Titanium(IV)-EDTA complex - Kinetics of thermal decomposition by non-isothermal procedures

This work aims the evaluation of the kinetic triplets corresponding to the two successive steps of thermal decomposition of Ti(IV)-ethylenediaminetetraacetate complex. Applying the isoconversional Wall-Flynn-Ozawa method on the DSC curves, average activation energy: E=172.4 +/- 9.7 and 205.3 +/- 12.8 kJ mol(-1), and pre-exponential factor: logA = 16.38 +/- 0.84 and 18.96 +/- 1.21 min(-1) at 95% confidence interval could be obtained, regarding the partial formation of anhydride and subsequent thermal decomposition of uncoordinated carboxylate groups, respectively.From E and logA values, Dollimore and Malek methods could be applied suggesting PT (Prout-Tompkins) and R3 (contracting volume) as the kinetic model to the partial formation of anhydride and thermal decomposition of the carboxylate groups, respectively.

Kinetics of B cell response during Yersinia enterocolitica infection in resistant and susceptible strains of mice

In this study we analyze the B-cell response in murine yersiniosis. To this end, we determined whether polyclonal activation of B-lymphocytes occurs during infection of susceptible (BALB/c) and resistant (C57BL/6) mice with Y. enterocolitica 0:8 and compared the immunoglobulin (Ig) isotypes produced in response to the infection by the two strains. The number of splenic cells secreting nonspecific and specific immunoglobulins was determined by ELISPOT. The presence of anti-Yersinia antibodies in serum was detected by ELISA. In both strains, the number of specific Ig-secreting cells was relatively low. Polyclonal B-cell activation was observed in both strains of mice, and the greatest activation was observed in the BALB/c mice, mainly for lgG(1)- and IgG(3)- secreting cells. The C57BL/6 mice showed a predominance of IgG(2a)-secreting cells. The peak production of anti-Yersinia IgG antibodies in the sera of BALB/c mice was seen on the 28th day after infection. The greatest increase in IgM occurred on the 14th day. A progressive increase of specific IgG antibodies was observed in C57BL/6 mice up to the 28th day after infection while IgM increased on the 21st day after infection. The production of specific IgA antibodies was not detected in either BALB/c or C57BL/6 mice. We conclude that polyclonal. activation of B lymphocytes occurs in both the Yersinia resistant and Yersinia-susceptible mice and that the more intense activation of B lymphocytes observed in the susceptible BALB/c mice does not enhance their resistance to Y. enterocolitica infection.

Air-drying of fresh and osmotically pre-treated pineapple slices: Fixed air temperature versus fixed slice temperature drying kinetics

In this investigation, the air drying characteristics of fresh and osmotically pre-treated pineapple slices in a tray dryer were studied under different operating conditions. The air velocity varied from 1.5 to 2.5 m/s and the air temperature from 40 to 70 degreesC. The analytical solution of the second Fick's law for an infinite slab was used to calculate effective diffusion coefficients and their temperature dependence could be well represented by an Arrhenius-type equation. Comparison of the results showed that the diffusion coefficients were lower for the pre-treated fruit. By means of automatic control, it was possible to obtain drying curves under conditions of constant product temperature, which showed to be an alternative to reduce the drying time of pineapple slices.

Capacitance Spectroscopy: A Versatile Approach To Resolving the Redox Density of States and Kinetics in Redox-Active Self-Assembled Monolayers

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

Electrogravimetric Real-Time and in Situ Michaelis-Menten Enzimatic Kinetics: Progress Curve of Acetylcholinesterase Hydrolysis

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

Aerobic fitness level typical of elite athletes is not associated with even faster VO2 kinetics during cycling exercise

The aim of this study was to address the question if the VO2 kinetics is further improved as the aerobic training status increases from trained to elite level athletes. Maximal oxygen uptake (VO(2)max), work-rate associated to VO(2)max (IVO(2)max) and VO2 kinetics of moderate (Mod) and maximal exercise (Max) were determined in fifty-five subjects. Then, they were assigned into three groups: low (LF), intermediate (IF) and high (HF) aerobic fitness level. In average, the VO(2)max of LF, IF and HF groups were, respectively, 36.0 +/- 3.1, 51.1 +/- 4.5 and 68.1 +/- 3.9 ml . kg . min(-1) (p <= 0.05 among each other). VO2 kinetics mean response time of both exercise intensities were significantly faster (p <= 0.05) in HF (Mod, 27.5 +/- 5.5 s; Max, 32.6 +/- 8.3 s) and IF (Mod, 25.0 +/- 3.1 s; Max, 42.6 +/- 10.4 s) when compared to LF (Mod, 35.7 +/- 7.9 s; Max: 57.8 +/- 17.8 s). We can conclude that VO2 kinetics is improved as the fitness level is increased from low to intermediate but not further improved as the aerobic fitness level increases from intermediate to high.

Different inflammatory stimuli in the footpad of mice influence the kinetics of resident peritoneal cells

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

Kinetics and mechanism of the forward and reverse reactions between N,N′-dimethyl-4,4′-bipyridinium and hexacyanoferrate(II)

The kinetics of the hexacyanoferrate(III)-N,N′-dimethyl-4,4′-bipyridinium radical (MV+) reaction was studied by a laser flash photolysis technique. The radical was generated, in the presence of Fe(CN)6 3-, by quenching the excited state *Ru(bpy)3 2+ with MV2+. The second-order rate constant for the Fe(CN)6 3--MV+ reaction is (7.6 ± 0.5) × 109 M-1 s-1 at 23°C and ionic strength 0.10 M. Comparison with the rate constants calculated for the diffusion-controlled reaction (4.7 × 109 M-1 s-1) and the activation-controlled reaction (5.2 × 1012 M-1 s-1, on the basis of self-exchange rate constants of 8.0 × 105 M-1 s-1 and 1.9 × 104 M-1 s-1 for the MV2+/+ and Fe(CN)6 3-/4- couples, respectively) leads to the conclusion that the Fe(CN)6 3--MV+ reaction is diffusion controlled. The rate constant for the Fe(CN)6-MV2+ reaction, calculated from the rate constant for the Fe(CN)6 3--MV+ reaction and the appropriate equilibrium constant, is 2.4 × 10-5 M-1 s-1 at 23°C and ionic strength 0.10 M. Microscopic reversibility considerations require that the Fe(CN)6 4--MV2+ reaction be controlled by the dissociation of the successor complex Fe(CN)6 3-|MV+. The thermal and optical electron transfers in the ion pair Fe(CN)6 4-|MV2+ and in related systems are analyzed and discussed. © 1982 American Chemical Society.

Kinetics of the reaction of alkylamines with 7,7,8,8-tetracyanoquinodimethane (TCNQ) in organic solvents

The following sequence of substitution reactions was studied spectrophotometrically in organic solvents: RNH2 + TCNQ →-HCN 7-substituted TCNQ →-HCN +RNH2 7.7-disubstituted TCNQ where R = butyl, octyl, dodecyl, and hexadecyl. The production of 7-(alkylamino)-7,7,8-tricyanoquinodimethanes proceeds via the formation of the anion radical of TCNQ (TCNQ-·) whose rate of appearance was found to be a function of the chain length of R, reaching a maximum for octylamine. The formation of TCNQ-· was sensitive to the solvent polarity and electron-donor power and was associated with a small enthalpy and a highly negative entropy of activation. Above a certain [C8H17NH2] the rate of disappearance of TCNQ-· was independent of the amine concentration, and the reaction had a much higher enthalpy and entropy of activation. The occurrence of tautomerism precluded an investigation of the conversion of 7-(octylamino)-7,8,8-tricyanoquinodimethane into 7,7-bis(octylamino)-8,8-dicyanoquinodimethane. A study of the reaction of octylamine with 7-morpholino-7,8,8-tricyanoquinodimethane (which does not exist in tautomeric forms) showed that the second substitution step proceeds with the same mechanism as the first one. The only difference between the two compounds (TCNQ and its monosubstituted morpholino derivative) is one of reactivity. © 1985 American Chemical Society.

Kinetics, electrochemistry and resonance raman spectra of the (2-mercaptopyridine) (edta)ruthenium(III) complex

The chemistry of the pentadentate edta complexes of ruthenium(III) and (II) with 2-mercaptopyridine (HSpy) has been investigated based on spectroscopic, kinetic and electrochemical techniques. The reaction of [Ru(III)(edta)H2O]- with HSpy proceeds with a specific rate of 1.05 × 104 M-1 S -1 (25°C, I = 0.10 M, acetate buffer), forming a red complex (λmax = 550 nm) which undergoes a relaxation process as a function of pH, with an apparent pKa = 4.35 and kobs = 0.31 S -1. The second reaction depends on the concentration of HSpy and leads to a stable green product (λmax = 630 mn). A pronounced enhancement has been observed in the Raman spectra of the complexes, particularly in the region of the metal-ligand vibrations. The electronic and resonance Raman spectra are consistent with the coordination of HSpy via the sulfur atom in the red complex, and with a chelate binding in the green species. © 1987.

Kinetics of the polarization reversal process in a non-constant applied electric field and the generalized superposition principle

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)