首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Infrared multiple photon dissociation action spectroscopy and computational studies of mass-selected gas-phase fluorescein and 2′,7′- dichlorofluorescein ions
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Infrared multiple photon dissociation action spectroscopy and computational studies of mass-selected gas-phase fluorescein and 2′,7′- dichlorofluorescein ions

机译:质谱选择的气相荧光素和2',7'-二氯荧光素离子的红外多光子解离光谱和计算研究

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摘要

Fluorescein (FL) and its derivative 2′,7′-dichlorofluoroescein (DCF) are well-known fluorescent dyes used in many biological and biochemical applications. Although extensive studies have been carried out to investigate their chemical and photophysical properties in different solvent media, little is known about their intrinsic behaviors in the gas phase. Here, infrared multiple photon dissociation (IRMPD) action spectra are reported for the three charged prototropic forms of FL and DCF and compared with computed IR spectra from electronic structure calculations. In each case, the measured spectra show good agreement with the calculated spectra of the lowest energy computed conformer. Moreover, the major bands of the monoanion IRMPD spectra show striking similarities to those of the dianions and are quite different from those of the cations. These experimental results clearly indicate that the gaseous monoanions are predominantly deprotonated on the xanthene chromophore, rather than the benzoate deprotonation site favored in solution. Investigations such as this, which provide a better understanding of intrinsic properties of ionic dyes, forms a baseline from which to elucidate solvent effects and will aid the rational design of dyes possessing desirable fluorescence properties.
机译:荧光素(FL)及其衍生物2',7'-二氯氟乙烯(DCF)是在许多生物和生化应用中使用的众所周知的荧光染料。尽管已经进行了广泛的研究以研究它们在不同溶剂介质中的化学和光物理性质,但对其在气相中的固有行为知之甚少。在此,报告了FL和DCF三种带电质子形式的红外多光子离解(IRMPD)作用谱,并将其与根据电子结构计算得出的IR谱进行了比较。在每种情况下,测得的光谱与最低能量计算的构象异构体的计算光谱显示出良好的一致性。此外,单阴离子IRMPD谱的主要谱带显示出与二价阴离子显着的相似性,并且与阳离子的谱带有很大不同。这些实验结果清楚地表明,气态单阴离子主要在the吨发色团上去质子化,而不是溶液中有利的苯甲酸酯去质子化位点。诸如此类的研究可以更好地理解离子染料的内在特性,从而为阐明溶剂效应奠定了基础,并将有助于合理设计具有所需荧光特性的染料。

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