CHEMILUMINESCENCE OF ORGANIC COMPOUNDS

本提案的目的是阐明称为 电子激发态的化学产生。 在一些情况下 激发态发光，整个过程称为 化学发光（或生物发光，如果该过程是催化的， 酶）。 在其他情况下，激发态（单重态和三重态） 转化为化学和生物化学反应。 因为它的高灵敏度 在室内测量“黑体”的光发射 温度化学发光显示出作为许多化学发光的安全替代品的希望。 利用放射性的技术。 例如，环酰肼， 十年前研究的抗体目前被用于抗体结合 测定。 化学发光也被广泛用于测定叶酸，ATP， 酶促产生的过氧化物等。 本提案旨在理解：（1）生成 来自环酰肼如鲁米诺的激发态。 我们建议（a） 5-甲基去氢萤火虫单酰肼的合成及测试 其用于氧化发光，（B）合成高效 衍生自N，N-二丁基异鲁米诺的荧光酞嗪二酮，（c） 尝试双环过氧化物的低温合成与研究 被认为是环酰肼化学发光中的关键中间体， 和（d）在低温下研究酰基二氮烯的基本化学， 在没有氧气的情况下 (2)激发态的产生， 基于高荧光吖啶环的二氧杂环丁烷和二氧杂环丁烷酮 系统. 两种溶液中弱酸性吖啶酮的排放 将比较化学发光和荧光;数据可能允许 关于CIEEL机制是否在这些国家运作的决定 分子内的兴奋 合成，结构和 基于9-取代的光化学生成的过氧化物化学 将检查吖啶环系统。 (3)兴奋的一代 从萤火虫的状态。 重点将放在快速反应上 最初形成的激发态产生（可能？）黄绿色 发光分子-在努力完善一个模型系统， 萤火虫发出的黄绿色光。 分析纯的LH 2AMP将 为这项研究做好准备。 物理有机方法将被用于强调低温 光谱技术

The objective of this proposal is the elucidation of the process known as the chemical production of electronically excited states. In some cases the excited states emit light, and the overall process is termed chemiluminescence (or bioluminescence if the process is catalyzed by an enzyme). In other cases the excited states (singlet and triplet) enter into chemical and biochemical reactions. Because of the high sensitivity of the measurement of light emission from "black bodies" at room temperature chemiluminescence shows promise as a safe replacement for many techniques utilizing radioactivity. For example, the cyclic hydrazides we investigated a decade ago are currently being used in antibody binding assays. Chemiluminescence is also used widely to assay foretals, ATP, enzymatically generated peroxides, etc. The present proposal is aimed at an understanding of: (1) the generation of excited states from cyclic hydrazides such as luminol. We propose to (a) synthesize the monohydrazide of 5-methyldehydroluciferin (firefly) and test it for light emission on oxidation, (b) synthesize efficient chemiluminescent phthalazinediones derived from N,N-dibutylisoluminol, (c) attempt a low temperature synthesis and study of the bicyclic peroxides proposed to be crucial intermediates in cyclic hydrazide chemiluminescence, and (d) examine the basic chemistry of acyldiazenes at low temperatures and in the absence of oxygen. (2) the generation of excited states from dioxetanes and dioxetaneones based on the highly fluorescent acridine ring systems. Emission from the weakly acidic acridone in both chemiluminescence and fluorescece will be compared; the data may permit a decision as to whether the CIEEL mechanism is operating in these intramolecular cases of excitation. The synthesis, structure, and chemistry of photochemically produced peroxides based on 9-substituted acridine ring systems will be examined. (3) the generation of excited states from firefly luciferin. Emphasis will be placed on fast reactions of the initially formed excited state to yield (possibly?) a yellow-green light-emitting molecule-in an effort to perfect a model system for the yellow-green light emission of the firefly. Analytically pure LH2AMP will be prepared for this study. Physical-organic approaches will be used with emphasis on low temperature spectroscopic techniques.