Hori K, Anderson J M, Ward W W, Cormier M J
Biochemistry. 1975 Jun 3;14(11):2371-6. doi: 10.1021/bi00682a016.
A study was made of the effects of pH and protic and aprotic solvents on the spectral properties of Renilla (sea pansy) luciferin and a number of its analogs. The results have made possible the assignment of two tautomeric forms of Renilla luciferin, one which absorbs maximally at 435 nm and another which exhibits an absorption maximum at 454 nm. Furthermore the results provide an explanation for the visible absorption characteristics of the photoproteins aequorin (lambda-max 454 nm) and mnemiopsin (lambda-max 435 nm). In addition a Renilla-like luciferin can be extracted from both of these photoproteins. This luciferin produces light with Renilla luciferase, at a rate dependent upon the concentration of dissolved oxygen, and in other respects is indistinguishable from Renilla luciferin in this bioluminescent reaction. The results suggest that the native chromophore in both photoproteins is Renilla luciferin (or a nearly identical derivative). The results also suggest that a hydroperoxide intermediate probably exists in photoproteins, on energetic grounds, and to account for the oxygen concentration independency of the rate of photoprotein reactions. This hydroperoxide may be attached initially to an amino-acid side chain (possibly indolyl-OOH, imidazoyl-OOH, or -SOOH) rather than to the luciferin chromophore.
研究了pH值、质子性和非质子性溶剂对海肾（海笔）荧光素及其一些类似物光谱性质的影响。这些结果使得确定海肾荧光素的两种互变异构形式成为可能，一种在435nm处有最大吸收，另一种在454nm处有最大吸收。此外，这些结果为光蛋白水母发光蛋白（最大吸收波长454nm）和多线带水母荧光蛋白（最大吸收波长435nm）的可见吸收特性提供了解释。另外，可以从这两种光蛋白中提取出海肾样荧光素。这种荧光素与海肾荧光素酶反应产生光，其速率取决于溶解氧的浓度，并且在其他方面，在这种生物发光反应中与海肾荧光素无法区分。结果表明，两种光蛋白中的天然发色团是海肾荧光素（或几乎相同的衍生物）。结果还表明，基于能量原因，光蛋白中可能存在氢过氧化物中间体，以解释光蛋白反应速率与氧浓度无关的现象。这种氢过氧化物最初可能连接在氨基酸侧链上（可能是吲哚基 - OOH、咪唑基 - OOH或 - SOOH），而不是连接在荧光素发色团上。
