Transition metal ions at the crossroads of mucosal immunity and microbial pathogenesis.

Transition metal ions are essential micronutrients for all living organisms. In mammals, these ions are often protein-bound and sequestered within cells, limiting their availability to microbes. Moreover, in response to infection, mammalian hosts further reduce the availability of metal nutrients by activating epithelial cells and recruiting neutrophils, both of which release metal-binding proteins with antimicrobial function. Microorganisms, in turn, have evolved sophisticated systems to overcome these limitations and acquire the metal ions essential for their growth. Here we review some of the mechanisms employed by the host and by pathogenic microorganisms to compete for transition metal ions, with a discussion of how evading "nutritional immunity" benefits pathogens. Furthermore, we provide new insights on the mechanisms of host-microbe competition for metal ions in the mucosa, particularly in the inflamed gut

Water Soluble Cationic Porphyrin Sensor for Detection of Hg2+, Pb2+, Cd2+, and Cu2+

Here we report the sensing properties of the aqueous solution of mesotetra(N-methyl-4-pyridyl)porphine tetrachloride (1) for simultaneous detection of toxic metal ions by using UV-vis spectroscopy. Cationic porphyrin 1 displayed different electronic absorptions in UV-vis region upon interacting with Hg2+, Pb2+, Cd2+, and Cu2+ ions in neutral water solution at room temperature. Quite interestingly, the porphyrin 1 showed that it can function as a single optical chemical sensor and/ or metal ion receptor capable of detecting two or more toxic metal ions, particularly, Hg2+, Pb2+, and Cd2+ ions coexisting in a water sample. Porphyrin 1 in an aqueous solution provides a unique UV-vis sensing system for the determination of Cd2+ in the presence of larger metal ions such as Hg2+, or Pb2+. Finally, the examination of the sensing properties of 1 demonstrated that it can operate as a Cu2+ ion selective sensor via metal displacement from the 1-Hg2+ , 1-Pb2+ , and 1-Cd2+

Metal enrichment by radiation pressure in active galactic nucleus outflows -- theory and observations

Outflows from active galactic nuclei may be produced by absorption of continuum radiation by UV resonance lines of abundant metal ions, as observed in broad absorption line quasars (BALQs). The radiation pressure exerted on the metal ions is coupled to the rest of the gas through Coulomb collisions of the metal ions. We calculate the photon density and gas density which allow decoupling of the metal ions from the rest of the gas. These conditions may lead to an outflow composed mostly of the metal ions. We derive a method to constrain the metals/H ratio of observed UV outflows, based on the Ly {\alpha} and Si iv {\lambda}{\lambda}1394, 1403 absorption profiles. We apply this method to an SDSS sample of BALQs to derive a handful of candidate outflows with a higher than solar metal/H ratio. This mechanism can produce ultra fast UV outflows, if a shield of the continuum source with a strong absorption edge is present.Comment: 16 pages, 7 figures; accepted for publication in MNRA

A New Strategy to Stabilize Oxytocin in Aqueous Solutions: I. The Effects of Divalent Metal Ions and Citrate Buffer

In the current study, the effect of metal ions in combination with buffers (citrate, acetate, pH 4.5) on the stability of aqueous solutions of oxytocin was investigated. and divalent metal ions (Ca2+, Mg2+, and Zn2+) were tested all as chloride salts. The effect of combinations of buffers and metal ions on the stability of aqueous oxytocin solutions was determined by RP-HPLC and HP-SEC after 4 weeks of storage at either 4°C or 55°C. Addition of sodium or potassium ions to acetate- or citrate-buffered solutions did not increase stability, nor did the addition of divalent metal ions to acetate buffer. However, the stability of aqueous oxytocin in aqueous formulations was improved in the presence of 5 and 10 mM citrate buffer in combination with at least 2 mM CaCl2, MgCl2, or ZnCl2 and depended on the divalent metal ion concentration. Isothermal titration calorimetric measurements were predictive for the stabilization effects observed during the stability study. Formulations in citrate buffer that had an improved stability displayed a strong interaction between oxytocin and Ca2+, Mg2+, or Zn2+, while formulations in acetate buffer did not. In conclusion, our study shows that divalent metal ions in combination with citrate buffer strongly improved the stability of oxytocin in aqueous solutions

A COMPLEX SURFACE FORMATION MODEL ON CHITOSAN ADSORPTION TO METALS

The aim of the first year research is: to predict a complex surface formation between chitosan and metal ions. This prediction is according to the plot adsorptive capacity and the bonding tendency between chitosan and some metals. Chitosan as adsorbent isolated from Green Crab’s shell. Metal ions used in this research are Cr(III), Cu(II), Ni(II), Zn(II), Fe(II) and Pb(II). The subject of this research is green crab’s shell (Scylla serata) and the object is the adsorptive capacity chitosan to some metal ions. Chitosan was prepared in three steps: deproteination, demineralization and deacetylation. This chitosan are impurities by 20 %- 30%kitin. The adsorption experiment was carried out at room temperature for 24 hours. A half gram of chitosan was added into 50 mL of various metals solution at pH system 5. This experiment was performed in two methods. An each ion metal was adsorbed by chitosan and some metal ions i.e: Cr(III), Cu(II), and Ni(II) (1:1:1) were adsorbed simultaneous. Chitosan was characterized by FTIR. Metal ions concentration before and after adsorption was measured by by AAS. Adsorptive capacity is defined as differences of metal ion concentration due to the adsorption per gram chitosan. Then the obtained data was plotted through Langmuir isotherm and Freundlich isotherm equations. The result of this work concludes that adsorptive capacity of chitosan in order for some metals ion are Cr(III) > Fe(II)> pb(II) = Zn(II)> Ni(II) = Cu(II). The interaction chitosan with metal ions is indicated complex surface formation by -NH2 groups or –OH groups. A multilayer are formatted by active site chitosan and metal ion interactions, but the interaction of chitosan to copper(II) is prefer a monolayer formation. Key words: chitosan, adsorption, multilay FMIPA, 2006 (PEND. KIMIA

Schemes Of Solid-phase Spectrophotometric Analysis Of Food Objects

The aim of research is development of approaches to the development of schemes for microelement analysis of food objects. This will make it possible to monitor food quality by simple and affordable methods in factory laboratories.Based on data on the immobilization of dyes on ion exchangers and on the interaction of metal ions or their complexes with immobilized dyes, solid-phase spectrophotometric (SPS) and photometric methods for determining metal ions in food technology, biotechnology and the environment have been developed.Techniques are sensitive. High distribution coefficients (D³104 cm3/g) of metal ions help to reduce the detection limit when using immobilized dye as compared to the reaction in solution. Based on the detection limit values (DLV), the proposed sorption-spectrophotometric methods for determining metal ions are second only to the atomic absorption (AAS) determination of Cd (II) and Hg (II) ions and the polarographic determination of Cd (II) ions. However, the proposed methods for the determination of these metal ions are sufficient for the determination of Cd (II) and Hg (II) ions in food products at the MPC level. In the case of determination of Pb (II), Zn (II), Cu (II), Fe (III) ions, the developed methods have advantages over standard methods for determination of metal ions in food products, since they make it possible to determine these ions at a level ≤0.1…0.5 MPC;Ion exchangers with immobilized dyes and solid-phase spectrophotometric determination methods with their participation are environmentally safe, since they do not require the use of toxic organic reagents; are simple in execution and economically advantageous because of the low cost of used materials and reagents.The correctness of the results of the determination by the developed methods is proved: by comparison with the results of determinations on standard methods at various analysis objects using the method of additives, standard samples. The relative standard deviation of the developed SPS determination procedures does not exceed 0.10, which indicates satisfactory reproducibility of the results. The developed methods exceed the majority of standard and best analogs, known from the literature, for sensitivity and selectivity. The used methods of analysis are characterized by the simplicity of the experiment, ecological safety, do not require special expensive equipment, highly qualified personnel and a stationary laboratory

Divalent Metal Binding Properties of the Methionyl Aminopeptidase from \u3cem\u3eEscherichia coli\u3c/em\u3e

The metal-binding properties of the methionyl aminopeptidase from Escherichia coli (MetAP) were investigated. Measurements of catalytic activity as a function of added Co(II) and Fe(II) revealed that maximal enzymatic activity is observed after the addition of only 1 equiv of divalent metal ion. Based on these studies, metal binding constants for the first metal binding event were found to be 0.3 ± 0.2 μM and 0.2 ± 0.2 μM for Co(II)- and Fe(II)-substituted MetAP, respectively. Binding of excess metal ions (\u3e50 equiv) resulted in the loss of ∼50% of the catalytic activity. Electronic absorption spectral titration of a 1 mM sample of MetAP with Co(II) provided a binding constant of 2.5 ± 0.5 mM for the second metal binding site. Furthermore, the electronic absorption spectra of Co(II)-loaded MetAP indicated that both metal ions reside in a pentacoordinate geometry. Consistent with the absorption data, electron paramagnetic resonance (EPR) spectra of [CoCo(MetAP)] also indicated that the Co(II) geometries are not highly constrained, suggesting that each Co(II) ion in MetAP resides in a pentacoordinate geometry. EPR studies on [CoCo(MetAP)] also revealed that at pH 7.5 there is no significant spin-coupling between the two Co(II) ions, though a small proportion (∼5%) of the sample exhibited detectable spin−spin interactions at pH values \u3e 9.6. EPR studies on [Fe(III)_(MetAP)] and [Fe(III)Fe(III)(MetAP)] also suggested no spin-coupling between the two metal ions. 1H nuclear magnetic resonance (NMR) spectra of [Co(II)_(MetAP)] in both H2O and D2O buffer indicated that the first metal binding site contains the only active-site histidine residue, His171. Mechanistic implications of the observed binding properties of divalent metal ions to the MetAP from E. coli are discussed

Synthesis and inclusion behavior of a heterotritopic receptor based on hexahomotrioxacalix[3]arene

A heterotritopic hexahomotrioxacalix[3]arene receptor with the capability of binding two alkali metals and a transition metal in a cooperative fashion was synthesized. The binding model was investigated by using ¹H NMR titration experiments in CDCl₃–CD₃CN (10:1, v/v), and the results revealed that the transition metal was bound at the upper rim and the alkali metals at the lower and upper rims. Interestingly, the alkali metal ions Li⁺ and Na⁺ bind at the lower and upper rim respectively depending on the dimensions of the alkali metal ions versus the size of the cavities formed by the calix[3]arene derivative. The hexahomotrioxacalix[3]arene receptor acts as a heterotritopic receptor, binding with the transition metal ion Ag⁺ and the alkali metals ions Li⁺ and Na⁺. These findings were not applicable to other different sized alkali metals, such as K⁺ and Cs⁺

Valorization of keratin biofibers for removing heavy metals from aqueous solutions

Four common waste keratin biofibers (human hair, dog hair, chicken feathers, and degreased wool) have been used as biosorbents for the removal of heavy metal ions from aqueous solutions. Different parameters of the biosorption processes were optimized in batch systems. For multiple-metal systems, consisting of a mixture of eight metal ions [Cr(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II)], the total metal biosorption increased in the order: degreased wool¿>¿chicken feathers¿>¿human hair¿>¿dog hair. From the kinetic models tested, the pseudo-second-order model provided better results. Furthermore, biosorption isotherms of Pb(II) with the different keratin biofibers fitted the Langmuir model. Surface morphology of the biosorbents were analyzed before and after the sorption using Fourier transform infrared spectroscopy and scanning electron microscopy. The keratin biofibers tested are potentially good sorbents of metal ions, with degreased wool and chicken feathers being the more efficient onesPostprint (author's final draft