阳离子铝酞菁-血卟啉单甲醚缔合物荧光探针对黄连素的特异性响应及其应用

Construction of a Red-Emitting Associate Fluorescent Probe Consisting of a Cationic Aluminum Phthalocyanine and Hematopophyrin Monomethylether: Its Response to Berberine and Application

黄连素(BBR)在医学领域有广泛的应用,其定量分析对指导临床治疗具有重要价值。常见的黄连素检测方法的灵敏度、响应范围、检测成本等方面尚存在不足。本研究发现,带有负电基团的血卟啉单甲醚(HMME)对红区发射的强荧光化合物阳离子铝酞菁(TTMAAlPc)具有高效荧光猝灭作用,形成几乎无荧光的离子缔合物,而在盐酸小檗碱的存在下,体系重新发出酞菁特有的红色荧光,且荧光恢复程度与盐酸小檗碱的浓度呈正相关。这一现象的发生是由于血卟啉单甲醚与阳离子铝酞菁分子通过平面疏水作用、静电作用和水分子介导的氢键作用等超分子作用力而形成缔合物(HMME-TTMAAlPc),而盐酸小檗碱则通过强竞争结合作用,使阳离子铝酞菁从缔合物中被释放出来,导致体系荧光显著恢复。据此发现,建立了盐酸小檗碱荧光增强定量分析新方法。考察了各种因素对方法的影响,在最优条件下,标准工作曲线的方程为ΔIf=12.85c+66.30,线性区间为0.3~69.0 mg·L^-1,检测限为15.0μg·L^-1,相关系数r=0.9972。研究表明,该方法特异性强、操作简便、成本低廉。该方法已用于实际样品的测定,取得了满意的结果。该研究开拓了酞菁红色荧光探针在药物分析领域中的应用。

Berberine(BBR)is widely used and of significant importance in medical field,and its quantitative analysis is of great value in guiding clinical treatment.There still be some shortcomings remaining in the determination of berberine by traditional methods,such as less sensitivity,narrow response range,or high testing cost.In this study,we found that hematoporphyrin monomethyl ether(HMME)with negative groups had a high fluorescence quenching effect on Tetra(trimethylammonia)aluminum phthalocyanine(TTMAAlPc),a cationic phthalocyanine compound emitting strong red fluorescence,due to the formation of an almost non-fluorescent ion associate.Interestingly,it was found that the fluorescence of TTMAAlPc-HMME associate re-emitted in the presence of berberine.The recovery of fluorescence of TTMAAlPc was positively correlated with the concentration of berberine.The mechanism of the above-mentioned phenomena was discussed.We believed that the high-efficiency fluorescence quenching effect of HMME on TTMAAlPc can be attributed to the formation of associate consisting of hematoporphyrin monomethyl ether and the cationic aluminium phthalocyanine(HMME-TTMAAlPc)through supramolecular interactions including planar hydrophobic interaction,π-bond stacking,electrostatic interaction and hydrogen bonding mediated by water molecules.The fluorescence recovery was due to the strong competitive binding to release the cationic aluminum phthalocyanine from the associate by berberine with a molecular structure matches TTMAAlPc.A new fluorescence-enhanced quantitative analysis method for berberine was established based on the above-findings.The factors including pH,sorts of buffer,reaction temperature,usages of HMME and TTMAAlPc and reaction time that affected the determination were investigated.Under the optimum conditions,the equation of calibration curve was If=12.85c+66.30 with a correlation coefficient(R)of 0.9972,the linear range was 0.3~69.0 mg·L^-1,and the detection limit was 0.01~5.0 mg·L^-1.The study indicated that this method bears the merits of strong specificity,simple operation and low cost.The established method has been applied to the determination of practical samples with satisfactory results.This study not only presents a new strategy for the construction of phthalocyanine-based optical probes,but also opens up the application of red-emitting phthalocyanines in the field of drug analysis.