Determination of activation energy distributions for chemisorption of oxygen on carbon: an improved approach

The present paper proposes an approach to obtaining the activation energy distribution for chemisorption of oxygen onto carbon surfaces, while simultaneously allowing for the activation energy dependence of the pre-exponential factor of the rate constant. Prior studies in this area have considered this factor to be uniform, thereby biasing estimated distributions. The results show that the derived activation energy distribution is not sensitive to the chemisorption mechanism because of the step function like property of the coverage. The activation energy distribution is essentially uniform for some carbons, and has two or possibly more discrete stages, suggestive of at least two types of sites, each with its own uniform distribution. The pre-exponential factors of the reactions are determined directly from the experimental data, and are found not to be constant as assumed in earlier work, but correlated with the activation energy. The latter results empirically follow an exponential function, supporting some earlier statistical and experimental work. The activation energy distribution obtained in the present paper permits improved correlation of chemisorption data in comparison to earlier studies. (C) 2000 Elsevier Science Ltd. All rights reserved.

Apparent metabolizable energy from microalgae spirulina maxima for broiler chickens.

2016

Desarrollo de materiales nanocristalinos de base hierro por aleado mecánico

Two alloys, Fe80Nb10B10 and Fe70Ni14Zr6B10, were produced by mechanical alloying. The formation of thenanocrystallites (about 7-8 nm at 80h MA) was detected by X-ray diffraction. After milling for 80 h, differentialscanning calorimetry scans show low-temperature recovery processes and several crystallization processes related with crystal growth and reordering of crystalline phases. The apparent activation energy values are 315 ± 40 kJ mol–1 for alloy A, and 295 ± 20 kJ mol–1 and 320 ± 25 kJ mol–1 for alloy B. Furthermore, a melt-spun Fe-based ribbon was mechanically alloyed to obtain a powdered-like alloy. The increase of the rotation speed and the ball-to-powderweight ratio reduces the necessary time to obtain the powdered form

FANCD2 binds MCM proteins and controls replisome function upon activation of s phase checkpoint signaling.

Proteins disabled in Fanconi anemia (FA) are necessary for the maintenance of genome stability during cell proliferation. Upon replication stress signaling by ATR, the FA core complex monoubiquitinates FANCD2 and FANCI in order to activate DNA repair. Here, we identified FANCD2 and FANCI in a proteomic screen of replisome-associated factors bound to nascent DNA in response to replication arrest. We found that FANCD2 can interact directly with minichromosome maintenance (MCM) proteins. ATR signaling promoted the transient association of endogenous FANCD2 with the MCM2-MCM7 replicative helicase independently of FANCD2 monoubiquitination. FANCD2 was necessary for human primary cells to restrain DNA synthesis in the presence of a reduced pool of nucleotides and prevented the accumulation of single-stranded DNA, the induction of p21, and the entry of cells into senescence. These data reveal that FANCD2 is an effector of ATR signaling implicated in a general replisome surveillance mechanism that is necessary for sustaining cell proliferation and attenuating carcinogenesis.

Biochemical characterization of the GM2 gangliosidosis B1 variant

The deficiency of the A isoenzyme of ß-hexosaminidase (Hex) produced by different mutations of the gene that codes for the alpha subunit (Tay-Sachs disease) has two variants with enzymological differences: the B variant consists of the absence of Hex A isoenzyme and the B1 variant produces an inactive Hex A isoenzyme for the hydrolysis of the GM2 ganglioside and synthetic substrates with negative charge. In contrast to the early childhood form of the B variant, the B1 variant appears at a later clinical stage (3 to 7 years of age) with neurodegenerative symptoms leading to the death of the patient in the second decade of life. The most frequent mutation responsible for the GM2 gangliosidosis B1 variant is R178H, which has a widespread geographic and ethnic distribution. The highest incidence has been described in Portugal, which has been suggested as the point of origin of this mutation. Biochemical characterization of this lysosomal disease is carried out using negatively charged synthetic alpha subunit-specific sulfated substrates, since Hex A isoenzyme heat-inactivation assays are not applicable. However, the determination of the apparent activation energy of Hex using the neutral substrate 3,3'-dichlorophenolsulfonphthaleinyl N-acetyl-ß-D-glucosaminide, may offer a valid alternative. The presence of an alpha subunit in the alphaß heterodimer Hex A means that its activation energy (41.8 kJ/mol) is significantly lower than that of the ßß homodimer Hex B (75.1 kJ/mol); however, as mutation inactivates the alpha subunit, the Hex A of the B1 variant presents an activation energy that is similar to that of the Hex B isoenzyme.

Polyphenol oxidase from yacon roots (Smallanthus sonchifolius)

Polyphenol oxidase (E.C. 1.14.18.1) (PPO) extracted from yacon roots (Smallanthus sonchifolius) was partially purified by ammonium sulfate fractionation and separation on Sephadex G-100. The enzyme had a molecular weight of 45 490 +/- 3500 da and K-m values of 0.23, 1.14, 1.34, and 5.0 mM for the substrates caffeic acid, chlorogenic acid, 4-methylcatechol, and catechol, respectively. When assayed with resorcinol, DL-DOPA, pyrogallol, protocatechuic, p-coumaric, ferulic, and cinnamic acids, catechin, and quercetin, the PPO showed no activity. The optimum pH varied from 5.0 to 6.6, depending on substrate. PPO activity was inhibited by various phenolic and nonphenolic compounds. p-Coumaric and cinnamic acids showed competitive inhibition, with K-i values of 0.017 and 0.011 mM, respectively, using chlorogenic acid as substrate. Heat inactivation from 60 to 90 degrees C showed the enzyme to be relatively stable at 60-70 degrees C, with progressive inactivation when incubated at 80 and 90 degrees C. The E-a (apparent activation energy) for inactivation was 93.69 kJ mol(-1). Sucrose, maltose, glucose, fructose, and trehalose at high concentrations appeared to protect yacon PPO against thermal inactivation at 75 and 80 degrees C.

Ionically bound peroxidase from peach fruit

Soluble, ionically bound peroxidase (POD) and polyphenoloxidase (PPO) were extracted from the pulp of peach fruit during ripening at 20degreesC Ionically bound form was purified 6.1 -fold by DEAE-cellulose and Sephadex G-100 chromatography. The purified enzyme showed only one peak of activity on Sephadex G-100 and PAGE revealed that the enzyme was purified by the procedures adopted. The purified enzyme showed a molecular weight of 29000 Da, maximum activity at pH 5.0 and at 40degreesC the calculated apparent activation energy (Ea) for the reaction was 10.04 kcal/mol. The enzyme was heat-labile in the temperature range of 60 to 75degreesC with a fast inactivation at 75degreesC Measurement of residual activity showed a stabilizing effect of sucrose at various temperature/sugar concentrations (0, 10, 20 %, w/w), with an activation energy (Ea) for inactivation increasing with sucrose concentration from 0 to 20% (w/w). The Km and V-max values were 9.35 and 15.38 mM for O-dianisidine and H2O2, respectively. The bound enzyme was inhibited competitively by (.)ferulic, caffeic and protocatechuic acids with different values of Ki,. L-cysteine, p-coumaric and indolacetic acid and Fe++ also inhibited the enzyme but at a lower grade. N-ethylmaleimide and p-CMB were not effective to inhibit the enzyme demonstrating the non-essentiality of SH groups.

The Poisson-exponential regression model under different latent activation schemes

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

A CALORIMETRIC STUDY OF THE ULTRASOUND-STIMULATED HYDROLYSIS OF SOLVENTLESS TEOS-WATER MIXTURES

The kinetics of ultrasound-stimulated and HCl-catalyzed hydrolysis of solventless TEOS-water mixtures was studied as a function of temperature ranging from 10 degrees C up to 65 degrees C by means of flux calorimetry measurements. A specially designed device was utilized for this purpose. The exothermic peak arising few minutes after sonication began has been attributed mainly to the hydrolysis reaction. The overall hydrolysis process, which was measured through the irradiation time up to the hydrolysis peak, was found to be thermally activated, with an apparent activation energy Delta E = 36.4 kJ/mol. The alcohol produced at the early hydrolysis due to sonication seems to further enhance the reaction, via a parallel autocatalytic path, which is controlled by a faster pseudo second order rate constant (k'). Our modeling yielded k' = 6.3 x 10(-2) M(-1) min(-1) at 20 degrees C, which is in a reasonable agreement with the literature, and an activation energy Delta E = 40.4 kJ/mol for the specific process of hydrolysis in presence of alcohol.

Apparent digestible energy and nutrient digestibility coefficients of diet ingredients for pacu Piaractus brachypomus

The digestible energy and apparent nutrient digestibility coefficients of common diet ingredients were determined for pacu Piaractus brachypomus (370.21 ± 17.56 g). Fish were fed with pelleted practical diets to apparent satiation and the feces were collected by siphoning. The digestibility value for each ingredient was determined by comparison of the digestibility of a test diet with a reference diet (24.5% crude protein and 1% chromic oxide). The digestible energy values of soybean meal (SBM), fish meal (FM), corn (CN), and wheat bran (WB) were 2382, 3826, 3353, and 1784 kcal/kg, respectively. The apparent dry matter digestibility coefficients were 83.72, 90.14, 89.13, and 82.05% for SBM, FM, CN, and WB, respectively. The apparent crude protein digestibility coefficients were 75.88, 90.49, 85.06, and 61.62% for SBM, FM, CN, and WB, respectively. The apparent lipid digestibility coefficients were 63.03, 77.00, 83.01, and 82.45% for SBM, FM, CN, and WB, respectively. The digestibility of protein, lipid, and energy from SBM were somewhat low compared to values for other warmwater omnivorous fishes, but similar to values reported for pacu-caranha P. mesopotamicus. Otherwise, the nutrient and energy availability of the ingredients to P. brachypomus was similar to that of other fish. This information will be useful in formulating nutritious, economical diets for pacus. © by the World Aquaculture Society 2004.

Chemical Composition, Rumen Fermentation Kinetics, Digestibility and Energy Value of Cassava Leaves Hay at Different Storage Times

Cassava leaves have been widely used as a protein source for ruminants in the tropics. However, these leaves contain high level of hydro-cyanic acid (HCN) and condensed tannins (CT). There are evidences that making hay can eliminate more than 90% of HCN and that long-term storage can reduce CT levels. A complete randomized design with four replicates was conducted to determine the effect of different storage times (0-control, 60, 90 and 120 days) on chemical composition, in vitro rumen fermentation kinetics, digestibility and energy value of cassava leaves hay. Treatments were compared by analyzing variables using the GLM procedure (SAS 9.1, SAS Institute, Inc., Cary, NC). Crude protein (CP) and ether extract (EE) of the cassava hay were not affected (P > 0.05) by storage time (17.7% and 3.0%, respectively). Neutral detergent fiber, acid detergent fiber, total carbohydrate and non-fiber carbohydrate were not affected either (P>0.05) by storage time (47.5, 32.6, 72.3 and 25.8% respectively). However, other parameters were influenced. CT was lower (P<0.05) in hay after 120 days of storage compared with control (1.75% versus 3.75%, respectively). Lignin and insoluble nitrogen in neutral detergent, analyzed without sodium sulfite, were higher (P<0.01) after 120 days of storage, compared with the control (11.22 versus 13.57 and 1.65 versus 3.81% respectively). This suggests that the CT has bound to the fiber or CP and became inactive. Consequently, the in vitro digestibility of organic matter (50.36%), total digestible nutrients (44.79%) and energy (1.61 Mcal/KgMS), obtained from gas production data at 72 h of incubation, has increased (P<0.05) with storage times (56.83%, 51.53% and 1.86 Mcal/KgMS, respectively). The chemical composition and fermentative characteristics of cassava hay suffered variations during the storage period. The best values were obtained after 90 days of storage. This is probably due to the reduction in condensed tannins.

The Poisson-exponential regression model under different latent activation schemes

In this paper, a new family of survival distributions is presented. It is derived by considering that the latent number of failure causes follows a Poisson distribution and the time for these causes to be activated follows an exponential distribution. Three different activation schemes are also considered. Moreover, we propose the inclusion of covariates in the model formulation in order to study their effect on the expected value of the number of causes and on the failure rate function. Inferential procedure based on the maximum likelihood method is discussed and evaluated via simulation. The developed methodology is illustrated on a real data set on ovarian cancer.

Meta-model for calculating the mean energy demand of automated storage and retrieval systems

Energy efficiency has become an important research topic in intralogistics. Especially in this field the focus is placed on automated storage and retrieval systems (AS/RS) utilizing stacker cranes as these systems are widespread and consume a significant portion of the total energy demand of intralogistical systems. Numerical simulation models were developed to calculate the energy demand rather precisely for discrete single and dual command cycles. Unfortunately these simulation models are not suitable to perform fast calculations to determine a mean energy demand value of a complete storage aisle. For this purpose analytical approaches would be more convenient but until now analytical approaches only deliver results for certain configurations. In particular, for commonly used stacker cranes equipped with an intermediate circuit connection within their drive configuration there is no analytical approach available to calculate the mean energy demand. This article should address this research gap and present a calculation approach which enables planners to quickly calculate the energy demand of these systems.