関: bisulfite

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出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2017/08/07 19:33:30」(JST)

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A ball-and-stick model of the most commonly stated structure (the one having C_3v symmetry) for the bisulfite ion in solution and in the solid state. Note that the hydrogen is bonded to the sulfur atom.

Bisulfite ion (IUPAC-recommended nomenclature: hydrogen sulfite) is the ion HSO₃⁻. Salts containing the HSO₃⁻ ion are termed bisulfites also known as sulfite lyes. For example, sodium bisulfite is NaHSO₃.

Structure

Bisulfite tautomers in equilibrium

Ball-and-stick models of the proposed bisulfite equilibrium. The tautomer on the right has C_3v symmetry.

Some evidence may suggest that the proton in bisulfite ion is located on sulfur, giving rise to C_3v symmetry. There is, however, some evidence from ¹⁷O NMR spectroscopy to suggest that two tautomeric forms of HSO₃⁻ exist in dynamic equilibrium, one which has the proton attached to sulfur (HSO₃⁻) and one which is protonated at oxygen (HOSO₂⁻).^[1] The C_3v structure is supported by X-ray crystallography and, in aqueous solution, by Raman spectroscopy (ν(S–H) = 2500 cm⁻¹).

Reactions

Bisulfite salts are typically prepared by treatment of alkaline solutions with excess sulfur dioxide:

SO₂ + NaOH → NaHSO₃

HSO₃⁻ is the conjugate base of sulfurous acid, H₂SO₃:

H₂SO₃ ⇌ HSO₃⁻ + H⁺

Sulfurous acid is not an isolable compound and does not appear to exist in solution either. An equilibrium that is much more consistent with spectroscopic evidence is given :

SO₂ + H₂O ⇌ HSO₃⁻ + H⁺

HSO₃⁻ is a weak acidic species with a pK_a of 6.97. Its conjugate base is the sulfite ion, SO₃²⁻:

HSO₃⁻ ⇌ SO₃²⁻ + H⁺

Bisulfites are reducing agents, as are all sulfites and sulfur dioxide, which contains sulfur in the same oxidation state (+4).

Medicine

Bisulfite salts are common additives to the drug epinephrine in order to prevent its oxidation to adrenochrome and resulting inactivation. Bisulfites can sometimes cause an allergic reaction. This is different from the common sulfa drugs allergy. The quantity of bisulfite in medical pain blockers that initiates Type 1 hypersensitivity has been determined by Fraser and Huang.^[2]

References

^ Horner, D. A.; Connick, R. E. (1986). "Equilibrium quotient for the isomerization of bisulfite ion from HSO₃⁻ to SO₃H⁻". Inorganic Chemistry. 25 (14): 2414–2417. doi:10.1021/ic00234a026.
^ Fraser, W. A.; Huang, A. S. (1984). "Are sulfites additives really safe?". New England Journal of Medicine. 311 (8): 542. doi:10.1056/NEJM198408233110824.

English Journal

Voyage to the bottom of the 'seaquence'.

Wash R1, Soria CD1.
Nature reviews. Microbiology.Nat Rev Microbiol.2014 Sep;12(9):597. doi: 10.1038/nrmicro3341. Epub 2014 Aug 14.
PMID 25118883

The "bacterial heterodisulfide" DsrC is a key protein in dissimilatory sulfur metabolism.

Venceslau SS1, Stockdreher Y2, Dahl C2, Pereira IA3.
Biochimica et biophysica acta.Biochim Biophys Acta.2014 Jul;1837(7):1148-64. doi: 10.1016/j.bbabio.2014.03.007. Epub 2014 Mar 22.
DsrC is a small protein present in organisms that dissimilate sulfur compounds, working as a physiological partner of the DsrAB sulfite reductase. DsrC contains two redox active cysteines in a flexible carboxy-terminal arm that are involved in the process of sulfite reduction or sulfur(1) compound o
PMID 24662917

Sulfur oxidation genes in diverse deep-sea viruses.

Anantharaman K1, Duhaime MB2, Breier JA3, Wendt KA4, Toner BM4, Dick GJ5.
Science (New York, N.Y.).Science.2014 May 16;344(6185):757-60. doi: 10.1126/science.1252229. Epub 2014 May 1.
Viruses are the most abundant biological entities in the oceans and a pervasive cause of mortality of microorganisms that drive biogeochemical cycles. Although the ecological and evolutionary effects of viruses on marine phototrophs are well recognized, little is known about their impact on ubiquito
PMID 24789974