Chelating 8-hydroxyquinoline

Complexes of 8-hydroxyquinoline and chromium(III) have been known for many years.1139 Complexes have been mercurated and the deuterated quinoline isolated.1139 The bromination of chelated 8-hydroxyquinoline proceeds about thirty-five times faster than that of the free ligand.1140 Tris(8-hydroxyquinolinato)chromium(III) absorbs large amounts of hydrochloric, hydrobromic and hydrofluoric acids. Chemical reaction with the complex was considered a more likely explanation than solid solution or clathrate formation, even though more than one mole of acid was absorbed per mole of complex.1141... 

Copper quinolinolate (oxine copper) is the chelate of divalent copper and 8-hydroxyquinoline and shares most of its market with copper naphthenate, which is a complex copper salt of mixed naphthenic acids. The principal uses are in wood treatments and some military textiles, where the green color is not objectionable. Copper naphthenate has an odor but is cheaper than oxine. Both copper naphthenate and 2inc naphthenate have performed well in environment tests, with exposure to soil above-ground, as well as concrete (33). 

The extraction of metal ions depends on the chelating ability of 8-hydroxyquinoline. Modification of the stmcture can improve its properties, eg, higher solubility in organic solvents (91). The extraction of nickel, cobalt, copper, and zinc from acid sulfates has been accompHshed using 8-hydroxyquinohne in an immiscible solvent (92). In the presence of oximes, halo-substituted 8-hydroxyquinolines have been used to recover copper and zinc from aqueous solutions (93). Dilute solutions of heavy metals such as mercury, ca dmium, copper, lead, and zinc can be purified using quinoline-8-carboxyhc acid adsorbed on various substrates (94). 

In acidic solution, the degradation results in the formation of furfural, furfuryl alcohol, 2-furoic acid, 3-hydroxyfurfural, furoin, 2-methyl-3,8-dihydroxychroman, ethylglyoxal, and several condensation products (36). Many metals, especially copper, cataly2e the oxidation of L-ascorbic acid. Oxalic acid and copper form a chelate complex which prevents the ascorbic acid-copper-complex formation and therefore oxalic acid inhibits effectively the oxidation of L-ascorbic acid. L-Ascorbic acid can also be stabilized with metaphosphoric acid, amino acids, 8-hydroxyquinoline, glycols, sugars, and trichloracetic acid (38). Another catalytic reaction which accounts for loss of L-ascorbic acid occurs with enzymes, eg, L-ascorbic acid oxidase, a copper protein-containing enzyme. 

Elimination of a cofactor needed for luminescence. The chelators EDTA and EGTA efficiently quench the luminescence of Ca2+-activated systems such as aequorin, obelin and mnemiopsin. The luminescence systems that require ferrous ions, such as extracts of the polychaete Chaetopterus, can be inhibited by 8-hydroxyquinoline and... 

Sometimes antimicrobial agents such as thymol or 8-hydroxyquinoline may be present (Wilson, 1975b). The latter is also capable of forming a cementitious chelate with zinc. 

In a molecule of 2-phenyl-l-boraadamantane there are two markedly different types of B-C bonds two of them are boron-alkyl and one is boron-benzyl. On treatment of THF complex 34 with 8-hydroxyquinoline at 20 °C, mpture of the 1-boraadamantane core takes place, resulting in a mixture of boron chelates 52-54 (Scheme 16). When trimethylamine adduct 16 is used as the starting compound, reaction takes place only in boiling toluene. Interestingly, all the products result from the protolysis of B-CH2 bonds only <2006UP1>. 

The protolytic cleavage of THF-2,2-dimethyl-l-boraadamantane 23 with pivalic acid also proceeds regiospecifi-cally giving rise, after treatment with 8-hydroxyquinoline, to boron chelate 55 (Scheme 17) <2004MI1>. 

Owing to inadequate detection limits by direct analysis, various workers examined preconcentration procedures, including dithiocarbamate preconcentration [447,732-734], ion exchange preconcentration [735-737], chelation solvent extraction [736], coprecipitation [738], and preconcentration in silica-immobilised 8-hydroxyquinoline [129]. 

Burns et al. [106] used electrothermal AAS to determine inorganic and butyltin in seawater. The butyltin is extracted into toluene and the inorganic tin extracted as its Sn(IV) 8-hydroxyquinoline chelate into chloroform. The detection limit was 0.7 ng of tin. 

Despite the ubiquity of aluminum hydroxyquinolinate chelates as ETMs, other metal chelates of substituted 8-hydroxyquinoline, such as Group II metal ions of Zn2+ and Be2+ have also been used as the ETM in OLEDs (Scheme 3.28) [131-133],... 

B.J. Chen, X.W. Sun, and Y.K. Li, Influences of central metal ions on the electroluminescence and transport properties of tris-8-hydroxyquinoline metal chelates, Appl. Phys. Lett., 82 3017-JO 19 (2003). 

Compound 113 (O-TRENSOX) is a promising water-soluble iron chelator based on 3 hydroxyquinoline sub-units (548) which forms... 

Class 2 fluorophores that can reversibly bind an analyte. If the analyte is a proton, the term fluorescent pH indicator is often used. If the analyte is an ion, the term fluorescent chelating agent is appropriate. Fluorescence can be either quenched upon binding (CEQ type Chelation Enhancement of Quenching), or enhanced (CEF type Chelation Enhancement of Fluorescence). In the latter case, the compound is said to be fluorogenic [e.g. 8-hydroxyquinoline (oxine)]. 

An extractive spectrophotometric procedure based on the complexation of reduced Iron(II) with 5-Chloro-7-iodo-8-hydroxyquinoline (CIHQ) for the estimation of micro amounts of vitamin C. The resulting brown colored complex was extracted into chloroform to give a reddish brown extract which shows an absorption band at 485 nm. This chelate was formed immediately and the apparent molar absorptivity and Sandell s sensitivity for vitamin C was found to be 8.5 x 105 dm3 mol"1 cm 1 and 2.072xl0 4g cm 2. Linear relationship between absorbance and concentration of ascorbic acid is observed up to 0.8 pg ml"1. Interference studies of different substances including sugars, vitamins and amino acids, metal ions and organic acids were carried out. The utility of the method was tested by analysing some of the marketed products of vitamin C... 

Such a fluorescence enhancement in these compounds 32-34 is similar to that observed in metal chelates with 8-hydroxyquinoline (oxine) and its derivatives but is not fully understood yet. 

If a hydroxyester function is incorporated into a potential chelating system then the ability even of a labile metal ion to catalyze the hydrolysis can be assessed. The 8-hydroxyquinoline 17 and 2,2 -phenanthroline 18 frameworks have proved popular for this purpose. 

The nonideality of electrolyte solntions, cansed nltimately by the electrical fields of the ions present, extends also to any nonelectrolyte that may be present in the aqueous solution. The nonelecttolyte may be a co-solvent that may be added to affect the properties of the solntion (e.g., lower the relative permittivity, e, or increase the solubility of other nonelecttolytes). For example, ethanol may be added to the aqueous solution to increase the solnbility of 8-hydroxyqni-noline in it. The nonelectrolyte considered may also be a reagent that does not dissociate into ions, or one where the dissociation is snppressed by the presence of hydrogen ions at a sufficient concentration (low pH cf Chapter 3), snch as the chelating agent 8-hydroxyquinoline. 

Ashbrook, A. W. Commercial chelating solvent extraction reagents, II. w-Al-kenyl-8-hydroxyquinoline Purification and properties, Metallurgy Division, Mines Branch, Dept. Energy, Mines and Resources, Canada Report EMA 73-34 1973. 

Extrinsic fluors are produced via a chemical reaction where the added reagent either enhances emission of a weak emitter through association or the analyte is derivatized with a fluor tag. 8-Hydroxyquinoline (HQS) is an example of an extrinsic complexing reagent (Reaction 11.1) where the native ligand is a marginal fluorophore but forms intense emitting metal chelates. This approach affords sensitive detection of... 

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