Flow Injection Analysis of Maleic Hydrazide Using an Electrochemical Sensor Based on Palladium‐Dispersed Carbon Paste Electrode

A new analytical methodology for the electrochemical detection of the herbicide maleic hydrazide (3,6‐dihydroxypyridazine) by flow injection analysis is presented. This method is supported by the novel application of a palladium‐dispersed carbon paste electrode as an amperometric sensor for this herbicide. Maleic hydrazide shows anodic electrochemical activity on carbon‐based electrodes (glassy carbon or carbon paste electrodes) in all the pH range. This electrochemical activity is enhanced using metal‐dispersed carbon paste electrodes, especially at Pd‐dispersed CPE which displays good oxidation signals at 690 mV (0.050 M phosphate buffer pH 7.0), 140 mV lower than at unmodified electrodes. Under the optimized conditions, the electroanalytical performance of Pd‐dispersed CPE in flow injection analysis was excellent, with good reproducibility (RSD 3.3%) and a wide linear range (1.9×10^?7 to 1.0×10^?4 mol L^?1). A detection limit of 1.4×10^?8 mol L^?1 (0.14 ng maleic hydrazide) was obtained for a sample loop of 100 μL at a fixed potential of 700 mV in 0.050 M phosphate buffer solution at pH 7.0 and a flow rate of 2.0 mL min^?1. The proposed method was applied for the maleic hydrazide detection in natural drinking water samples.     

Adsorption, separation, and thermochemical data on the herbicide picloram anchored on silica gel and its cation interaction behavior

The herbicide 4-amino-3,5,6-trichloropicolinic acid (picloram), chemically anchored on silica gel surface (SiPi), has been used for divalent cation M(2+) (Cu, Ni, Zn, and Cd) adsorption from aqueous solutions at room temperature. The series of adsorption isotherms were adjusted to a modified Langmuir equation from data obtained by suspending the solid with MCl(2) solutions, which gave the maximum number of moles adsorbed as 9.27, 7.54, 5.12, and 1.54 x 10(-4) molg(-1) for Cu, Ni, Zn, and Cd, respectively. The minimum cation retention capacity from aqueous solution was observed at pH 1, increasing up to pH 4, and was maintained constant at pH 5 for all cations. The maximum retention capacity followed the sequence Cu>Ni>Zn>Cd. SiPi-M (Cu, Ni) interactions presented endothermic enthalpic values, which contrasted with exothermic values for SiPi-M (Zn, Cd) interactions. The anchored herbicide was also used to separate the cations when loaded in a column. Their resolutions were determined as the ability of this surface to separate cations, to give Rs(Cd-Zn)=2.33, Rs(Cd-Ni)=3.16, Rs(Cd-Cu)=7.21, Rs(Zn-Ni)=1.31, Rs(Zn-Cu)=2.55, and Rs(Ni-Cu)=0.72.     

Genetic evidence of an Asian background in heteroplasmic Iberian cattle (Bos taurus): effect on food authentication studies based on polymerase chain reaction-restriction fragment length polymorphism analysis

This work was aimed at identifying nucleotide polymorphic sites in a 359 bp region of the cytochrome b (cytb) mitochondrial gene of Iberian cattle (Bos taurus). This region is widely used as target in polymerase chain reaction-restriction fragment length polymorphism (PCR-RFLP) species identification studies in foodstuffs destined for human and animal consumption. Two different coexisting restriction patterns were observed in four of the six animals studied when the 359 bp DNA fragment was cleaved with PalI, HinfI, MvaI, RsaI, or MboI. The amplification of both genotypes with the mitochondrial-specific primers L14735 and H15149 revealed the absence of nuclear pseudo-cytb genes, confirming the existence of mitochondrial heteroplasmy. The two coexisting mtDNA fragments were selectively sequenced in PCR extracts in which one genotype predominated over the other, both exhibiting a sequence variation of 10.4%. From the 37 nucleotide mismatches observed between genotypes, 32 were transitions and five were transversions. While 31 of the nucleotide mismatches between genotypes resulted to be conservative at the amino acid level, six changes implied amino acid substitutions, five of them being located in the variable transmembrane region. Genetic analysis suggests the presence of an Asian background in the mitochondria of Iberian cattle: while one of the genotypes matched the published sequence for Bos taurus, the other genotype clustered with a B. primigenius indicus animal and close to an Asian Bos taurus animal. These results also suggest that a number of current PCR-RFLP species identification methods based on cytb sequences may not be reliable for the accurate detection and identification of bovine material: an alternative battery of enzymes consisting of MmeI, NlaIV, and AluI is proposed.     

Will black holes eventually engulf the Universe?

The Babichev–Dokuchaev–Eroshenko model for the accretion of dark energy onto black holes has been extended to deal with black holes with non-static metrics. The possibility that for an asymptotic observer a black hole with large mass will rapidly increase and eventually engulf the Universe at a finite time in the future has been studied by using reasonable values for astronomical parameters. It is concluded that such a phenomenon is forbidden for all black holes in quintessential cosmological models.     

Dark energy accretion onto black holes in a cosmic scenario

In this paper we study the accretion of dark energy onto a black hole in the cases that dark energy is equipped with a positive cosmological constant and when the space-time is described by a Schwarzschild-de Sitter metric. While the first case is the same as the usual accretion procedure for a more complicated fluid, the second one give rise to a consistent cosmic scenario for the mentioned phenomenon.     

Self-organized criticality in the olami-feder-christensen model

A system is in a self-organized critical state if the distribution of some measured events obeys a power law. The finite-size scaling of this distribution with the lattice size is usually enough to assume that the system displays self-organized criticality. This approach, however, can be misleading. In this paper we analyze the behavior of the branching rate sigma of the events to establish whether a system is in a critical state. We apply this method to the Olami-Feder-Christensen model to obtain evidence that, in contrast to previous results, the model is critical in the conservative regime only.     

Salt effects on reactivity for the formation and dissociation of bis-(ethane-1,2-diamine)cobalt(III)-μ-pyrazinecarboxylato-pentacyanoferrate(II)

Dependences of rate constants on added salt concentrations have been established for approach to equilibrium for reaction of pyrazinecarboxylato-bis-1,2-diaminoethane-cobalt(III) with the pentacyanoferrate(II) complex [Fe(CN)₅L]^3– with L = MeCN. Added salt effects on dissociation of the binuclear bis-1,2-diaminoethanecobalt(III)(-pyrazine-carboxylato)pentacyanoferrate(II), [(en)₂Co(-pzCO₂)Fe(CN)₅]^–, produced in this reaction are compared with those on dissociation of other pentacyanoferrate(II) complexes. The activation volume for dissociation of this binuclear complex has been derived from the observed salt effects via the dependence of rate constants on surface tension and the thence-derived surface area of activation.     

Electrochemical analysis of nucleic acids at boron-doped diamond electrodes

Highly conductive boron-doped diamond (BDD) electrodes are well suited for performing electrochemical measurements of nucleic acids in aqueous solution under diffusion-only control. The advantageous properties of this electrodic material in this context include reproducibility and the small background currents observed at very positive potentials, along with its robustness under extreme conditions so offering promising capabilities in future applications involving thermal heating or ultrasonic treatment. tRNA, single and double stranded DNA and 2'-deoxyguanosine 5'-monophosphate (dGMP) have been studied and well defined peaks were observed in all cases, directly assignable to the electro-oxidation of deoxyguanosine monophosphate.     

Intra-well and cross-well chaos in membranes and shells liable to buckling

Nonlinear Dynamics - This work presents the mathematical modeling for the nonlinear vibration analysis of membrane and shell structures of arbitrary shape. These structures are usually the optimal...