Fluoride recognition

H12. Harris, H., and Whittaker, M., Differential inhibition of human serum cholinesterase with fluoride Recognition of two new phenotypes. Nature (London) 191, 496-498 (1961). 

Dusemuncl. C. Sandanayake, M.R.A.S. Shinkai. S. Selective fluoride recognition with ferroceneboronic acid. Chem. Commun. 1995. 3. 333. 

The macrocychc hexaimine stmcture of Figure 19a forms a homodinuclear cryptate with Cu(I) (122), whereas crown ether boron receptors (Fig. 19b) have been appHed for the simultaneous and selective recognition of complementary cation—anion species such as potassium and fluoride (123) or ammonium and alkoxide ions (124) to yield a heterodinuclear complex (120). 

Potentiometry (discussed in Chapter 5), which is of great practical importance, is a static (zero current) technique in which the information about the sample composition is obtained from measurement of the potential established across a membrane. Different types of membrane materials, possessing different ion-recognition processes, have been developed to impart high selectivity. The resulting potentiometric probes have thus been widely used for several decades for direct monitoring of ionic species such as protons or calcium, fluoride, and potassium ions in complex samples. 

In the area of ion sensing, cation recognition by electrodes containing functionalized redox-active polymers has been an area of considerable interest. Fabre and co-workers have reported the development of a boronate-functionalized polypyrrole as a fluoride anion-responsive electroactive polymer film. The electropolymerizable polypyrrole precursor (11) (Fig. 11) was synthesized by the hydroboration reaction of l-(phenylsulfonyl)-3-vinylpyrrole with diisopinocampheylborane followed by treatment with pinacol and the deprotection of the pyrrole ring.33 The same methodology was utilized for the production of several electropolymerizable aromatic compounds (of pyrrole (12) (Fig. 11), thiophene (13 and 14) (Fig. 11), and aniline) bearing boronic acid and boronate substituents as precursors of fluoride- and/or chloride-responsive conjugated polymer.34... 

Phosphate-polymer control, in industrial water treatment, 26 132-133 Phosphate recognition, 16 794 Phosphate refractory dental dies, compressive strength, 8 289t Phosphate rock, 11 119, 120 minerals in, 19 5, 14 recovery of fluoride from, 14 12-13 U.S. imports for consumption of, 19 15t U.S. production of, 19 17 Phosphates, 18 814-863 19 19. See also Phosphate Polyphosphates aluminum acid, 18 839 ammonium, 11 487 18 835-836 analysis of, 18 851-852 calcium, 18 836-839 condensed, 18 841-852 crystalline, 18 839 dispersants, 8 710t economic aspects of, 18 859-860... 

There are a limited number of fluorescent sensors for anion recognition. An outstanding example is the diprotonated form of hexadecyltetramethylsapphyrin (A-7) that contains a pentaaza macrocydic core (Figure 10.31) the selectivity for fluoride ion was indeed found to be very high in methanol (stability constant of the complex 105) with respect to chloride and bromide (stability constants < 102). Such selectivity can be explained by the fact that F (ionic radius 1.19 A) can be accommodated within the sapphyrin cavity to form a 1 1 complex with the anion in the plane of the sapphyrin, whereas Cl and Br are too big (ionic radii 1.67 and 1.82 A, respectively) and form out-of-plane ion-paired complexes. A two-fold enhancement of the fluorescent intensity is observed upon addition of fluoride. Such enhancement can be explained by the fact that the presence of F reduces the quenching due to coupling of the inner protons with the solvent. 

In the book by Hyde and Andersson (1989), the Nowotny phases are presented as a special case of a group of ID, columnar misfit structures which also include compounds such as Bam(Fe2S4) and other complex sulphides. Layer misfit structures, such as those of some oxide-fluorides, arseno-sulphides, etc., are also presented and classified with reference to a concept of structure commensurability based on the recognition that (along one or more axes) the ratios between the different repeat units of various interpenetrating substructures can (or cannot) be represented as ratios between integer numbers. 

A simple synthesis of these salts became available with the recognition that oxygen, fluorine, and arsenic or antimony-(V) fluoride, at pressures near atmospheric, react to form the appropriate dioxygenyl salts when exposed to ordinary sunlight Filtered by Pyrex glass.4 Thus, the atmospheric-pressure, photochemical synthesis is the safest and most convenient one to date. 

Recognition of fluoride in aqueous media is particularly difficult due to the strongly hydrated nature of the anion. Shinkai and co-workers have demonstrated that ferrocene-boronic acid 27 acts as a selective redox sensor for fluoride which operates in H20 [23]. The favourable interaction between boron and fluoride (a hard acid and hard base, respectively) generates a stability constant of 700 M"1 for the fluoride-ferrocenium complex. Stability constants for both the bromide and chloride complexes are <2 M"1. 

Probably the most precious occurrence of anion recognition is that related to size exclusion selectivity. This takes place when the receptor, providing for instance a spheroidal cavity, includes only spherical anions of radius less than or equal to a definite value. In this context, the smallest anion, fluoride, has offered vast opportunities. 

---