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Stoichiometric Ratio (stoichiometric + ratio)
Selected AbstractsCrystal growth and magnetic properties of the copper coordination polymer [Cu(µ -C2O4)(4-aminopyridine)2(H2O)]nCRYSTAL RESEARCH AND TECHNOLOGY, Issue 4 2007A. V. Prokofiev Abstract In this paper, we consider various ways of crystal growth of the polymer [Cu(µ -C2O4)(4-aminopyridine)2(H2O)]n. Single crystals of the size of 1.5×1.5×0.2 mm3 have been grown by a slow diffusion technique from solutions of the monoammine copper complex and of the mixture of potassium oxalate and aminopyridine with the stoichiometric ratio. Magnetic susceptibility and ESR measurements have been performed on single crystals large enough for investigating anisotropic properties. The susceptibility can be well described within the model of a Heisenberg antiferromagnetic spin chain. The magnetic measurements reveal a small concentration of paramagnetic moments reflecting the high quality of the single crystals. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Facilitated Transfer of Alkali Metal Ions by a Tetraester Derivative of Thiacalix[4]arene at the Liquid,Liquid InterfaceELECTROANALYSIS, Issue 12 2008Akgemci, Emine Guler Abstract The facilitated transfer of alkali metal ions (Na+, K+, Rb+, and Cs+) by 25,26,27,28-tetraethoxycarbonylmethoxy-thiacalix[4]arene across the water/1,2-dichloroethane interface was investigated by cyclic voltammetry. The dependence of the half-wave transfer potential on the metal and ligand concentrations was used to formulate the stoichiometric ratio and to evaluate the association constants of the complexes formed between ionophore and metal ions. While the facilitated transfer of Li+ ion was not observed across the water/1,2-dichloroethane interface, the facilitated transfers were observed by formation of 1,:,1 (metal:ionophore) complex for Na+, K+, and Rb+ ions except for Cs+ ion. In the case of Cs+ a 1,:,2 (metal:ionophore) complex was obtained from its special electrochemical response to the variation of ligand concentrations in the organic phase. The logarithms of the complex association constants, for facilitated transfer of Na+, K+, Rb+, and Cs+, were estimated as 6.52, 7.75, 7.91 (log ,1°), and 8.36 (log ,2°), respectively. [source] Adsorbing colloid flotation for removal of metal ions in waters from base metal minesENVIRONMENTAL PROGRESS & SUSTAINABLE ENERGY, Issue 1 2002H. Sabti Adsorbing Colloid Flotation (ACF) has been shown in laboratory experiments to be effective for the removal of heavy metals (Zn, Cu, Cd and Pb) from dilute solutions. Sodium dodecyl sulphate (SDS) and sodium oleate (NaOl) were used as surfactants in single or mixed form, with Fe(OH)3 as a flocculant for colloid formation. These reagents worked best for zinc and copper ions for a feed concentration of 50 parts per million (ppm). The removal of lead improved significantly by the use of Fe(OH)3 and NaLS (Sodium lauryl sulphate), while the best removal of cadmium was achieved by the use of Al(OH)3 and HTMABr (hexadecyltrimethylammonium bromide). Flotation experiments were conducted with feed concentrations of 50 and 500 parts per billion (ppb) and 50 ppm (parts per million). The experimental results showed that the residual concentration of metal ions decreased significantly with the decrease in the feed concentration. This could be the effect of excessive (much more than stoichiometric ratio) amounts of surfactant and flocculant, compared to the feed concentrations, required in the effective flotation of dilute feed solutions. The surfactant concentration and feed pH had the largest effects on the process, as observed in the case of cadmium removal. This can be attributed to the flocformation and flotation tendencies of the colloid-metal complexes at various solution pH and surfactant concentrations. The ACF method was applied to a number of natural drainage solutions from the metal mines at Te Aroha, New Zealand, and the experimental results demonstrate that significant removal is achieved for most of the heavy metals. [source] Synthesis, Structural, Thermal and Magnetic Characterization of a Pyrophosphato-Bridged Cobalt(II) ComplexEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 17 2008Oluwatayo F. Ikotun Abstract The reaction in water of CoII sulfate heptahydrate with 1,10-phenanthroline (phen) and sodium pyrophosphate (Na4P2O7) in a 2:4:1 stoichiometric ratio resulted in the crystallization of a neutral dinuclear CoII complex, {[Co(phen)2]2(,-P2O7)}·6MeOH (1), as revealed by a single-crystal X-ray diffraction study. The bridging pyrophosphato ligand between the two [Co(phen)2]2+ units in a bis(bidentate) coordination mode places the adjacent metal centers at 4.857 Å distance, and its conformation gives rise to intramolecular ,,, stacking interaction between adjacent phen ligands. Indeed, intermolecular ,,, stacking interactions between phen ligands from adjacent dinuclear complexes create a supramolecular 2D network in 1. Magnetic susceptibility measurements on a polycrystalline sample of 1 in the temperature range 1.9,295 K are typical of an overall antiferromagnetic coupling with a maximum of the magnetic susceptibility at 3.0 K. The analysis of the magnetic data in the whole temperature range allows the determination of the value of the intramolecular magnetic coupling (J = ,1.23 cm,1). The ability of the pyrophosphato ligand to mediate magnetic interactions between different first-row transition-metal ions when adopting the bis(bidentate) bridging mode is analyzed and discussed in the light of the small number of magneto-structural reports on this type of compound, bearing in mind the number of unpaired electrons and type of magnetic orbitals on each metal center. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Solvothermal Synthesis, Crystal Structures, and Properties of New Selenidoantimonates [Ln(en)4(SbSe4)] (Ln = La, Nd) and [Sm(en)4]SbSe4·0.5en: The First Example of an SbSe43, Anion Acting as a Ligand to a Lanthanide ComplexEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 14 2006Ding-Xian Jia Abstract Three new lanthanide selenidoantimonates [Ln(en)4(SbSe4)] [Ln = La (1), Nd (2)] and [Sm(en)4]SbSe4·0.5en (3) (en = ethylenediamine) were first synthesized by treating LnCl3, Sb, and Se in a stoichiometric ratio with en under mild solvothermal conditions. Compounds 1 and 2 are isostructural. The Ln3+ ion has a nine-coordinate environment involving eight N atoms from four en ligands and one Se atom from the SbSe43, anion forming a distorted bicapped pentagonal bipyramid. [La(en)4(SbSe4)] and [Nd(en)4(SbSe4)] are the first examples of solvothermally synthesized selenidoantimonates with an SbSe43, anion acting as a ligand in a lanthanide complex. The crystal structure of 3 contains an isolated bicapped trigonal-prismatic coordinated [Sm(en)4]3+ cation, a tetrahedral SbSe43, anion, and half a free en molecule in its asymmetric unit. The bandgaps of 2.22 eV for 1, 2.33 eV for 2, and 2.54 eV for 3 have been derived from optical absorption spectra. Compound 1 loses the en ligands in one step, whereas compound 2 loses them in two steps. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] A Facile Strategy for Preparing Self-Healing Polymer Composites by Incorporation of Cationic Catalyst-Loaded Vegetable FibersADVANCED FUNCTIONAL MATERIALS, Issue 14 2009Ding Shu Xiao Abstract A two-component healing agent, consisting of epoxy-loaded microcapsules and an extremely active catalyst (boron trifluoride diethyl etherate, (C2H5)2O,·,BF3)), is incorporated into epoxy composites to provide the latter with rapid self-healing capability. To avoid deactivation of the catalyst during composite manufacturing, (C2H5)2O,·,BF3 is firstly absorbed by fibrous carriers (i.e., short sisal fibers), and then the fibers are coated with polystyrene and embedded in the epoxy matrix together with the encapsulated epoxy monomer. Because of gradual diffusion of the absorbed (C2H5)2O,·,BF3 from the sisal into the surrounding matrix, the catalyst is eventually distributed throughout the composites and acts as a latent hardener. Upon cracking of the composites, the epoxy monomer is released from the broken capsules, spreading over the cracked planes. As a result, polymerization, triggered by the dispersed (C2H5)2O,·,BF3, takes place and the damaged sites are rebonded. Since the epoxy,BF3 cure belongs to a cationic chain polymerization, the exact stoichiometric ratio of the reaction components required by other healing chemistries is no longer necessary. Only a small amount of (C2H5)2O,·,BF3 is sufficient to initiate very fast healing (e.g., a 76% recovery of impact strength is observed within 30,min at 20,°C). [source] Preparation and Characteristics of Esculin-Imprinted PolymersHELVETICA CHIMICA ACTA, Issue 6 2007Guo-Song Wang Abstract Four molecularly imprinted polymers (MIPs) were prepared in MeOH with esculin (=6,7-dihydroxycoumarin 6-(, - D -glucopyranoside)=6-(, - D -glucopyranosyloxy)-7-hydroxy-2H -1-benzopyran-2-one) as the imprinted molecule, methacrylic acid (=2-methylprop-2-enoic acid; MAA), acrylamide (=prop-2-enamide; AM), 4-vinylpyridine (=4-ethenylpyridine; 4-VP), or 2-vinylpyridine (=2-ethenylpyridine; 2-VP) as the functional monomer, respectively, as well as ethylene glycol dimethacrylate (=2-methylprop-2-enoic acid ethane-1,2-diyl ester; EGDMA) as the cross-linking agent. The interaction between the template and the functional monomers was investigated by fluorescence and UV spectrophotometry, respectively, which revealed the presence of esculin/monomer complexes in the stoichiometric ratio 1,:,2 in the pre-polymerization mixture. The resultant polymers were studied in equilibrium binding experiments to evaluate the recognition ability and the binding capacity towards esculin. The results showed that MIP1, prepared with MAA as the functional monomer, exhibited advantageous characteristics of high binding capacity, optimal imprinting effect, and good selectivity towards esculin. The Scatchard analysis indicated that there are two types of binding sites in MIP1, and its binding parameters including the apparent maximum numbers of binding sites and the dissociation constants were calculated. Finally, by packing an SPE column (SPE=solid-phase extraction) with MIP1, the esculin was separated and enriched successfully by this sorbent from samples of Cortex fraxini, and the average recovery was up to 74.7%. [source] Novel Synthesis of SrBi2Nb2O9 Powders From Hydroxide PrecursorsINTERNATIONAL JOURNAL OF APPLIED CERAMIC TECHNOLOGY, Issue 1 2008Upendra Nath Gupta Simple hydroxide precursors were used for the first time for the synthesis of a typical Aurivillius compound (SrBi2Nb2O9 (SBN)) at a low temperature. This method is very advantageous because it circumvents the use of SrCO3 in the case of conventional ceramics as well in the coprecipitation methods, thereby lowering the formation of the product phase. Commercially purchased strontium hydroxide is mixed thoroughly with freshly precipitated bismuth and niobium hydroxides in a stoichiometric ratio and heated at different temperatures ranging from 100°C to 750°C for 12 h. The sequence of the reaction and evolution of the product phase was monitored by X-ray diffraction (XRD) studies by recording the XRD for samples calcined at different temperatures. The incipient SBN phase begins to form at temperatures as low as 400°C, and phase formation was complete only at 650°C as revealed by the XRD observations. The differential thermal/thermogravimetric analyses) also corroborate this result. The morphology and average particle size of these powders were investigated by transmission electron microscopy studies. [source] Molecular imprinted solid-phase extraction of huperzine A from Huperzia SerrataJOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2009Guosong Wang Abstract On the basis of the non-covalent interaction between template and monomer, porous molecularly imprinted polymers (MIPs) were synthesized by a thermal-initiated polymerization method using huperzine A as template, acrylamide, or methacrylic acid as function monomer, ethylene glycol dimethacrylate as cross-linking agent. The interaction between template and functional monomers was studied by UV spectrophotometry, which showed a formation of huperzine A-monomer complexes with stoichiometric ratio of 1 : 2 in the pre-polymerized systems. The resultant MIP particles were tested in the equilibrium binding experiment to analyze their adsorption ability to huperzine A, and were characterized by Fourier Transform Infrared (FTIR) study. The recognition properties of MIP were estimated in solid-phase extraction by selecting four compounds (isolated from the Chinese herb Huperzia serrata) as substrates, and were compared with and prior to those of the NIP. High affinity and adsorption of MIP1 which was prepared in chloroform with huperzine A as imprinted molecule, and acrylamide (AM) as functional monomer, made an attractive application of MIP1 in separation processes. In final, using MIP1 solid-phase extraction micro-column, huperzine A was enriched and separated from the real extraction sample of Huperzia serrata. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] Supercritical water oxidation of quinoline in a continuous plug flow reactor,part 2: kineticsJOURNAL OF CHEMICAL TECHNOLOGY & BIOTECHNOLOGY, Issue 6 2006Lisete DS Pinto Abstract The results of a detailed investigation into the kinetics of quinoline oxidation in supercritical water are presented. The novel kinetic data presented were obtained in a continuously operated, plug flow reactor where parameters such as temperature, pressure, residence time and stoichiometric ratio of oxidant to quinoline were investigated and detailed in the companion paper (Pinto LDS, Freitas dos Santos LMF, Al-Duri B and Santos RCD, Supercritical water oxidation of quinoline in a continuous plug flow reactor,part 1: effect of key operating parameters. J Chem Technol Biotechnol). An induction time was experimentally observed, ranging from 1.5 to 3.5 s, with longer times observed in experiments carried out at lower temperatures. A pseudo-first-order rate expression with respect to quinoline concentration (with oxygen excess) was first adopted and the activation energy of 234 kJ mol,1 and a pre-exponential factor of 2.1 × 1014 s,1 were estimated. Furthermore, an integral power rate model expression was established, attributing a reaction order for quinoline as 1 and for oxygen as 0.36. An activation energy and pre-exponential factor for this model were determined as 224 kJ mol,1 and 3.68 × 1014 M,0.36 s,1, respectively. A global rate expression was then regressed for the quinoline reaction rate from the complete set of data. The resulting activation energy was 226 ± 19 kJ mol,1 and the pre-exponential factor was 2.7 × 1013 ± 2 M,0.1 s,1. The reaction orders for quinoline and oxygen were 0.8 ± 0.1 and 0.3 ± 0.1, respectively. It was shown that the least-squares regression method provided the best-fit model for experimental results investigated in this study. Copyright © 2006 Society of Chemical Industry [source] Effect of surface modifying macromolecules stoichiometric ratio on composite hydrophobic/hydrophilic membranes characteristics and performance in direct contact membrane distillationAICHE JOURNAL, Issue 12 2009M. Qtaishat Abstract The stoichiometric ratio for the synthesis components of hydrophobic new surface modifying macromolecules (nSMM) was altered systematically to produce three different types of nSMMs, which are called hereafter nSMM1, nSMM2, and nSMM3. The newly synthesized SMMs were characterized for fluorine content, average molecular weight, and glass transition temperature. The results showed that fluorine content decreased with increasing the ratio of ,,,-aminopropyl poly(dimethyl siloxane) to 4,4,-methylene bis(phenyl isocyanate). The synthesized nSMMs were blended into hydrophilic polyetherimide (PEI) host polymer to form porous hydrophobic/hydrophilic composite membranes by the phase inversion method. The prepared membranes were characterized by the contact angle measurement, X-ray photoelectron spectroscopy, gas permeation test, measurement of liquid entry pressure of water, and scanning electron microscopy. Finally, these membranes were tested for desalination by direct contact membrane distillation and the results were compared with those of commercial polytetraflouroethylene membrane. The effects of the nSMM type on the membrane morphology were identified, which enabled us to link the membrane morphology to the membrane performance. It was found that the nSMM2/PEI membrane yielded the best performance among the tested membranes. In particular, it should be emphasized that the above membrane was superior to the commercial one. © 2009 American Institute of Chemical Engineers AIChE J, 2009 [source] Determination of binding sites in carboplatin-bound cytochrome c using electrospray ionization mass spectrometry and tandem mass spectrometryJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 8 2005Gaosheng Yang Abstract Interaction of carboplatin with cytochrome c (Cyt. c) has been investigated by electrospray ionization mass spectrometry (ESI-MS) and tandem mass spectrometry (MS/MS). ESI-MS studies revealed that the ring-opened adducts of carboplatin with Cyt. c were formed in the stoichiometric ratio of 1 : 1 and 2 : 1 at pH 5.0 and 37 °C and in the stoichiometric ratio of 1 : 1 only at pH 7.0 and 37 °C. It was also found that Cyt. c could be cleaved by carboplatin at pH 2.5 and 50 °C. The cleaved fragments of Cyt. c were determined by ESI-MS and MS/MS analysis to be Glu66,Met80, Ac-Gly01,Met65, Glu66,Glu104, Ac-Gly01,Met80 and Ile81,Glu104. The carboplatin prefers to anchor to Met65 first, then to Met80. To further confirm the binding site of Met, AcMet-Gly was used as the model molecule to investigate its interaction with carboplatin and its hydrolysis reaction. On the basis of species detected during the reaction monitored by ESI-MS, a possible pathway of the cleavage reaction was proposed. Copyright © 2005 John Wiley & Sons, Ltd. [source] Sulfonated naphthalene dianhydride based polyimide copolymers for proton-exchange-membrane fuel cells.JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 4 2004Abstract A novel sulfonated diamine, 3,3,-disulfonic acid-bis[4-(3-aminophenoxy)phenyl]sulfone (SA-DADPS), was prepared from m -aminophenol and disodium-3,3,-disulfonate-4,4,-dichlorodiphenylsulfone. The conditions necessary to synthesize and purify SA-DADPS in high yields were investigated in some detail. This disulfonated aromatic diamine, containing ether and sulfone linkages, was used to prepare N -methyl-2-pyrrolidinone-soluble, six-membered ring polyimide copolymers containing pendent sulfonic acid groups by a catalyzed one-step high-temperature polycondensation in m -cresol. These materials showed much improved hydrolytic stability with respect to phthalimides. High-molecular-weight film-forming statistical copolymers with controlled degrees of disulfonation were prepared through variations in the stoichiometric ratio of disulfonated diamine (SA-DADPS) in its soluble triethylamine salt form to several unsulfonated diamines. Three unsulfonated diamines, bis[4-(3-aminophenoxy)phenyl] sulfone, 4,4,-oxydianiline, and 1,3-phenylenediamine, were used to prepare the copolymers. The characterization of the copolymers by 1H NMR, Fourier transform infrared, ion-exchange capacity, and thermogravimetric analysis demonstrated that SA-DADPS was quantitatively incorporated into the copolymers. Solution-cast films of the sulfonated copolymers were prepared and afforded tough, ductile membranes with high glass-transition temperatures. Methods were developed to acidify the triethylammonium salt membranes into their disulfonic acid form, this being necessary for proton conduction in a fuel cell. The synthesis and characterization of these materials are described in this article. Future articles will describe the performance of these copolymers as proton-exchange membranes in hydrogen/air and direct methanol fuel cells. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 862,874, 2004 [source] Titanium Diboride,Tungsten Diboride Solid Solutions Formed by Induction-Field-Activated Combustion SynthesisJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 4 2003Masachika Shibuya Solid solutions of titanium diboride,tungsten diboride (TiB2,WB2) were synthesized by induction-field-activated combustion synthesis (IFACS) using elemental reactants. In sharp contrast to conventional methods, solid solutions could be formed by the IFACS method within a very short time, ,2 min. Solutions with compositions ranging from 40,60 mol% WB2 were synthesized with a stoichiometric ratio (Ti + W)/B =½; however, samples with excess boron were also made to counter the loss of boron by evaporation. The dependence of the lattice constants of the resulting solid solutions on composition was determined. The "a" parameter decreased only slightly with an increase in the WB2 content, whereas the "c" parameter exhibited a significant decrease over the range 40,60 mol% WB2. Solid-solution powders formed by the IFACS method were subsequently sintered in a spark plasma sintering (SPS) apparatus. After 10 min at 1800°C, the samples densified to relative density 86%. XRD analysis showed the presence of only the solid-solution phase. [source] Surfactant-Induced Amorphous Aggregation of Tobacco Mosaic Virus Coat Protein: A Physical Methods ApproachMACROMOLECULAR BIOSCIENCE, Issue 2 2008Yuliy V. Panyukov Abstract The interactions of non-ionic surfactant Triton X-100 and the coat protein of tobacco mosaic virus, which is an established model for both ordered and non-ordered protein aggregation, were studied using turbidimetry, differential scanning calorimetry, isothermal titration calorimetry, and dynamic light scattering. It was found that at the critical aggregation concentration (equal to critical micelle concentration) of 138,×,10,6M, Triton X-100 induces partial denaturation of tobacco mosaic virus coat protein molecules followed by protein amorphous aggregation. Protein aggregation has profound ionic strength dependence and proceeds due to hydrophobic sticking of surfactant-protein complexes (start aggregates) with initial radii of 46 nm. It has been suggested that the anionic surfactant sodium dodecyl sulfate forms mixed micelles with Triton X-100 and therefore reverses protein amorphous aggregation with release of protein molecules from the amorphous aggregates. A stoichiometric ratio of 5 was found for Triton X-100-sodium dodecyl sulfate interactions. [source] Influence of Grafting on the Solution Properties and the Dissociation Behavior of Ionic/Nonionic Grafted CopolymersMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 6 2007Jens Weber Abstract A new synthetic approach towards grafted terpolymers based on a poly[(methyl vinyl ether)- alt -(maleic anhydride)] backbone and poly(ethylene glycol) monomethyl ether (MPEG) side chains is presented. Resulting comb polymers with controllable grafting degree still have highly reactive anhydride moieties along the polymer backbone, as proved by IR spectroscopy. Grafting degree depends on the anhydride hydroxide stoichiometric ratio. It is not influenced by the molecular weight of MPEG. An increase in the grafting degree leads to a contraction of the polymer in the solution. Evaluation of potentiometric titration data gave a deeper insight into the dissociation process. The copolymers showed a two-step dissociation behavior. No significant influence of the grafting degree on the acidic strength was observed, whilst there is a strong effect of the grafting degree on the free energy change upon neutralization ,Gel. Grafting leads to a higher change in free energy ,Gel,1 for the first step but to lower ,Gel,2 required for the second step. [source] Electrodeposited CuGa(Se,Te)2 thin-film prepared from sulfate bathPHYSICA STATUS SOLIDI (C) - CURRENT TOPICS IN SOLID STATE PHYSICS, Issue 8 2006Yusuke Oda Abstract CuGa(Se,Te)2 (CGST) thin films were prepared on a soda-lime glass substrate sputter coated with molybdenum by electrodeposition. The aqueous solution which contained CuSO4 -5H2O, Ga2(SO4)3 -19.3H2O, H2SeO3, H6TeO6, Li2SO4 and gelatin was adjusted to pH 2.6 with dilute H2SO4 and NaOH. It has been observed that (i) a crack-less and smooth CGST film with a composition close to the stoichiometric ratio was deposited at -600 mV (vs. Ag/AgCl) when Te was hardly included in the film and (ii) cracks and products on the surface increased with increasing Te content in the film. Annealing at 600 °C for 10 min improved the crystallinity of the as-deposited films. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Prediction of flammability speciation for the lower alkanes, carboxylic acids, and estersPROCESS SAFETY PROGRESS, Issue 1 2007M. Palucis Abstract A Gibbs energy minimization procedure is used to predict the flammability envelopes of alkanes, carboxylic acids, and acetates. In addition to providing the calculated adiabatic flame temperature (CAFT), the product profiles reveal regions of incomplete combustion products and the onset of methane formation above 0.0001 mole fraction. Temperatures at the predicted onset of methane production appear to be closely related to the temperature at the upper flammability limit (UFL). Although a fixed CAFT value could be related to the lower flammability limit (LFL), it was found that this was not the case with the UFL and only for acetic acid could a single CAFT value of 1200K be used to conservatively predict the flammable region. Rather, in general, a single CAFT value could not conservatively predict the upper flammable region. The predictions also reveal local maxima and minima in the concentrations of reaction products. These maps of incomplete combustion products for the flammability region predict that incomplete combustion products are produced at fuel/oxygen ratios significantly below the fuel/oxygen stoichiometric ratio. This region decreases as the limiting oxygen concentration is approached. © 2006 American Institute of Chemical Engineers Process Saf Prog, 2006 [source] 4,4,-Methylenediphenol,4,4,-bipyridine (2/3): decarboxylation of 5,5,-methylenedisalicylic acid under hydrothermal conditionsACTA CRYSTALLOGRAPHICA SECTION C, Issue 9 2009Zhi-Hui Zhang Reaction of 5,5,-methylenedisalicylic acid (5,5,-H4mdsa) with 4,4,-bipyridine (4,4,-bipy) and manganese(II) acetate under hydrothermal conditions led to the unexpected 2:3 binary cocrystal 4,4,-methylenediphenol,4,4,-bipyridine (2/3), C13H12O2·1.5C10H8N2 or (4,4,-H2dhdp)(4,4,-bipy)1.5, which is formed with a concomitant decarboxylation. The asymmetric unit contains one and a half 4,4,-bipy molecules, one of which straddles a centre of inversion, and one 4,4,-H2dhdp molecule. O,H...N interactions between the hydroxy and pyridyl groups lead to a discrete ribbon motif with an unusual 2:3 stoichiometric ratio of strong hydrogen-bonding donors and acceptors. One of the pyridyl N-atom donors is not involved in hydrogen-bond formation. Additional weak C,H...O interactions between 4,4,-bipy and 4,4,-H2dhdp molecules complete a two-dimensional bilayer supramolecular structure. [source] Enhanced arsenic accumulation by engineered yeast cells expressing Arabidopsis thaliana phytochelatin synthase,BIOTECHNOLOGY & BIOENGINEERING, Issue 2 2008Shailendra Singh Abstract Phytochelatins (PCs) are naturally occurring peptides with high-binding capabilities for a wide range of heavy metals including arsenic (As). PCs are enzymatically synthesized by phytochelatin synthases and contain a (,-Glu-Cys)n moiety terminated by a Gly residue that makes them relatively proteolysis resistant. In this study, PCs were introduced by expressing Arabidopsis thaliana Phytochelatin Synthase (AtPCS) in the yeast Saccharomyces cerevisiae for enhanced As accumulation and removal. PCs production in yeast resulted in six times higher As accumulation as compared to the control strain under a wide range of As concentrations. For the high-arsenic concentration, PCs production led to a substantial decrease in levels of PC precursors such as glutathione (GSH) and ,-glutamyl cysteine (,-EC). The levels of As(III) accumulation were found to be similar between AtPCS-expressing wild type strain and AtPCS-expressing acr3, strain lacking the arsenic efflux system, suggesting that the arsenic uptake may become limiting. This is further supported by the roughly 1:3 stoichiometric ratio between arsenic and PC2 (n,=,2) level (comparing with a theoretical value of 1:2), indicating an excess availability of PCs inside the cells. However, at lower As(III) concentration, PC production became limiting and an additive effect on arsenic accumulation was observed for strain lacking the efflux system. More importantly, even resting cells expressing AtPCS pre-cultured in Zn2+ enriched media showed PCs production and two times higher arsenic removal than the control strain. These results open up the possibility of using cells expressing AtPCS as an inexpensive sorbent for the removal of toxic arsenic. Biotechnol. Bioeng. 2008;99: 333,340. © 2007 Wiley Periodicals, Inc. [source] Growth of Hafnium Dioxide Thin Films by MOCVD Using a New Series of Cyclopentadienyl Hafnium Compounds,CHEMICAL VAPOR DEPOSITION, Issue 11 2007G. Carta Abstract Thin films of HfO2 are grown by metal-organic (MO)CVD on Si(001) and fused quartz substrates in the temperature range 400,500,°C, using a new series of bis-cyclopentadienyl bis-amino-alkoxide hafnium precursors, namely [(C5H5)2Hf{OC(CH3)2CH2N(CH3)2}2] and [(C5H5)2Hf{OCH(CH3)CH2N(CH3)2}2], stable in air because of their strong coordination to the metal center. The films obtained are investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Rutherford backscattering spectroscopy (RBS), and atomic force microscopy (AFM). Monoclinic phase HfO2 (baddeleyite) films, characterized by a correct stoichiometric ratio and a granular surface morphology with a roughness/thickness ratio that decreases with increasing deposition rate, are obtained. [source] Separating the influence of resource ,availability' from resource ,imbalance' on productivity,diversity relationshipsECOLOGY LETTERS, Issue 6 2009Bradley J. Cardinale Abstract One of the oldest and richest questions in biology is that of how species diversity is related to the availability of resources that limit the productivity of ecosystems. Researchers from a variety of disciplines have pursued this question from at least three different theoretical perspectives. Species energy theory has argued that the summed quantities of all resources influence species richness by controlling population sizes and the probability of stochastic extinction. Resource ratio theory has argued that the imbalance in the supply of two or more resources, relative to the stoichiometric needs of the competitors, can dictate the strength of competition and, in turn, the diversity of coexisting species. In contrast to these, the field of Biodiversity and Ecosystem Functioning has argued that species diversity acts as an independent variable that controls how efficiently limited resources are utilized and converted into new tissue. Here we propose that all three of these fields give necessary, but not sufficient, conditions to explain productivity,diversity relationships (PDR) in nature. However, when taken collectively, these three paradigms suggest that PDR can be explained by interactions among four distinct, non-interchangeable variables: (i) the overall quantity of limiting resources, (ii) the stoichiometric ratios of different limiting resources, (iii) the summed biomass produced by a group of potential competitors and (iv) the richness of co-occurring species in a local competitive community. We detail a new multivariate hypothesis that outlines one way in which these four variables are directly and indirectly related to one another. We show how the predictions of this model can be fit to patterns of covariation relating the richness and biomass of lake phytoplankton to three biologically essential resources (N, P and light) in a large number of Norwegian lakes. [source] Pilot scale SO2 control by dry sodium bicarbonate injection and an electrostatic precipitatorENVIRONMENTAL PROGRESS & SUSTAINABLE ENERGY, Issue 3 2007Michael J. Pilat Abstract A 500 actual cubic feet gas per minute (acfm) pilot-scale SO2 control study was undertaken to investigate flue gas desulfurization (FGD) by dry sodium sorbents in 400°F (204.5°C) flue gases emitted from a coal fired boiler with flue gas concentrations between 350 and 2500 ppm SO2. Powdered sodium alkaline reagents were injected into the hot flue gas downstream of the air preheater and the spent reagents were collected using an electrostatic precipitator. Three different sorbents were used: processed sodium bicarbonate of two particle sizes; solution mined sodium bicarbonate, and processed sodium sesquicarbonate. SO2 concentrations were measured upstream of the reagent injection, 25-ft (7.62 m) downstream of the injection point, and downstream of the electrostatic precipitator. SO2 collection efficiencies ranged from 40 to 80% using sodium bicarbonate stoichiometric ratios from 0.5 to 3.0. Much of the in-duct SO2 removal occurred during the first second of reagent reaction time, indicating that the sulfur dioxide,sodium reaction rates may be faster than have been measured for fixed bed measurements reported in the literature. © 2007 American Institute of Chemical Engineers Environ Prog, 2007 [source] Global trends in senesced-leaf nitrogen and phosphorusGLOBAL ECOLOGY, Issue 5 2009Zhiyou Yuan ABSTRACT Aim, Senesced-leaf litter plays an important role in the functioning of terrestrial ecosystems. While green-leaf nutrients have been reported to be affected by climatic factors at the global scale, the global patterns of senesced-leaf nutrients are not well understood. Location, Global. Methods, Here, bringing together a global dataset of senesced-leaf N and P spanning 1253 observations and 638 plant species at 365 sites and of associated mean climatic indices, we describe the world-wide trends in senesced-leaf N and P and their stoichiometric ratios. Results, Concentration of senesced-leaf N was highest in tropical forests, intermediate in boreal, temperate, and mediterranean forests and grasslands, and lowest in tundra, whereas P concentration was highest in grasslands, lowest in tropical forests and intermediate in other ecosystems. Tropical forests had the highest N : P and C : P ratios in senesced leaves. When all data were pooled, N concentration significantly increased, but senesced-leaf P concentration decreased with increasing mean annual temperature (MAT) and mean annual precipitation (MAP). The N : P and C : P ratios also increased with MAT and MAP, but C : N ratios decreased. Plant functional type (PFT), i.e. life-form (grass, herb, shrub or tree), phylogeny (angiosperm versus gymnosperm) and leaf habit (deciduous versus evergreen), affected senesced-leaf N, P, N : P, C : N and C : P with a ranking of senesced-leaf N from high to low: forbs , shrubs , trees > grasses, while the ranking of P was forbs , shrubs , trees < grasses. The climatic trends of senesced-leaf N and P and their stoichiometric ratios were similar between PFTs. Main conclusions, Globally, senesced-leaf N and P concentrations differed among ecosystem types, from tropical forest to tundra. Differences were significantly related to global climate variables such as MAT and MAP and also related to plant functional types. These results at the global scale suggest that nutrient feedback to soil through leaf senescence depends on both the climatic conditions and the plant composition of an ecosystem. [source] In situ crosslinked hydrogels formed using Cu(I)-free Huisgen cycloaddition reactionPOLYMER INTERNATIONAL, Issue 10 2009Meredith Clark Abstract BACKGROUND: ,Click' chemistry, or the 1,3-dipolar cycloaddition of organic azides with alkynes, has been evaluated for many biomedical purposes; however, its utility in crosslinking hydrogels in situ is limited by the toxicity of the requisite copper(I) catalyst. We report the first use of catalyst-free Huisgen cycloaddition to generate crosslinked hydrogels under physiological conditions using multivalent azide-functionalized polymers and an electron-deficient dialkyne crosslinker. RESULTS: Water-soluble azide-functionalized polymers were crosslinked with an electron-deficient dialkyne crosslinker to form hydrogels at physiological temperature without the addition of copper(I) catalyst. Crosslinking was confirmed using scanning electron microscopy, Fourier transform infrared and 1H NMR analyses. Flow by vial inversion and dynamic rheological methodologies were implemented to evaluate gelation kinetics at 37 °C of variable polymer compositions, concentrations and stoichiometric ratios. Kinetic studies revealed gelation in as little as 12 h at 37 °C, although strong gels that withstand inversion were observed by 1,8 days. CONCLUSION: The ability to form hydrogel networks under mild conditions demonstrates the potential viability of the catalyst-free ,click' crosslinking chemistry for in situ gelling and other biological applications. Further chemical modifications in the crosslinking moieties, as well as polymer and crosslinker conformations, are expected to enhance gelation kinetics to a more biomedically practical rate. Copyright © 2009 Society of Chemical Industry [source] | |||||||||||||||||||||||||||||||