Laccase-Mediated Transformations of Endocrine Disrupting Chemicals Abolish Binding Affinities to Estrogen Receptors and Their Estrogenic Activity in Zebrafish

Endocrine disrupting chemicals (EDCs) are known to mainly affect aquatic organisms, producing negative effects in aquaculture. Transformation of the estrogenic compounds 17??-estradiol (E2), bisphenol-A (BPA), nonylphenol (NP), and triclosan (TCS) by laccase of Coriolopsis gallica was studied. Laccase is able to efficiently transform them into polymers. The estrogenic activity of the EDCs and their laccase transformation products was evaluated in vitro as their affinity for the human estrogen receptor alpha (hER??) and for the ligand binding domain of zebrafish (Danio rerio) estrogen receptor alpha (zfER??LBD). E2, BPA, NP, and TCS showed higher affinity for the zfER??LBD than for hER??. After laccase treatment, no affinity was found, except a marginal affinity of E2 products for the zfER??LBD. Endocrine disruption studies in vivo on zebrafish were performed using the induction of vitellogenin 1 as a biomarker (VTG1 mRNA levels). The use of enzymatic bioreactors, containing immobilized laccase, efficiently eliminates the endocrine activity of BPA and TCS, and significantly reduces the effects of E2. The potential use of enzymatic reactors to eliminate the endocrine activity of EDCs in supply water for aquaculture is discussed.     

Invariance Conditions for Random Curvature Models

A class of probability models is introduced with the objective of representing certain properties of the geometric optics of the human eye. Astigmatic probability laws are those in which the extreme curvature values in the anterior corneal surface, measured at circularly arranged and equally spaced locations, are displaced by an approximate 90 deg angular separation. The relationship between the symmetry invariance of these probability laws for curvature data and probability laws for the ranking permutations associated with the ordering of these data is obtained. A distinction is made between the condition in which the components of the curvature ensemble are represented as real numbers from that in which these curvatures are color-coded and take value on a finite totally ordered set. A constructive principle for astigmatic laws is outlined based on algebraic arguments for the analysis of structured data.     

Shape Effects in the Partial Molar Volume of Tetraethylphosphonium and Ammonium Iodides in Six Nonaqueous Solvents

Densities of dilute solutions of the electrolytes tetraethylphosphonium iodide and tetraethylammonium iodide in the nonaqueous solvents methanol, ethanol, 1-propanol, 1-butanol, acetonitrile, and 2-propanone were measured at 25^°C. Using published values for the Debye-Hückel limiting slopes A _V, apparent molar volume data were fitted to the Pitzer equation yielding infinite-dilution partial molar volumes and deviation parameters B _V. It is found that the variation in the van der Waals volume of the cationic central atoms is about one half the experimental volume change in 2-propanone solutions, but twice that value in the other five solvents. This finding is interpreted in terms of openness of solute structure and solvent penetration. Parameter B _V for each salt is shown to be solvent dependent. An interesting approximate linear variation between A _V and B _V parameters is suggested by the data. This empirical relationship would entail correlation of short- and long-range interionic interactions in solution.     

Dynamical Effects in Confined Plasma Turbulence

Plasma turbulence at the edge of tokamaks is an issue of major importance in the study of the anomalous transport of particles and energy. Although the behavior of a turbulent plasma seems intractable, it turns out that many of its aspects can be described by low-dimensional non-integrable dynamical models. In this paper, we consider a number of dynamical effects occurring in tokamak plasma edge—in particular the role of internal transport barriers. Furthermore, we present experimental results on turbulent-driven transport for two machines—the Brazilian TCABR tokamak and University of Texas’ Helimak—that can be explained by those theoretical models.     

Dynamical changes from harmonic vibrations of a limited power supply driving a Duffing oscillator

The harmonic oscillations of a Duffing oscillator driven by a limited power supply are investigated as a function of the alternative strength of the rotor. The semi-trivial and non-trivial solutions are derived. We examine the stability of these solutions and then explore the complex behaviors associated with the bifurcations sequences. Interestingly, a 3D diagram provides a global view of the effects of alternate strength on the appearance of chaos and hyperchaos on the system.     

Characterizing topological and dynamical properties of complex networks without border effects

The properties of complex networks are highly influenced by border effects frequently found as a consequence of the finite nature of real-world networks as well as network sampling. Therefore, it becomes critical to devise effective means for sound estimation of network topological and dynamical properties while avoiding these types of artifacts. In the current work, an algorithm for minimization of border effects is proposed and discussed, and its potential is illustrated with respect to two real-world networks, namely bone canals and air transportation.     

Biomimetical catalytic activity of iron(III) porphyrins encapsulated in the zeolite X

The approach adopted for the obtention of zeolite-encapsulated FeP led to clean syntheses of biomimetical catalyst. The catalysts were obtained through the zeolite synthesis method, where NaX zeolite was synthesised around one of the cationic FePs: iron(III) 5,10,15,20-tetrakis(4-N-methylpyridyl)porphyrin (FeP1) or iron(III) 5-mono(2,6-dichloro-phenyl)10,15,20-tris(4-N-methylpyridyl)porphyrin (FeP2). The syntheses yielded pure FeP1NaX and FeP2NaX catalysts without any by-products blocking the zeolite nanopores. FeP1NaX and FeP2NaX efficiently catalysed the epoxidation of (Z)-cyclooctene by iodosylbenzene (PhIO) in DCE, giving rise to cis-epoxycyclooctane yields of 85% and 95%, respectively. Hydroxylation of adamantane shows a preferable alkane oxidation at the tertiary C---H bond, indicating a hydrogen abstraction through the Fe^IV(O)P^·+species in the initial step. The total adamantanol yields were 52% and 45% for FeP1NaX and FeP2NaX, respectively. Concerning selectivity, FeP1NaX and FeP2NaX gave an 1-adamantanol (Ad-1-ol)/2-adamantanol (Ad-2-ol) ratio of 20:1 and 11:1, respectively (after statistical correction). Therefore, these results indicate a free radical activation of the C---H bonds of adamantane as expected for P-450 models. In the cyclohexane oxidation catalysed by FeP1NaX in DCE, a cyclohexanol (C₆-ol) yield of 50% and an alcohol/ketone ratio of 10 was obtained. The hydroxylation occurs according to the so-called oxygen rebound mechanism, as expected for a P-450 model system. FeP2NaX is less selective (C₆-ol yield=25% and alcohol/ketone=1.2). One possible explanation is that a Russell-type mechanism involving O₂ imprisoned within the zeolite cages may be operating parallelly, generating both C₆-ol and cyclohexanone.