Room Temperature Phosphorescence from Tryptophan and Halogenated Tryptophan Analogs in Amorphous Sucrose
Room Temperature Phosphorescence from Tryptophan and Halogenated Tryptophan Analogs in Amorphous Sucrose
复制标题
无定形蔗糖中色氨酸和卤化色氨酸类似物的室温磷光
DOI：
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发表时间：
1999
期刊：
影响因子：
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通讯作者：
R. Ludescher
中科院分区：
文献类型：
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作者：
Colin P. McCaul;R. Ludescher
抽象。色氨酸磷光寿命和量子产率对局部环境敏感。然而，色氨酸类似物的磷光还没有被研究过。我们在此报告了色氨酸、4-、5-和6-氟-DL-色氨酸（4-F-trp、5-F-trp和6-F-trp）和5-溴-DL-色氨酸（5-Br-trp）包埋在冷冻干燥蔗糖玻璃状粉末中的室温磷光数据。在水溶液中，类似物的吸收相对于色氨酸发生蓝移（4-F-trp）、红移（5-F-trp和5-Br-trp）或不发生蓝移（6-F-trp）。与trp（442 nm）相比，所有类似物的磷光发射光谱均发生红移，在446 nm（5-F-trp）、451 nm（6-F-trp）、452 nm（5-Br-trp）和469 nm（4-F-trp）处具有最大值。5-F-trp和6-F-trp类似物具有与色氨酸相似的发射强度（与色氨酸相比，相对量子产率分别为0.68和0.91），而4-F和5-Br类似物的强度较低（相对量子产率分别为0.039和0.022）。所有类似物表现出复杂的衰减行为，需要几个指数的适当的拟合，平均寿命都低于色氨酸（1039毫秒）。氟化类似物的平均寿命（5-F，721 ms; 6-F，482 ms和4-F，35 ms）与相对量子产率大致成比例，而5-Br的平均寿命（0.53 ms）显著较低。对单个寿命的分析表明，氟化类似物对环境相互作用的敏感性不同，5-F-和6-F-trp的淬灭效率是色氨酸的1.5 - 2倍，4-F-trp的淬灭效率是色氨酸的23倍。红移的5-F-胰蛋白酶类似物，已被纳入蛋白质，可以提供一个替代的磷光探针，用于选择性磷光检测复杂混合物中的特定蛋白质。
Abstract. Tryptophan phosphorescence lifetime and quantum yield are sensitive to the local environment. The phosphorescence from tryptophan analogs, however, has not been studied. We report here data on the room temperature phosphorescence of tryptophan, 4‐, 5‐ and 6‐fluoro‐DL‐tryptophan (4‐F‐trp, 5‐F‐trp and 6‐F‐trp) and 5‐bromo‐DL‐tryptophan (5‐Br‐trp) embedded in glassy powders of freeze‐dried sucrose. In aqueous solution, the absorption of the analogs was either blue‐shifted (4‐F‐trp), red‐shifted (5‐F‐trp and 5‐Br‐trp) or not shifted (6‐F‐trp) with respect to tryptophan. The phosphorescence emission spectra of all analogs were red‐shifted compared to trp (442 nm) with maxima at 446 nm (5‐F‐trp), 451 mn (6‐F‐trp), 452 nm (5‐Br‐trp) and 469 nm (4‐F‐trp). The 5‐F‐trp and 6‐F‐trp analogs had emission intensities similar to tryptophan (relative quantum yields of 0.68 and 0.91, respectively, compared to tryptophan), while the intensities of the 4‐F and 5‐Br analogs were lower (relative quantum yields of 0.039 and 0.022, respectively). All analogs exhibited complex decay behavior requiring several exponentials for an adequate fit; the average lifetimes were all lower than that of trp (1039 ms). The average lifetimes of the fluorinated analogs (5‐F, 721 ms; 6‐F, 482 ms and 4‐F, 35 ms) scaled approximately with the relative quantum yields while that of 5‐Br (0.53 ms) was significantly lower. Analysis of the individual lifetimes suggested that the fluorinated analogs differ in their sensitivity to environmental interactions, with 5‐F‐ and 6‐F‐trp quenched 1.5‐2‐fold and 4‐F‐trp about 23‐fold more efficiently than tryptophan. The red‐shifted 5‐F‐trypto‐phan analog, which has been incorporated into proteins, may provide an alternative phosphorescence probe for selective phosphorescence detection of a specific protein in a complex mixture.
影响因子：
56.9
作者：
J. Vanderkooi;D. B. Calhoun;S. Englander
通讯作者：
J. Vanderkooi;D. B. Calhoun;S. Englander
用色氨酸类似物增强蛋白质光谱：蛋白质-蛋白质和蛋白质-核酸相互作用的荧光光谱。
影响因子：
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作者：
Ross,JB;Szabo,AG;Hogue,CW
通讯作者：
Hogue,CW