Metal ion complexation by soft nanoparticles: the effect of Ca2+ on electrostatic and chemical contributions to the Eigen-type reaction rate

2015 ◽  
Vol 12 (2) ◽  
pp. 130 ◽  
Author(s):  
Raewyn M. Town
Keyword(s):  
Humic Acid ◽  
Trace Metal ◽  
Metal Ions ◽  
Electrostatic Field ◽  
Metal Binding ◽  
Metal Ion ◽  
Bulk Solution ◽  
Trace Metal Ions ◽  
Charged Nanoparticles ◽  
Soft Nanoparticles

Environmental context The speciation of trace metals in the environment is often dominated by complexation with natural organic matter such as humic acid. Humic acid is a negatively charged soft nanoparticle and its electrostatic properties play an important role in its reactivity with metal ions. The presence of major cations, such as Ca2+, can decrease the effective negative charge in the humic acid particle body and thus modify the chemodynamics of its interactions with trace metal ions. Abstract The effect of Ca2+ on the chemodynamics of PbII complexation by humic acid (HA) is interpreted in terms of theory for permeable charged nanoparticles. The effect of the electrostatic field of a negatively charged nanoparticle on its rate of association with metal cations is governed by the interplay of (i) conductive enhancement of the diffusion of cations from the medium to the particle and (ii) ionic Boltzmann equilibration with the bulk solution leading to accumulation of cations in the particle body. Calcium ions accumulate electrostatically within the HA body and thus lower the magnitude of the negative potential in the particle. For the case where trace metal complexation takes place in a medium in which the particulate electrostatic field is set by pre-equilibration in the electrolyte, the lability of Pb-HA complexes is found to be significantly increased in Ca2+-containing electrolyte, consistent with the predicted change in particle potential. Furthermore, the rate-limiting step changes from diffusive supply to the particle body in a 1–1 electrolyte, to inner-sphere complexation in a 2–1 electrolyte. The results provide insights into the electrostatic and covalent contributions to the thermodynamics and kinetics of trace metal binding by soft nanoparticles.

Effect of humic acid on sorption of trace metal ions by sodium aluminosilicate

Desalination ◽  
2011 ◽  
Vol 268 (1-3) ◽  
pp. 189-194 ◽  
Author(s):  
B.K. Singh ◽  
Jyoti Bhadauria ◽  
Radha Tomar ◽  
B.S. Tomar
Keyword(s):  
Humic Acid ◽  
Trace Metal ◽  
Metal Ions ◽  
Trace Metal Ions ◽  
Sodium Aluminosilicate

The transfer and persistence of metals in latent fingermarks

2021 ◽  
Author(s):  
Rhiannon Boseley ◽  
Daryl Howard ◽  
Mark Hackett ◽  
Simon Lewis
Keyword(s):  
Trace Metal ◽  
Metal Ions ◽  
Forensic Science ◽  
Spatial Resolution ◽  
Metal Ion ◽  
Activity Level ◽  
X Ray ◽  
Trace Metal Ions ◽  
Gun Barrel ◽  
Trace Metal Detection

In forensic science, knowledge and understanding of material transfer and persistence is inherent to the interpretation of trace evidence and can provide vital information on the activity level surrounding a crime. Detecting metal ions in fingermark residue has long been of interest in the field of forensic science, due to the possibility of linking trace metal ion profiles to prior activity with specific metal objects (e.g. gun or explosive handling). Unfortunately, the imaging capability to visualise trace metal ions at sufficient spatial resolution to determine their distribution within a fingermark (micron level) was not previously available. Here, we demonstrate for the first time transfer and persistence of metals in fingermarks, at micron spatial resolution, using synchrotron sourced x-ray fluorescence microscopy. Fingermarks were taken before and after brief handling of a gun barrel, ammunition cartridge case and party sparkler to demonstrate the transfer of metals. The results reveal increased metal content after contact with these objects, and critically, a differential pattern of metal ion increase was observed after handling different objects. Persistence studies indicate that these metals are removed as easily as they are transferred, with a brief period of hand washing appearing to successfully remove metallic residue from subsequent fingermarks. Preliminary work using x-ray absorption near edge structure spectroscopic mapping highlighted the potential use of this technique to differentiate between different chemical forms of metals and metal ions in latent fingermarks. It is anticipated that these findings can now be used to assist future work for the advancement of trace metal detection tests and fingermark development procedures

scholarly journals TRPM7 Provides an Ion Channel Mechanism for Cellular Entry of Trace Metal Ions

2002 ◽  
Vol 121 (1) ◽  
pp. 49-60 ◽  
Author(s):  
Mahealani K. Monteilh-Zoller ◽  
Meredith C. Hermosura ◽  
Monica J.S. Nadler ◽  
Andrew M. Scharenberg ◽  
Reinhold Penner ◽  
...  
Keyword(s):  
Trace Metal ◽  
Ion Channel ◽  
Metal Ions ◽  
Metal Ion ◽  
Divalent Cations ◽  
Divalent Metal Ions ◽  
Hek 293 ◽  
Trace Metal Ions ◽  
293 Cells ◽  
Better Than

Trace metal ions such as Zn2+, Fe2+, Cu2+, Mn2+, and Co2+ are required cofactors for many essential cellular enzymes, yet little is known about the mechanisms through which they enter into cells. We have shown previously that the widely expressed ion channel TRPM7 (LTRPC7, ChaK1, TRP-PLIK) functions as a Ca2+- and Mg2+-permeable cation channel, whose activity is regulated by intracellular Mg2+ and Mg2+·ATP and have designated native TRPM7-mediated currents as magnesium-nucleotide–regulated metal ion currents (MagNuM). Here we report that heterologously overexpressed TRPM7 in HEK-293 cells conducts a range of essential and toxic divalent metal ions with strong preference for Zn2+ and Ni2+, which both permeate TRPM7 up to four times better than Ca2+. Similarly, native MagNuM currents are also able to support Zn2+ entry. Furthermore, TRPM7 allows other essential metals such as Mn2+ and Co2+ to permeate, and permits significant entry of nonphysiologic or toxic metals such as Cd2+, Ba2+, and Sr2+. Equimolar replacement studies substituting 10 mM Ca2+ with the respective divalent ions reveal a unique permeation profile for TRPM7 with a permeability sequence of Zn2+ ≈ Ni2+ >> Ba2+ > Co2+ > Mg2+ ≥ Mn2+ ≥ Sr2+ ≥ Cd2+ ≥ Ca2+, while trivalent ions such as La3+ and Gd3+ are not measurably permeable. With the exception of Mg2+, which exerts strong negative feedback from the intracellular side of the pore, this sequence is faithfully maintained when isotonic solutions of these divalent cations are used. Fura-2 quenching experiments with Mn2+, Co2+, or Ni2+ suggest that these can be transported by TRPM7 in the presence of physiological levels of Ca2+ and Mg2+, suggesting that TRPM7 represents a novel ion-channel mechanism for cellular metal ion entry into vertebrate cells.

scholarly journals Acylated Anthocyanins from Red Cabbage and Purple Sweet Potato Can Bind Metal Ions and Produce Stable Blue Colors

2021 ◽  
Vol 22 (9) ◽  
pp. 4551
Author(s):  
Julie-Anne Fenger ◽  
Gregory T. Sigurdson ◽  
Rebecca J. Robbins ◽  
Thomas M. Collins ◽  
M. Mónica Giusti ◽  
...  
Keyword(s):  
Metal Ions ◽  
Sweet Potato ◽  
Metal Binding ◽  
Metal Ion ◽  
High Resolution Mass Spectrometry ◽  
Large Set ◽  
Water Addition ◽  
Red Cabbage ◽  
Aluminum Ions ◽  
Purple Sweet Potato

Red cabbage (RC) and purple sweet potato (PSP) are naturally rich in acylated cyanidin glycosides that can bind metal ions and develop intramolecular π-stacking interactions between the cyanidin chromophore and the phenolic acyl residues. In this work, a large set of RC and PSP anthocyanins was investigated for its coloring properties in the presence of iron and aluminum ions. Although relatively modest, the structural differences between RC and PSP anthocyanins, i.e., the acylation site at the external glucose of the sophorosyl moiety (C2-OH for RC vs. C6-OH for PSP) and the presence of coordinating acyl groups (caffeoyl) in PSP anthocyanins only, made a large difference in the color expressed by their metal complexes. For instance, the Al3+-induced bathochromic shifts for RC anthocyanins reached ca. 50 nm at pH 6 and pH 7, vs. at best ca. 20 nm for PSP anthocyanins. With Fe2+ (quickly oxidized to Fe3+ in the complexes), the bathochromic shifts for RC anthocyanins were higher, i.e., up to ca. 90 nm at pH 7 and 110 nm at pH 5.7. A kinetic analysis at different metal/ligand molar ratios combined with an investigation by high-resolution mass spectrometry suggested the formation of metal–anthocyanin complexes of 1:1, 1:2, and 1:3 stoichiometries. Contrary to predictions based on steric hindrance, acylation by noncoordinating acyl residues favored metal binding and resulted in complexes having much higher molar absorption coefficients. Moreover, the competition between metal binding and water addition to the free ligands (leading to colorless forms) was less severe, although very dependent on the acylation site(s). Overall, anthocyanins from purple sweet potato, and even more from red cabbage, have a strong potential for development as food colorants expressing red to blue hues depending on pH and metal ion.

ChemInform Abstract: Complexes of Some Trace Metal Ions with 5-Fluorouracil.

ChemInform ◽  
1987 ◽  
Vol 18 (32) ◽  
Author(s):  
U. P. SINGH ◽  
R. GHOSE ◽  
A. K. GHOSE
Keyword(s):  
Trace Metal ◽  
Metal Ions ◽  
Trace Metal Ions

scholarly journals Hypochlorite and superoxide radicals can act synergistically to induce fragmentation of hyaluronan and chondroitin sulphates

2004 ◽  
Vol 381 (1) ◽  
pp. 175-184 ◽  
Author(s):  
Martin D. REES ◽  
Clare L. HAWKINS ◽  
Michael J. DAVIES
Keyword(s):  
Metal Ions ◽  
Metal Ion ◽  
Transition Metal Ions ◽  
Chloride Ions ◽  
Superoxide Radicals ◽  
Thermal Source ◽  
Site Specific ◽  
Trace Metal Ions ◽  
Electron Reduction ◽  
Polymer Fragmentation

Activated phagocytes release the haem enzyme MPO (myeloperoxidase) and also generate superoxide radicals (O2•−), and hence H2O2, via an oxidative burst. Reaction of MPO with H2O2 in the presence of chloride ions generates HOCl (the physiological mixture of hypochlorous acid and its anion present at pH 7.4). Exposure of glycosaminoglycans to a MPO–H2O2–Cl− system or reagent HOCl generates long-lived chloramides [R-NCl-C(O)-R′] derived from the glycosamine N-acetyl functions. Decomposition of these species by transition metal ions gives polymer-derived amidyl (nitrogen-centred) radicals [R-N•-C(O)-R′], polymer-derived carbon-centred radicals and site-specific strand scission. In the present study, we have shown that exposure of glycosaminoglycan chloramides to O2•− also promotes chloramide decomposition and glycosaminoglycan fragmentation. These processes are inhibited by superoxide dismutase, metal ion chelators and the metal ion-binding protein BSA, consistent with chloramide decomposition and polymer fragmentation occurring via O2•−-dependent one-electron reduction, possibly catalysed by trace metal ions. Polymer fragmentation induced by O2•− [generated by the superoxide thermal source 1, di-(4-carboxybenzyl)hyponitrite] was demonstrated to be entirely chloramide dependent as no fragmentation occurred with the native polymers or when the chloramides were quenched by prior treatment with methionine. EPR spin-trapping experiments using 5,5-dimethyl1-pyrroline-N-oxide and 2-methyl-2-nitrosopropane have provided evidence for both O2•− and polymer-derived carbon-centred radicals as intermediates. The results obtained are consistent with a mechanism involving one-electron reduction of the chloramides to yield polymer-derived amidyl radicals, which subsequently undergo intramolecular hydrogen atom abstraction reactions to give carbon-centred radicals. The latter undergo fragmentation reactions in a site-specific manner. This synergistic damage to glycosaminoglycans induced by HOCl and O2•− may be of significance at sites of inflammation where both oxidants are generated concurrently.

Simple semiquantitative determination of trace metal ions by use of reagent gel columns—II

Talanta ◽  
1976 ◽  
Vol 23 (3) ◽  
pp. 244-246 ◽  
Author(s):  
Yong Keun Lee ◽  
Kyu Ja Whang ◽  
Keihei Ueno
Keyword(s):  
Trace Metal ◽  
Metal Ions ◽  
Trace Metal Ions ◽  
Semiquantitative Determination
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