Organic Metal Chelates

The flame ionization detector (FID), which, for fluorinated compounds, has the advantage of a greater linearity range in spite of its lower sensitivity in comparison with the electron capture detector (BCD), has been extensively applied to organic metal chelates in particular. Comparisons of the different detectors were carried out (Table 1.2) For special analyses such as the determination of SO2 by reaction to SO2F2 with the radioactive F-isotope or by utilization of H-labelled 3-diketon-ates, radiometric measurements for detection are employed ... 

An on-line concentration, isolation, and Hquid chromatographic separation method for the analysis of trace organics in natural waters has been described (63). Concentration and isolation are accompHshed with two precolumns connected in series the first acts as a filter for removal of interferences the second actually concentrates target solutes. The technique is appHcable even if no selective sorbent is available for the specific analyte of interest. Detection limits of less than 0.1 ppb were achieved for polar herbicides (qv) in the chlorotriazine and phenylurea classes. A novel method for deterrnination of tetracyclines in animal tissues and fluids was developed with sample extraction and cleanup based on tendency of tetracyclines to chelate with divalent metal ions (64). The metal chelate affinity precolumn was connected on-line to reversed-phase hplc column, and detection limits for several different tetracyclines in a variety of matrices were in the 10—50 ppb range. 

Metal chelation is also a means of insoliihilizing organic molecules. For example. Cl Pigment Green 10 [51931 -46-5] (138) (Cl 12775) is a 2 1 nickel complex of a bidentate o-hydroxyazo ligand. 

Some of these organics have chelated trace metals, such as iron and manganese within their structure, which can cause serious deposition problems in a cooling system. 

The literature of polyimines is extensive [164-173]. A number of researchers have tried to synthesize high molecular weight polymers but failed due to poor solubility in organic solvents. Polyimines are of great interest because of their high thermal stability [174-176], ability to form metal chelates [174-177], and their semiconducting properties [178-181]. Due to insolubility and infusibility, which impeded characterization of the molecular structure, the application of these polymers is very limited and of little commercial importance. 

In the case of inorganic solutes we are concerned largely with samples in aqueous solution so that it is necessary to produce substances, such as neutral metal chelates and ion-association complexes, which are capable of extraction into organic solvents. For organic solutes, however, the extraction system may sometimes involve two immiscible organic solvents rather than the aqueous-organic type of extraction. 

An alternative to the formation of neutral metal chelates for solvent extraction is that in which the species of analytical interest associates with oppositely charged ions to form a neutral extractable species.6 Such complexes may form clusters with increasing concentration which are larger than just simple ion pairs, particularly in organic solvents of low dielectric constant. The following types of ion association complexes may be recognised. 

Metal deactivators—Organic compounds capable of forming coordination complexes with metals are known to be useful in inhibiting metal-activated oxidation. These compounds have multiple coordination sites and are capable of forming cyclic strucmres, which cage the pro-oxidant metal ions. EDTA and its various salts are examples of this type of metal chelating compounds. 

Upon formation of a metal chelate or complex, the next rate-limiting step in delivering iron to the cell is the diffusion of iron complexes through the. soil in response to diffusion gradients. In the vicinity of plant roots, metal chelates and complexes may also move by bulk flow in the transpiration stream as water moves from the soil into the plant. However, depending on their charge characteristics and hydrophobicity, metal chelators and complexes can become adsorbed to clay and organic matter, which may then decrease their mobility and bioavail-... 

In the rhizosphere, microorganisms utilize either organic acids or phytosiderophores to transport iron or produce their own low-molecular-weight metal chelators, called siderophores. There are a wide variety of siderophores in nature and some of them have now been identified and chemically purified (54). Pre.sently, three general mechanisms are recognized for utilization of these compounds by microorganisms. These include a shuttle mechanism in which chelators deliver iron to a reductase on the cell surface, direct uptake of metallated siderophores with destructive hydrolysis of the chelator inside the cell, and direct uptake followed by reductive removal of iron and resecretion of the chelator (for reviews, see Refs. 29 and 54). 

Liquid chromatographic methods are well suited to the separation and determination of metal chelates that can be extracted into organic solvents. Many chelates also absorb strongly in the UV onAisible regions, facilitating detection. The... 

The given structure shows two molecules of TTA to have reacted with a cobalt ion to form the cobalt-TTA complex, in which the cobalt atom forms a valence bond solid lines) with one, and a coordinate bond (broken lines) with the other, oxygen atom of each TTA molecule. Thus, in the cobalt-TTA complex there is a six-membered ring formed by each TTA molecule with the cobalt atom. Metal chelate complexes of this type have good stability, they are nonpolar and soluble in the organic phase. The usefulness of the chelating extractants in solvent extraction is therefore obvious. 

Alkaline phosphatases [AP, orthophosphoric-monoester phosphorylase (alkaline optimum) EC 3.1.3.1] represent a large family of almost ubiquitous isoenzymes found in organisms from bacteria to animals. In mammals, there are two forms of AP, one form present in a variety of tissues and another form found only in the intestines. They share common attributes in that the phosphatase activity is optimal at pH 8-10, is activated by the presence of divalent cations, and is inhibited by cysteine, cyanides, arsenate, various metal chelators, and phosphate ions. Most conjugates created with AP utilize the form isolated from calf intestine. 

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