Biological and chemical interaction of oxygen on the reduction of Fe(III)EDTA in a chemical absorption–biological reduction integrated NO x removal system

A promising chemical absorption–biological reduction integrated process has been proposed. A major problem of the process is oxidation of the active absorbent, ferrous ethylenediaminetetraacetate (Fe(II)EDTA), to the ferric species, leading to a significant decrease in NO removal efficiency. Thus the biological reduction of Fe(III)EDTA is vitally important for the continuous NO removal. Oxygen, an oxidizing agent and biological inhibitor, is typically present in the flue gas. It can significantly retard the application of the integrated process. This study investigated the influence mechanism of oxygen on the regeneration of Fe(II)EDTA in order to provide insight on how to eliminate or decrease the oxygen influence. The experimental results revealed that the dissolved oxygen and Fe(III)EDTA simultaneously served as electron acceptor for the microorganism. The Fe(III)EDTA reduction activity were directly inhibited by the dissolved oxygen. When the bioreactor was supplied with 3% and 8% oxygen in the gas phase, the concentration of initial dissolved oxygen in the liquid phase was 0.28 and 0.68 mg l⁻¹. Correspondingly, the instinct Fe(III)EDTA reduction activity of the microorganism determined under anoxic condition in a rotation shaker decreased from 1.09 to 0.84 and 0.49 mM h⁻¹. The oxidation of Fe(II)EDTA with dissolved oxygen prevented more dissolved oxygen access to the microorganism and eased the inhibition of dissolved oxygen on the microorganisms.     

Structure of microbial communities performing the simultaneous reduction of Fe(II)EDTA.NO2−and Fe(III)EDTA−

BioDeNOx is a combined physicochemical and biological process for the removal of nitrogen oxides (NOx) from flue gas. In the present study, two anaerobic bioreactors performing BioDeNOx were run consecutively (RUN-1 and RUN-2) at a dilution rate of 0.01 h⁻¹ with Fe(II)EDTA.NO²⁻ and Fe(III)EDTA⁻ as electron acceptors and ethanol as electron donor. The measured protein concentration of the reactor biomass of both runs was 120 mg/l. Different molecular methods were used to determine the identity and abundance of the bacterial populations in both bioreactors. Bacillus azotoformans strain KT-1 was recognized as a key player in Fe(II)EDTA.NO²⁻ reduction. PCR-denaturing gradient gel electrophoresis analysis of the reactor biomass showed a greater diversity in RUN-2 than in RUN-1. Enrichments of Fe(II)EDTA.NO²⁻ and Fe(III)EDTA⁻ reducers and activity assays were conducted using the biomass from RUN-2 as an inoculum. The results on substrate turnover, overall microbial diversity, and enrichments and finally activity assays confirmed that ethanol was used as electron donor for Fe(II)EDTA.NO²⁻ reduction. In addition, the Fe(III)EDTA⁻ reduction rate of the microbial community proved to be feasible enough to run the bioreactors, ruling out the chemical reduction of Fe(III)EDTA⁻ with sulfide as was proposed by other researchers.     

Spectroscopic and calorimetric studies on trazodone hydrochloride–phosphatidylcholine liposome interactions in the presence and absence of cholesterol

The interaction of antidepressant drug trazodone hydrochloride (TRZ) with dipalmitoyl phosphatidylcholine (DPPC) multilamellar liposomes (MLVs) in the presence and absence of cholesterol (CHO) was investigated as a function of temperature by using Electron Paramagnetic Resonance (EPR) spin labeling, Fourier Transform Infrared (FTIR) Spectroscopy and Differential Scanning Calorimetry (DSC) techniques. These interactions were also examined for dimyristoyl phosphatidylcholine (DMPC) multilamellar liposomes by using Electron Paramagnetic Resonance (EPR) spin labeling technique. In the EPR spin labeling studies, 5- and 16-doxyl stearic acid (5-DS and 16-DS) spin labels were used to monitor the head group and alkyl chain region of phospholipids respectively. The results indicated that TRZ incorporation causes changes in the physical properties of PC liposomes by decreasing the main phase transition temperature, abolishing the pre-transition, broadening the phase transition profile, and disordering the system around the head group region. The interaction of TRZ with unilamellar (LUV) DPPC liposomes was also examined. The most pronounced effect of TRZ on DPPC LUVs was observed as the further decrease of main phase transition temperature in comparison with DPPC MLVs. The mentioned changes in lipid structure and dynamics caused by TRZ may modulate the biophysical activity of membrane associated receptors and in turn the pharmacological action of TRZ.     

Ecological–genetic approach in modeling the natural evolution of a population: Prospects and special aspects of verification

This study presents a complex approach for modeling the natural evolution of a population in terms of population number and dynamics of the genetic structure. A set of dynamic models that consider various types of natural selection was applied to describe possible mechanisms underlying the formation of existing genetic variations in litter sizes in coastal, inland, and farmed arctic fox populations (Alopex lagopus, family Canidae, order Carnivora). The r–K selection model for uniform population and the models with natural selection were assessed on various life cycle stages in a two-age population. The life cycle of arctic fox was fitted to the population model with two age stages. The different reproductive potentials and survivability of progeny on the early stage of life cycle were genetically determined using the model with a single diallelic gene. A monomorphism was obtained for a considered characteristic in a population of coastal arctic fox with constant food supply. Meanwhile, a polymorphism with cyclic fluctuations in population number and gene frequency was obtained in inland arctic fox populations, which could be due to cyclic fluctuations of prey. In farmed fox populations, the considered gene becomes pleiotropic (defines the survival rate of individuals on early and late stages of the life cycle) because of artificial selection performed by farmers to increase the reproductive success of breeders. The application of an appropriate model (with selection by pleiotropic gene) can be used to determine the elimination rate of low litter size alleles from the farmed populations. The possible applications of the proposed models for formulating and solving optimal control tasks in arctic fox populations are discussed too.     

Induction of iron(III) and copper(II) reduction in pea (Pisum sativum L.) roots by Fe and Cu status: Does the root-cell plasmalemma Fe(III)-chelate reductase perform a general role in regulating cation uptake?

We investigated the effects of Fe and Cu status of pea (Pisum sativum L.) seedlings on the regulation of the putative root plasma-membrane Fe(III)-chelate reductase that is involved in Fe(III)-chelate reduction and Fe²⁺ absorption in dicotyledons and nongraminaceous monocotyledons. Additionally, we investigated the ability of this reductase system to reduce Cu(II)-chelates as well as Fe(III)-chelates. Pea seedlings were grown in full nutrient solutions under control, -Fe, and -Cu conditions for up to 18 d. Iron(III) and Cu(II) reductase activity was visualized by placing roots in an agarose gel containing either Fe(III)-EDTA and the Fe(II) chelate, Na₂bathophenanthrolinedisulfonic acid (BPDS), for Fe(III) reduction, or CuSO₄, Na₃citrate, and Na₂-2,9-dimethyl-4,7-diphenyl-1, 10-phenanthrolinedisulfonic acid (BCDS) for Cu(II) reduction. Rates of root Fe(III) and Cu(II) reduction were determined via spectrophotometric assay of the Fe(II)-BPDS or the Cu(I)-BCDS chromophore. Reductase activity was induced or stimulated by either Fe deficiency or Cu depletion of the seedlings. Roots from both Fe-deficient and Cu-depleted plants were able to reduce exogenous Cu(II)-chelate as well as Fe(III)-chelate. When this reductase was induced by Fe deficiency, the accumulation of a number of mineral cations (i.e., Cu, Mn, Fe, Mg, and K) in leaves of pea seedlings was significantly increased. We suggest that, in addition to playing a critical role in Fe absorption, this plasma-membrane reductase system also plays a more general role in the regulation of cation absorption by root cells, possibly via the reduction of critical sulfhydryl groups in transport proteins involved in divalent-cation transport (divalent-cation channels?) across the root-cell plasmalemma.     

Frequency of micronuclei in 4–8 cell mouse embryos generated after maternal gamma-irradiation in the presence and in the absence of vitamin C

The objective of this investigation was to evaluate the frequency of chromosomal aberrations expressed as micronuclei (MN) in 4–8 cell embryos generated by gamma-irradiation of female mice in the absence and in the presence of vitamin C. Female NMRI mice were whole body exposed to 4 Gy gamma-irradiation after intraperitoneal (i.p.) injection of pregnant mare’s serum gonadotrophin (PMSG) followed by injection of human chorionic gonadotrophin (HCG) and mating with non-irradiated NMRI male mice. Pregnant animals were sacrificed and embryos flushed from the oviducts and fixed on slides. Cells were treated for MN observation using standard method. To investigate the protective effect of vitamin C (ascorbic acid) on the frequency of MN, 100 mg/kg vitamin C was i.p. injected 1 h before irradiation. Results show that the frequency of MN generated in the embryos of irradiated mother compared to those of control in the non-irradiated group increased dramatically (P < 0.001). Frequency of MN in embryos generated in irradiated female mice treated with vitamin C dramatically and statistically decreased relative to the frequency observed in the irradiation only group (P < 0.001). This decrease returned the combined treatment group to a level that was not statistically different from the controls (P > 0.05). Thus, irradiation of preovulatory stage oocytes leads to stable chromosome abnormalities expressed as micronuclei in successive preimplantation embryos. Vitamin C reduces these clastogenic effects of radiation in preovulatory oocytes and thus the reduced frequency of MN in embryos is probably due to its antioxidation and radical scavenging properties.     

Spin-trapping studies on the reactions of Cr(III) with hydrogen peroxide in the presence of biological reductants: is Cr(III) non-toxic?

Cr(III), which is thought to be relatively non-toxic, was reduced to Cr(II) ion by biological reductants such as L-cysteine and NADH and Cr(II) thus formed could easily react with hydrogen peroxide (H2O2) to yield very reactive active oxygen species, hydroxyl radical (.OH). The formation of hydroxyl radical was detected by water-soluble spin-traps, alpha-(4-pyridyl-1-oxide)-N-tert-butylnitrone (POBN) and 5,5-dimethyl-1-pyrroline N-oxide (DMPO). This result indicates that non-toxic Cr(III) compounds have the possibility of causing dangerous effects to living organism in the presence of biological reductants.     

Binding of α-synuclein with Fe(III) and with Fe(II) and biological implications of the resultant complexes

Parkinson’s disease (PD) is hallmarked by the abnormal intracellular inclusions (Lewy bodies or LBs) in dopaminergic cells. Amyloidogenic protein α-synuclein (α-syn) and iron (including both Fe(III) and Fe(II)) are both found to be present in LBs. The interaction between iron and α-syn might have important biological relevance to PD etiology. Previously, a moderate binding affinity between α-syn and Fe(II) (5.8 × 10³ M⁻¹) has been measured, but studies on the binding between α-syn and Fe(III) have not been reported. In this work, electrospray mass spectrometry (ES-MS), cyclic voltammetry (CV), and fluorescence spectroscopy were used to study the binding between α-syn and Fe(II) and the redox property of the resultant α-syn-Fe(II) complex. The complex is of a 1:1 stoichiometry and can be readily oxidized electrochemically and chemically (by O₂) to the putative α-syn-Fe(III) complex, with H₂O₂ as a co-product. The reduction potential was estimated to be 0.025 V vs. Ag/AgCl, which represents a shift by −0.550 V vs. the standard reduction potential of the free Fe(III)/Fe(II) couple. Such a shift allows a binding constant between α-syn and Fe(III), 1.2 × 10¹³ M⁻¹, to be deduced. Despite the relatively high binding affinity, α-syn-Fe(III) generated from the oxidation of α-syn-Fe(II) still dissociates due to the stronger tendency of Fe(III) to hydrolyze to Fe(OH)₃ and/or ferrihydrite gel. The roles of α-syn and its interaction with Fe(III) and/or Fe(II) are discussed in the context of oxidative stress, metal-catalyzed α-syn aggregation, and iron transfer processes.     

K(V)4.3 N-terminal deletion mutant Δ2-39: effects on inactivation and recovery characteristics in both the absence and presence of KChIP2b

Gating transitions in the K(V)4.3 N-terminal deletion mutant Δ2-39 were characterized in the absence and presence of KChIP2b. We particularly focused on gating characteristics of macroscopic (open state) versus closed state inactivation (CSI) and recovery. In the absence of KChIP2b Δ2-39 did not significantly alter the steady-state activation "a(4)" relationship or general CSI characteristics, but it did slow the kinetics of deactivation, macroscopic inactivation, and macroscopic recovery. Recovery kinetics (for both WT K(V)4.3 and Δ2-39) were complicated and displayed sigmoidicity, a process which was enhanced by Δ2-39. Deletion of the proximal N-terminal domain therefore appeared to specifically slow mechanisms involved in regulating gating transitions occurring after the channel open state(s) had been reached. In the presence of KChIP2b Δ2-39 recovery kinetics (from both macroscopic and CSI) were accelerated, with an apparent reduction in initial sigmoidicity. Hyperpolarizing shifts in both "a(4)" and isochronal inactivation "i" were also produced. KChIP2b-mediated remodeling of K(V)4.3 gating transitions was therefore not obligatorily dependent upon an intact N-terminus. To account for these effects we propose that KChIP2 regulatory domains exist in K(V)4.3 a subunit regions outside of the proximal N-terminal. In addition to regulating macroscopic inactivation, we also propose that the K(V)4.3 N-terminus may act as a novel regulator of deactivation-recovery coupling.     

Redox activation of Fe(III)–thiosemicarbazones and Fe(III)–bleomycin by thioredoxin reductase: specificity of enzymatic redox centers and analysis of reactive species formation by ESR spin trapping

Thiosemicarbazones such as Triapine (Tp) and Dp44mT are tridentate iron (Fe) chelators that have well-documented antineoplastic activity. Although Fe–thiosemicarbazones can undergo redox cycling to generate reactive species that may have important roles in their cytotoxicity, there is only limited insight into specific cellular agents that can rapidly reduce Fe(III)–thiosemicarbazones and thereby promote their redox activity. Here we report that thioredoxin reductase-1 (TrxR1) and glutathione reductase (GR) have this activity and that there is considerable specificity to the interactions between specific redox centers in these enzymes and various Fe(III) complexes. Site-directed variants of TrxR1 demonstrate that the selenocysteine (Sec) of the enzyme is not required, whereas the C59 residue and the flavin have important roles. Although TrxR1 and GR have analogous C59/flavin motifs, TrxR is considerably faster than GR. For both enzymes, Fe(III)(Tp)₂ is reduced faster than Fe(III)(Dp44mT)₂. This reduction promotes redox cycling and the generation of hydroxyl radical (HO) in a peroxide-dependent manner, even with low-micromolar levels of Fe(Tp)₂. TrxR also reduces Fe(III)–bleomycin and this activity is Sec-dependent. TrxR cannot reduce Fe(III)–EDTA at significant rates. Our findings are the first to demonstrate pro-oxidant reductive activation of Fe(III)-based antitumor thiosemicarbazones by interactions with specific enzyme species. The marked elevation of TrxR1 in many tumors could contribute to the selective tumor toxicity of these drugs by enhancing the redox activation of Fe(III)–thiosemicarbazones and the generation of reactive oxygen species such as HO.     

Sol–gel encapsulation of pullulanase in the presence of hybrid magnetic (Fe3O4–chitosan) nanoparticles improves thermal and operational stability

Bioprocess and Biosystems Engineering - Pullulanase was sol–gel encapsulated in the presence of magnetic chitosan/Fe3O4 nanoparticles. The resulting immobilized pullulanase was characterized...     

Prediction of marine species distribution from presence–absence acoustic data: comparing the fitting efficiency and the predictive capacity of conventional and novel distribution models

The accurate representation of species distribution derived from sampled data is essential for management purposes and to underpin population modelling. Additionally, the prediction of species distribution for an expanded area, beyond the sampling area can reduce sampling costs. Here, several well-established and recently developed habitat modelling techniques are investigated in order to identify the most suitable approach to use with presence–absence acoustic data. The fitting efficiency of the modelling techniques are initially tested on the training dataset while their predictive capacity is evaluated using a verification set. For the comparison among models, Receiver Operating Characteristics (ROC), Kappa statistics, correlation and confusion matrices are used. Boosted Regression Trees (BRT) and Associative Neural Networks (ASNN), which are both within the machine learning category, outperformed the other modelling approaches tested.     

New thiocyanato and azido adducts of the redox-active Fe(η-C5Me5)(η-dppe) center: Synthesis and study of the Fe(II) and Fe(III) complexes

The new thiocyanato- (5) and azido- (6) complexes were synthesized and studied under their Fe(II) and Fe(III) redox states. For the first time among the various [Fe(η⁵-C₅Me₅)(η²-dppe)]-based cationic radicals studied so far, the magnitude and spatial orientation of the g-tensor diagonal values were experimentally determined for 5[PF₆]. These data are in good agreement with those issued from a DFT modelization. The changes experienced by the electronic structure of the Fe(II) complexes subsequent to oxidation are reminiscent of these previously observed for the known arylalkynyl analogues, albeit some differences can be pointed out. Thus, the differences observed in the ¹H NMR spectra of 5[PF₆] and 6[PF₆] are attributed to a slower electronic spin relaxation and to the differently oriented magnetic anisotropy. The sizeable spin density evidenced by DFT on the terminal atom of the ligands of the Fe(III) complexes renders these new paramagnetic metallo-ligands quite appealing for accessing larger polynuclear molecular assemblies with magnetically interacting centers.     

Assignment of six enzyme loci to multipoint linkage groups in Fishes of the genusPoeciliopsis (Poeciliidae): Designation of linkage groups III–V

Three new linkage groups of enzyme loci are described usingPoeciliopsis monacha × P. viriosa-derived interspecific backcross hybrids. Comparison to known linkage groups of the confamilial genusXiphophorus shows homology betweenXiphophorus linkage group I andPoeciliopsis linkage group III,Xiphophorus linkage group II andPoeciliopsis linkage group I, andXiphophorus linkage group IV andPoeciliopsis linkage group IV. Comparison of the gene content of other fish, amphibians, and mammal syntenic groups suggests retention of plesiomorphic vertebrate gene arrangements in at least two poeciliid linkage groups. Expansion of thePoeciliopsis gene map should be of utility in the identification of tumor regulatory genes through demonstration of linkage to biochemical markers.This work was supported by NSF Grants BSR 19355 and BSR 16569 and NIH Grants CA 44303 and CA 39729 to R. S. Nairn and D.C.M. and NIEHS Grant EHS 1P50ES 0384801A1 to R.J.S.     

Anti-Semitism in Britain: continuity and the absence of a resurgence?

Abstract

It has become the orthodoxy in recent years to assume that anti-Semitism globally is not only rising but also taking a new form – it is a ‘new anti-Semitism’ or even a new phenomenon: Judeophobia. This article takes a different perspective. It initially covers approaches to anti-Semitism and how, especially in the light of the Holocaust, it has been viewed academically as no longer the fault of the Jews but as a natural and constant feature of history since antiquity. A critique is provided of the idea of a continuous history of anti-Semitism and of the metaphors used to describe it. There then follows a case study of anti-Semitism in Britain. The British case is valuable as it is seen as a key example of the ‘new anti-Semitism’, and one that is more striking given the alleged absence of previous hostility towards Jews in that country. By employing a comparative approach – both temporal and in relation to responses to other groups – change and continuity are charted through a study of racial violence. Such comparisons, it is argued, allow a more nuanced and balanced analysis of this issue, which has created much alarm and little sober reflection.     

Computational modeling of the dizinc–ferroxidase complex of human H ferritin: direct comparison of the density functional theory calculated and experimental structures

Density functional theory optimizations of structures of dizinc(II) complexes with a six-residue model of the ferroxidase center of human H ferritin have been performed and the results compared with the crystallographically determined structure of the complex as presented in Protein Data Bank file 2CEI. The model employs the full structures of Glu27, Glu62, His65, Glu107, Gln141, and Ala144, and the structural effect of Tyr34 is also examined. The mean absolute deviation from experiment of atomic positions in the best calculated structures is less than 0.3 Å. The experimental structure is reproduced well enough to determine the coordination environment of the metal ions. Each zinc(II) center is pentacoordinate with a single water ligand, and the two centers are bridged by a hydroxide ion. Ala144 interacts weakly and repulsively with the rest of the complex. Tyr34 displays a weak attraction through a hydrogen bond to Glu107 that affects the orientation of that group.