BIOMIMITICS OF OXIDASE AND OXYGENASE THE ELECTRONIC SPECTRA AND THE OXYGEN UPTAKE KINTICS FOR MPc AND MTPP (M = Fe, Co, Cu, Pc AND TFP - ARE DIANIONS OF PHTHALOCYANIN AND TETRAPHENYLPORPHYRINE, RESPECTIVELY)

The reaction rates of MTPP with oxygen in air are Inas than that with pure oxygen, the ratio is roughly the same as to the partial presence of imygen in air, The influences of S-ligand etbanethiol and O- litand Vc on the above Systems have also been investigated, the former makes the MP hands having more changes and the reaction rate constants becoming greater, the latter has less influence.

ELECTROCATALYSIS OF POLYPYRROLE-METHYLENE BLUE FILM MODIFIED ELECTRODE FOR DIRECT REDOX REACTION OF CYTOCHROME-C

The electron transfer process of hemeproteins on the electrode surface is considered a promising subject in the area of bioelectrochemistry. Electrochemists believe that electron transfer between electroactive proteins and electrode surface might be expected to simulate the electron transfer between proteins. This research provides information about the electron transfer mechanism in biological system. Cytochrome c is a typical electron transferring protein,

Investigation of EscA as a chaperone for the Edwardsiella tarda type III secretion system putative translocon component EseC

Edwardsiella tarda is an important Gram-negative enteric pathogen affecting both animals and humans. It possesses a type III secretion system (T3SS) essential for pathogenesis. EseB, EseC and EseD have been shown to form a translocon complex after secretion, while EscC functions as a T3SS chaperone for EseB and EseD. In this paper we identify EscA, a protein required for accumulation and proper secretion of another translocon component, EseC. The escA gene is located upstream of eseC and the EscA protein has the characteristics of T3SS chaperones. Cell fractionation experiments indicated that EscA is located in the cytoplasm and on the cytoplasmic membrane. Mutation with in-frame deletion of escA greatly decreased the secretion of EseC, while complementation of escA restored the wild-type secretion phenotype. The stabilization and accumulation of EseC in the cytoplasm were also affected in the absence of EscA. Mutation of escA did not affect the transcription of eseC but reduced the accumulation level of EseC as measured by using an EseC-LacZ fusion protein in Ed. tarda. Co-purification and co-immunoprecipitation studies demonstrated a specific interaction between EscA and EseC. Further analysis showed that residues 31-137 of EseC are required for EseC-EscA interaction, Mutation of EseC residues 31-137 reduced the secretion and accumulation of EseC in Ed. tarda. Finally, infection experiments showed that mutations of EscA and residues 31-137 of EseC increased the LD50 by approximately 10-fold in blue gourami fish. These results indicated that EscA functions as a specific chaperone for EseC and contributes to the virulence of Ed. tarda.

EscC is a chaperone for the Edwardsiella tarda type III secretion system putative translocon components EseB and EseD

Edwardsiella tarda is a Gram-negative enteric pathogen that causes disease in both humans and animals. Recently, a type III secretion system (T3SS) has been found to contribute to Ed. tarda pathogenesis. EseB, EseC and EseD were shown to be secreted by the T3SS and to be the major components of the extracellular proteins (ECPs). Based on sequence similarity, they have been proposed to function as the 'translocon' of the T3SS needle structure. In this study, it was shown that EseB, EseC and EseD formed a protein complex after secretion, which is consistent with their possible roles as translocon components. The secretion of EseB and EseD was dependent on EscC (previously named Orf2). EscC has the characteristics of a chaperone; it is a small protein (13 kDa), located next to the translocators in the T3SS gene cluster, and has a coiled-coil structure at the N-terminal region as predicted by COILS. An in-frame deletion of escC abolished the secretion of EseB and EseD, and complementation of Delta escC restored the export of EseB and EseD into the culture supernatant. Further studies showed that EscC is not a secreted protein and is located on the membrane and in the cytoplasm. Mutation of escC did not affect the transcription of eseB but reduced the amount of EseB as measured by using an EseB-LacZ fusion protein in Ed. tarda. Co-purification studies demonstrated that EscC formed complexes with EseB and EseD. The results suggest that EscC functions as a T3SS chaperone for the putative translocon components EseB and EseD in Ed. tarda.

Response of cyanobacterial carbon concentrating system to light intensity: a simulated analysis

Cyanobacteria possess a delicate system known as the carbon concentrating mechanism (CCM), which can efficiently elevate the intracellular inorganic carbon (Ci) concentration via active transportation. The system requires energy supplied by photosystems; therefore, the activity of the Ci transporter is closely related to light intensity. However, the relationship between CCM and light intensity has rarely been evaluated. Here, we present an improved quantitative model of CCM in which light is incorporated, and developed a CCM model that modified after Fridlyand et al. in 1996. Some equations used in this model were inducted to describe the relationship between transport capacity and light intensity, by which the response of the CCM to light change is simulated. Our results indicate that the efficiency of the carbon concentrating system is sensitive to light intensity. When the external Ci concentration was low, CO2 uptake dominated the total Ci uptake with increasing light intensity, while under high external Ci concentrations HCO3- uptake primarily contributed to the total Ci uptake. Variations in the ratio of energy allocated between the transport systems could markedly affect the operation of CCM. Indeed, our simulations suggest that various combinations of Ci fluxes can provide a possible approach to detect the way by which the cell distributes energy produced by the photosystems to the two active Ci transport processes. The proportion of the energy consumed on CCM to the total energy expenditure for the fixation of one CO2 molecule was determined at 18%-40%.

Methane aromatization in the absence of an added oxidant and the bench scale reaction test

A bench scale reaction test for methane aromatization in the absence of an added oxidant was performed and its reaction result evaluated based on the carbon balance of the system. The result was compared with those obtained from the micro-reaction test to ensure the accuracy of the internal standard analyzing method employed in this paper. The catalytic performances of modified Mo/HZSM-5 catalysts were examined. It was found that pre-treatment by steam on HZSM-5 weakened the serious deposition of coke, and pre-impregnation of n-ethyl silicate on HZSM-5 could improve the conversion of CH4, but had little effect on coke formation. A low temperature activation procedure including pre-reduction of the catalyst with methane prevents the zeolite lattice from being seriously destroyed by high valence state Mo species when the Mo loading is high. It was suggested that Mo2C species detected by XRD spectra was the active phase for CH4 aromatization.

Nickel-promoted ligand-free palladium-catalyzed Suzuki coupling reaction

A Ni-promoted ligand-free palladium catalyst system for Suzuki coupling of aryl bromides has been developed in high efficiency under mild reaction conditions. It was obtained in situ by introducing NiCl2 to PdCl2/PVP using a parallel high-throughput screening technique. A wide range of aryl bromides bearing a variety of functional groups was evaluated.

Low-temperature oxidation of CO over Pd/CeO2-TiO2 catalysts with different pretreatments

A comprehensive study of the low-temperature oxidation of CO was conducted over Pd/TiO2, Pd/CeO2, and Pd/CeO2-TiO2 pretreated by a series of calcination and reduction processes. The catalysts were characterized by N-2 adsorption, XRD, H-2 chemisorption, and diffuse-reflectance infrared Fourier transform spectroscopy. The results indicated that Pd/CeO2-TiO2 has the highest activity among these catalysts, whether in the calcined state or in the reduced state. The activity of all of the catalysts can be improved significantly by the pre-reduction, and it seems that the reduction at low temperature (LTR. 150 degrees C) is more effective than that at high temperature (HTR, 500 degrees C), especially for Pd/CeO2 and Pd/TiO2. The catalysts with various supports and pretreatments are also different in the reaction mechanisms for CO oxidation at low temperature. Over Pd/TiO2, the reaction may proceed through a surface reaction between the weakly adsorbed CO and oxygen (Langmuir-Hinshelwood). For Ce-containing catalysts, however, an alteration of reaction mechanism with temperature and the involvement of the oxygen activation at different sites were observed, and the light-off profiles of the calcined Pd/CeO2 and Pd/CeOi-TiO2 show a distortion before CO conversion achieves 100%. At low temperature, CO oxidation proceeds mainly via the reaction between the adsorbed CO on Pd-0 sites and the lattice oxygen of surface CeO2 at the Pd-Ce interface, whereas at high temperature it proceeds via the reaction between the adsorbed CO and oxygen. The high activity of Pd/CeO2-TiO2 for the low-temperature CO oxidation was probably due to the enhancements of both CO activation, caused by the facilitated reduction of Pd2+ to Pd-0, and oxygen activation, through the improvement of the surface oxygen supply and the oxygen vacancies formation. The reduction pretreatment enhances metal-support interactions and oxygen vacancy formation and hence improves the activity of CO oxidation. (c) 2005 Elsevier Inc. All rights reserved.

The formation of Co2C species in activated carbon supported cobalt-based catalysts and its impact on Fischer-Tropsch reaction

The cobalt carbide (Co2C) species was formed in some activated carbon supported cobalt-based (Co/AC) catalysts during the activation of catalysts. It was found that the activity of Fischer-Tropsch reaction over Co-based catalysts decreased due to the formation of cobalt carbide species. Some promoters and pretreatment of activated carbon with steam could restrain the formation of cobalt carbide.

Autothermal reforming of n-octane on Ru-based catalysts

In an attempt to effectively integrate catalytic partial oxidation (CPO) and steam reforming (SR) reactions on the same catalyst, autothermal reforming (ATR) of n-octane was addressed based on thermodynamic analysis and carried out on a non-pyrophoric catalyst 0.3 wt.% Ru/K2O-CeO2/gamma-Al2O3. The ATR of n-octane was more efficient at the molar ratio Of O-2/C 0.35-0.45 and H2O/C 1.6-2.2 (independent parameters), respectively, and reforming temperature of 750-800 degrees C (dependent parameter). Among the sophisticated reaction network, the main reaction thread was deducted as: long-chain hydrocarbon -> CH4, short-chain hydrocarbon -> CO2, CO and H-2 formation by steam reforming, although the parallel CPO, decomposition and reverse water gas shift reaction took place on the same catalyst. Low temperature and high steam partial pressure had more positive effect on CH4 SR to produce CO2 other than CO. This was verified by the tendency of the outlet reformate to the equilibrium at different operation conditions. Furthermore, the loss of active components and the formation of stable but less active components in the catalyst in the harsh ATR atmosphere firstly make the CO inhibition capability suffer, then eventually aggravated the ATR performance, which was verified by the characterizations of X-ray fluorescence, BET specific surface areas and temperature programmed reduction. (c) 2005 Elsevier B.V. All rights reserved.

CO adsorption and correlation between CO surface coverage and activity/selectivity of preferential CO oxidation over supported Ag catalyst: an in situ FTIR study

In situ IR measurements for CO adsorption and preferential CO oxidation in H-2-rich gases over Ag/SiO2 catalysts are presented in this paper. CO adsorbed on the Ag/SiO2 pretreated with oxygen shows a band centered around 2169 cm(-1), which is assigned to CO linearly bonded to Ag+ sites. The amount of adsorbed CO on the silver particles ( manifested by an IR band at 2169 cm(-1)) depends strongly on the CO partial pressure and the temperature. The steady-state coverage on the Ag surface is shown to be significantly below saturation, and the oxidation of CO with surface oxygen species is probably via a non-competitive Langmuir Hinshelwood mechanism on the silver catalyst which occurs in the high-rate branch on a surface covered with CO below saturation. A low reactant concentration on the Ag surface indicates that the reaction order with respect to Pco is positive, and the selectivity towards CO2 decreases with the decrease of Pco. On the other hand, the decrease of the selectivity with the reaction temperature also reflects the higher apparent activation energy for H-2 oxidation than that for CO oxidation.

Formation of subsurface oxygen species and its high activity toward CO oxidation over silver catalysts

Silver is well known to show peculiar catalytic activities in several oxidation reactions. In the present paper, we investigate the catalytic activity of silver catalysts toward CO-gelective oxidation in H-2. XRD, TEM, TPD, and in situ FTIR techniques were used to characterize the catalysts. The pretreatment of the catalysts was found to have great influence on their performance. The pretreatment in 02 improves the activity of the silver catalyst, whereas He pretreatment at 700 degreesC or direct hydrogen pretreatment shows an inverse effect. Silver catalysts undergo massive structural change during oxygen pretreatment at high temperatures (> 500 degreesC), and there is solid evidence for the formation of subsurface oxygen species. The existence of this silver-subsurface oxygen structure facilitates the formation of active sites on silver catalysts for CO oxidation, which are related to the size, morphology, and exposed crystal planes of the silver particles. Its formation requires a certain temperature, and a higher pretreatment temperature with oxygen is required for the silver catalyst with a smaller particle size. It is observed, for the first time, that adsorbed CO on the surface of silver particles can directly react with subsurface oxygen species at low temperatures (e.g., RT), and the surface oxygen can migrate into and refill these subsurface sites after the consumption of subsurface oxygen by the reaction with CO. This finding provides a new reaction pathway for CO oxidation on silver catalyst. (C) 2004 Published by Elsevier Inc.