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題名 | Temperature and Solvent Effects on the Photoisomerzation Rates of 8-Anilino-1-Naphthalenesulfonates in Protic Solvents=溫度和溶劑對溶於質子性溶劑中的8-苯胺基-1-萘磺酸光異構化速率的影響 |
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作者 | 張自立; | 書刊名 | 臺北師院學報 |
卷期 | 11 1998.06[民87.06] |
頁次 | 頁439-451 |
分類號 | 341.3482 |
關鍵詞 | 溫度; 溶劑; 8-苯胺基-1-萘磺酸; |
語文 | 英文(English) |
中文摘要 | Weber和Laurence在1954年首先發現:8-苯胺基-1-�B磺酸(1,8-ANS)的螢光 光譜極大值波長及量子產率的變化對溶劑是非常敏感的。在水中,1,8-ANS幾乎沒 有螢光,但在非極性有機溶劑中,或當與蛋白質結合時,就會表現出很強的螢光及 相對於在水中螢光的藍移現象。很多不同的機制被提出來解釋1,8-ANS螢光與溶劑 間的關係。但是, 這些機制都無法提供一個定量的方法來檢驗溶劑對非輻射路徑的 影響。我們曾經使用Grabowski 所提關於對二甲胺苯甲�蘌钂疇�的模型及由我們所 推導的一個經驗性公式,定量地檢驗了1,8-ANS在水和乙醇混合溶劑的非輻射速率 (Chang and Cheung,1990)。此研究結果顯示非輻射速率和溶劑極性有極密切的關 係。在本研究中,我們除了溶劑極性之外,更考慮了溶劑黏滯性和溫度的影響。我 們重新檢驗1,8-ANS在質子性溶劑中的非輻射速率,及當1,8-ANS在水中且溫度升 高時,發生不尋常量子產率增加的現象。本研究結果顯示出不尋常量子產率增加現 象是由3個因素所造成:(1)溶劑極性對1,8-ANS的光異構化速率影響很大,(2)水是 極性最大的溶劑,及(3)1,8-ANS在TMS溶劑中的障壁高度不是非常大。 |
英文摘要 | The sensitivity of the fluorescence maxima and quantum yields of 8-anilino-1-naphthalenesulfonates(1,8-ANS) was first recognized by Weber and Laurence in 1954, In water, 1,8-ANS is almost nonfluorescent but in nonpolar organic solvents, or when bound to proteins, exhibits a strong fluorescene and a blue shift of fluorescence maximum as compared with that in water. Various machanisms have been proposed to explain the solvent sensitivity of 1,8-ANS fluorescence. However, none of them can provide a quantitative way to examine the solvent effects on the nature of the nonradiative pathway. Using the Grabowski model originally proposed to explain the dual fluorescence of p-dimethylaminobenzonitriles and an empirical formula derived by us, we have quantitativel examined the nonradiative rates of 1,8ANS in water-ethanol mixed solvents (Chang and Cheung, 1990). In that work it is clearly shown that the nonradiative rates depend on dolvent polarity. Aside from sdlvent polarity, we consider solvent viscosity and temperature effects in this work. We re-examined the nonradiative rates of 1,8-ANS in protic solvents and the uncommon increase of quantum yield for 1,8-ANS in H�烙 at elevated temperatures. Our analysis indicates that the uncommon increase of quantum yield is observed because of three fabtors:(1)solvent polarity effect is quite large for the photoisomerization rate of 1,8-ANS in protic solvents, (2)H�烙 is the solvent with the greatest polarity, and (3)the barrier height of 1,8-ANS in tetramethylsilane (TMS) is not too large. |
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