Fluoride

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This article is about the chemical ion F −. For the addition of fluoride ions to water supplies, see Water fluoridation.

Fluoride is the reduced form of fluorine. Both organic and inorganic compounds containing the element fluorine are considered fluorides. As a halogen, fluorine forms a monovalent ion (−1 charge). The range of fluorides is considerable as fluorine forms compounds with all elements except He and Ne[1][2]. Fluorides range from severe toxins such as sarin to life-saving pharmaceuticals such as efavirenz and from refractory materials such as calcium fluoride to highly reactive sulfur tetrafluoride.

Contents

[edit] Occurrence

The mineral fluorite.
The mineral fluorite.

Solutions of inorganic fluorides in water contain F− and bifluoride HF2−.[3] Few inorganic fluorides are soluble in water without undergoing significant hydrolysis. Examples of inorganic fluorides include hydrofluoric acid (HF), sodium fluoride (NaF), and uranium hexafluoride (UF6). In terms of its reactivity, fluoride differs significantly from chloride and other halides, and is more strongly solvated due to its smaller radius/charge ratio. Its closest chemical relative is hydroxide. The Si-F linkage is one of the strongest single bonds. In contrast, other silyl halides are easily hydrolyzed.

Many fluoride minerals are known, but paramount in commercial importance are fluorite and fluoroapatite. Fluoride is found naturally in low concentration in drinking water and foods. Water with underground sources is more likely to have higher levels of fluoride, whereas the concentration in seawater averages 1.3 parts per million (ppm).[4] Fresh water supplies generally contain between 0.01-0.3 ppm, while the ocean contains between 1.2 and 1.5 ppm.[5]

[edit] Applications

Fluorides are pervasive in modern technology. Hydrofluoric acid is the most important fluoride synthesized. It is principally used in the production of fluorocarbons and aluminium fluorides. Hydrofluoric acid has a variety of specialized applications, including its ability to dissolve glass.[6]

[edit] Organic synthesis

Fluoride reagents are significant in synthetic organic chemistry. Due to the affinity of silicon for fluoride, and the ability of silicon to expand its coordination number, silyl ether protecting groups can be easily removed by the fluoride sources such as sodium fluoride and tetra-n-butylammonium fluoride (TBAF).

[edit] Enzyme inhibitors

In biochemistry, fluoride salts are commonly used to inhibit the activity of phosphatases, such as serine/threonine phosphatases.[7] It may do this by replacing the nucleophilic hydroxyl ion in these enzymes' active sites.[8] Beryllium fluoride and aluminium fluoride are also used as phosphatase inhibitors, since these compounds are structural mimics of the phosphate group and can act as analogues of the transition state of the reaction.[9][10]

[edit] Inorganic materials

Sulfur hexafluoride is an inert, nontoxic insulator that is used in electrical transformers. Uranium hexafluoride is used in the separation of isotopes of uranium between the fissile isotope U-235 and the non-fissile isotope U-238 in preparation of nuclear reactor fuel and atomic bombs.

PTFE is often used to coat non-stick frying pans as it is not water-wettable and possesses high heat resistance.
PTFE is often used to coat non-stick frying pans as it is not water-wettable and possesses high heat resistance.

[edit] Fluoropolymers

Fluoropolymers such as polytetrafluoroethylene, Teflon, are used as chemically inert and biocompatible materials for a variety of applications, including as surgical implants such as coronary bypass grafts,[11] and a replacement for soft tissue in cosmetic and reconstructive surgery.[12] These compounds are also commonly used as non-stick surfaces in cookware and bakeware, and the fluoropolymer fabric Gore-Tex used in breathable garments for outdoor use.

[edit] Cavity-prevention

Main article: Fluoride therapy

Fluoride-containing compounds are used in topical and systemic fluoride therapy for preventing tooth decay. They are used for water fluoridation and in many products associated with oral hygiene.[13] Originally, sodium fluoride was used to fluoridate water, however, hexafluorosilicic acid (H2SiF6) and its salt sodium hexafluorosilicate (Na2SiF6) are more commonly used additives, especially in the United States. The fluoridation of water prevents tooth decay[14][15] and is considered by the U.S. Centers for Disease Control and Prevention as "one of 10 great public health achievements of the 20th century".[16] In some countries where large, centralized water systems are uncommon, fluoride is delivered to the populace by fluoridating table salt. Fluoridation of water is not without critics, however (see water fluoridation opposition).[17]

Structure of halothane.
Structure of halothane.

[edit] Biomedical applications

Positron emission tomography is commonly carried out using fluoride-containing pharmaceuticals such as fluorodeoxyglucose, which is labelled with the radioactive isotope fluorine-18 that emits positrons when it decays into 18O.

Fluorine is also part of a large variety of drugs including: antipsychotics such as fluphenazine, HIV protease inhibitors such as tipranavir, antibiotics such as ofloxacin and trovafloxacin, and anesthetics such as halothane.[18] These atoms are incorporated in the drug structures to reduce drug metabolism, as the strong C-F bond resists deactivation in the liver by cytochrome P450 oxidases.[19]

[edit] Toxicology

Main article: fluoride poisoning

Fluoride-containing compounds are so diverse that it is not possible to generalize on their toxicity, which depends on their reactivity and structure, and in the case of salts, their solubility and ability to release fluoride ions.

Reaction of the irreversible inhibitor diisopropylfluorophosphate with a serine protease
Reaction of the irreversible inhibitor diisopropylfluorophosphate with a serine protease

Soluble fluoride salts, of which NaF is the most common, are mildly toxic but have resulted in both accidental and suicidal deaths from acute poisoning.[6] While the minimum fatal dose in humans is not known, a case of a fatal poisoning of an adult with 4 grams of NaF is documented.[20] Sodium fluorosilicate, Na2SiF6 with its higher fluorine content, can cause death with as little as 0.2 g. The fatal period ranges from 5 min to 12 hours.[20] The mechanism of toxicity involves the combination of the fluoride anion with the calcium ions in the blood to form insoluble calcium fluoride, resulting in hypocalcemia; calcium is indispensable for the function of the nervous system, and the condition can be fatal. Treatment may involve oral administration of dilute calcium hydroxide or calcium chloride to prevent further absorption, and injection of calcium gluconate to increase the calcium levels in the blood.[20] Hydrogen fluoride is more dangerous than salts such as NaF because it is corrosive and volatile, and can result in fatal exposure through inhalation or contact with the skin; calcium gluconate gel is the usual antidote.[21]

A few organofluorine compounds are extremely toxic, such as organophosphates like sarin and diisopropylfluorophosphate that react with the cholinesterase enzyme at neuromuscular junctions and thus block the transmission of nerve impulses to the muscles.[22] Here, a reactive fluorine-phosphorous bond in the inhibitor is the site of nucleophilic attack by a serine residue in the enzyme's active site, causing the loss of a F- ion and alkylation and inactivation of the enzyme.

While PTFE itself is chemically inert and non-toxic, it begins to deteriorate after the temperature of cookware reaches about 500 °F (260 °C), and decompose above 660 °F (350 °C).[23] These degradation products can be lethal to birds, and can cause flu-like symptoms in humans.[23] In comparison, cooking fats, oils, and butter will begin to scorch and smoke at about 392 °F (200 °C), and meat is usually fried between 400–450 °F (200–230 °C), but empty cookware can exceed this temperature if left unattended on a hot burner.

A 1959 study, (conducted before the Food and Drug Administration approved the material for use in food processing equipment) showed that the toxicity of fumes given off by the coated pan on dry heating was less than that of fumes given off by ordinary cooking oils.[24]

[edit] See also

[edit] References

  1. ^ Greenwood, N. N.; Earnshaw, A. (1997). Chemistry of the Elements, 2nd Edition, Oxford:Butterworth-Heinemann. ISBN 0-7506-3365-4.  p. 804
  2. ^ Khriachtchev, Leonid; Mika Pettersson, Nino Runeberg, Jan Lundell & Markku Räsänen (24 August 2000). "A stable argon compound". Nature 406: 874–876. doi:10.1038/35022551. 
  3. ^ Holleman, A. F.; Wiberg, E. "Inorganic Chemistry" Academic Press: San Diego, 2001. ISBN 0-12-352651-5.
  4. ^ Fluoride in Drinking-water: Background document for development of WHO Guidelines for Drinking-water Quality. World Health Organization, 2004, page 2. Page accessed on February 22, 2007.
  5. ^ Environmental Health Criteria 227: Fluorides. World Health Organization, 2002, page 38. Page accessed on February 22, 2007.
  6. ^ a b Jean Aigueperse, Paul Mollard, Didier Devilliers, Marius Chemla, Robert Faron, Renée Romano, Jean Pierre Cuer, “Fluorine Compounds, Inorganic” in Ullmann’s Encyclopedia of Industrial Chemistry 2005 Wiley-VCH, Weinheim. DOI 10.1002/14356007.a11 307
  7. ^ Nakai C, Thomas JA (1974). "Properties of a phosphoprotein phosphatase from bovine heart with activity on glycogen synthase, phosphorylase, and histone". J. Biol. Chem. 249 (20): 6459-67. PMID 4370977. 
  8. ^ Schenk G, Elliott TW, Leung E, et al (2008). "Crystal structures of a purple acid phosphatase, representing different steps of this enzyme's catalytic cycle". BMC Struct. Biol. 8 (1): 6. doi:10.1186/1472-6807-8-6. PMID 18234116. 
  9. ^ Wang W, Cho HS, Kim R, et al (2002). "Structural characterization of the reaction pathway in phosphoserine phosphatase: crystallographic "snapshots" of intermediate states". J. Mol. Biol. 319 (2): 421-31. doi:10.1016/S0022-2836(02)00324-8. PMID 12051918. 
  10. ^ Cho H, Wang W, Kim R, et al (2001). "BeF(3)(-) acts as a phosphate analog in proteins phosphorylated on aspartate: structure of a BeF(3)(-) complex with phosphoserine phosphatase". Proc. Natl. Acad. Sci. U.S.A. 98 (15): 8525-30. doi:10.1073/pnas.131213698. PMID 11438683. 
  11. ^ Kannan RY, Salacinski HJ, Butler PE, Hamilton G, Seifalian AM (2005). "Current status of prosthetic bypass grafts: a review". J. Biomed. Mater. Res. Part B Appl. Biomater. 74 (1): 570-81. doi:10.1002/jbm.b.30247. PMID 15889440. 
  12. ^ Singh S, Baker JL (2000). "Use of expanded polytetrafluoroethylene in aesthetic surgery of the face". Clin Plast Surg 27 (4): 579-93. PMID 11039891. 
  13. ^ McDonagh M S, Whiting P F, Wilson P M, Sutton A J, Chestnutt I, Cooper J, Misso K, Bradley M, Treasure E, & Kleijnen J. (2000). "Systematic review of water fluoridation". British Medical Journal 321 (7265): 855-859. doi:10.1136/bmj.321.7265.855. 
  14. ^ Griffin SO, Regnier E, Griffin PM, Huntley V (2007). "Effectiveness of fluoride in preventing caries in adults". J. Dent. Res. 86 (5): 410-5. PMID 17452559. 
  15. ^ Winston AE, Bhaskar SN (1998). "Caries prevention in the 21st century". J Am Dent Assoc 129 (11): 1579-87. PMID 9818575. 
  16. ^ [1]
  17. ^ Newbrun E (1996). "The fluoridation war: a scientific dispute or a religious argument?". J Public Health Dent 56 (5 Spec No): 246-52. doi:10.1111/j.1752-7325.1996.tb02447.x. PMID 9034969. 
  18. ^ Park BK, Kitteringham NR, O'Neill PM (2001). "Metabolism of fluorine-containing drugs". Annu. Rev. Pharmacol. Toxicol. 41: 443-70. doi:10.1146/annurev.pharmtox.41.1.443. PMID 11264465. 
  19. ^ Fisher MB, Henne KR, Boer J (2006). "The complexities inherent in attempts to decrease drug clearance by blocking sites of CYP-mediated metabolism". Curr Opin Drug Discov Devel 9 (1): 101-9. PMID 16445122. 
  20. ^ a b c I. M. Rabinowitch. Acute Fluoride Poisoning. Can Med Assoc J. 1945, 52, 345–349. [2]
  21. ^ Muriale L, Lee E, Genovese J, Trend S. Fatality due to acute fluoride poisoning following dermal contact with hydrofluoric acid in a palynology laboratory. Ann Occup Hyg. 1996 40, 705-710. PMID 8958774.
  22. ^ Marrs TC (1993). "Organophosphate poisoning". Pharmacol. Ther. 58 (1): 51-66. doi:10.1016/0163-7258(93)90066-M. PMID 8415873. 
  23. ^ a b DuPont, Key Questions About Teflon®, accessed on 03 Dec 2007.
  24. ^ Dale Blumenthal. Is That Newfangled Cookware Safe?. Food and Drug Administration. Retrieved on 2006-05-20.