一、利用電子激發態分子探測釕金屬修飾蛋白質內的長距離電子傳遞及檢測十二烷基硫酸鈉的濃度 二、七種台灣精油的化學組成及對大腸桿菌的抗菌效果

Abstract

本研究合成出釕金屬聯吡啶錯合物([Ru((CH3)2bpy)2(im)2]2+與[Ru((COO−)2bpy)2(im)2]2−)，並將其修飾在細胞色素c (cyt c)上，再藉由閃光淬熄法來探測蛋白質內的電子傳遞。修飾上推電子取代基的[Ru((CH3)2bpy)2(im)2]2+與Ru(NH3)63+反應後，得到25.1%的激發態淬熄率和42.0%的三價釕金屬([RuIII( )2(im)2]3+)生成率；修飾上拉電子取代基的[Ru((COO−)2bpy)2(im)2]2−則有65.2%激發態淬熄率和19.6%的三價釕金屬生成率。同樣將釕金屬修飾蛋白質與Ru(NH3)63+反應，發現Ru((CH3)2bpy)2(im)(His33)-Fe2+-cyt c的分子內電子傳遞之量子產率是17.6%，而Ru((COO−)2bpy)2(im)(His33)-Fe2+-cyt c的分子內電子傳遞之量子產率則是11.9%。儘管反應驅動力預測Ru((COO−)2bpy)2(im)(His33)-Fe2+-cyt c有較大的量子產率，但還要考慮另外兩個變數的影響(籠蔽效應跟化學反應)。 利用Ru(bpy)2dppz2+的光開關性質來檢測十二烷基硫酸鈉的濃度，隨著十二烷基硫酸鈉的濃度增加，Ru(bpy)2dppz2+的磷光強度也增加。然而，當十二烷基硫酸鈉的濃度小於0.1%時，Ru(bpy)2dppz2+會沉澱析出，因此換用溴化乙錠。在低濃度的十二烷基硫酸鈉(0−0.1%)，溴化乙錠的吸收波長最大值會紅位移而螢光強度會降低；當十二烷基硫酸鈉的濃度超過0.1%，溴化乙錠的吸收波長最大值會藍位移而螢光強度會增強；當十二烷基硫酸鈉的濃度超過臨界微胞濃度後，溴化乙錠的螢光強度維持不變。利用上述現象，溴化乙錠可以拿來檢測十二烷基硫酸鈉的濃度。 利用氣相層析質譜儀分離鑑定七種台灣精油，再透過NIST 08資料庫的比對，可以清楚辨識主要的化學成分。藉由定量分析的實驗，可以得知精油的主要成分含量，比較文獻後發現，不同產地的精油其組成成分會有很大的差異。將七種精油分別加入大腸桿菌培養液中，經過24小時後，發現廣藿香的抑菌效果非常好，只要0.05%的濃度就可以完全抑制大腸桿菌的生長；而丁香羅勒和甜馬鬱蘭的抑菌效果也不差，兩者的最低抑菌濃度都是0.1%。Ruthenium bipyridine-type compounds, [Ru((CH3)2bpy)2(im)2]2+ and [Ru((COO−)2bpy)2(im)2]2−, were synthesized to evaluate the protein electron transfer property by flash-quench method. After reacting with Ru(NH3)63+, [Ru((CH3)2bpy)2(im)2]2+, with electron donating substitutents, gives quenching yield of 25.1% and formation yield of [RuIII( )2(im)2]3+ species of 42.0%. While [Ru((COO−)2bpy)2(im)2]2−, with electron withdrawing substitutents, has 65.2% of quenching yield and 19.6% of formation yield of [RuIII( )2(im)2]3+ species. In those ruthenium modified cytochrome c, Ru((CH3)2bpy)2(im)(His33)-Fe2+-cyt c has the largest quantum yield of intramolecular electron transfer (17.6%) and the smallest for Ru((COO−)2bpy)2(im)(His33)-Fe2+-cyt c (11.9%). Although driving force favors for Ru((COO−)2bpy)2(im)(His33)-Fe2+-cyt c, cage effect and chemical reaction are other variable factors in the trend. Ru(bpy)2dppz2+, known for its light switch property, had been utilized to evaluate the concentration of SDS. As the concentration of SDS increases, the emission intensity of Ru(bpy)2dppz2+ increases. Unfortunately, at the attempt to lower the SDS concentration below 0.1%, Ru(bpy)2dppz2+ precipitates, therefore, ethidium bromide (EtdBr) was employed. In the low concentration of SDS (0−0.1%), the wavelength of absorption maximum red shifts and the emission intensity decreases. While the concentration of SDS is above 0.1%, the wavelength of absorption maximum blue shifts and the emission intensity is recovering. At above the CMC of SDS, the emission intensity remains unchanged and is higher than that without SDS. An assay for evaluating of SDS concentration by EtdBr has been proposed. Chemical compositions of seven essential oils from Taiwan had been analyzed by gas chromatography−mass spectroscopy. The eluates had been identified by matching the mass fragment patents to the NIST 08 database. Quantitatively analysis showed the major components are somewhat different from the same essential oils reported that are obtained from other origins. The antibacterial activity of the essential oils against Escherichia coli was evaluated by optical density method. Patchouli is a very effective inhibitor that completely inhibits the growth of E. coli at 0.05%. Clove basil and sweet marjoram are good inhibitors and their upper limits of minimum inhibitory concentration are 0.1%.