CHEMILUMINESCENCE OF ORGANIC COMPOUNDS

这项提议的目标是阐明被称为 电子激发态的化学产生。在某些情况下 激发态发出光，整个过程称为 化学发光(或生物发光，如果该过程是由一种 酶)。在其他情况下，激发态(单重态和三重态)进入 转化为化学反应和生化反应。因为它的高灵敏度 测量房间内“黑体”的光发射 温度化学发光有望成为许多药物的安全替代品 利用放射性的技术。例如，环肼类化合物 十年前研究的抗体目前被用于抗体结合 化验。化学发光法也被广泛用于测定前体、三磷酸腺苷、 酶促生成的过氧化氢等。 本提案的目的是了解：(1)产生 来自环肼的激发态，如鲁米诺。我们建议(A) 5-甲基脱氢荧光素(萤火虫)单酰肼的合成及检测 它在氧化上发光，(B)合成效率高 N，N-二丁基异鲁米诺衍生的化学发光二氮杂二酮，(C) 尝试低温合成双环过氧化氢化合物的研究 被认为是环肼化学发光的关键中间体， 和(D)在低温下研究酰基二氮烯的基本化学和 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己烷和二氧杂环己酮 系统。弱酸性吖啶酮在两种情况下的发射 将化学发光和荧光进行比较；数据可能允许 关于CIEEL机制是否在这些地区运行的决定 分子内激发的情况。它的合成、结构和 基于9-取代基光化学产生的过氧化氢的化学 我们将研究吖啶环系统。(3)激发的产生 状态从萤火虫的荧光素。重点放在快速反应上 初始形成的激发态的屈服(可能吗？)黄绿色的 发光分子-为了完善一个模型系统， 萤火虫发出黄绿色的光。分析纯LH2 AMP将 为这次研究做好准备。 将使用物理-有机方法，重点是低温 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.