Activation of Alkanes by Gold-Modified Lanthanum Oxide

Functionalization of alkanes is much sought after for the production of fine and bulk chemicals. In particular, the oxidative activation of alkanes and their conversion to ethene and propene has been studied extensively, owing to the use of these alkenes in polymerization reactions. The greater reactivity of the products in comparison with the reactants has proven a major issue in this reaction as this can result in overoxidation, producing CO and CO2 and, therefore, reducing the alkene yield. Herein, the first application of supported gold catalysts for the direct activation of C2+ aliphatic alkanes with oxygen to form alkenes is demonstrated. This catalyst is particularly notable as it is highly active, selective to propene and ethene, and stable on stream over a 48 h period. Maintaining cationic gold is thought to be critical for the stability and this catalyst design provides the possibility of applying gold-based catalysts over a much wider temperature range than has been reported.

Nitride-strengthened reduced activation ferritic/martensitic steels

Two nitride-strengthened reduced activation ferritic/martensitic (RAFM) steels with different Mn contents were investigated. The experimental steels were designed based on the chemical composition of Eurofer 97 steel but the C content was reduced to an extremely low level. Microstructure observation and hardness tests showed that the steel with low Mn content (0.47 wt.%) could not obtain a full martensitic microstructure due to the inevitable δ-ferrite independent of cooling rate after soaking. This steel showed similar room temperature strength and higher strength at 600 °C, but lower impact toughness, compared with Eurofer 97 steel. Fractography of the Charpy impact specimen revealed that the low room temperature toughness should be related to the Ta-rich inclusions initiating the cleavage fracture. The larger amount of V-rich nitrides and more dissolved Cr in the matrix could be responsible for the strength being similar to Eurofer 97 steel. In the second steel developed from the first steel by increasing the Mn content from 0.47 wt.% to 3.73 wt.%, a microstructure of full martensite could be obtained.

Low-Temperature Selective Catalytic Reduction (SCR) of NOx with n-Octane Using Solvent-Free Mechanochemically Prepared Ag/Al2O3 Catalysts

Low-temperature (<200 degrees C) hydrocarbon selective catalytic reduction of NOx has been achieved for the first time in the absence of hydrogen using a solvent-free mechanochemically prepared Ag/Al2O3 catalyst. Catalysts prepared by this ball-milling method show a remarkable increase in activity for the reduction of nitrogen oxides with octane by lowering the light-off temperature by up to 150 degrees C compared with a state-of-the-art 2 wt %Ag/Al2O3 catalyst prepared by wet impregnation. The best catalyst prepared from silver oxide showed 50% NOx conversion at 240 degrees C and 99%, at 302 degrees C. The increased activity is not due to an increased surface area of the support, but may be associated with a change in.the'defeet structure of the alumina surface, leading to the formation of the small silver clusters necessary for the activation of the octane without leading to total combustion. On the other hand, since one possible role of hydrogen is to remove inhibiting species from the silver, we cannot exclude some change in the chemical properties of the silver as a result of the ball-milling treatment.

Hexavalent Chromium Adsorption by a Novel Activated Carbon Prepared by Microwave Activation

Microwave heating reduces the preparation time and improves the adsorption quality of activated carbon. In this study, activated carbon was prepared by impregnation of palm kernel fiber with phosphoric acid followed by microwave activation. Three different types of activated carbon were prepared, having high surface areas of 872 m2 g-1, 1256 m2 g-1, and 952 m2 g-1 and pore volumes of 0.598 cc g-1, 1.010 cc g-1, and 0.778 cc g-1, respectively. The combined effects of the different process parameters, such as the initial adsorbate concentration, pH, and temperature, on adsorption efficiency were explored with the help of Box-Behnken design for response surface methodology (RSM). The adsorption rate could be expressed by a polynomial equation as the function of the independent variables. The hexavalent chromium adsorption rate was found to be 19.1 mg g-1 at the optimized conditions of the process parameters, i.e., initial concentration of 60 mg L-1, pH of 3, and operating temperature of 50 oC. Adsorption of Cr(VI) by the prepared activated carbon was spontaneous and followed second-order kinetics. The adsorption mechanism can be described by the Freundlich Isotherm model. The prepared activated carbon has demonstrated comparable performance to other available activated carbons for the adsorption of Cr(VI).

A low temperature, isothermal gas-phase system for conversion of methane to methanol over Cu-ZSM-5

A low temperature, isothermal, gas-phase, recyclable process is described for the partial oxidation of methane to methanol over Cu–ZSM-5. Activation in NO at 150 °C followed by methane reaction and steam extraction (both at 150 °C) allowed direct observation of methanol at the reactor outlet.

Conductivity/activation energy relationships for cement-based materials undergoing cyclic thermal excursions

The electrical conductivity of a range of concrete mixes, with and without supplementary cementitious materials (SCM), is studied through multiple cycles of heating and cooling over the extended temperature range −30/+70 °C. When presented in an Arrhenius format, the experimental results display hysteresis effects at the low-temperature end of the thermal cycle and, in those concretes containing supplementary cementitious materials at higher water/binder ratios, hysteresis effects were evident over the entire temperature range becoming more discernible with increasing number of thermal cycles. The depression in both the freezing and thawing point could be clearly identified and was used to estimate pore-neck and pore-cavity radii. A simplified approach is presented to evaluate the volumetric ratio of frozen pore water in terms of conductivity measurements. The results also show that the conductivity and activation energy of the concrete specimens were related to the water/binder ratio, type of SCM, physical state of the pore water and the thermal cycling regime.

Low cycle fatigue properties of CLAM steel at room temperature

The low cycle fatigue (LCF) properties and the fracture behavior of China Low Activation Martensitic (CLAM) steel have been studied over a range of total strain amplitudes from 0.2 to 2.0%. The specimens were cycled using tension-compression loading under total strain amplitude control. The CLAM steel displayed initial hardening followed by continuous softening to failure at room temperature in air. The relationship between strain and fatigue life was predicted using the parameters obtained from fatigue test. The factors effecting on low cycle fatigue of CLAM steel consisted of initial state of matrix dislocation arrangement, magnitude of cyclic stress, magnitude of total strain amplitude and microstructure. The potential mechanisms controlling the stress response, cyclic strain resistance and low cycle fatigue life have been evaluated.

Activation of Progesterone Receptor by ATP

Progesterone-receptor complex from freshly prepared hen oviduct cytosol acquired the ability to bind to isolated nuclei, DNA-cellulose and ATP-Sepharose when incubated with 5-10 mM ATP at 4°C. The extent of this ATP-dependent activation was higher when compared with heat-activation achieved by warming the progesterone- receptor complex at 23 °C. The transformation of progesterone-receptor complex which occurred in a time-dependent manner was only partially dependent on hormone presence. The ATP effect was selective in causing this transformation whereas ADP, AMP and cAMP failed to show any such effect. The non-hydrolizable analogs of ATP, adenosine 5'-[a,/3-methylene]triphosphate and adenosine 5-[/l,y-imido]triphosphate were also found to be ineffective. Presence of 10 mM sodium molybdate blocked both the ATP and the heat-activation of progesterone-receptor complex. Mn" or Mg` had no detectable effect on the receptor activation but the presence of Ca" increased the extent of ATP-activation slightly. EDTA presence (> 5 mM) decreased the extent of receptor activation by about 40 % and was, therefore, not included in the buffers used for activation studies. Divalent cations were also ineffective when tested in the presence of 1- 5 mM EDTA. The properties of progesterone-receptor complex remained intact under the above conditions when analyzed for steroid-binding specificity and Scatchard analysis. However, the ATP-activated progesterone-receptor complex lost the ability to aggregate when tested on low-salt sucrose gradients. ATP was equally effective in activating the rat-uterine estradiol-receptor complex at 4 "C and influenced the transformation of 4-S receptor form into a 5-S form when analyzed on sucrose gradients containing 0.3 M KCI. The presence of ATP also increased the rate of activation of progesterone-receptor complex at 23 °C. These findings suggest a role for ATP in receptor function and offer a convenient method of studying the process of receptor activation at low temperature and mild assay conditions.

Distinct Unfolding and Refolding Pathways of Ribonuclease A Revealed by Heating and Cooling Temperature Jumps

Heating and cooling temperature jumps (T-jumps) were performed using a newly developed technique to trigger unfolding and refolding of wild-type ribonuclease A and a tryptophan-containing variant (Y115W). From the linear Arrhenius plots of the microscopic folding and unfolding rate constants, activation enthalpy (ΔH#), and activation entropy (ΔS#) were determined to characterize the kinetic transition states (TS) for the unfolding and refolding reactions. The single TS of the wild-type protein was split into three for the Y115W variant. Two of these transition states, TS1 and TS2, characterize a slow kinetic phase, and one, TS3, a fast phase. Heating T-jumps induced protein unfolding via TS2 and TS3; cooling T-jumps induced refolding via TS1 and TS3. The observed speed of the fast phase increased at lower temperature, due to a strongly negative ΔH# of the folding-rate constant. The results are consistent with a path-dependent protein folding/unfolding mechanism. TS1 and TS2 are likely to reflect X-Pro114 isomerization in the folded and unfolded protein, respectively, and TS3 the local conformational change of the β-hairpin comprising Trp115. A very fast protein folding/unfolding phase appears to precede both processes. The path dependence of the observed kinetics is suggestive of a rugged energy protein folding funne

Formulation of a live bacterial vaccine for stable room temperature storage results in loss of acid, bile and bile salt resistance

Live bacterial vaccines have great promise both as vaccines against enteric pathogens and as heterologous antigen vectors against diverse diseases. Ideally, room temperature stable dry formulations of live bacterial vaccines will allow oral vaccination without cold-chain storage or injections. Attenuated Salmonella can cross the intestinal wall and deliver replicating antigen plus innate immune activation signals directly to the intestinal immune tissues, however the ingested bacteria must survive firstly gastric acid and secondly the antimicrobial defences of the small intestine. We found that the way in which cells are grown prior to formulation markedly affects sensitivity to acid and bile. Using a previously published stable storage formulation that maintained over 10% viability after 56 days storage at room temperature, we found dried samples of an attenuated S. typhimurium vaccine lost acid and bile resistance compared to the same bacteria taken from fresh culture. The stable formulation utilised osmotic preconditioning in defined medium plus elevated salt concentration to induce intracellular trehalose accumulation before drying. Dried bacteria grown in rich media without osmotic preconditioning showed more resistance to bile, but less stability during storage, suggesting a trade-off between bile resistance and stability. Further optimization is needed to produce the ultimate room-temperature stable oral live bacterial vaccine formulation.

Microwave activation of the electro-oxidation of glucose in alkaline media

The oxidation of glucose is a complex process usually requiring catalytically active electrode surfaces or enzyme modified electrodes. In this study the effect of high intensity microwave radiation on the oxidation of glucose in alkaline solution at Au, Cu, and Ni electrodes is reported. Calibration experiments with the Fe(CN)(6)(3-/4-) redox system in aqueous 0.1 M NaOH indicate that strong thermal effects occur at both 50 and 500 mu m diameter electrodes with temperatures reaching 380 K. Extreme mass transport effects with mass transport coefficients of k(mt) > 0.01 m s(-1) (or k(mt) > 1.0 cm s(-1)) are observed at 50 mu m diameter electrodes in the presence of microwaves. The electrocatalytic oxidation of glucose at 500 mu m diameter Au, Cu, or Ni electrodes immersed in 0.1 M NaOH and in the presence of microwave radiation is shown to be dominated by kinetic control. The magnitude of glucose oxidation currents at Cu electrodes is shown to depend on the thickness of a pre-formed oxide layer. At 50 mu m diameter Au, Cu, or Ni electrodes microwave enhanced current densities are generally higher, but only at Au electrodes is a significantly increased rate for the electrocatalytic oxidation of glucose to gluconolactone observed. This rate enhancement appears to be independent of temperature but microwave intensity dependent, and therefore non-thermal in nature. Voltammetric currents observed at Ni electrodes in the presence of microwaves show the best correlation with glucose concentration and are therefore analytically most useful.

Microwave activation of the electro-oxidation of glucose in alkaline media

The oxidation of glucose is a complex process usually requiring catalytically active electrode surfaces or enzyme-modified electrodes. In this study the effect of high intensity microwave radiation on the oxidation of glucose in alkaline solution at Au, Cu, and Ni electrodes is reported. Calibration experiments with the Fe(CN)63–/4– redox system in aqueous 0.1 M NaOH indicate that strong thermal effects occur at both 50 and 500 µm diameter electrodes with temperatures reaching 380 K. Extreme mass transport effects with mass transport coefficients of kmt > 0.01 m s–1(or kmt > 1.0 cm s–1) are observed at 50 µm diameter electrodes in the presence of microwaves. The electrocatalytic oxidation of glucose at 500 µm diameter Au, Cu, or Ni electrodes immersed in 0.1 M NaOH and in the presence of microwave radiation is shown to be dominated by kinetic control. The magnitude of glucose oxidation currents at Cu electrodes is shown to depend on the thickness of a pre-formed oxide layer. At 50 µm diameter Au, Cu, or Ni electrodes microwave enhanced current densities are generally higher, but only at Au electrodes is a significantly increased rate for the electrocatalytic oxidation of glucose to gluconolactone observed. This rate enhancement appears to be independent of temperature but microwave intensity dependent, and therefore non-thermal in nature. Voltammetric currents observed at Ni electrodes in the presence of microwaves show the best correlation with glucose concentration and are therefore analytically most useful.

Photocatalytic degradation of humic acid in saline waters. Part 1. Artificial seawater: influence of TiO2, temperature, pH, and air-flow

We report the first systematic study on the photocatalytic oxidation of humic acid (HA) in artificial seawater (ASW). TiO2 (Degussa P25) dispersions were used as the catalyst with irradiation from a medium-pressure mercury lamp. The optimum quantity of catalyst was found to be between 2 and 2.5 g l(-1); whiled the decomposition was fastest at low pH values (pH 4.5 in the range examined), and the optimum air-flow, using an immersion well reactor with a capacity of 400 ml, was 850 ml min(-1). Reactivity increased with air-flow up to this figure, above which foaming prevented operation of the reactor. Using pure. oxygen, an optimal flow rate was observed at 300 nil min(-1), above which reactivity remains essentially constant. Following treatment for 1 h, low-salinity water (2700 mg l(-1)) was completely mineralised, whereas ASW (46000 mg l(-1)) had traces of HA remaining. These effects are interpreted and kinetic data presented. To avoid problems of precipitation due to change of ionic strength humic substances were prepared directly in ASW, and the effects of ASW on catalyst suspension and precipitation have been taken into account. The Langmuir-Hinshelwood kinetic model has been shown to be followed only approximately for the catalytic oxidation of HA in ASW. The activation energy for the reaction derived from an Arrhenius treatment was 17 ( +/-0.6) kJ mol(-1). (C) 2003 Elsevier Science Ltd. All rights reserved.

A low-temperature ammonium ylid rearrangement: enhanced reactivity engendered by rigidity

Sigmatropic rearrangement of tetrahydropyridine-derived ammonium is a valuable method for the preparation of substituted prolines. These reaction normally require elevated temperatures to proceed, but bicyclic tetrahydropyridine-like ylid I undergoes rearrangement at -15 degrees C; the extra rigidity of the azabicyclo[3.3.0]octene system preorganizes the transition state and lowers the activation energy for rearrangement.

Deprotection, tethering, and activation of a catalytically active metalloporphyrin to a chemically active metal surface: [SAc](4)P-Mn(III)Cl on Ag(100)

The adsorption and subsequent thermal chemistry of the acetyl-protected manganese porphyrin, [SA(C)](4)P-Mn(III)Cl on Ag(100) have been studied by high resolution XPS and temperature-programmed desorption. The deprotection event, leading to formation of the covalently bound thioporphyrin, has been characterized and the conditions necessary for removal of the axial chlorine ligand have been determined, thus establishing a methodology for creating tethered activated species that could serve as catalytic sites for delicate oxidation reactions. Surface-mediated acetyl deprotection occurs at 298 K, at which temperature porphyrin diffusion is limited. At temperatures above similar to 425 K porphyrin desorption, diffusion and deprotection occur and at >470 K the axial chlorine is removed.