Department of Chemistry, Queen's University, 90 Bader Lane, Kingston, Ontario, Canada K7L 3N6.
J Am Chem Soc. 2010 Dec 1;132(47):16759-61. doi: 10.1021/ja1083046. Epub 2010 Nov 4.
A persistent triptycenyl sulfenic acid is used as a model for cysteine-derived and other biologically relevant sulfenic acids in experiments which define their redox chemistry. EPR spectroscopy reveals that sulfinyl radicals are persistent and unreactive toward O(2), allowing the O-H bonding dissociation enthalpy (BDE) of the sulfenic acid to be readily determined by equilibration with TEMPO as 71.9 kcal/mol. The E° (RSO•/RSO(-)) and pK(a) of this sulfenic acid are also reported.
一种持久的三苯并[g,p]硫杂环戊二烯基亚磺酸被用作半胱氨酸衍生的和其他生物相关的亚磺酸的模型，用于定义它们的氧化还原化学。电子顺磁共振波谱学揭示了亚磺酰基自由基是持久的，并且与 O(2)不反应，这使得通过与 TEMPO 平衡很容易确定亚磺酸的 O-H 键离解焓（BDE）为 71.9 kcal/mol。还报道了这种亚磺酸的 E°(RSO•/RSO(-))和 pK(a)。
