X-ray Fluorescence Uptake Measurement of Functionalized Gold Nanoparticles in Tumor Cell Microsamples

Quantitative cellular in vitro nanoparticle uptake measurements are possible with a large number of different techniques, however, all have their respective restrictions. Here, we demonstrate the application of synchrotron-based X-ray fluorescence imaging (XFI) on prostate tumor cells, which have internalized differently functionalized gold nanoparticles. Total nanoparticle uptake on the order of a few hundred picograms could be conveniently observed with microsamples consisting of only a few hundreds of cells. A comparison with mass spectroscopy quantification is provided, experimental results are both supported and sensitivity limits of this XFI approach extrapolated by Monte-Carlo simulations, yielding a minimum detectable nanoparticle mass of just 5 pg. This study demonstrates the high sensitivity level of XFI, allowing non-destructive uptake measurements with very small microsamples within just seconds of irradiation time.     

NO reduction by CH4 over Pd/Co-sulfated zirconia catalysts

A series of sulfated zirconia supported Pd/Co catalysts was synthesized by the sol–gel method and examined for NO_x reduction by methane. The NO conversion increased up to a Co/S ratio of 0.43, and then decreased at a higher Co loading (Co/S = 0.95). Sulfate content was also essential for obtaining high selectivity to molecular nitrogen. A catalyst loaded with 0.06 wt.% Pd, 2.1 wt.% Co and 2.1 wt.% S (Pd/Co-SZ-2) exhibited remarkable performance under lean conditions and displayed stability in a long-term durability test using a synthetic reaction mixture containing 10% water vapor. This catalyst exhibited the highest sulfur retention most probably as cobalt sulfide. Besides, the catalytic oxidation of NO to NO_y groups was confirmed by FT-IR, in agreement with the general mechanism for the SCR of NO by hydrocarbons. In the absence of oxygen in the feed stream, the catalyst was highly active for NO reduction with methane. IR stretching bands assigned to N₂O and adsorbed nitro groups were identified upon adsorbing NO on Pd/Co-SZ-2. This indicates that under rich conditions disproportionation of NO to N₂O and NO₂ occurs and confirms that the formation of NO₂ species is an essential step for NO reduction by CH₄.     

The effect of specific β‐nucleation on morphology and mechanical behavior of isotactic polypropylene

The commercial grade of isotactic polypropylene was modified by a specific β‐nucleating agent in a broad concentration range. The supermolecular structure of the specimens prepared by injection molding was characterized by X‐ray scattering and correlated with mechanical behavior. It was found that at a critical nucleant concentration of 0.03 wt % the content of the β‐modification virtually reaches a saturation level. With further addition of the nucleant, the β‐phase content increases only slightly. The long period passes through a distinct maximum at the same nucleant concentration. This singularity in structure remarkably correlates with a minimum of the yield stress and maxima of strain at break and fracture toughness. Such general behavior is also reflected in the correlation between the β‐phase concentration and fracture toughness profiles along the injection‐molded bars. It is suggested that in the critically nucleated material an optimum thickness of the amorphous interlayer with connecting chains between the β‐crystallites is established, rendering the material the highest possible ductility and toughness. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1174–1184, 2002     

Engineering plastics from lignin. XVI. Starlike macromers with propylene oxide

Starlike macromers were prepared from hydroxypropyl organosolv lignin by reaction with propylene oxide, and they were analyzed by a combination of conventional analysis techniques. The average number of arms per macromer was controlled by partial capping with an alkoxy group; and the average length of arms by the degree of chain extension with propylene oxide. Analysis methods included treatment with hydriodic acid followed by gas chromatographic separation of alkyl iodides (HI/GC), UV spectroscopy, H-NMR spectroscopy, and thermal analysis. The results were consistent with a hypothetical pentameric model structure having between two and six radiating arms, each with a length of between 1 and 4 propylene oxide units. The UV method was best qualified to determine degree of chain extension, while HI/GC was best suited for analyzing average number of arms per macromer fragment. The synthesis and analysis of starlike macromers from lignin is viewed as an important stepping stone for the formulation of lignin-based engineering plastics and multiphase materials.     

Engineering plastics from lignin. XV. Polyurethane films from chain-extended hydroxypropyl lignin

A series of polyurethane (PU) films was prepared from chain-extended hydroxypropyl lignins (CEHPL). In appearance, these films ranged from brittle and dark brown to rubbery and bronze. The thermal, mechanical, and network properties of these PUs were investigated by DMTA and DSC analysis. All films exhibited single T_g's which varied between ?53° and 101°C, depending on lignin content. From swelling experiments, molecular weight between crosslinks (M _c) was determined and found to vary over 2.5 orders of magnitude. The M _c's were related to the change in T_g that accompanied network formation. Stress–strain experiments showed a variation in Young's modulus between 7 and 1300 MPa. Most of the variation in material properties was related to lignin content and to a lesser extent to diisocyanate type, hexamethylene diisocyanate, or toluene diisocyanate. The source of the CEHPL had no effect on the observed properties. From these results it was concluded that the properties of PUs can be controlled and engineered for a wide variety of practical uses.     

Bleaching of indigo-dyed denim fabric by electrochemical formation of hypohalogenites in situ

The use of hypochlorite, formed in situ by anodic oxidation of sodium chloride solution, for bleaching indigo-dyed denim has been studied at room temperature and at 50 °C. A direct relationship between the charge flow applied and the bleaching effect was observed. This enables consistent oxidative bleaching to be achieved by controlling the electrochemical process. The use of mixed anolytes containing small concentrations of bromide ions enhanced the bleaching effect considerably, even after lowering the temperature to room temperature. The molar concentration of bromide ions required was much lower than that of chloride in the anolyte.