Differential effects of low-temperature inhibition on the propylene induced autocatalysis of ethylene production, respiration and ripening of 'Hayward' kiwifruit

Previous studies (Stavroulakis and Sfakiotakis, 1993) have shown an inhibition of propylene-induced ethylene production in kiwifruit below a critical temperature range of 11-14.8 degrees C. The aim of this research was to identify the biochemical basis of this inhibition in kiwifruit below 11-14.8 degrees C. 'Hayward' kiwifruit were treated with increasing propylene concentrations at 10 and 20 degrees C. Ethylene biosynthesis pathways and fruit ripening were investigated. Kiwifruit at 20 degrees C in air started autocatalysis of ethylene production and ripened after 19 d with a concomitant increase in respiration. Ethylene production and the respiration rise appeared earlier with increased propylene concentrations. Ripening proceeded immediately after propylene treatment, while ethylene autocatalysis needed a lag period of 24-72 h. The latter event was attributed to the delay found in the induction of 1-aminocyclopropane-1-carboxylate synthase (ACC synthase) activity and consequently to the delayed increase of l-aminocyclopropane l-carboxylic acid (ACC) content. In contrast propylene treatment induced 1-aminocyclopropane-1-carboxylate oxidase (ACC oxidase) activity with no lag period. Moreover, transcription of ACC synthase and ACC oxidase genes was active only in ethylene-producing kiwifruit at 20 degrees C. In contrast, treatment at 10 degrees C with propylene strongly inhibited ethylene production, which was attributed to the low activities of both ACC synthase and ACC oxidase as well as the low initial ACC level. Interestingly, fruit treated with propylene at 10 degrees C appeared to be able to transcribe the ACC oxidase but not the ACC synthase gene. However, propylene induced ripening of that fruit almost as rapidly as in the propylene-treated fruit at 20 degrees C. Respiration rate was increased together with propylene concentration. It is concluded that kiwifruit stored at 20 degrees C behaves as a typical climacteric fruit, while at 10 degrees C behaves like a non-climacteric fruit. We propose that the main reasons for the inhibition of the propylene induced (autocatalytic) ethylene production in kiwifruit at low temperature (less than or equal to 10 degrees C), are primarily the suppression of the propylene-induced ACC synthase gene expression and the possible post-transcriptional modification of ACC oxidase.

SELECTED CHEMOAUTOTROPHIC PROCESSES IN WASTEWATER TREATMENT: LOW TEMPERATURE NITRIFICATION INHIBITION BY AN AZO DYE AND BIOFILTRATION FOR ODOR CONTROL OF HYDROGEN SULFIDE

Biochemical processes by chemoautotrophs such as nitrifiers and sulfide and iron oxidizers are used extensively in wastewater treatment. The research described in this dissertation involved the study of two selected biological processes utilized in wastewater treatment mediated by chemoautotrophic bacteria: nitrification (biological removal of ammonia and nitrogen) and hydrogen sulfide (H2S) removal from odorous air using biofiltration. A municipal wastewater treatment plant (WWTP) receiving industrial dyeing discharge containing the azo dye, acid black 1 (AB1) failed to meet discharge limits, especially during the winter. Dyeing discharge mixed with domestic sewage was fed to sequencing batch reactors at 22oC and 7oC. Complete nitrification failure occurred at 7oC with more rapid nitrification failure as the dye concentration increased; slight nitrification inhibition occurred at 22oC. Dye-bearing wastewater reduced chemical oxygen demand (COD) removal at 7oC and 22oC, increased i effluent total suspended solids (TSS) at 7oC, and reduced activated sludge quality at 7oC. Decreasing AB1 loading resulted in partial nitrification recovery. Eliminating the dye-bearing discharge to the full-scale WWTP led to improved performance bringing the WWTP into regulatory compliance. BiofilterTM, a dynamic model describing the biofiltration processes for hydrogen sulfide removal from odorous air emissions, was calibrated and validated using pilot- and full-scale biofilter data. In addition, the model predicted the trend of the measured data under field conditions of changing input concentration and low effluent concentrations. The model demonstrated that increasing gas residence time and temperature and decreasing influent concentration decreases effluent concentration. Model simulations also showed that longer residence times are required to treat loading spikes. BiofilterTM was also used in the preliminary design of a full-scale biofilter for the removal of H2S from odorous air. Model simulations illustrated that plots of effluent concentration as a function of residence time or bed area were useful to characterize and design biofilters. Also, decreasing temperature significantly increased the effluent concentration. Model simulations showed that at a given temperature, a biofilter cannot reduce H2S emissions below a minimum value, no matter how large the biofilter.

High Pressure and Low Temperature Study of Ammonia Borane and Lithium Amidoborane

Hydrogen has been considered as a potentially efficient and environmentally friendly alternative energy solution. However, one of the most important scientific and technical challenges that the “hydrogen economy” faces is the development of safe and economically viable on-board hydrogen storage for fuel cell applications, especially to the transportation sector. Ammonia borane (BH3NH3), a solid state hydrogen storage material, possesses exceptionally high hydrogen content (19.6 wt%).However, a fairly high temperature is required to release all the hydrogen atoms, along with the emission of toxic borazine. Recently research interests are focusing on the improvement of H2 discharge from ammonia borane (AB) including lowering the dehydrogenation temperature and enhancing hydrogen release rate using different techniques. Till now the detailed information about the bonding characteristics of AB is not sufficient to understand details about its phases and structures. Elemental substitution of ammonia borane produces metal amidoboranes. Introduction of metal atoms to the ammonia borane structure may alter the bonding characteristics. Lithium amidoborane is synthesized by ball milling of ammonia borane and lithium hydride. High pressure study of molecular crystal provides unique insight into the intermolecular bonding forces and phase stability. During this dissertation, Raman spectroscopic study of lithium amidoborane has been carried out at high pressure in a diamond anvil cell. It has been identified that there is no dihydrogen bond in the lithium amidoborane structure, whereas dihydrogen bond is the characteristic bond of the parent compound ammonia borane. It has also been identified that the B-H bond becomes weaker, whereas B-N and N-H bonds become stronger than those in the parent compound ammonia borane. At high pressure up to 15 GPa, Raman spectroscopic study indicates two phase transformations of lithium amidoborane, whereas synchrotron X-ray diffraction data indicates only one phase transformation of this material. Pressure and temperature has a significant effect on the structural stability of ammonia borane. This dissertation explored the phase transformation behavior of ammonia borane at high pressure and low temperature using in situ Raman spectroscopy. The P-T phase boundary between the tetragonal (I4mm) and orthorhombic (Pmn21) phases of ammonia borane has been determined. The transition has a positive Clapeyron slope which indicates the transition is of exothermic in nature. Influence of nanoconfinemment on the I4mm to Pmn21 phase transition of ammonia borane was also investigated. Mesoporus silica scaffolds SBA-15 with pore size of ~8 nm and MCM-41 with pore size of 2.1-2.7 nm, were used to nanoconfine ammonia borane. During cooling down, the I4mm to Pmn21 phase transition was not observed in MCM-41 nanoconfined ammonia borane, whereas the SBA-15 nanocondfined ammonia borane shows the phase transition at ~195 K. Four new phases of ammonia borane were also identified at high pressure up to 15 GPa and low temperature down to 90 K.

Ultra-Low Temperature Partial Oxidation: Detailed Kinetics, Safety, and Environmental Issues

The innovation in several industrial sectors has been recently characterized by the need for reducing the operative temperature either for economic or environmental related aspects. Promising technological solutions require the acquisition of fundamental-based knowledge to produce safe and robust systems. In this sense, reactive systems often represent the bottleneck. For these reasons, this work was focused on the integration of chemical (i.e., detailed kinetic mechanism) and physical (i.e., computational fluid dynamics) models. A theoretical-based kinetic mechanism mimicking the behaviour of oxygenated fuels and their intermediates under oxidative conditions in a wide range of temperature and pressure was developed. Its validity was tested against experimental data collected in this work by using the heat flux burner, as well as measurements retrieved from the current literature. Besides, estimations deriving from existing models considered as the benchmark in the combustion field were compared with the newly generated mechanism. The latter was found to be the most accurate for the investigated conditions and fuels. Most influential species and reactions on the combustion of butyl acetate were identified. The corresponding thermodynamic parameter and rate coefficients were quantified through ab initio calculations. A reduced detailed kinetic mechanism was produced and implemented in an open-source computational fluid dynamics model to characterize pool fires caused by the accidental release of aviation fuel and liquefied natural gas, at first. Eventually, partial oxidation processes involving light alkenes were optimized following the quick, fair, and smoot (QFS) paradigm. The proposed procedure represents a comprehensive and multidisciplinary approach for the construction and validation of accurate models, allowing for the characterization of developing industrial sectors and techniques.

Silicon-containing species in used lube oil re-refining

Nowadays, the re-refining of the used lube oils has gained worldwide a lot of attention due to the necessity for added environmental protection and increasingly stringent environmental legislation. One of the parameters determining the quality of the produced base oils is the composition of feedstock. Estimation of the chemical composition of the used oil collected from several European locations showed that the hydrocarbon structure of the motor oil is changed insignificantly during its operation and the major part of the changes is accounted for with depleted oil additives. In the lube oil re-refining industry silicon, coming mainly from antifoaming agents, is recognized to be a contaminant generating undesired solid deposits in various locations in the re-refining units. In this thesis, a particular attention was paid to the mechanism of solid product formation during the alkali treatment process of silicon-containing used lube oils. The transformations of a model siloxane, tetramethyldisiloxane (TMDS), were studied in a batch reactor at industrially relevant alkali treatment conditions (low temperature, short reaction time) using different alkali agents. The reaction mechanism involving solid alkali metal silanolates was proposed. The experimental data obtained demonstrated that the solids were dominant products at low temperature and short reaction time. The liquid products in the low temperature reactions were represented mainly by linear siloxanes. The prolongation of reaction time resulted in reduction of solids, whereas both temperature and time increase led to dominance of cyclic products in the reaction mixture. Experiments with the varied reaction time demonstrated that the concentration of cyclic trimer being the dominant in the beginning of the reaction diminished with time, whereas the cyclic tetramer tended to increase. Experiments with lower sodium hydroxide concentration showed the same effect. In addition, a decrease of alkali agent concentration in the initial reaction mixture accelerated TMDS transformation reactions resulting in solely liquid cyclic siloxanes yields. Comparison of sodium and potassium hydroxides applied as an alkali agent demonstrated that potassium hydroxide was more efficient, since the activation energy in KOH presence was almost 2-fold lower than that for sodium hydroxide containing reaction mixture. Application of potassium hydroxide for TMDS transformation at 100° C with 3 hours reaction time resulted in 20 % decrease of solid yields compared to NaOH-containing mixture. Moreover, TMDS transformations in the presence of sodium silanolate applied as an alkali agent led to formation of only liquid products without formation of the undesired solids. On the basis of experimental data and the proposed reaction mechanism, a kinetic model was developed, which provided a satisfactory description of the experimental results. Suitability of the selected siloxane as a relevant model of industrial silicon-containing compounds was verified by investigation of the commercially available antifoam agent in base-catalyzed conditions.

Numerical modelling of double diffusion driven reactive flow transport in deformable fluid-saturated porous media with particular consideration of temperature-dependent chemical reaction rates

Numerical methods ave used to solve double diffusion driven reactive flow transport problems in deformable fluid-saturated porous media. in particular, thp temperature dependent reaction rate in the non-equilibrium chemical reactions is considered. A general numerical solution method, which is a combination of the finite difference method in FLAG and the finite element method in FIDAP, to solve the fully coupled problem involving material deformation, pore-fluid flow, heat transfer and species transport/chemical reactions in deformable fluid-saturated porous media has been developed The coupled problem is divided into two subproblems which are solved interactively until the convergence requirement is met. Owing to the approximate nature of the numerical method, if is essential to justify the numerical solutions through some kind of theoretical analysis. This has been highlighted in this paper The related numerical results, which are justified by the theoretical analysis, have demonstrated that the proposed solution method is useful for and applicable to a wide range of fully coupled problems in the field of science and engineering.

Time-dependent master equation simulation of complex elementary reactions in combustion: Application to the reaction of (CH2)-C-1 with C2H2 from 300-2000 K

Computational simulations of the title reaction are presented, covering a temperature range from 300 to 2000 K. At lower temperatures we find that initial formation of the cyclopropene complex by addition of methylene to acetylene is irreversible, as is the stabilisation process via collisional energy transfer. Product branching between propargyl and the stable isomers is predicted at 300 K as a function of pressure for the first time. At intermediate temperatures (1200 K), complex temporal evolution involving multiple steady states begins to emerge. At high temperatures (2000 K) the timescale for subsequent unimolecular decay of thermalized intermediates begins to impinge on the timescale for reaction of methylene, such that the rate of formation of propargyl product does not admit a simple analysis in terms of a single time-independent rate constant until the methylene supply becomes depleted. Likewise, at the elevated temperatures the thermalized intermediates cannot be regarded as irreversible product channels. Our solution algorithm involves spectral propagation of a symmetrised version of the discretized master equation matrix, and is implemented in a high precision environment which makes hitherto unachievable low-temperature modelling a reality.

Sonogashira coupling on an extended gold surface in vacuo: reaction of phenylacetylene with iodobenzene on Au(111)

Temperature-programmed reaction measurements supported by scanning tunneling microscopy have shown that phenylacetylene and iodobenzene react on smooth Au(111) under vacuum conditions to yield biphenyl and diphenyldiacetylene, the result of homocoupling of the reactant molecules. They also produce diphenylacetylene, the result of Sonogashira cross-coupling, prototypical of a class of reactions that are of paramount importance in synthetic organic chemistry and whose mechanism remains controversial. Roughened Au(111) is completely inert toward all three reactions, indicating that the availability of crystallographically well-defined adsorption sites is crucially important. High-resolution X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy show that the reactants are initially present as intact, essentially flat-lying molecules and that the temperature threshold for Sonogashira coupling coincides with that for C−I bond scission in the iodobenzene reactant. The fractional-order kinetics and low temperature associated with desorption of the Sonogashira product suggest that the reaction occurs at the boundaries of islands of adsorbed reactants and that its appearance in the gas phase is rate-limited by the surface reaction. These findings demonstrate unambiguously and for the first time that this heterogeneous cross-coupling chemistry is an intrinsic property of extended, metallic pure gold surfaces: no other species, including solvent molecules, basic or charged (ionic) species are necessary to mediate the process.

Time-resolved gas-phase kinetic and quantum chemical studies of the reaction of silylene with nitric oxide

Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by laser flash photolysis of phenylsilane, have been carried out to obtain rate constants for its bimolecular reaction with NO. The reaction was studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas at five temperatures in the range 299-592 K. The second-order rate constants at 10 Torr fitted the Arrhenius equation log(k/cm(3) molecule(-1) s(-1)) = (- 11.66 +/- 0.01) + (6.20 +/- 0.10 kJ mol(-1))IRT In 10 The rate constants showed a variation with pressure of a factor of ca. 2 over the available range, almost independent of temperature. The data could not be fitted by RRKM calculations to a simple third body assisted association reaction alone. However, a mechanistic model with an additional (pressure independent) side channel gave a reasonable fit to the data. Ab initio calculations at the G3 level supported a mechanism in which the initial adduct, bent H2SiNO, can ring close to form cyclo-H2SiNO, which is partially collisionally stabilized. In addition, bent H2SiNO can undergo a low barrier isomerization reaction leading, via a sequence of steps, ultimately to dissociation products of which the lowest energy pair are NH2 + SiO. The rate controlling barrier for this latter pathway is only 16 kJ mol(-1) below the energy of SiH2 + NO. This is consistent with the kinetic findings. A particular outcome of this work is that, despite the pressure dependence and the effects of the secondary barrier (in the side reaction), the initial encounter of SiH2 with NO occurs at the collision rate. Thus, silylene can be as reactive with odd electron molecules as with many even electron species. Some comparisons are drawn with the reactions of CH2 + NO and SiCl2 + NO.

Chemoselective catalytic hydrogenation of acrolein on Ag(111): effect of molecular orientation on reaction selectivity

The adsorption and hydrogenation of acrolein on the Ag(111) surface has been investigated by high resolution synchrotron XPS, NEXAFS, and temperature programmed reaction. The molecule adsorbs intact at all coverages and its adsorption geometry is critically important in determining chemoselectivity toward the formation of allyl alcohol, the desired but thermodynamically disfavored product. In the absence of hydrogen adatoms (H(a)), acrolein lies almost parallel to the metal surface; high coverages force the C=C bond to tilt markedly, likely rendering it less vulnerable toward reaction with hydrogen adatoms. Reaction with coadsorbed H(a) yields allyl alcohol, propionaldehyde, and propanol, consistent with the behavior of practical dispersed Ag catalysts operated at atmospheric pressure: formation of all three hydrogenation products is surface reaction rate limited. Overall chemoselectivity is strongly influenced by secondary reactions of allyl alcohol. At low H(a) coverages, the C=C bond in the newly formed allyl alcohol molecule is strongly tilted with respect to the surface, rendering it immune to attack by H(a) and leading to desorption of the unsaturated alcohol. In contrast with this, at high H(a) coverages, the C=C bond in allyl alcohol lies almost parallel to the surface, undergoes hydrogenation by H(a), and the saturated alcohol (propanol) desorbs.

A study of co-precipitated bimetallic gold catalysts for water-gas shift reaction

Synthesis, testing and characterisation of bimetallic gold, Au-M on ceria as catalysts were carried out for low temperature water-gas shift reaction (WGS). Amongst the entire screened catalysts 3 wt% (AU-Pt)/CeO2 displayed the best WGS activity than the monometallic promotors, giving the light-off curve at the lowest temperature in the range 100-300 degrees C. (Au-Pd)/CeO2 also achieved the same activity but at a higher temperature. It was also found that WGS activity was strongly correlated with the surface reducibility which in turn depended on the modified local electronic band structure of promoted ceria. These results clearly suggest that the key role of bimetallic promoter may involve in facilitating the creation of defective reduced surface by exerting its local electronic effect on ceria to form the surface germinal -OH groups in water which act as active sites for enhanced WGS activity. (C) 2008 Elsevier B.V. All rights reserved.

Study of Water-Gas-Shift Reaction over La((1-y))Sr(y)Ni(x)Co((1-x))O(3) Perovskite as Precursors

The performance of La((1-y))Sr(y)Ni(x)Co((1-x))O(3) perovskites for the water gas shift reaction (WGSR) was investigated. The samples were prepared by the co- precipitation method and were performed by the BET method, XRD, TPR, and XPS. The catalytic tests were performed at 300 and 400 A degrees C and H(2)O(v)/CO = 2.3/1 (molar ratio). The sample with the highest surface area is La(0.70)Sr(0.30)NiO(3). The XRD results showed the formation of perovskite structure for all samples, and the La(0.70)Sr(0.30)NiO(3) sample also presented peaks corresponding to La(2)NiO(4) and NiO, indicating that the solubility limit of Sr in the perovskite lattice was surpassed. The replacement of Co by Ni favored the reduction of the species at lower temperatures, and the sample containing Sr presented the highest amount of reducible species, as identified by TPR results. All samples were active, the Sr containing perovskite appearing the most active due to the highest surface area, presence of the La(2)NiO(4) phase, and higher content of Cu in the surface, as detected by XPS. Among the samples containing Co, the most active one was that with x = 0.70 (60% of CO conversion).

Effects of the partial replacement of La by M (M=Ce, Ca and Sr) in La(2-x)M(x)CuO(4) perovskites on catalysis of the water-gas shift reaction

The performance of La(2-x)M(x)CuO(4) perovskites (where M = Ce, Ca or Sr) as catalysts for the water-gas shift reaction was investigated at 290 degrees C and 360 degrees C. The catalysts were characterized by EDS, XRD, N(2) adsorption-desorption, XPS and XANES. The XRD results showed that all the perovskites exhibited a single phase (the presence of perovskite structure), suggesting the incorporation of metals in the perovskite structure. The XPS and XANES results showed the presence of Cu(2+) on the surface. The perovskites that exhibited the best catalytic performance were La(2-x)Ce(x)CuO(4) perovslcites, with CO conversions of 85%-90%. Moreover, these perovskites have higher surface areas and larger amounts of Cu on the surface. And Ce has a higher filled energy level than the other metals, increasing the energy of the valence band of Ce and providing more electrons for the reaction. Besides, the La(1.80)Ca(0.20)CuO(4) perovskite showed a good catalytic performance.

Voltage-composition profile and synchrotron X-ray structural analysis of low and high temperature LixCoO2 host material

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

In situ solid state oxidation reaction for La1-xSrxMnO3 (x=0, 0.1, 0.2 and 0.3) formation

In situ solid state oxidation reaction for an alternative La1-xSrxMnO3 (x = 0, 0.1, 0.2 and 0.3) formation is reported. Samples have been obtained by using strontium peroxide, lanthanum and manganese (III) oxide reagents. Strontium peroxide has induced the oxidation of Mn+3 to Mn+4. Lanthanum strontium-doped manganite was obtained without secondary phase formation. La0.825Sr0.175MnO3 showed two structural transitions. The first from 88 to 373 K and the second at 1073 K. which are explained by Jahn-Teller effect at low temperature and cation displacement at high temperature. (C) 2001 Elsevier B.V. B.V. All rights reserved.