /2000 MAO. In the case of homopolymerization of propylene the highest activity (A_P) was obtained at a ratio of 25/15 for Al_DEAC/Ni. Trialkylaluminium compounds were also found to act as cocatalysts for 1 . The PE synthesized with four different cocatalysts was found by ¹³C NMR to have dissimilar branching distributions. 1 /DEAC shows no activity for the polymerization of proximately substituted polar monomers. The introduction of dibutylmagnesium, (DBM) activates the 1 /DEAC system to copolymerize ethylene and a number of proximately substituted polar monomers. Compared with the 1 /MAO/monomer.AlR₃ catalyst system the former is three times more active for copolymerization of 5‐hexene‐1‐ol or 10‐undecen‐1‐oic acid with ethylene. The activity of copolymerization is 1 /24, 1 /5 and 1 /2 as active as homopolymerization, respectively, in the case of methyl vinyl ketone, vinyl acetate and ?‐caprolactam. In the case of tetrahydrofuran/ethylene, the 1 /MAO catalyst produced copolymers using AlR₃ pretreated THF whereas the 1 /DEAC/DBM catalyst produces homopolyethylene only. No polymerization occurred with an acrylonitrile/ethylene mixture in the presence of 1 /DBM/DEAC catalyst. © 2002 Society of Chemical Industry     

Functionalization of sisal fibers and high‐density polyethylene by cold plasma treatment

Chopped sisal fibers and finely powdered high‐density polyethylene were surface functionalized using dichlorosilane (DS) under radio frequency (RF)‐plasma conditions and characterized by electron spectroscopy for chemical analysis (ESCA) and fluorescence labeling techniques. A high‐capacity (10 L), rotating, 13.56 MHz, electrodeless plasma installation, specially designed to allow the uniform surface modification of powdery and particulate matter of irregular shape, was used. A three‐factor fractional experimental design was employed to evaluate the effect of RF‐power, pressure, and reaction time on the ESCA‐based relative atomic composition of plasma‐treated samples. It was demonstrated that ? SiH_xCl_y functionalities are present on plasma‐exposed surfaces and these functionalization reactions can be controlled by selecting proper plasma parameters. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2145–2154, 2002     

阿特拉斯·科普柯Craelius公司——岩芯钻机的先驱

在阿特拉斯科·普柯Craelius公司总部,瑞典首都斯德哥尔摩附近Marsta的入口处,长期摆放着该公司制造的第一台蒸汽驱动钻机(图1),以时刻提醒公司的创新意识。也许仅有少数人知道这家从事金刚石取芯钻机制造的小公司是在100多年前由Per Anton Craelius先生创立的,如今已成为一家勘探钻进设备的主要供应商。     

On-chip, cell-based microarray immunofluorescence assay for high-throughput analysis of target proteins

We have developed an immunofluorescence-based assay for high-throughput analysis of target proteins on a three-dimensional cellular microarray platform. This process integrates the use of three-dimensional cellular microarrays, which should better mimic the cellular microenvironment, with sensitive immunofluorescence detection and provides quantitative information on cell function. To demonstrate this assay platform, we examined the accumulation of the alpha subunit of the hypoxia-inducible factor (HIF-1alpha) after chemical stimulation of human pancreatic tumor cells encapsulated in 3D alginate spots in volumes as low as 60 nL. We also tested the effect of the known dysregulator of HIF-1alpha, 2-methoxyestradiol (2ME2), on the levels of HIF-1alpha using a dual microarray stamping technique. This chip-based in situ Western immunoassay protocol was able to provide quantitative information on cell function, namely, the cellular response to hypoxia mimicking conditions and the reduction of HIF-1alpha levels after cell treatment with 2ME2. This system is the first to enable high-content screening of cellular protein levels on a 3D human cell microarray platform.     

Structural and morphological changes in Poly(caprolactone)/poly(vinyl chloride) blends caused by UV irradiation

Films made from a blend of poly(ε-caprolactone) and poly(vinyl chloride) (PCL/PVC) retained high crystallinity in a segregated PCL phase. Structural and morphological changes produced when the films were exposed to high potency ultraviolet (UV) irradiation for 10 h were measured by UV-Vis spectroscopy (UV-Vis), Fourier Transform Infrared Spectroscopy (FTIR), and Scanning Electron Microscopy (SEM). They were different to those observed with homopolymer PCL and PVC films treated under the same conditions. The FTIR spectra of the PCL/PVC blend suggest that blending decreased the susceptibility of the PCL to crystallize when irradiated. Similarly, although scanning electron micrographs of PCL showed evidence of growth of crystalline domains, particularly after UV irradiation, the images of PCL/PVC were fairly featureless. It is apparent that the degradation behavior is strongly influenced by the interaction of the two polymers in the amorphous phase.     

Strain analysis of photocatalytic TiO2 thin films on polymer substrates

Titania (TiO₂) thin films have been deposited on polymer sheets by magnetron sputtering at room temperature. Previous X-ray diffraction experiments revealed, for a wide range of deposition parameters, that the as-deposited titania thin films are predominantly amorphous; however, Raman scattering experiments revealed small traces of crystalline phases. The photocatalytic behaviour of the titania coatings was determined by combined ultra-violet (UV) irradiation and absorption measurements of a chosen dye (pollutants) in the presence of this catalyst. In order to assess the mechanical behaviour of the as-sputtered films, the film/substrate composite system was loaded unidirectionally using a tensile testing machine. As the system was stretched, cracks transverse to the loading direction developed in the film. The number of cracks increased as the applied strain increased, thus the relation between the measured crack density and the applied strain has been used to characterize the film strength and has also been correlated with the film photocatalytic efficiency. As a result of moderate fissuring on the titania film, it was found that for strain deformations up to 5% the photocatalytic activity is enhanced due to the exposure of more catalyst surface area for the pollutant to be adsorbed and subsequently dissociated upon UV illumination.     

The influence of the synthesis routes of MgAl2O4 on its properties and behavior as support of dehydrogenation catalysts

In order to synthesize MgAl₂O₄, three methods were used: (a) a solid phase reaction of MgO and γ-Al₂O₃ oxides at 900 °C for 24 h (ceramic method), (b) wet milling during 24 h of the mixture of oxides followed by the reaction at 900 °C for 12 h (mechanochemical synthesis), and (c) coprecipitation of Mg(NO₃)₂·6H₂O and Al(NO₃)₃·9H₂O with ammonia solution followed by a calcination in a flow of air at 800 °C during 4 h (coprecipitation method). The synthesized materials were characterized by XRD, BET isotherm, isopropanol dehydration reaction, TGA/DTA and SEM. The results indicate that in all the cases the MgAl₂O₄ spinel was formed. Besides, a residue of MgO in the samples obtained by the ceramic method and mechanochemical synthesis was found, which was eliminated by purification. The surface area of MgAl₂O₄ obtained by mechanochemical synthesis and coprecipitation method are much higher than that of the spinel synthesized by the ceramic method. Pt (0.3%) catalysts were prepared by impregnating the three supports with H₂PtCl₆. The metallic dispersion of Pt/MgAl₂O₄ obtained by mechanochemical synthesis was higher than that of Pt catalysts supported on the other spinels, in agreement with the catalytic behavior observed in n-butane dehydrogenation reaction and test reactions of the metallic phase.     

Flow injection preconcentration system using a new functionalized resin for determination of cadmium and nickel in tobacco samples

A solid-phase extraction method combined with flow injection (FI) on-line flame atomic absorption spectrometry (FAAS) for the determination of cadmium and nickel in tobacco samples is presented. The 2-aminothiophenol functionalized Amberlite XAD-4 (AT-XAD) resin was synthesized by covalent coupling of the ligand with the copolymer through a methylene group. A minicolumn packed with AT-XAD was connected into the automated on-line preconcentration system. Elution of metal ions from minicolumn can be made with 0.50 mol L⁻¹ hydrochloric acid solution. With a consumption of 21.0 mL of sample solution, detection limits (3 s) of 0.3 (Cd) and 0.8 μg L⁻¹ (Ni) were achieved at a sample throughput of 18 h⁻¹. Enrichment factors (EF) of 99 (cadmium) and 43 (nickel) were obtained compared with the slope of the linear portion of the calibration curves before and after preconcentration. The contents of Cd and Ni in a certified reference material (NIST 1570a, spinach leaves) determined by the present method was in good agreement with the certified value. The developed procedure was also successfully applied to the determination of Cd and Ni in local tobacco samples.     

Facile biocatalytic access to 9-fluorenylmethyl polyglycosides: evaluation of antiviral activity on immunocompetent cells

The biological activities of a series of mono- and oligosaccharides (beta-xylosides and alpha-glucosides) of 9-fluorenylmethanol were investigated together with mono-beta-galactoside and beta-glucoside of this aglycone, produced by biocatalytic routes. By using marine glycoside hydrolases and inexpensive donors such as maltose or xylan, access to mono-alpha-glucoside or mono-beta-xyloside of 9-fluorenylmethanol was obtained. Additionally, interesting polyglycoside derivatives were isolated. Biological testing indicated that in vitro treatment with these carbohydrate derivatives may influence the balance of cytokines in the environment of human peripheral blood mononuclear cells (PBMC), restricting the harmful effect of herpes simplex type 2 replication. In fact, these carbohydrate derivatives tested in WISH cells did not show any significant antiviral activity.     

Diversity and antifungal susceptibility of yeasts from tropical freshwater environments in Southeastern Brazil

Yeast communities were isolated from water and sediment samples of two unpolluted natural lakes, located inside Rio Doce State Park, and two rivers located outside of this Park in Southeastern Brazil. A total of 134 yeast isolates were obtained and identified as belonging to 36 species. The numbers of fecal coliforms and yeast species were higher in rivers than in lakes. The genus Candida had the highest number of species with the presence of opportunistic pathogens such as Candida krusei, C. tropicalis, C. guilliermondii and C. parapsilosis. Yeasts able to grow at 37 degrees C were tested in relation to their susceptibility to common used antifungal drugs. Yeast isolates (13%) were susceptible to ketoconazole, 79% to fluconazole, 31% to terbinafine and 78% of the strains were susceptible to amphotericin B. Seven isolates from different Candida species were resistant to all antifungals tested. The high number of fecal coliforms found in these aquatic environments and the presence of resistant yeast strains to common used antifungal drugs suggest that these environments can pose potential health risks for people utilizing the contaminated waters.