Kinetic studies on the reactions of Ru(II) tetraammines with CS2N- 3

The kinetics of the reactions of Ru(II) complexes with CS2N- 3 ions were studied spectrophotometrically. The formation rate constants data for trans-[Ru(NH3)4L(CS2N3)] are 2.2 × 102, 1.8 × 10 and 1.3 × 102 M-1 s-1 for L = SO2- 3, HSO- 3 and P(OEt)3), respectively [μ = 1.0 M (NaCF3COO), 25°C]. Under the same experimental conditions, the values of k-1 (specific rate for the aquation reaction) are 1.5 × 10-2, 5.0 × 10-2 and 4.5 × 10 s-1 for L = SO2- 3, HSO- 3 and P(OEt)3, respectively. The free-energy change (ΔG≠) for the systems where L = P(OEt)3 and SO2- 3 are in agreement within the experimental error. It was observed that the affinity of the CS2N- 3 ion decreases with the increasing π-acidity of the auxiliary ligand L. The order of affinity of the CS2N- 3 ion for the Ru(II) center studies is SO2- 3 > HSO- 3 > P(OEt)3 >SO2. © 1986.

Hydration-dependent conformational states of hemoglobin. Equilibrium and kinetic behavior

The equilibrium and kinetics of methemoglobin conversion to hemichrome induced by dehydration were investigated by visible absorption spectroscopy. Below about 0.20 g water per g hemoglobin only hemichrome was present in the sample; above this value, an increasing proportion of methemoglobin appeared with the increase in hydration. The transition between the two derivatives showed a time-dependent biphasic behavior and was observed to be reversible. The rates obtained for the transition of methemoglobin to hemichrome were 0.31 and 1.93 min-1 and for hemichrome to methemoglobin 0.05 and 0.47 min-1. We suggest that hemichrome is a reversible conformational state of hemoglobin and that the two rates observed for the transition between the two derivatives reflect the α- and β-chains of hemoglobin.

Kinetic properties of de-repressible alkaline phosphatase (EC 3.1.3.1) from Neurospora crassa

De-repressible alkaline phosphatase from N. crassa shows inhibition by PNP-P and a hyperbolic mixed-type inhibition by Pi. Both increasing concentrations of Pi and decreases in assay pH abolished inhibition by the substrate. Also, Pi promoted polymerization of the enzyme molecule, whose effect may account for the inhibitory behaviour shown by the enzyme in the presence of low Pi concentrations. © 1991 Rapid Communications of Oxford Ltd.

A kinetic model of phosphorus metabolism in growing goats

The effect of increasing phosphorus (P) intake on P utilization was investigated in balance experiments using 12 Saanen goats, 4 to 5 mo of age and weighing 20 to 30 kg. The goats were given similar diets with various concentrations of P, and 32P was injected to trace the movement of P in the body. A P metabolism model with four pools was developed to compute P exchanges in the system. The results showed that P absorption, bone resorption, and excretion of urinary P and endogenous and fecal P all play a part in the homeostatic control of P. Endogenous fecal output was positively correlated to P intake (P < .01). Bone resorption of P was not influenced by intake of P, and P recycling from tissues to the blood pool was lesser for low P intake. Endogenous P loss occurred even in animals fed an inadequate P diet, resulting in a negative P balance. The extrapolated minimum endogenous loss in feces was .067 g of P/d. The minimum P intake for maintenance in Saanen goats was calculated to be .61 g of P/ d or .055 g of P/(kg.75·d) at 25 kg BW. Model outputs indicate greater P flow from the blood pool to the gut and vice versa as P intake increased. Intake of P did not significantly affect P flow from bone and soft tissue to blood. The kinetic model and regressions could be used to estimate P requirement and the fate of P in goats and could also be extrapolated to both sheep and cattle.

A joint theoretical and kinetic investigation on the fragmentation of (N-halo)-2-amino cycloalkanecarboxylates

A combined theoretical and experimental study to elucidate the molecular mechanism for the Grob fragmentation of different (N-halo)-2-amino cyclocarboxylates with the nitrogen atom in exocyclic position: (N-Cl)-2-amino cyclopropanecarboxylate (1), (N-Cl)-2-amino cyclobutanecarboxylate (2), (N-Cl)-2-amino cyclopentanecarboxylate (3) and (N-Cl)-2-amino cyclohexanecarboxylate (4), and the corresponding acyclic compounds, (N-Cl)-2-amino isobutyric acid (A), (N-Cl)-2-amino butyric acid (B), has been carried out. The kinetics of decomposition for these compounds and related bromine derivatives were experimentally determined by conventional and stopped-flow UV spectrophotometry. The reaction products have been analyzed by GC and spectrophotometry. Theoretical analysis is based in the localization of stationary points (reactants and transition structures) on the potential energy surface. Calculations were carried out at B3LYP/6-31+G* and MP2/6-31+G* computing methods in the gas phase, while solvent effects have been included by means the self-consistent reaction field theory, PCM continuum model, at MP2/6-31+G* and MP4/6-31+G*//MP2/6-31+G* calculation levels. Based on both experimental and theoretical results, the different Grob fragmentation processes show a global synchronicity index close to 0.9, corresponding to a nearly concerted process. At the TSs, the N-Cl bond breaking is more advanced than the C-C cleavage process. An antiperiplanar configuration of these bonds is reached at the TSs, and this geometrical arrangement is the key factor governing the decomposition. In the case of 1 and 2 the ring strain prevents this spatial disposition, leading to a larger value of the activation barrier. Natural population analysis shows that the polarization of the N-Cl and C-C bonds along the bond-breaking process can be considered the driving force for the decomposition and that a negative charge flows from the carboxylate group to the chlorine atom to assist the reaction pathway. A comparison of theoretical and experimental results shows the relevance of calculation level and the inclusion of solvent effects for determining accurate unimolecular rate coefficients for the decomposition process. © 2002 Published by Elsevier Science B.V.

Can one cure the nonunitarity of three-dimensional quadratic gravity using a topological Chern-Simons term?

Quadratic gravity in (2+1)D is nonunitarity at the tree level. When a topological Chern-Simons term is added to this theory, the harmless massive scalar mode of the former gives rise to a troublesome massive spin-0 ghost, while the massive spin-2 ghost is replaced by two massive physical particles both of spin-2. Therefore, unlike what it is claimed in the literature, quadratic Chern-Simons gravity in (2+1)D is nonunitary at the tree level. © 2004 Published by Elsevier B.V.

Synthesis and characterization of poly-o-toluidine: Kinetic and structural aspects

Poly(o-methylaniline) (poly-o-toluidine, PTOL) was synthesized by chemical oxidation of o-toluidine with ammonium peroxydisulfate in an aqueous 1.0 mol L -1 HCl solution. The progress of polymerization was followed by measuring the open-circuit potential (OCP) of a Pt electrode immersed in the reaction medium with the polymerization time. The chemical synthesis of PTOL was carried out at different monomer:oxidant (M:O) molar ratios (4:1, 2:1, 1.5:1, 1:1, and 0.66:1), and the products obtained were characterized by infrared spectroscopy, gel permeation chromatography, and X-ray diffraction. The molecular weight and percentage of crystallinity of PTOL are higher for samples synthesized in an excess of the monomer, i.e. at higher M:O ratios. However, the yield of PTOL prepared at higher M:O ratios is considerably low, in particular at a 4:1 M:O ratio, which is the M:O ratio most commonly used in the literature to synthesize polyaniline and its derivatives.

Kinetic study of the plastoquinone pool availability correlated with H2O2 release in seawater and antioxidant responses in the red alga Kappaphycus alvarezii exposed to single or combined high light, chilling and chemical stresses

Under biotic/abiotic stresses, the red alga Kappaphycus alvarezii reportedly releases massive amounts of H2O2 into the surrounding seawater. As an essential redox signal, the role of chloroplast-originated H2O2 in the orchestration of overall antioxidant responses in algal species has thus been questioned. This work purported to study the kinetic decay profiles of the redox-sensitive plastoquinone pool correlated to H2O2 release in seawater, parameters of oxidative lesions and antioxidant enzyme activities in the red alga Kappaphycus alvarezii under the single or combined effects of high light, low temperature, and sub-lethal doses of 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU) and 2,5-dibromo-3-methyl-6-isopropyl-p-benzoquinone (DBMIB), which are inhibitors of the thylakoid electron transport system. Within 24 h, high light and chilling stresses distinctly affected the availability of the PQ pool for photosynthesis, following Gaussian and exponential kinetic profiles, respectively, whereas combined stimuli were mostly reflected in exponential decays. No significant correlation was found in a comparison of the PQ pool levels after 24 h with either catalase (CAT) or ascorbate peroxidase (APX) activities, although the H2O2 concentration in seawater (R = 0.673), total superoxide dismutase activity (R = 0.689), and particularly indexes of protein (R = 0.869) and lipid oxidation (R = 0.864), were moderately correlated. These data suggest that the release of H2O2 from plastids into seawater possibly impaired efficient and immediate responses of pivotal H2O2-scavenging activities of CAT and APX in the red alga K. alvarezii, culminating in short-term exacerbated levels of protein and lipid oxidation. These facts provided a molecular basis for the recognized limited resistance of the red alga K. alvarezii under unfavorable conditions, especially under chilling stress. © 2006 Elsevier B.V. All rights reserved.

Changes on degree of conversion of dual-cure luting light-cured with blue LED

The indirect adhesive procedures constitute recently a substantial portion of contemporary esthetic restorative treatments. The resin cements have been used to bond tooth substrate and restorative materials. Due to recently introduction of the self-bonding resin luting cement based on a new monomer, filler and initiation technology has become important to study the degree of conversion of these new materials. In the present work the polymerization reaction and the filler content of dual-cured dental resin cements were studied by means of infra-red spectroscopy (FT-IR) and thermogravimetry (TG). Twenty specimens were made in a metallic mold (8 mm diameter × 1 mm thick) from each of 2 cements, Panavia® F2.0 (Kuraray) and RelyX™ Unicem Applicap (3M/ESPE). Each specimen was cured with blue LED with power density of 500 mW/cm 2 for 30 s. Immediately after curing, 24 and 48 h, and 7 days DC was determined. For each time interval 5 specimens were pulverized, pressed with KBr and analyzed with FT-IR. The TG measurements were performed in Netzsch TG 209 under oxygen atmosphere and heating rate of 10°C/min from 25 to 700°C. A two-way ANOVA showed DC (%) mean values statistically significance differences between two cements (p < 0.05). The Tukey's test showed no significant difference only for the 24 and 48 h after light irradiation for both resin cements (p > 0.05). The Relx-Y™ Unicem mean values were significantly higher than Panavia® F 2.0. The degree of conversion means values increasing with the storage time and the filler content showed similar for both resin cements. © 2009 Pleiades Publishing, Ltd.

Kinetic parameters for thermal decomposition of supramolecular polymers derived from diclofenac-meglumine supramolecular adducts

Meglumine is an aminocarbohydrate able to form supramolecular adducts with organic acids. The recognition is based on hydrogen bonds and the structures resulting from the complexation have high solubility in water. This property has been exploited by the pharmaceutical industry in the improvement of existing drugs, and the successful example of this approach involves the poorly soluble non-steroidal anti-inflammatory drugs (NSAIDs). Investigation of the thermal behavior of adduct obtained from meglumine and the NSAID diclofenac revealed that a polymer-like material is formed from the self-assembly of diclofenac-meglumine adducts in the melt. This polymer showed a high molecular weight around 2.0×105kDa. The kinetic parameters for the thermal decomposition step of the polymer were determined by the Capela-Ribeiro non-linear isoconversional method. From data for the TG curves in nitrogen atmosphere and heating rates of 5, 10, 15 and 20°Cmin-1, the Eα and Bα terms could be determined, and consequently the pre-exponential factor, Aα, as well as the kinetic model, g(α). © 2012 Elsevier B.V.

Effect of ceramic shade on the degree of conversion of a dual-cure resin cement analyzed by FTIR

Objectives: The aim of this research was to evaluate the degree of monomer conversion of different resin cement shades when photocured under different feldspathic ceramic shades. The photocuring time was also evaluated as well as the translucency of each ceramic shade. Methods: Three VITA VM7 ceramic shades (Base Dentin 0M1, Base Dentin 2M2 and Base Dentin 5M3) were used to determine the translucency percentage. A spectrophotometer MiniScan was used to measure the opacity percentage of each specimen (2-mm-thick) and then the translucency was calculated. To measure the degree of conversion (DC), the resin cement (Variolink II; A3 Yellow and transparent) specimens (thickness: 100 μm) were photocured under a ceramic block (2-mm-thick) for 20 or 40 s. Specimens photocured without the ceramic block were used as control. Sixteen groups (n = 3) were evaluated. Micro-ATR/FTIR spectrometry was used to evaluate the extent of polymerization of all specimens after 24 h. The %DC was calculated of experimentally polymerized versus maximally polymerized composite. Results: The translucency percentages of 0M1, 2M2 and 5M3 ceramics were 12.41 (1.02)%, 5.75 (1.91)% and 1.07 (0.03)%, respectively. The %DC of both resin cement shades cured under ceramic 5M3 was significantly lower than the other groups (p < 0.05). The %DC of 0M1 groups exhibited no significant difference from 2M2 groups (p > 0.05), with the exception of the transparent cement photocured for 40 s. Conclusion: Photocuring under 2 mm ceramic showed that the increase in chroma saturation significantly decreased Variolink II resin cement %DC (100-μm-thick). © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Subcellular localization and kinetic characterization of a gill (Na +, K+)-ATPase from the giant freshwater prawn macrobrachium rosenbergii

The stimulation by Mg2+, Na+, K+, NH 4 +, and ATP of (Na+, K+)-ATPase activity in a gill microsomal fraction from the freshwater prawn Macrobrachium rosenbergii was examined. Immunofluorescence labeling revealed that the (Na +, K+)-ATPase α-subunit is distributed predominantly within the intralamellar septum, while Western blotting revealed a single α-subunit isoform of about 108 kDa M r. Under saturating Mg2+, Na+, and K+ concentrations, the enzyme hydrolyzed ATP, obeying cooperative kinetics with V M = 115.0 ± 2.3 U mg-1, K 0.5 = 0.10 ± 0.01 mmol L-1. Stimulation by Na+ (V M = 110.0 ± 3.3 U mg-1, K 0.5 = 1.30 ± 0.03 mmol L -1), Mg2+ (V M = 115.0 ± 4.6 U mg -1, K 0.5 = 0.96 ± 0.03 mmol L-1), NH4 + (V M = 141.0 ± 5.6 U mg -1, K 0.5 = 1.90 ± 0.04 mmol L-1), and K+ (V M = 120.0 ± 2.4 U mg-1, K M = 2.74 ± 0.08 mmol L-1) followed single saturation curves and, except for K+, exhibited site-site interaction kinetics. Ouabain inhibited ATPase activity by around 73 % with K I = 12.4 ± 1.3 mol L-1. Complementary inhibition studies suggest the presence of F0F1-, Na+-, or K +-ATPases, but not V(H+)- or Ca2+-ATPases, in the gill microsomal preparation. K+ and NH4 + synergistically stimulated enzyme activity (≈25 %), suggesting that these ions bind to different sites on the molecule. We propose a mechanism for the stimulation by both NH4 +, and K+ of the gill enzyme. © 2013 Springer Science+Business Media New York.

Kinetic parameters for thermal decomposition of hydrazine

The propulsion of most of the operating satellites comprises monopropellant (hydrazine - N2H4) or bipropellant (monometilydrazine - MMH and nitrogen tetroxide) chemical systems. When some sample of the propellant tested fails, the entire sample lot shall be rejected, and this action has turned into a health problem due to the high toxicity of N2H 4. Thus, it is interesting to know hydrazine thermal behavior in several storage conditions. The kinetic parameters for thermal decomposition of hydrazine in oxygen and nitrogen atmospheres were determined by Capela-Ribeiro nonlinear isoconversional method. From TG data at heating rates of 5, 10, and 20 C min-1, kinetic parameters could be determined in nitrogen (E = 47.3 ± 3.1 kJ mol-1, lnA = 14.2 ± 0.9 and T b = 69 C) and oxygen (E = 64.9 ± 8.6 kJ mol-1, lnA = 20.7 ± 3.1 and T b = 75 C) atmospheres. It was not possible to identify a specific kinetic model for hydrazine thermal decomposition due to high heterogeneity in reaction; however, experimental f(α)g(α) master-plot curves were closed to F 1/3 model. © 2013 Akadémiai Kiadó, Budapest, Hungary.

Shvo's catalyst in chemoenzymatic dynamic kinetic resolution of amines-inner or outer sphere mechanism?

Evidence is provided for the inner-sphere mechanism with actual metal coordination of the racemic amine in the crucial hydrogen transfer step promoted by Shvo's catalyst of the chemoenzymatic dynamic kinetic resolution (DKR) of amines. Key intermediates involved in this H-transfer step were intercepted and continuously monitored by electrospray ionization mass spectrometry (ESI-MS) and characterized by their dissociation chemistries via ESI-MS/MS. © 2013 The Royal Society of Chemistry.