Low-temperature activation of methane over rare earth metals promoted Zn/HZSM-5 zeolite catalysts in the presence of ethylene

At low temperature of 723 K, methane can be easily activated in the presence of ethylene in the feed, and converted to higher hydrocarbons (C2–C4) and aromatics (C6–C10), through its reaction over rare metals modified Zn/HZSM-5 zeolite catalysts without undesirable carbon oxides formation. Methane can get 37.3% conversion over the above catalysts under low temperature, and the catalysts show a longer lifetime than usual metal supported HZSM-5 zeolite catalysts without adding any rare earth metals. The effects of methane activation over various rare earth metal promoted Zn/HZSM-5 catalysts on the products and influences of several reaction conditions such as temperature, catalyst lifetime and molar ratio of CH4/C2H4 have been discussed.     

中微肥的生产及其应用

综述了中量和微量元素肥料生产的必要性、生产工艺的改进和在不同土壤条件、作物品种、肥料形式和栽培条件下的应用方法.解决好这一重要问题的关键在于:中微肥的生产,只有综合利用矿产资源和工业废弃资源,才能有效地降低生产成本;只有采取有机螯合的方法,才能保持中微肥的活性;以大量元素肥料为载体,可方便农民使用.     

Synthesis and thermal properties of antimony doped tin oxide/waterborne polyurethane nanocomposite films as heat insulating materials

The waterborne polyurethane (WPU) was synthesized from the polycondensation between isophorone diisocyanate (IPDI) and polyoxypropylene glycol (N‐210) and then dispersed into water. Subsequently, the WPU emulsion was modified with antimony doped tin oxide (ATO) nanoparticle by ultrasonic dispersion. The ATO/WPU emulsion was cast onto Teflon molds. After being dried, ATO/WPU films were prepared. TEM indicated that the ATO nanoparticles were homogeneously dispersed in the polymer matrix at the nanometer scale. DSC showed that the ATO/WPU nanocomposites displayed increased glass transition temperatures compared to the control WPU. The mechanical properties of the films were characterized by dynamic‐mechanical analysis (DMA). The higher glass transition temperature and storage modulus indicates the superior mechanical properties of WPU modified by ATO nanoparticles over the conventional unmodified WPU. The thermal behaviors of the films were evaluated by thermogravimetric analysis (TGA). It could be found that the incorporation of ATO into WPU can improve the thermal stability dramatically. The results from UV–visible–near infrared spectra indicated that the ATO/WPU films could decrease the infrared transmission effectively. The heat‐insulation measurements showed that glass coated with ATO/WPU films possessed better heat‐insulating effect than empty glass. Copyright © 2010 John Wiley & Sons, Ltd.     

Antioxidant activity of papaya seed extracts

The antioxidant activities of the ethanol, petroleum ether, ethyl acetate, n-butanol and water extract fractions from the seeds of papaya were evaluated in this study. The ethyl acetate fraction showed the strongest DPPH and hydroxyl free radical-scavenging activities, and its activities were stronger than those of ascorbic acid and sodium benzoate, respectively. The n-butanol fraction demonstrated the greatest ABTS? radicals scavenging activity. The ethyl acetate fraction and the n-butanol fraction not only showed higher antioxidant activities than the petroleum ether fraction, water fraction and ethanol fraction, but also showed higher superoxide anion and hydrogen peroxide radicals scavenging activities than those of the other extract fractions. The high amount of total phenolics and total flavonoids in the ethyl acetate and n-butanol fractions contributed to their antioxidant activities. The ethyl acetate fraction was subjected to column chromatography, to yield two phenolic compounds, p-hydroxybenzoic acid and vanillic acid, which possessed significant antioxidant activities. Therefore, the seeds of papaya and these compounds might be used as natural antioxidants.     

Pumping-induced perturbation of flow in microfluidic channels and its implications for on-chip cell culture

We study the rate of response to changes in the rate of flow and the perturbations in flow in polydimethylsiloxane (PDMS) microfluidic chips that are subjected to several common flow-control systems. We find that the flow rate of liquid delivered from a syringe pump equipped with a glass syringe responds faster to the changes in the conditions of flow than the same liquid delivered from a plastic syringe; and the rate of flow delivered from compressed air responds faster than that from a glass syringe. We discover that the rate of flow that is driven by a syringe pump and regulated by an integrated pneumatic valve responds even faster, but this flow-control method is characterized by large perturbations. We also examine the possible effects of these large perturbations on NIH 3T3 cells in microfluidic channels and find that they could cause the detachment of NIH 3T3 cells in the microchannels.     

Facile synthesis of spiroisoquinolines based on photocycloaddition of isoquinoline-1,3,4-trione with oxazoles

Photocycloaddition of isoquinoline-1,3,4-trione and 5-methoxyoxazoles affords spiroisoquinolineoxetanes with high regio- and diastereoselectivity. The spiroisoquinolineoxetanes can be conveniently converted into novel spiroisoquinolineoxazoline derivatives through acid catalyzed sequential reactions.     

Bis(diamino-diamido)-tetrathiafulvalene, a redox active sensor for proton, anions, and cations

A bis(diamino-diamido) tetrathiafulvalene (TTF) derivative H(4)L(2) has been designed and synthesized. Experiments of pH titration reveal that integrating the redox active TTF unit with the diamino-diamido moiety adds new properties to the traditional ligand. Oxidation of the TTF moiety increases the acidity of the amido group, and the coordination of metal ions is also sensitive to the oxidation state of the ligand. This compound is capable of acting as a leaving or accepting ligand for proton and metal ions. The electrochemistry of the protonated TTF derivative of H(4)L(2) was studied in the presence of a series of oxo anions and metal cations. The results indicate that the redox potentials selectively respond to HC(2)O(4)(-) and SO(4)(2-) anions, and Ni(II) and Cu(II) cations. Solid-state structures of a cation-anion salt H(8)L(2)·2SO(4)·8H(2)O and a nickel coordination compound [Ni(2)L(2)]·2DMF have been characterized by means of X-ray crystallography which are helpful in understanding the inter-ion interactions.     

Metal-carboxylate coordination polymers with redox-active moiety of tetrathiafulvalene (TTF)

Though numerous metal-organic frameworks or polymers have been reported, the organic building blocks are usually not redox-active. On the other hand, some mono-, di- or tri-nuclear compounds with tetrathiafulvalene (TTF) have been prepared, although little is known about the coordination polymers combined with paramagnetic metals and organic TTF ligands. We report herein a series of coordination polymers of copper(II) and manganese(II) with TTF dicarboxylate ligand (L). Compound 1, [CuL(2,2-bpy)](n), is a one-dimensional (1-D) coordination polymer with five-coordinated square-pyramidal Cu(II) centers. Mn(II) complex 2, [MnL(2,2-bpy)](n), also takes a 1-D structure, showing a double-bridged mode by carboxylate groups. The 4,4-bipyridine compound 3, [MnL(4,4-bpy)(H(2)O)](n)·CH(3)CN, takes a 2-D grid network. A zinc(II) compound 4, [ZnL(4,4-bpy)(H(2)O)](n)·CH(3)CN, isomorphous structure with 3, is also presented. The electrochemical properties of the solid-state compounds were investigated by cyclic voltammetry using surface-modified electrodes. As usually observed in TTF derivatives, two sets of redox-waves were observed. The values of E(1/2)(1) of compounds 1-4 are in the order of 2(Mn) ≈ 3(Mn) < 1(Cu) < 4(Zn), indicating that the metal coordination can affect the potential shift of the TTF ligand. Weak antiferromagnetic exchanges are observed for compounds 1, 2, and 3.     

Heteroleptic ruthenium complexes containing uncommon 5,5'-disubstituted-2,2'-bipyridine chromophores for dye-sensitized solar cells

Four new heteroleptic ruthenium sensitizers [Ru(4,4'-carboxylic acid-2,2'-bipyridine)(L)(NCS)(2)] (L = 5,5'-bis(4-octylthiophen-2-yl)-2,2'-bipyridine (1), 5,5'-bis(N,N-diphenyl-4-aminophenyl)-2,2'-bipyridine (2), 5,5'-bis(5-(N,N-diphenyl-4-aminophenyl)-thiophen-2-yl)-2,2'-bipyridine (3) and 5,5'-bis(4-octyl-5-(N,N-diphenyl-4-aminophenyl)-thiophen-2-yl)-2,2'-bipyridine (4)) were synthesized, characterized by physicochemical and computational methods, and utilized as photosensitizers in nanocrystalline dye-sensitized solar cells (DSSCs). The λ(max) of the metal-to-ligand charge transfer (MLCT) absorption of these four ruthenium dyes (527 nm for 1, 535 nm for 2, 585 nm for 3 and 553 nm for 4) can be tuned by various structural modifications of the ancillary ligand and it was shown that increasing the conjugation length of such ligand reduces the energy as well as the molar absorption coefficient of the MLCT band. The maximum incident photon to current conversion efficiency (IPCE) of 41.4% at 550 nm, 38.6% at 480 nm, 39.4% at 470 nm and 31.1% at 480 nm for 1-, 2-, 3- and 4-sensitized solar cells were obtained. Respectable power conversion efficiencies of 3.00%, 2.51%, 2.00% and 2.03% were realized, respectively, when the sensitizers 1, 2, 3 and 4 were used in DSSCs under the standard air mass (AM) 1.5 sunlight illumination (versus 5.9% for standard N719).     

The synthesis of the near-spherical AgCl crystal for visible light photocatalytic applications

The near-spherical AgCl micro-crystals were prepared by an ionic liquids-assisted hydrothermal method. The influence of ionic liquids (C(x)MimCl x = 4, 8, 12, 16) on (001) facet growth of AgCl was studied systemically. The composition of the as-prepared samples was characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA) and FTIR spectra. The morphological structures were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Based on experimental data and the classical crystal growth theory, a plausible growth mechanism of the near-spherical AgCl was proposed. The plasmonic photocatalyst Ag@AgCl prepared from the near-spherical AgCl showed higher activity than that of cubic morphologies.