Aluminum effects on marine phytoplankton: implications for a revised Iron Hypothesis (Iron–Aluminum Hypothesis)

In contrast to substantial studies and established knowledge of aluminum (Al) effects (mainly toxicity) on freshwater organisms and terrestrial plants, and even on human health, only a few studies of Al effects on marine organisms have been reported, and our understanding of the role of Al in marine biogeochemistry is limited. In this paper, we review the results of both field and laboratory experiments on the effects of Al on marine organisms, including Al toxicity to marine phytoplankton and the beneficial effects of Al on marine phytoplankton growth, and we discuss possible links of Al to the biological pump and the global carbon cycle. We propose a revised Iron (Fe) Hypothesis, i.e., the Fe–Al Hypothesis that introduces the idea that Al as well as Fe play an important role in the glacial-interglacial change in atmospheric CO₂ concentrations and climate change. We propose that Al could not only facilitate Fe utilization, dissolved organic phosphorus utilization and nitrogen fixation by marine phytoplankton, enhancing phytoplankton biomass and carbon fixation in the upper oceans, but also reduce the decomposition and decay of biogenic matter. As a result, Al allows potentially more carbon to be exported and sequestered in the ocean depths through the biological pump. We also propose that Al binds to superoxide to form an Al-superoxide complex, which could catalyze the reduction of Fe(III) to Fe(II) and thus facilitate Fe utilization by marine phytoplankton and other microbes. Further ocean fertilization experiments with Fe and Al are suggested, to clarify the role of Al in the stimulation of phytoplankton growth and carbon sequestration in the ocean depths.     

Iron–sulfur protein folds,iron–sulfur chemistry,and evolution

An inventory of unique local protein folds around Fe–S clusters has been derived from the analysis of protein structure databases. Nearly 50 such folds have been identified, and over 90% of them harbor low-potential [2Fe–2S]^2+,+ or [4Fe–4S]^2+,+ clusters. In contrast, high-potential Fe–S clusters, notwithstanding their structural diversity, occur in only three different protein folds. These observations suggest that the extant population of Fe–S protein folds has to a large extent been shaped in the reducing iron- and sulfur-rich environment that is believed to have predominated on this planet until approximately two billion years ago. High-potential active sites are then surmised to be rarer because they emerged later, in a more oxidizing biosphere, in conditions where iron and sulfide had become poorly available, Fe–S clusters were less stable, and in addition faced competition from heme iron and copper active sites. Among the low-potential Fe–S active sites, protein folds hosting [4Fe–4S]^2+,+ clusters outnumber those with [2Fe–2S]^2+,+ ones by a factor of 3 at least. This is in keeping with the higher chemical stability and versatility of the tetranuclear clusters, compared with the binuclear ones. It is therefore suggested that, at least while novel Fe–S sites are evolving within proteins, the intrinsic chemical stability of the inorganic moiety may be more important than the stabilizing effect of the polypeptide chain. The discovery rate of novel Fe–S-containing protein folds underwent a sharp increase around 1995, and has remained stable to this day. The current trend suggests that the mapping of the Fe–S fold space is not near completion, in agreement with predictions made for protein folds in general. Altogether, the data collected and analyzed here suggest that the extant structural landscape of Fe–S proteins has been shaped to a large extent by primeval geochemical conditions on one hand, and iron–sulfur chemistry on the other.     

Iron–sulfur cluster scaffold (ISCU) gene is duplicated in salmonid fish and tissue and temperature dependent expressed in rainbow trout

The iron–sulfur cluster protein ISCU is a scaffold protein tasked with the building and mediation of iron–sulfur [Fe–S]-clusters. These are crucial for [Fe–S]-enzymes, which are involved in essential biological cell processes like metabolism or ion transport. Analysis of ISCU in rainbow trout (Oncorhynchus mykiss) and maraena whitefish (Coregonus maraena) revealed the existence of two gene variants in each of the two salmonids. This study presents the characterization of the duplicated ISCU cDNA sequences in both species as well as the comparative functional analysis of the genes in healthy and affected fish of two rainbow trout strains differing in trait robustness under regional aquaculture conditions. Coding sequences of trout ISCUA and ISCUB genes are spanning over five exons. Open reading frames (ORF) of trout (ISCUA: 495 bp, ISCUB: 498 bp) and whitefish (ISCUA and ISCUB: 495 bp) genes encode for evolutionary highly conserved proteins and share 72% sequence similarity with human ISCU.     

Charge Transport in Poly(dG)–Poly(dC) and Poly(dA)–Poly(dT) DNA Polymers

We investigate the charge transport in synthetic DNA polymers built up from single type of base pairs. In the context of a polaronlike model, for which an electronic tight-binding system and bond vibrations of the double helix are coupled, we present estimates for the electron-vibration coupling strengths utilizing a quantum-chemical procedure. Subsequent studies concerning the mobility of polaron solutions, representing the state of a localized charge in unison with its associated helix deformation, show that the system for poly(dG)–poly(dC) and poly(dA)–poly(dT) DNA polymers, respectively possess quantitatively distinct transport properties. While the former supports unidirectionally moving electron breathers attributed to highly efficient long-range conductivity, the breather mobility in the latter case is comparatively restrained, inhibiting charge transport. Our results are in agreement with recent experimental results demonstrating that poly(dG)–poly(dC) DNA molecules acts as a semiconducting nanowire and exhibit better conductance than poly(dA)–poly(dT) ones.     

Distribution of Copper, Iron, and Zinc in Biological Samples (Scalp Hair, Serum, Blood, and Urine) of Pakistani Viral Hepatitis (A–E) Patients and Controls

The aim of the present study was to compare the level of copper (Cu), iron (Fe) and zinc (Zn) in biological samples (serum, blood, urine, and scalp hair) of patients suffering from different viral hepatitis (A, B, C, D, and E; n?=?521) of both gender age ranged 31–45 years. For comparative study, 255 age-matched control subjects, of both genders residing in the same city were selected as referents. The elements in the biological samples were analyzed by flame atomic absorption spectrophotometry, prior to microwave-assisted acid digestion. The validity and accuracy of the methodology was checked by using certified reference materials (CRMs) and with those values obtained by conventional wet acid digestion method on same CRMs. The results of this study showed that the mean values of Cu and Fe were higher in blood, sera, and scalp hair samples of hepatitis patients, while Zn level was found to be lower than age-matched control subjects. The urinary levels of these elements were found to be higher in the hepatitis patients than in the age-matched healthy controls (p?<?0.05). These results are consistent with literature-reported data, confirming that the deficiency of zinc and hepatic iron and copper overload can directly cause lipid peroxidation and eventually hepatic damage.     

INFLAM – INFLAMmation in Brain and Vessels with Iron Nanoparticles and Cell Trafficking: A Multiscale Approach of Tissue Microenvironment,Iron Nanostructure and Iron Biotransformation

Background

Inflammation is a share process in atherosclerosis and stroke and is thought to be a key player in the evolution of these diseases. Ten years ago, inflammation imaging with magnetic resonance imaging (MRI) was considered very promising for both pre-clinical and clinical studies of atherosclerosis and stroke.

Iron–sulfur cluster biosynthesis in photosynthetic organisms

Iron–sulfur (Fe/S) cluster containing proteins are widely distributed in nature and are involved in numerous processes including electron transfer, metabolic reactions, sensing, signaling, and regulation of gene expression. The knowledge about the biogenesis of Fe/S clusters, and the assembly and maturation of Fe/S cluster containing proteins is still limited, especially in photosynthetic organisms. In most organisms analyzed so far the biogenesis of Fe/S clusters involves more than one machinery. The additional compartment in photoautotrophic organisms, the plastids, presents an additional challenge for the regulation of Fe/S cluster biogenesis. The requirement for Fe/S proteins in multiple chloroplast processes argues that Fe/S cluster assembly is an essential part of plastid functionality. This review focuses on the interesting and unique aspects of Fe/S cluster biogenesis in photosynthetic organisms and compares them to what is known in other organisms.     

Rieske Iron–Sulfur Proteins from Extremophilic Organisms

Proteins located on the outside of the membranes of organisms thriving under extreme conditions like high or low pH, or high salinity face special challenges maintaining their structural integrity. This review is focused on the Rieske iron-sulfur proteins from these organisms. Rieske proteins are essential subunits of the cytochrome bc-complexes, which are often of crucial importance for the energy metabolism of the cells. On the basis of the available data we propose strategies by which these proteins are able to stabilize their noncovalent bound cofactor and adapt to the function under extreme conditions.     

The Iron age of host–microbe interactions

Microbes exert a major impact on human health and disease by either promoting or disrupting homeostasis, in the latter instance leading to the development of infectious diseases. Such disparate outcomes are driven by the ever-evolving genetic diversity of microbes and the countervailing host responses that minimize their pathogenic impact. Host defense strategies that limit microbial pathogenicity include resistance mechanisms that exert a negative impact on microbes, and disease tolerance mechanisms that sustain host homeostasis without interfering directly with microbes. While genetically distinct, these host defense strategies are functionally integrated, via mechanisms that remain incompletely defined. Here, we explore the general principles via which host adaptive responses regulating iron (Fe) metabolism impact on resistance and disease tolerance to infection.     

Synthesis and properties of (2-pyridyl)alkylamine- and (2-pyridyl)alkylamine–amide-coordinated copper(II) complexes: Structures and non-covalent interactions

Reaction of the ligand N-methyl-N-((6-pivaloylamido-2-pyridyl)methyl)-N-(2-pyridylethyl)amine (mpppa) with equimolar amounts of [Cu(H₂O)₆][ClO₄]₂ or CuCl₂ · 2H₂O in MeCN afforded mononuclear copper(II) complexes [Cu(mpppa)][ClO₄]₂ (1) and [Cu(mpppa)Cl₂] (2). Crystal structure analysis reveals CuN₃O (two pyridyl, an aliphatic amine, and an amide oxygen) coordination in 1 and CuN₃Cl₂ (two pyridyl, an aliphatic amine, and two chlorides) coordination in 2. Crystal packing diagram of 1 reveals that one of the perchlorate counteranions provides weak coordination to copper(II) centers and in turn the copper(II) centers assume pseudo-six-coordination, generating 1D chain. Notably, one of the copper(II)-coordinated chloride ions in 2 participates in an intramolecular N–H?Cl interaction. Intermolecular C–H?Cl interactions in the solid state generate helical structure. Spectroscopic (IR, UV–Vis, and EPR) and redox properties of the two complexes have been investigated and compared.     

Structures and free energy landscapes of aqueous zinc(II)-bound amyloid-β(1–40) and zinc(II)-bound amyloid-β(1–42) with dynamics

Binding of divalent metal ions with intrinsically disordered fibrillogenic proteins, such as amyloid-β (Aβ), influences the aggregation process and the severity of neurodegenerative diseases. The Aβ monomers and oligomers are the building blocks of the aggregates. In this work, we report the structures and free energy landscapes of the monomeric zinc(II)-bound Aβ40 (Zn:Aβ40) and zinc(II)-bound Aβ42 (Zn:Aβ42) intrinsically disordered fibrillogenic metallopeptides in an aqueous solution by utilizing an approach that employs first principles calculations and parallel tempering molecular dynamics simulations. The structural and thermodynamic properties, including the secondary and tertiary structures and conformational Gibbs free energies of these intrinsically disordered metallopeptide alloforms, are presented. The results show distinct differing characteristics for these metallopeptides. For example, prominent β-sheet formation in the N-terminal region (Asp1, Arg5, and Tyr10) of Zn:Aβ40 is significantly decreased or lacking in Zn:Aβ42. Our findings indicate that blocking multiple reactive residues forming abundant β-sheet structure located in the central hydrophobic core and C-terminal regions of Zn:Aβ42 via antibodies or small organic molecules might help to reduce the aggregation of Zn(II)-bound Aβ42. Furthermore, we find that helix formation increases but β-sheet formation decreases in the C-terminal region upon Zn(II) binding to Aβ. This depressed β-sheet formation in the C-terminal region (Gly33-Gly38) in monomeric Zn:Aβ42 might be linked to the formation of amorphous instead of fibrillar aggregates of Zn:Aβ42.     

The IRP1-HIF-2α Axis Coordinates Iron and Oxygen Sensing with Erythropoiesis and Iron Absorption

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Highlights? Derepression of HIF-2α mRNA in Irp1^?/? mice causes age-dependent polycythemia ? HIF-2α hyperactivity is observed in multiple tissues of Irp1^?/? mice ? The mRNA regulons of IRP1 and IRP2 are separable in vivo ? The IRP1-HIF-2α axis is a therapeutic target for hematologic or oncologic disorders     

Degradation of Crude Oil and PAHs in Iron–Manganese Concretions and Sediment from the Northern Baltic Sea

The ability of different sea bottom types to recover from oil contamination under oxic and anoxic conditions is poorly known in the brackish Baltic Sea. We carried out microcosm experiments to examine the capacity of iron–manganese concretions and sediment to remove petroleum compounds at 10°C. The biological degradation potential of polycyclic aromatic hydrocarbons (PAHs) was indicated by the 1000-fold increase in the copy numbers of PAH-degradation genes resulting in 2.2 × 10⁶ gene copies g^?1 DW. In the experiments 35?81% of the crude oil and 96% of PAHs disappeared through abiotic and biotic pathways, and there was little difference between the concretions and sediment. Bacterial community analysis revealed that the bacterial sequences obtained from the oil-treated concretions were affiliated to groups typical for concretions and metal-rich environments, whereas oil-treated sediment sequences were similar to those originating from sediments and oil-contaminated environments. The high frequency of concretion clones affiliated with specific taxonomic groups of α-, β-, γ-, and δ-proteobacteria may indicate the existence of new clades of bacteria within the Rhizobiales and Rhodospirillales of the α-proteobacteria, Burkholderiales—incertae sedis of the β-proteobacteria, Chromatiales of the γ-proteobacteria and the Syntrophobacteriales of the δ-proteobacteria. Our study suggests that concretions and bottom sediment maintain rich, distinct bacterial communities under oil exposure that have the potential to remove petroleum compounds in oxic and anoxic conditions.     

Chromium and Manganese Levels in Biological Samples of Normal and Night Blindness Children of Age Groups (3–7) and (8–12) Years

This study was designed to compare the levels of chromium (Cr) and manganese (Mn) in scalp hair, blood, and urine of night blindness in children age ranged (3–7) and (8–12) years of both genders, comparing them to sex- and age-matched controls. A microwave-assisted wet acid digestion procedure, was developed as a sample pretreatment, for the determination of Cr and Mn in biological samples of night blindness children. The proposed method was validated by using conventional wet digestion and certified reference samples of hair, blood and urine. The digests of all biological samples were analyzed for Cr and Mn by electrothermal atomic absorption spectrometry. The results indicated significantly higher levels of Cr, whilst low level of Mn in the biological samples (blood and scalp hair) of male and female night blindness children, compared with control subjects of both genders. These data present guidance to clinicians and other professional investigating deficiency of Mn and excessive level of Cr in biological samples (scalp hair and blood) of night blindness children.     

Dose-dependent Incorporation of Tea Catechins, (–)-Epigallocatechin-3-gallate and (–)-Epigallocatechin,into Human Plasma

Tea catechins, (–)-epigallocatechin-3-gallate (EGCg) and (–)-epigallocatechin (EGC), have been reported to suppress oxidation of plasma low density lipoprotein (LDL) in vitro. If dietary catechins can be efficiently incorporated into human blood plasma, anti-atherosclerotic effects in preventing oxidative modification of LDL would be expected. In this study, a newly developed chemiluminescence detection-high pressure liquid chromatography (CL-HPLC) method for measuring plasma catechins was used and the incorporation of EGCg and EGC into human plasma was investigated. Healthy subjects orally ingested 3, 5, or 7 capsules of green tea extract (corresponding to 225, 375, and 525 mg EGCg and 7.5, 12.5, and 17.5 mg EGC, respectively). The plasma EGCg and EGC concentrations before the administration were all below the detection limit (< 2 pmol/ml), but 90 min after, significantly and dose-dependently increased to 657, 4300, and 4410 pmol EGCg/ml, and 35, 144, and 255 pmol EGC/ml, in the subjects who received 3, 5, and 7 capsules, respectively. Both EGCg and EGC levels detected in plasma corresponded to 0.2–2.0% of the ingested amount. Catechin intake had no effect on the basal level of endogenous antioxidants (α-tocopherol, β-carotene, and lycopene) or of lipids in plasma. These results suggested that drinking green tea daily would contribute to maintain plasma catechin levels sufficient to exert antioxidant activity against oxidative modification of lipoproteins in blood circulation systems.     

Crops and agriculture during the Iron Age and late antiquity in Cerdanyola del Vallès (Catalonia,Spain)

Various sites in the valley of the Sant Cugat stream in Cerdanyola del Vallès (Catalonia) were subject to systematic archaeobotanical sampling to obtain an overview of the crops and agriculture of the area during the Iron Age and late antiquity. In all cases, the most numerous taxa were crop plants. Among these, cereals were clearly predominant at all sites investigated, especially Hordeum vulgare var. vulgare (hulled barley) and Triticum aestivum/durum (bread or macaroni wheat), both in numbers and frequency. Other cereals, such as Triticum dicoccum (emmer) or Setaria italica (foxtail bristle-grass), were regularly present in considerably lower numbers but in fairly high frequencies. Pulses were much less numerous, although their presence increases in terms of frequency. Among them, clearly the best represented was Lens culinaris (lentil). The results show that the agriculture in the period considered was principally based on winter cereals, with a gradual substitution of hulled barley by bread/hard wheat, accompanied by other cereals of minor importance, led by Triticum dicoccum (emmer), and pulses. The appearance of Vitis (grapevine) in the Iberian period is one of the important characteristics of agriculture in the Iberian world. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.