光谱学与光谱分析
光譜學與光譜分析
광보학여광보분석
Spectroscopy and Spectral Analysis
2015年
11期
3111-3116
,共6页
李燕琴%牟兰%曾晞%李俊%大和武彦
李燕琴%牟蘭%曾晞%李俊%大和武彥
리연금%모란%증희%리준%대화무언
香豆素%1 ,3交替硫杂杯4 芳烃%Fe3+%牛血红蛋白
香豆素%1 ,3交替硫雜杯4 芳烴%Fe3+%牛血紅蛋白
향두소%1 ,3교체류잡배4 방경%Fe3+%우혈홍단백
Coumarin%Thiacalix[4]arene Derivatives%Fe3+%Bovine Hemoglobin
以1,3‐交替二乙酯硫杂杯[4]芳烃和7‐羟基香豆素为原料,分步取代杯芳烃下沿,合成得到1,3‐交替香豆素‐硫杂杯[4]芳烃荧光探针1。在DMSO/H2 O (φ,3/7,pH 7)溶液中,探针1发射的强荧光被 Fe3+选择性猝灭;F e3+使探针1的紫外吸收显著增强。相同条件下其他常见金属离子的加入对探针1的荧光及吸收光谱无影响,探针在水溶液介质中仅对Fe3+高选择性识别,荧光和吸收光谱法的检测限均达10-8 mol?L -1。光谱滴定、等温滴定量热及质谱法均测出探针1与Fe3+形成1∶1配合物,作用常数达105 L?mol-1。从摩尔结合自由能和结合熵分别表明配合作用为自发过程。同时,在DMSO/H2 O (φ,1/9,Tris‐HCl ,pH 7,0.1 mol?L -1 NaCl)介质中,探针1能选择性猝灭识别牛血红蛋白(BHb),线性范围在0.2~3.0μg?mL -1,检测限达0.12μg?mL -1。为一种选择性识别Fe3+和BHb的杯芳烃荧光探针。
以1,3‐交替二乙酯硫雜杯[4]芳烴和7‐羥基香豆素為原料,分步取代杯芳烴下沿,閤成得到1,3‐交替香豆素‐硫雜杯[4]芳烴熒光探針1。在DMSO/H2 O (φ,3/7,pH 7)溶液中,探針1髮射的彊熒光被 Fe3+選擇性猝滅;F e3+使探針1的紫外吸收顯著增彊。相同條件下其他常見金屬離子的加入對探針1的熒光及吸收光譜無影響,探針在水溶液介質中僅對Fe3+高選擇性識彆,熒光和吸收光譜法的檢測限均達10-8 mol?L -1。光譜滴定、等溫滴定量熱及質譜法均測齣探針1與Fe3+形成1∶1配閤物,作用常數達105 L?mol-1。從摩爾結閤自由能和結閤熵分彆錶明配閤作用為自髮過程。同時,在DMSO/H2 O (φ,1/9,Tris‐HCl ,pH 7,0.1 mol?L -1 NaCl)介質中,探針1能選擇性猝滅識彆牛血紅蛋白(BHb),線性範圍在0.2~3.0μg?mL -1,檢測限達0.12μg?mL -1。為一種選擇性識彆Fe3+和BHb的杯芳烴熒光探針。
이1,3‐교체이을지류잡배[4]방경화7‐간기향두소위원료,분보취대배방경하연,합성득도1,3‐교체향두소‐류잡배[4]방경형광탐침1。재DMSO/H2 O (φ,3/7,pH 7)용액중,탐침1발사적강형광피 Fe3+선택성졸멸;F e3+사탐침1적자외흡수현저증강。상동조건하기타상견금속리자적가입대탐침1적형광급흡수광보무영향,탐침재수용액개질중부대Fe3+고선택성식별,형광화흡수광보법적검측한균체10-8 mol?L -1。광보적정、등온적정량열급질보법균측출탐침1여Fe3+형성1∶1배합물,작용상수체105 L?mol-1。종마이결합자유능화결합적분별표명배합작용위자발과정。동시,재DMSO/H2 O (φ,1/9,Tris‐HCl ,pH 7,0.1 mol?L -1 NaCl)개질중,탐침1능선택성졸멸식별우혈홍단백(BHb),선성범위재0.2~3.0μg?mL -1,검측한체0.12μg?mL -1。위일충선택성식별Fe3+화BHb적배방경형광탐침。
1 ,3‐alternate coumarin substituted thiacalix [4]arene fluorescent probe 1 was synthesised from 1 ,3‐alternate diethyl thiacalix[4]arene and 7‐hydroxycoumarin by‐step reactions .In DMSO/H2O (φ,3/7 ,pH 7) solution ,the strong fluorescence emission and UV absorption of probe 1 can be selectively quenched or significantly enhanced by Fe3+ ion .The probe 1 showed high Fe3+ selective fluorescence quenching or absorption enhancement over commonly coexistent metal ions in neutral aqueous media ,and the limit of detections were obtained as low as 10-8 mol?L -1 of Fe3+ by fluorescence and absorption spectrometry . Spectral titration ,isothermal titration calorimetry and mass spectrometry were showed that probe and Fe3+ form 1∶1 comple‐xes ,the constant up to 105 L?mol-1 and coordinate process was spontaneous by the mole binding free energy and entropy of probe with Fe3+ .In addition ,the probe can identification bovine hemoglobin (BHb) over other proteins through quenched its fluorescenceinDMSO/H2O(φ,1/9,Tris‐HCl,pH7,0.1mol?L -1NaCl)media.Thelimitofdetectionwasobtainedas0.12μg?mL -1 of BHb ,as well as a linearity of 0.2~3.0μg?mL -1 ,indicating the probe of high sensitivity and quantitation range . It can be used as a selective recognition Fe3+ and BHb of thiacalix[4] arene fluorescent probe .