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研究生:陳緯霖
研究生(外文):Wei-Lin Chen
論文名稱:槲皮素、蘆丁和花旗松素與過渡金屬錯合物之氧化還原反應
論文名稱(外文):The Redox Reactions of Quercetin、Rutin and Taxifolin with Transition Metal Complexes
指導教授:葉玉堂
指導教授(外文):Andrew Yeh
口試委員:林助傑高漢謀陳繼添
口試委員(外文):Chu-Chieh LinHan-Mou GauChi-Tien Chen
學位類別:碩士
校院名稱:東海大學
系所名稱:化學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2010
畢業學年度:98
語文別:中文
論文頁數:58
中文關鍵詞:槲皮素蘆丁花旗松素
外文關鍵詞:QuercetinRutinTaxifolin
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槲皮素、蘆丁及花旗松素與Co(edta)-,在pH = 9 – 13,μ = 0.10 M LiClO4條件下,T = 25℃的反應屬雙電子氧化,生成quinone產物,反應速率決定步驟為第一個電子氧化,形成semiquinone自由基中間產物,接著Co(edta)-錯合物再迅速將自由基氧化成quinone型式。反應動力學結果顯示槲皮素、蘆丁及花旗松素之k2及pKa2值分別為4.57×102 M-1s-1,11.40;1.43×10-1 M-1s-1,11.12;7.35×10-2 M-1s-1,12.62。槲皮素的反應速率比蘆丁及花旗松素大了3次冪以上,主要是由於C3上的羥基去氧化和pyrone與catechol之間的共振效應影響。pH = 1 - 2 類黃酮與Ru(NH3)5(pzCH3)4+的氧化反應同時也被探討,在此條件下槲皮素之C3上的OH基並未去質子化,所得k0值與蘆丁及花旗松素並無明顯差異。

The reactions of quercetin, rutin and taxifolin with Co(edta)- complex at pH = 9 - 13 proceeded by two election oxidation with quinone species as final products. The rate determining step of the reaction is the first electron oxidation to form semiquinone radical as intermediate, which is further oxidized by anther Co(edta)- complex at a fast rate to form the product. The kinetic results at μ = 0.10 M LiClO4 and T = 25℃ yielded values of k2 and pKa2 for quercetin, rutin and taxifolin as 4.57×102 M-1s-1, 11.40;1.43×10-1 M-1s-1, 11.12;and 7.35×10-2 M-1s-1, 12.62 respectively. The rate constant of oxidation for quercetin is greater than those of rutin and taxifolin by more than 3 orders of magnitude. The deprotonation of the C3-OH and the conjugation between pyrone and catechol rings due to C2-C3 double bond may account for this enormous rate difference. The kinetics of the oxidation of flavonoids by Ru(NH3)5(pzCH3)4+ complex at pH = 1 - 2, where the C3-OH of the quercetin remained protonated, were also investigated. The k0 value of the quercetin is comparable with those of rutin and taxifolin, as is expected.
總目錄
中文摘要--------------------------------------------------------------------------I
英文摘要--------------------------------------------------------------------------II
總目錄----------------------------------------------------------------------------III
圖目錄----------------------------------------------------------------------------V
表目錄---------------------------------------------------------------------------VII
第一章 序論----------------------------------------------------------------------1
第二章 實驗---------------------------------------------------------------------12
一、藥品----------------------------------------------------------------------12
二、藥品的純化與溶液配製----------------------------------------------14
三、去氧處理----------------------------------------------------------------16
四、合成----------------------------------------------------------------------19
五、分析儀器及方法-------------------------------------------------------23
第三章 結果---------------------------------------------------------------------26
一、光譜鑑定---------------------------------------------------------------26
二、氧化產物鑑定----------------------------------------------------------29
三、反應動力學-------------------------------------------------------------31
第四章 討論---------------------------------------------------------------------45
第五章 結論---------------------------------------------------------------------48
第六章 參考文獻---------------------------------------------------------------49
附錄一---------------------------------------------------------------------------52
附錄二---------------------------------------------------------------------------59






圖目錄
Figure 1.1、Eriodictyol之結構-------------------------------------------------4
Figure 1.2、類黃酮的基本結構------------------------------------------------5
Figure 1.3、類黃酮衍生物之結構---------------------------------------------6
Figure 2.1、隔氧處理系統示意圖---------------------------------------------17
Figure 2.2、注射器轉移錯合物溶液裝--------------------------------------18
Figure 2.3、李可瓶(Zwickel flask)示意圖-----------------------------------18
Figure 2.4、Co(edta)- 還原反應圖--------------------------------------------25
Figure 3.1、quercetin光譜氧化圖--------------------------------------------28
Figure 3.2、quercetin與Co(edta)-錯合物氧化圖--------------------------28
Figure 3.3、quercetin還原Co(edta)-錯合物之化學計量圖--------------29
Figure 3.4、quercetin-[Co(edta)-]反應物之ln(Ai- At)對時間(s)作圖-32
Figure 3.5、pH9.00-11.86,quercerin氧化反應之kobs vs. [Co(edta)- ]
錯合物圖-----------------------------------------------------------34
Figure 3.6、pH10.86-11.86,rutin氧化反應之kobs vs. [Co(edta)- ]
錯合物圖-----------------------------------------------------------35
Figure 3.7、[OH-] = 0.01-0.1M,taxifolin氧化反應之kobs vs. [Co(edta)- ]
錯合物圖-----------------------------------------------------------35
Figure 3.8、pH = 1.0 - 2.0,Ru(NH3)5(pzCH3)4+錯合物還原反應之kobs
vs. quercetin圖-----------------------------------------------------36
Figure 3.9、pH = 1.0 - 2.0,Ru(NH3)5(pzCH3)4+錯合物還原反應之kobs
vs. taxifolin圖-----------------------------------------------------36
Figure 3.10、pH 9.00-9.80,Co(edta)-錯合物與quercetin反應---------39
Figure 3.11、pH 10.86-11.86,Co(edta)-錯合物與quercetin反應------41
Figure 3.12、pH 10.01-10.99,Co(edta)-錯合物與rutin反應-----------41
Figure 3.13、[OH-] = 0.01-0.1M,Co(edta)-錯合物與taxifolin反應------42
Figure 3.14、pH = 1.0 - 2.0,Ru(NH3)5(pzCH3)4+錯合物與quercetin反
應------------------------------------------------------------------43
Figure 3.15、pH = 1.0 - 2.0,Ru(NH3)5(pzCH3)4+錯合物與taxifolin反
應------------------------------------------------------------------44



表目錄
Table 1、UV-vis光譜-----------------------------------------------------------27
Table 2、quercetin、rutin及(±)-taxifolina氧化前後之1H-NMR訊號
--------------------------------------------------------------------------30
Table 3、pH=9.0 -13.0 M,Co(edta)-錯合物與quercetin、rutin及taxifolin
還原反應之速率常數k----------------------------------------------37
Table 4、pH = 1.0 - 2.0,Ru(NH3)5(pzCH3)4+錯合物與quercetin及
taxifolin還原反應之速率常數k ---------------------------------38
Table 5、 Ru(NH3)5(pzCH3)4+ 、Co(edta)- 錯合物之還原反應速率常數
------------------------------------------------------------------------45
Table A1、pH = 1.0 - 2.0,Ru(NH3)5(pzCH3)4+錯合物與quercetin還原
反應之kobs----------------------------------------------------------53
Table A2、pH = 1.0 - 2.0,Ru(NH3)5(pzCH3)4+錯合物與taxifolin還原
反應之kobs----------------------------------------------------------54
Table A3、pH = 9.00 - 11.86,Co(edta)- 錯合物與quercetin氧化反應之
kobs--------------------------------------------------------------------55
Table A4、pH = 10.01 - 10.99,Co(edta)- 錯合物與rutin氧化反應之kobs
------------------------------------------------------------------------57
Table A5、[OH-] = 0.01 - 0.1M,Co(edta)- 錯合物與taxifolin氧化反應
之kobs-----------------------------------------------------------------58

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