Sequestration, metals

Alternatively, hydrophilic multi-hydroxyl poly(GMA-OH)-grafted MWCNTs could be converted into multicarboxyl polymer-functionalized CNTs by reaction with succinic anhydride and then used as templates to efficiently sequestrate metal ions such as Ag", Co ", Ni , Au , La and (Scheme 5.3), generating MWCNT-polymer/metal hybrid nanocomposites, nanowires or necklace-like nanostructures, depending on the grafted polymer content and the nature of the captured metals. The combination of SEM, TEM and energy dispersive spectroscopy (EDS) characterizations demonstrated the structure and elements of the hybrid nano-objects. 

Sodium diacetate Sodium gluconate sequestrant, metal cleaners Pentasodium aminotrimethylene phosphonate sequestrant, metal cleaning Ethylenediaminetetra (methylene phosphonic acid) Pentasodium diethylene triamine pentamethylene phosphonate 2-Phosphonobutane tricarboxylic acid-1,2,4 Sodium diethylenetriamine penta (methylene phosphonate) Sodium gluconate Tetrasodium etidronate sequestrant, metal finishing Pentasodium pentetate sequestrant, metal plating Lactic acid Sodium gluconate Trisodium citrate... 

Numerous other crown ether derivatives are described. They differ from one another in the size of the macrocycle and the number of oxygen atoms. These derivatives sequestrate metallic ions more or less selectively in proportion to the size of the cavity existing inside the cycle. Electrostatic interactions between the sequestrated metallic ion and the oxygen atoms of the cycle also play a part in the formation of this kind of complexes. This is why crown ether ligands, although recently discovered, can be considered classical ligands. 

Complex Ion Formation. Phosphates form water-soluble complex ions with metallic cations, a phenomenon commonly called sequestration. In contrast to many complexing agents, polyphosphates are nonspecific and form soluble, charged complexes with virtually all metallic cations. Alkali metals are weakly complexed, but alkaline-earth and transition metals form more strongly associated complexes (eg, eq. 16). Quaternary ammonium ions are complexed Htde if at all because of their low charge density. The amount of metal ion that can be sequestered by polyphosphates generally increases... 

Organophosphoms compounds, primarily phosphonic acids, are used as sequestrants, scale inhibitors, deflocculants, or ion-control agents in oil wells, cooling-tower waters, and boiler-feed waters. Organophosphates are also used as plasticizers and flame retardants in plastics and elastomers, which accounted for 22% of PCl consumed. Phosphites, in conjunction with Hquid mixed metals, such as calcium—zinc and barium—cadmium heat stabilizers, function as antioxidants and stabilizer adjutants. In 1992, such phosphoms-based chemicals amounted to slightly more than 6% of all such plastic additives and represented 8500 t of phosphoms. Because PVC production is expected to increase, the use of phosphoms additive should increase 3% aimually through 1999. 

The product is equal to the equilibrium constant X for the reaction shown in equation 30. It is generally considered that a salt is soluble if > 1. Thus sequestration or solubilization of moderate amounts of metal ion usually becomes practical as X. approaches or exceeds one. For smaller values of X the cost of the requited amount of chelating agent may be prohibitive. However, the dilution effect may allow economical sequestration, or solubilization of small amounts of deposits, at X values considerably less than one. In practical appHcations, calculations based on concentration equihbrium constants can be used as a guide for experimental studies that are usually necessary to determine the actual behavior of particular systems. 

Concentration Control. Sequestration, solubilization, and buffering depend on the concentration control feature of chelation. Traces of metal ions are almost universally present in Hquid systems, often arising from the materials of the handling equipment if not introduced by the process materials. Despite very low concentrations, some trace metals produce undesirable effects such as coloration or instabiHty. 

Many reactions catalyzed by the addition of simple metal ions involve chelation of the metal. The familiar autocatalysis of the oxidation of oxalate by permanganate results from the chelation of the oxalate and Mn (III) from the permanganate. Oxidation of ascorbic acid [50-81-7] C HgO, is catalyzed by copper (12). The stabilization of preparations containing ascorbic acid by the addition of a chelant appears to be negative catalysis of the oxidation but results from the sequestration of the copper. Many such inhibitions are the result of sequestration. Catalysis by chelation of metal ions with a reactant is usually accomphshed by polarization of the molecule, faciUtation of electron transfer by the metal, or orientation of reactants. 

Electrodeposition of Metals. Citric acid and its salts are used as sequestrants to control deposition rates in both electroplating and electroless plating of metals (153—171). The addition of citric acid to an electroless nickel plating bath results in a smooth, hard, nonporous metal finish. 

Metal surface cleaning, by virtue of (limited) sequestration, dispersing, surface-acting, and detergent properties. 

Ligands bite at one or more points. Chelants bite at two or more points, so all ligands are not necessarily chelants. Chelants forming water-soluble complexes with metal ions are called sequestrants (but not all sequestrants are chelants). The most commonly employed BW chelant, ethylenediaminetetraacetic acid (EDTA) produces coordination complexes with four points of attachment and is termed a tetraden-tate ligand. 

Chelants or sequestrants to provide a metal complexing and solubilizing action. 

The yielded product can be converted to a surface-active compound if at least one ester group has been transformed to the free acid or an alkali metal salt thereof [160]. There are also many compounds from phosphinic acid derivatives claimed to be useful as sequestrants and builders to improve detergency, especially bisphosphonylmethylphosphinic acids and polyphosphinic acids [structures (9) and (10)], respectively ... 

Metallothioneins are a group of small proteins (about 6.5 kDa), found in the cytosol of cells, particularly of liver, kidney, and intestine. They have a high content of cysteine and can bind copper, zinc, cadmium, and mercury. The SH groups of cysteine are involved in binding the metals. Acute intake (eg, by injection) of copper and of certain other metals increases the amount (induction) of these proteins in tissues, as does administration of certain hormones or cytokines. These proteins may function to store the above metals in a nontoxic form and are involved in their overall metaboHsm in the body. Sequestration of copper also diminishes the amount of this metal available to generate free radicals. 

Pasch, J.H. and Von Elbe, J.H., Betanine stability in bnffered solntions containing organic acids, metal cations, antioxidants, or sequestrants, J. Food Sci., 44, 72, 81, 1979. 

There are a number of different mechanisms by which microorganisms resist metal toxicity (Table 11.1). Five mechanisms that microbes use to mediate metal toxicity have been proposed and they include (1) formation of a permeability barrier,21-24 (2) active transport,25-29 (3) sequestration,30-32 (4) enzymatic detoxification,33 34 and (5) reduction in sensitivity.35,36 Microbes may use one or more of these mechanisms to exclude nonessential metals and regulate internal concentrations of essential metals. 

Microbes that lack a specific active transport system for removing toxic metals may be able to sequester heavy metals either inside or outside of the cell. Intracellular sequestration occurs when cytoplasmic metal-binding molecules are produced in response to metal stress, preventing the metals from interacting with vital cell structures. The two most common molecules used for intracellular... 

The disadvantage of the polyphosphates is that at the temperatures (100 °C or higher) used in many textile processes they can be hydrolysed into simpler phosphates that cannot retain the metal atom in the sequestered form. For example, dicalcium disodium hexametaphosphate hydrolyses on prolonged boiling to yield the insoluble calcium orthophosphate. This is one of the main reasons why polyphosphate sequestrants are used much less extensively than the more versatile and stable aminopolycarboxylates. 

Polycarboxylates may also be added to help prevent incrustations. It should be borne in mind, however, that magnesium is an essential component in most cases of stabilisation in peroxide systems, so any mixture of sequestrants should have minimum binding effect on this metal ion. 

Some dyes contain a coordinated transition metal as an essential part of their chromogenic structure and this must be left undisturbed by any sequestrant used to complex extraneous metal ions in the system. Hence a balance of properties is needed, phosphates and hydroxycarboxylates being useful. It is claimed that polycarboxylates can be molecularly engineered to give the required balance of properties. 

The sodium and calcium salts of EDTA (ethylenediaminetetraacetic acid, Fig. 9.3.1.) are common sequestrants in food products. A three-dimensional representation of EDTA is shown in color Fig. 9.3.2. The EDTA ion is an especially effective sequestrant, forming up to six coordinate covalent bonds with a metal ion. These bonds are so named because a lone pair of electrons on a single atom serves as the source of the shared electrons in the bond between the metal ion and EDTA. The two nitrogen atoms in the amino groups and the oxygen... 

A common form of EDTA used as a preservative is calcium disodium EDTA (CaNa2EDTA). What metals will this form of the sequestrant scavenge effectively The dissolution of the solid will yield calcium ions, sodium ions, and the EDTA anion. Any metal more effectively complexed than calcium will be readily scavenged, including all ions listed in Table 9.1 except silver (Ag+) and magnesium (Mg2+). (In the absence of the calcium counterion, as in the case of the acid form of EDTA, chelation of calcium in the body can occur. In fact, EDTA administered orally is an FDA-approved treatment for calcium deposits in the bloodstream that lead to cardiovascular disease.) Citric acid (Fig. 9.3.3) is another sequestrant of metal ions in foodstuffs. 

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