Phosphaannulation of Aryl‐ and Benzylphosphonic Acids with Unactivated Alkenes via Palladium‐Catalyzed C?H Activation/Oxidative Cyclization Reaction

An efficient phosphaannulation via palladium(II)‐catalyzed C H activation/oxidative cyclization by the 6‐endo mode is reported for the synthesis of 3‐substituted phosphaisocoumarins from the reaction of arylphosphonic acids with unactivated alkenes under aerobic conditions. Also, α,α‐disubstituted benzylphosphonic acids were phosphaannulated with unactivated alkenes, producing phosphaisochromanones having (Z)‐alkylidenyl groups via anti‐phosphoryloxypalladation by the 6‐exo mode.

     

Methane steam reforming for synthetic diesel fuel production from steam-hydrogasifier product gases

Steam-methane reforming (SMR) reaction was studied using a tubular reactor packed with NiO/γ-Al₂O₃ catalyst to obtain synthesis gases with H₂/CO ratios optimal for the production of synthetic diesel fuel from steam-hydrogasification of carbonaceous materials. Pure CH₄ and CH₄-CO₂ mixtures were used as reactants in the presence of steam. SMR runs were conducted at various operation parameters. Increasing temperature from 873 to 1,023 K decreased H₂/CO ratio from 20 to 12. H₂/CO ratio decreased from 16 to 12 with pressure decreasing from 12.8 to 1.7 bars. H₂/CO ratio also decreased from about 11 to 7 with steam/CH₄ ratio of feed decreasing from 5 to 2, the lowest limit to avoid severe coking. With pure CH₄ as the feed, H₂/CO ratio of synthesis gas could not be lowered to the optimal range of 4–5 by adjusting the operation parameters; however, the limitation in optimizing the H₂/CO ratio for synthetic diesel fuel production could be removed by introducing CO₂ to CH₄ feed to make CH₄-CO₂ mixtures. This effect can be primarily attributed to the contributions by CO₂ reforming of CH₄ as well as reverse water-gas shift reaction, which led to lower H₂/CO ratio for the synthesis gas. A simulation technique, ASPEN Plus, was applied to verify the consistency between experimental data and simulation results. The model satisfactorily simulated changes of H₂/CO ratio versus the operation parameters as well as the effect of CO₂ addition to CH₄ feed.     

Improvement in CO2 absorption and reduction of absorbent loss in aqueous NH3/triethanolamine/2-amino-2-methyl-1-propanol blends

Changes in the CO₂ absorption rates and capacities of the absorbent 2-amino-2-methyl-1-propanol (AMP), blended with NH₃ and other additives, were investigated toward performance improvement. The NH₃-blended absorbent removed CO₂ more efficiently than the AMP absorbent alone. However, absorbent loss through NH₃ evaporation was observed under these conditions. A second absorbent, the tertiary amine triethanolamine (TEA), which has a low vapor pressure, was selected and blended with the NH₃/AMP system to reduce NH₃ evaporation. Its effects on NH₃ loss and the absorption rate and capacity of the NH₃/AMP system were investigated, and the optimum blending ratios were determined. In addition, the absorbent blend at the optimum blending ratio was compared to AMP alone and the commercially available absorbent monoethanolamine at the same weight ratio. The thermal stabilities of the absorbents, under conditions used in the CO₂ absorption process, were compared by thermogravimetric analysis.     

Synthesis and characterization of novel hybrid polyoxazoline‐grafted multiwalled carbon nanotubes

The novel hybrid polyoxazoline‐grafted multiwalled carbon nanotubes (POZO‐grafted MWNTs) were synthesized by the reaction of partially hydrolyzed polyoxazolines (Hydrolyzed‐POZO) and MWNTs having carboxylic acid groups (MWNT‐COOH) in the presence of DCC as a condensing agent. Hydrolyzed‐POZO (degree of hydrolysis, 20.2 mol % by ¹H‐NMR) were produced from the hydrolysis of polyoxazolines in an aqueous NaOH solution at reflux for 72 h. MWNT‐COOH were prepared by acid treatment of pristine MWNTs. The composition, structure, thermal property, and surface morphology of the novel hybrid POZO‐grafted MWNTs were fully characterized by FT‐IR, Raman, ¹H‐NMR, DSC, TGA, SEM, and TEM. The obtained POZO‐grafted MWNTs are well soluble in various organic solvents and water. It was observed that the glass transition temperature (T_g) of POZO‐grafted MWNTs was lower than that of Hydrolyzed‐POZO due to the absence of hydrogen bonding interactions between Hydrolyzed‐POZO itself caused by the incorporation with MWNTs. It was also found that Hydrolyzed‐POZO was homogeneously attached to the surfaces of MWNTs through the “grafting‐to” method. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Photocatalytic activities of electrospun tin oxide doped titanium dioxide nanofibers

SnO₂ doped TiO₂ electropsun nanofiber photocatalysts were successfully prepared by means of electrospinning process. The surface morphology, structure and optical properties of the resultant products were characterized by field-emission electron microscopy (FE-SEM), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HR-TEM), X-ray photoelectron spectroscopy (XPS), UV–vis spectroscopy, photoluminescence (PL) and cathodoluminescence (CL) techniques. The utilized physiochemical analyses indicated that the introduced SnO₂ doped TiO₂ nanofibers have a smooth surface and uniform diameters along their lengths. The photocatalytic performance of the composite nanofibers was tested for degradation of methylene blue (MB) and methyl orange (MO) dye solution under ultraviolet (UV) irradiation. Under the UV irradiation, the photocatalytic reaction rate in case of utilizing SnO₂-doped TiO₂ nanofibers was rapidly increased than that of the pristine TiO₂ nanofibers. Overall, this study demonstrates cheap, stable and effective material for photocatalytic degradation at room temperature.     

Effects of gamma irradiation on the thermal and mechanical properties of chitosan/PVA nanofibrous mats

Chitosan/poly(vinyl alcohol) (PVA) nanofibrous mats were prepared by the electrospinning method. The morphology and structure of electrospun nanofibers were investigated by scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR) spectroscopy. SEM images showed that the uniform and bead-free fibers were obtained at concentrations greater than 8 wt%. Chitosan/PVA mats were irradiated with different doses (50–200 kGy) of ⁶⁰Co gamma rays. The effect of irradiation dose on the mechanical and thermal properties of these films was also investigated. Increasing the irradiation dose led to a decrease in tensile strength. FT-IR and DSC demonstrated that there were strong intermolecular hydrogen bonds between the chitosan and PVA molecules.     

Fatty Acids Released from Milk Fat by Lipoprotein Lipase and Lipolytic Psychrotrophs

ABSTRACT: The ability of 13 different strains of psychrotrophs to release free fatty acids in milk was evaluated by using GC analysis. The 13 strains could be categorized into 3 groups: Group 1 consisted of bacteria that grew well and released large quantities of free fatty acids, group 2 consisted of bacteria that grew well but released low amounts of free fatty acids, and group 3 consisted of bacteria that did not grow well nor released large quantities of fatty acids. In group 1, 3 strains were determined to be highly lipolytic, releasing short‐chain fatty acids in amounts greater than reported threshold values. Group 3 consisted of 2 strains, which did not grow well in heat‐treated milk, and the subsequent release of free fatty acids was minor during the 10‐d monitoring time. The other 8 strains tested showed no specific pattern of fatty acid release and quantities of short‐chain fatty acids were not large, despite the ability to grow to high numbers in the treated milk. This work indicates that the lipolytic activity of psychrotrophs common in raw milk is specific to the species and a general prediction of free fatty acid release may not be possible.     

Chemical reduction of U(VI) by Fe(II) at the solid-water interface using natural and synthetic Fe(III) oxides

Abiotic reduction of 0.1 mM U(VI) by Fe(II) in the presence of synthetic iron oxides (biogenic magnetite, goethite, and hematite) and natural Fe(III) oxide-containing solids was investigated in pH 6.8 artificial groundwater containing 10 mM NaHCO3. In most experiments, more than 95% of added U(VI) was sorbed to solids. U(VI) was rapidly and extensively (> or = 80%) reduced in the presence of synthetic Fe(III) oxides and highly Fe(II) oxide-enriched (18-35 wt % Fe) Atlantic coastal plain sediments. In contrast, long-term (20-60 d) U(VI) reduction was less than 30% in suspensions of six other natural solids with relatively low Fe(III) oxide content (1-5 wt % Fe). Fe(II) sorption site density was severalfold lower on these natural solids (0.2-1.1 Fe(II) nm(-2)) compared tothe synthetic Fe(lII) oxides (1.6-3.2 Fe(II) nm(-2)), which may explain the poor U(VI) reduction in the natural solid-containing systems. Addition of the reduced form of the electron shuttling compound anthrahydroquinone-2,6-disulfonate (AH2DS; final concentration 2.5 mM) to the natural solid suspensions enhanced the rate and extent of U(VI) reduction, suggesting that AH2DS reduced U(VI) at surface sites where reaction of U(VI) with sorbed Fe(II) was limited. This study demonstrates that abiotic, Fe(II)-driven U(VI) reduction is likely to be less efficient in natural soils and sediments than would be inferred from studies with synthetic Fe(III) oxides.     

Catalysts characteristics of Ni/YSZ core-shell according to plating conditions using electroless plating

This study aims to develop an anode catalyst for a solid oxide fuel cell (SOFC) using electroless nickel plating. We have proposed a new method for electroless plating of Ni metal on yttria-stabilized zirconia (YSZ) particles. We examine the uniformity of the Ni layer on the plated core-shell powder, in addition to the content of Ni and the reproducibility of the plating. We have also evaluated the carbon deposition rate and characteristics of the SOFC anode catalyst. To synthesize Ni-plated YSZ particles, the plated powder is heat-treated at 1200 °C. The resultant particles, which have an average size of 50 μm, were subsequently used in the experiment. The size of the Ni particles and the Ni content both increase with increasing plating temperature and plating time. The X-ray diffraction pattern reveals the growth of Ni particles. After heat-treatment, Ni is oxidized to NiO, leading to the co-existence of Ni and NiO; Ni₃P is also observed due to the presence of phosphorous in the plating solution. Following heat treatment for 1 h at 1200 °C, Ni is mostly oxidized to NiO. The carbon deposition rate of the reference YSZ powder is ~135%, while that of the Ni-plated YSZ is 1%-6%.