Determination of Mn2+ ion by solution scanometry as a new, simple and inexpensive method

In this research, scanometry was used as a new, simple, fast and inexpensive method for a colorimetric determination of Mn2+ ion in water samples and thermocouple wire through the use of periodate reagent in an acidic medium. The results showed the oxidization of colorless Mn2+ ion by periodate and the formation of a purplish MnO4- ion. The system had a linear range of 1.0 to 70.0 ��g mL-1 Mn2+ ion with a detection limit of 0.314 ��g mL-1 and a relative standard deviation of 2.77% for G color value. This method has the capability to determine low levels of Mn2+ ion in thermocouple wire and water samples.

Effect of divalent metal ions on the activity and stability of ��-galactosidase isolated from Kluyveromyces lactis

In this study, it was demonstrated that ��-galactosidase can be deactivated and reactivated with EDTA and divalent metal ions. The enzyme was deactivated after 20 minutes in EDTA solution. Maximal deactivation at the lowest EDTA concentration (10-3 mol.L-1) occurred in the presence of Tris-HCl buffer (pH 7.0). The enzyme recovered 50% of its initial activity after 10 minutes at Mg2+concentrations higher than 0.1 mmol.L-1. Experimental concentrations of 0.1 mmol.L-1 Mn2+ and 1.0 mmol.L-1 Co2+ were sufficient to reactivate the enzyme to around 300% of the control activity for the Mn2+ ion and nearly 100% for the Co2+ ion. The enzyme gradually lost its activity when the Co2+ concentration was 10-2 mol.L-1. Ni2+ and Zn2+ were unable to restore the catalytic activity. Km app and Vmax app were 1.95 �� 0.05 mmol.L-1 and 5.40 �� 0.86x10-2 mmol.min-1.mg-1, with o-NPG as substrate. Optimal temperature and pH were 34oC and 7.5. The half-life (t1/2) at 30��C was 17.5 min for the holoenzyme and 11.0 min for the apoenzyme. With respect to pH variation, the apoenzyme proved to be more sensitive than the holoenzyme. Keywords: ��-galactosidase. Divalent metallic ions. Enzyme activity. Stability. RESUMO Efeito de ��ons met��licos divalentes na atividade e estabilidade da ��-galactosidase isolada de Kluyveromyces lactis Este estudo demonstra como a ��-galactosidase pode ser desativada e reativada usando EDTA e ��ons met��licos divalentes. A enzima foi desativada ap��s 20 minutos na presen��a de EDTA. Desativa����o m��xima para a menor concentra����o de EDTA (10-3 mol.L-1) ocorreu na presen��a do tamp��o Tris-HCl. A enzima recuperou 50% de sua atividade inicial ap��s 10 minutos na presen��a de Mg2+ em concentra����es superiores a 0,1mmol.L-1. Concentra����es de 10-4 e 10-3mol.L-1 de Mn2+ e Co2+ foram suficientes para reativar a enzima em 300% comparado ao controle de ��ons Mn2+ e aproximadamente 100% para ��ons Co2+. A enzima perdeu gradualmente a sua atividade quando a concentra����o foi de 10-2 mol.L-1. Ni2+ e Zn2+ foram incapazes de restabelecer a atividade catal��tica. Km app e Vmax app foram 1,95 �� 0,05 mmol.L-1 e 5,40 �� 0,86 x 10-2 mmol.min-1.mg-1. A temperatura e pH ��timos foram 34��C e 7,5. A meia vida da holoenzima foi de 17,5 min a 30��C e para a apoenzima foi de 11,0 min a 30��C. Quanto �� varia����o de pH, a apoenzima provou ser mais sens��vel que a holoenzima. Palavras-chave: ��-galactosidase. ��ons met��licos divalentes. Atividade enzim��tica. Estabilidade.

A curved RNA helix incorporating an internal loop with G��A and A��A non-Watson���Crick���base���pairing

The crystal structure of the RNA dodecamer 5���-GGCC(GAAA)GGCC-3��� has been determined from x-ray diffraction data to 2.3-��� resolution. In the crystal, these oligomers form double helices around twofold symmetry axes. Four consecutive non-Watson���Crick base pairs make up an internal loop in the middle of the duplex, including sheared G��A pairs and novel asymmetric A��A pairs. This internal loop sequence produces a significant curvature and narrowing of the double helix. The helix is curved by 34�� from end to end and the diameter is narrowed by 24% in the internal loop. A Mn2+ ion is bound directly to the N7 of the first guanine in the Watson���Crick region following the internal loop and the phosphate of the preceding residue. This Mn2+ location corresponds to a metal binding site observed in the hammerhead catalytic RNA.

The extended environment of mononuclear metal centers in protein���structures

The objectives of this and the following paper are to identify commonalities and disparities of the extended environment of mononuclear metal sites centering on Cu, Fe, Mn, and Zn. The extended environment of a metal site within a protein embodies at least three layers: the metal core, the ligand group, and the second shell, which is defined here to consist of all residues distant less than 3.5 ��� from some ligand of the metal core. The ligands and second-shell residues can be characterized in terms of polarity, hydrophobicity, secondary structures, solvent accessibility, hydrogen-bonding interactions, and membership in statistically significant residue clusters of different kinds. Findings include the following: (i) Both histidine ligands of type I copper ions exclusively attach the N��1 nitrogen of the histidine imidazole ring to the metal, whereas histidine ligands for all mononuclear iron ions and nearly all type II copper ions are ligated via the N��2 nitrogen. By contrast, multinuclear copper centers are coordinated predominantly by histidine N��2, whereas diiron histidine contacts are predominantly N��1. Explanations in terms of steric differences between N��1 and N��2 are considered. (ii) Except for blue copper (type I), the second-shell composition favors polar residues. (iii) For blue copper, the second shell generally contains multiple methionine residues, which are elements of a statistically significant histidine���cysteine���methionine cluster. Almost half of the second shell of blue copper consists of solvent-accessible residues, putatively facilitating electron transfer. (iv) Mononuclear copper atoms are never found with acidic carboxylate ligands, whereas single Mn2+ ion ligands are predominantly acidic and the second shell tends to be mostly buried. (v) The extended environment of mononuclear Fe sites often is associated with histidine���tyrosine or histidine���acidic clusters.

The medial-Golgi Ion Pump Pmr1 Supplies the Yeast Secretory Pathway with Ca2+ and Mn2+ Required for Glycosylation, Sorting, and Endoplasmic Reticulum-Associated Protein Degradation

The yeast Ca2+ adenosine triphosphatase Pmr1, located in medial-Golgi, has been implicated in intracellular transport of Ca2+ and Mn2+ ions. We show here that addition of Mn2+ greatly alleviates defects of pmr1 mutants in N-linked and O-linked protein glycosylation. In contrast, accurate sorting of carboxypeptidase Y (CpY) to the vacuole requires a sufficient supply of intralumenal Ca2+. Most remarkably, pmr1 mutants are also unable to degrade CpY*, a misfolded soluble endoplasmic reticulum protein, and display phenotypes similar to mutants defective in the stress response to malfolded endoplasmic reticulum proteins. Growth inhibition of pmr1 mutants on Ca2+-deficient media is overcome by expression of other Ca2+ pumps, including a SERCA-type Ca2+ adenosine triphosphatase from rabbit, or by Vps10, a sorting receptor guiding non-native luminal proteins to the vacuole. Our analysis corroborates the dual function of Pmr1 in Ca2+ and Mn2+ transport and establishes a novel role of this secretory pathway pump in endoplasmic reticulum-associated processes.

Crystal structures of a family of layered coordination polymers containing divalent metal ions (Mn2+, Co2+, Ni2+ and Zn2+) and the 3-amino 4-methyl benzoate ion

Peer reviewed

Crystal structures of a family of layered coordination polymers containing divalent metal ions (Mn2+, Co2+, Ni2+ and Zn2+) and the 3-amino 4-methyl benzoate ion

Peer reviewed

Electroactive ion exchange membranes based on conducting polymers

Ion exchange membranes are indispensable for the separation of ionic species. They can discriminate between anions and cations depending on the type of fixed ionic group present in the membrane. These conventional ion exchange membranes (CIX) have exceptional ionic conductivity, which is advantageous in various electromembrane separation processes such as electrodialysis, electrodeionisation and electrochemical ion exchange. The main disadvantage of CIX membranes is their high electrical resistance owing to the fact that the membranes are electronically non conductive. An alternative can be electroactive ion exchange membranes, which are ionically and electronically conducting. Polypyrrole (PPy) is a type of electroactive ion exchange material as well as a commonly known conducting polymer. When PPy membranes are repeatedly reduced and oxidised, ions are pumped through the membrane. The main aim of this thesis was to develop electroactive cation transport membranes based on PPy for the selective transport of divalent cations. Membranes developed composed of PPy films deposited on commercially available support materials. To carry out this study, cation exchange membranes based on PPy doped with immobile anions were prepared. Two types of dopant anions known to interact with divalent metal ions were considered, namely 4-sulphonic calix[6]arene (C6S) and carboxylated multiwalled carbon nanotubes (CNT). The transport of ions across membranes containing PPy doped with polystyrene sulphonate (PSS) and PPy doped with para-toluene sulphonate (pTS) was also studied in order to understand the nature of ion transport and permeability across PPy(CNT) and PPy(C6S) membranes. In the course of these studies, membrane characterisation was performed using electrochemical quartz crystal microbalance (EQCM) and scanning electron microscopy (SEM). Permeability of the membranes towards divalent cations was explored using a two compartment transport cell. EQCM results demonstrated that the ion exchange behaviour of polypyrrole is dependent on a number of factors including the type of dopant anion present, the type of ions present in the surrounding medium, the scan rate used during the experiment and the previous history of the polymer film. The morphology of PPy films was found to change when the dopant anion was varied and even when the thickness of the film was altered in some cases. In nearly all cases the permeability of the membranes towards metal ions followed the order K+ > Ca2+ > Mn2+. The one exception was PPy(C6S), for which the permeability followed the order Ca2+ ��� K+ > Mn2+ > Co2+ > Cr3+. The above permeability sequences show a strong dependence on the size of the metal ions with metal ions having the smallest hydrated radii exhibiting the highest flux. Another factor that affected the permeability towards metal ions was the thickness of the PPy films. Films with the least thickness showed higher metal ion fluxes. Electrochemical control over ion transport across PPy(CNT) membrane was obtained when films composed of the latter were deposited on track-etched Nucleopore�� membranes as support material. In contrast, the flux of ions across the same film was concentration gradient dependent when the polymer was deposited on polyvinylidene difluoride membranes as support material. However, electrochemical control over metal ion transport was achieved with a bilayer type of PPy film consisting of PPy(pTS)/PPy(CNT), irrespective of the type of support material. In the course of studying macroscopic charge balance during transport experiments performed using a two compartment transport cell, it was observed that PPy films were non-permselective. A clear correlation between the change in pH in the receiving solution and the ions transported across the membrane was observed. A decrease in solution pH was detected when the polymer membrane acted primarily as an anion exchanger, while an increase in pH occurred when it functioned as a cation exchanger. When there was an approximately equal flux of anions and cations across the polymer membrane, the pH in the receiving solution was in the range 6 - 8. These observations suggest that macroscopic charge balance during the transport of cations and anions across polypyrrole membranes was maintained by introduction of anions (OH-) and cations (H+) produced via electrolysis of water.

A Chloride Ion-Selective Potentiometric Sensor Based on a Polymeric Schiff Base Complex

This paper describes the fabrication of an ion-selective electrode in which a polymeric Schiff base complex of cobalt(II) is used as the ionophore.The main advantage of the electrode is that it is mechanically stable upto 3 months..The electrode shows a linear response in the range of 2.5 �� 10-5-0.5 �� 10-1 mol dm-3. The response time of the electrode is 30 s.The pH range at which the electrode works is 3.8 to 6.8. The electrode was found to be selective towards chloride ion in the presence of ions like Na+, Ca2+, Mn2+, ,Fe3+, Co2+, Ni2+, Cu2+, Zn2+, CH3COO-, NO3-, SO42- ,Br- and NO2-.

Structural, electrical and electrochemical characterization of high frequency magnetron sputtered spinel oxide cathode films for lithium ion battery applications

The main challenges in the deposition of cathode materials in thin film form are the reproduction of stoichiometry close to the bulk material and attaining higher rates of deposition and excellent crystallinity at comparatively lower annealing temperatures. There are several methods available to develop stoichiometric thin film cathode materials including pulsed laser deposition; plasma enhanced chemical vapor deposition, electron beam evaporation, electrostatic spray deposition and RF magnetron sputtering. Among them the most versatile method is the sputtering technique, owing to its suitability for micro-fabricating the thin film batteries directly on chips in any shape or size, and on flexible substrates, with good capacity and cycle life. The main drawback of the conventional sputtering technique using RF frequency of 13.56MHz is its lower rate of deposition, compared to other deposition techniques A typical cathode layer for a thin film battery requires a thickness around one micron. To deposit such thick layers using convention RF sputtering, longer time of deposition is required, since the deposition rate is very low, which is typically 10-20 ��/min. This makes the conventional RF sputtering technique a less viable option for mass production in an economical way. There exists a host of theoretical and experimental evidences and results that higher excitation frequency can be efficiently used to deposit good quality films at higher deposition rates with glow discharge plasma. The effect of frequencies higher than the conventional one (13.56MHz) on the RF magnetron sputtering process has not been subjected to detailed investigations. Attempts have been made in the present work, to sputter deposit spinel oxide cathode films, using high frequency RF excitation source. Most importantly, the major challenge faced by the thin film battery based on the LiMn2O4 cathode material is the poor capacity retention during charge discharge cycling. The major causes for the capacity fading reported in LiMn2O4cathode materials are due to, Jahn-Teller distortion, Mn2+ dissolution into the electrolyte and oxygen loss in cathode material during cycling. The work discussed in this thesis is an attempt on overcoming the above said challenges and developing a high capacity thin film cathode material.

Magnetic resonance study of the crystallization behavior of InF3-based glasses doped with Cu2+, Mn2+ and Gd3+

The crystallization of fluoroindate glasses doped with Gd3+, Mn2+ and Cu2+ heat treated at different temperatures, ranging from the glass transition temperature (Tg) to the crystallization temperature (Tc), are investigated by electron paramagnetic resonance (EPR) and 19F nuclear magnetic resonance (NMR). The EPR spectra indicate that the Cu2+ ions in the glass are located in axially distorted octahedral sites. In the crystallized glass, the g-values agreed with those reported for Ba2ZnF6, which correspond to Cu2+ in a tetragonal compressed F- octahedron and to Cu2+ on interstitial sites with a square-planar F- co-ordination. The EPR spectra of the Mn2+ doped glasses exhibit a sextet structure due to the Mn2+ hyperfine interaction. These spectra suggest a highly ordered environment for the Mn2+ ions (close to octahedral symmetry) in the glass. The EPR spectra of the recrystallized sample exhibit resonances at the same position, suggesting that the Mn2+ ions are located in sites of highly symmetric crystalline field. The increase of the line intensity of the sextet and the decrease of the background line in the thermal treated samples suggest that the Mn2+ ions move to the highly ordered sites which contribute to the sextet structure. The EPR spectra of the Gd3+ doped glasses exhibit the typical U-spectrum of a s-state ion in a low symmetry site in disordered systems. The EPR of the crystallized glasses, in contrast, have shown a strong resonance in g ��� 2.0, suggesting Gd3+ ions in environment close to cubic symmetry. The 19F NMR spin-lattice relaxation rates were also strongly influenced by the crystallization process that takes over in samples annealed above Tc. For the glass samples (doped or undoped) the 19F magnetization recoveries were found to be adjusted by an exponential function and the spin-lattice relaxation was characterized by a single relaxation time. In contrast, for the samples treated above Tc, the 19F magnetization-recovery becomes non-exponential. A remarkable feature of our results is that the changes in the Cu2+, Mn2+, Gd3+ EPR spectra and NMR relaxation, are always observed for the samples annealed above Tc. �� 2006 Elsevier B.V. All rights reserved.

The migration of Mn2+ ions in Cd1-xMnxS nanocrystals: Thermal annealing control

This work reports evidence of the induced migration of Mn2+ ions in Cd(1-x)MnxS nanocrystals (NCs) by selecting a specific thermal treatment for each sample. The growth and characterization of these magnetic dots were investigated by atomic force microscopy (AFM), optical absorption (OA), and electronic paramagnetic resonance (EPR) techniques. The comparison of experimental and simulated EPR spectra confirms the incorporation of Mn2+ ions both in the core and at the dot surface regions. The thermal treatment of a magnetic sample, via selected annealing temperature and/or time, affects the fine and hyperfine interaction constants which modify the shape and the intensity of the EPR transition spectrum. The identification of these changes has allowed tracing the magnetic ion migration from core to surface regions of a dot as well as inferring the local density of the magnetic impurity ions. (C) 2011 Elsevier Ltd. All rights reserved.

Functional properties of multiple isoforms of human divalent metal-ion transporter 1 (DMT1)

DMT1 (divalent metal-ion transporter 1) is a widely expressed metal-ion transporter that is vital for intestinal iron absorption and iron utilization by most cell types throughout the body, including erythroid precursors. Mutations in DMT1 cause severe microcytic anaemia in animal models. Four DMT1 isoforms that differ in their N- and C-termini arise from mRNA transcripts that vary both at their 5'-ends (starting in exon 1A or exon 1B) and at their 3'-ends giving rise to mRNAs containing (+) or lacking (-) the 3'-IRE (iron-responsive element) and resulting in altered C-terminal coding sequences. To determine whether these variations result in functional differences between isoforms, we explored the functional properties of each isoform using the voltage clamp and radiotracer assays in cRNA-injected Xenopus oocytes. 1A/IRE+-DMT1 mediated Fe2+-evoked currents that were saturable (K(0.5)(Fe) approximately 1-2 microM), temperature-dependent (Q10 approximately 2), H+-dependent (K(0.5)(H) approximately 1 muM) and voltage-dependent. 1A/IRE+-DMT1 exhibited the provisional substrate profile (ranked on currents) Cd2+, Co2+, Fe2+, Mn2+>Ni2+, V3+>>Pb2+. Zn2+ also evoked large currents; however, the zinc-evoked current was accounted for by H+ and Cl- conductances and was not associated with significant Zn2+ transport. 1B/IRE+-DMT1 exhibited the same substrate profile, Fe2+ affinity and dependence on the H+ electrochemical gradient. Each isoform mediated 55Fe2+ uptake and Fe2+-evoked currents at low extracellular pH. Whereas iron transport activity varied markedly between the four isoforms, the activity for each correlated with the density of anti-DMT1 immunostaining in the plasma membrane, and the turnover rate of the Fe2+ transport cycle did not differ between isoforms. Therefore all four isoforms of human DMT1 function as metal-ion transporters of equivalent efficiency. Our results reveal that the N- and C-terminal sequence variations among the DMT1 isoforms do not alter DMT1 functional properties. We therefore propose that these variations serve as tissue-specific signals or cues to direct DMT1 to the appropriate subcellular compartments (e.g. in erythroid cells) or the plasma membrane (e.g. in intestine).

Explanation by the double-metal-ion mechanism of catalysis for the differential metal ion effects on the cleavage rates of 5���-oxy and 5���-thio substrates by a hammerhead���ribozyme

In a previous examination using natural all-RNA substrates that contained either a 5���-oxy or 5���-thio leaving group at the cleavage site, we demonstrated that (i) the attack by the 2���-oxygen at C17 on the phosphorus atom is the rate-limiting step only for the substrate that contains a 5���-thio group (R11S) and (ii) the departure of the 5��� leaving group is the rate-limiting step for the natural all-RNA substrate (R11O) in both nonenzymatic and hammerhead ribozyme-catalyzed reactions; the energy diagrams for these reactions were provided in our previous publication. In this report we found that the rate of cleavage of R11O by a hammerhead ribozyme was enhanced 14-fold when Mg2+ ions were replaced by Mn2+ ions, whereas the rate of cleavage of R11S was enhanced only 2.2-fold when Mg2+ ions were replaced by Mn2+ ions. This result appears to be exactly the opposite of that predicted from the direct coordination of the metal ion with the leaving 5���-oxygen, because a switch in metal ion specificity was not observed with the 5���-thio substrate. However, our quantitative analyses based on the previously provided energy diagram indicate that this result is in accord with the double-metal-ion mechanism of catalysis.

Optimization of aqueous Zn-ion batteries

MnHCF was synthesized by simple co-precipitation method. In this work we investigate the electrochemical behavior of manganese hexacyanoferrate in zinc sulfate (ZnSO4), ZnSO4+MnSO4 and zinc triflate (Zn(OTF)2) aqueous electrolytes. Electrochemical tests were performed by both El-cell which is designed for reflection investigation and coin cell. In cyclic voltammetry curves, we observed redox peaks of both Fe3+/2+ and Mn3+/2+ pairs. The results based on current shows that the capacity of battery is controlled by diffusion process in aqueous electrolyte system. MnHCF undergoes severe dissolution and zinc displacement during cycling. Compared to ZnSO4, anions of Zn (OTF)2 electrolyte are strongly adsorbed on the electrolyte surface, in turn hindering the water oxidation reaction and reducing the decomposition of MnHCF. The MnHCF/Zn battery using 3M Zn (OTF)2 delivers a specific capacity of 41 mAhg-1 at 50 mAg-1 while by using 3M ZnSO4+1M MnSO4 the specific capacity reaches to 400 mAhg-1 for the pure sample and around 250 mAhg-1 for the MnHCF+A. Our results suggest that the anions in the aqueous electrolyte are of great importance to optimize the electrochemical performance of metal hexacyanoferrates. The pre-addition of MnSO4 into ZnSO4 solution is capable of easing the Mn2+ dissolution from the cathode.