药物活性成份在线富集毛细管电泳分析方法及其与生物大分子之间相互作用的研究
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摘要
本论文将毛细管电泳分离技术与在线推扫富集技术、中空纤维液相微萃取技术相结合，建立了中草药和生物样品中的马钱子生物碱、卡马西平的高效、灵敏和选择性好的CE分离检测方法。并研究了中草药中的马钱子生物碱、防己生物碱、槲皮素以及卡马西平与血清白蛋白的相互作用。在系统查阅有关文献资料的基础上，进行了以下研究工作：
(1)采用在线推扫预富集—胶束毛细管电泳法建立了测定中草药中马钱子生物碱的新方法。经过实验优化，最佳分离条件为：分离缓冲溶液为50 mmol L~(-1) H_3PO_4(pH 2.0)，100 mmol L~(-1) SDS，20％乙腈(v／v)，分离电压-20 kV，在0.5 psi下进样270 s，检测波长为203 nm。与传统MEKC方法相比较，灵敏度提高了100倍(以峰高计)。以小檗碱为内标，士的宁与马钱子碱的浓度在0.5～15μg／mL范围内与其峰面积与内标峰面积的比值呈良好的线性关系，线性相关系数分别为0.998和0.997，检出限分别为0.05μg／mL和0.07μg／mL。本方法应用于测定中草药马钱子和中药制剂伸筋活络丸中马钱子碱的含量，获得满意结果。
(2)首次将中空纤维液相微萃取(HF-LPME)与在线推扫富集胶束电动色谱法相结合，建立了测定尿样中马钱子生物碱的新方法。以小檗碱为内标，士的宁、马钱子碱与内标峰面积的比值与分析物浓度在20～200 ng／mL范围内呈良好的线性关系，线性相关系数分别为0.996和0.997，士的宁与马钱子碱的检出限分别为1ng／mL和2 ng／mL(S／N=3∶1)。
(3)建立了在线推扫富集毛细管电泳紫外检测测定药物和人血清中卡马西平浓度的方法。以pH=3.0的50 mmol L~(-1) NaH_2PO_4，100 mmol L~(-1) SDS，20％乙腈为分离缓冲溶液，在0.5 psi下进样90 s，检测波长214 nm，分离电压为-20 kV。卡马西平浓度在0.5-40μg／mL范围内与其峰面积呈良好的线性关系，线性相关系数为0.998，检出限为0.1μg／mL(S／N=3∶1)。
(4)建立了毛细管区带电泳紫外检测测定血清中左旋多巴和甲基多巴的新方法，以pH=9.5的40 mmol L~(-1)硼砂为分离缓冲溶液，在0.5 psi压力下进样7 s，分离电压22 kV，检测波长200 nm，检测温度25℃的条件下进行测定，甲基多巴和左旋多巴浓度分别在0.001～0.064 mg／mL和0.001～0.071 mg／mL范围内与峰面积呈良好线性关系，线性相关系数分别为0.9998和0.9994，检出限分别为0.6μg／mL和0.8μg／mL(信噪比为3∶1)，已用于血清中甲基多巴和左旋多巴的测定。
(5)应用荧光光谱和紫外光谱法研究了马钱子碱与牛血清白蛋白(BSA)的结合反应，求得它们之间的结合常数K_A和结合位点数n，分别为K_A=6,3×10~3，n=0.94(27℃)；KA=7.7×10~3，n=0.97(37℃)。根据F(?)rster非辐射能量转移理论求出了马钱子碱与BSA之间的结合距离为3.99 nm(27℃)和4.21 nm(37℃)。探讨了马钱子碱的荧光猝灭机理，结果表明马钱子碱能够插入BSA内部形成基态复合物导致其内源荧光猝灭，猝灭机理主要是静态猝灭和非辐射能量转移。根据热力学参数确定了马钱子碱与BSA之间的作用力类型主要为疏水性相互作用。
(6)在不同温度下，用荧光猝灭光谱、同步荧光光谱、三维荧光光谱和紫外．可见吸收光谱，研究了防己诺林碱和粉防己碱与牛血清白蛋白和人血清白蛋白(HSA)之间的相互作用。结果表明，防己诺林碱和粉防己碱对血清白蛋白有较强的荧光猝灭作用，根据不同温度下防己诺林碱和粉防己碱对血清白蛋白的荧光猝灭作用，确定他们对血清白蛋白的荧光猝灭作用属于静态猝灭。并根据F(?)rster非辐射能量转移理论计算出防己诺林碱和粉防己碱与血清白蛋白间的结合距离r、结合常数K_A和结合位点数n。防己诺林碱与牛血清白蛋白之间的K_A=1.05×10~5，n=1.4，r=2.53(t=27℃)；K_A=3.31×10~5，n=1.3，r=2.70(t=37℃)；K_A=7.24×10~5，n=1.2，r=2.92(t=47℃)。防己诺林碱与人血清白蛋白之间的K_A=5.04×10~5，n=1.2，r=3.52(t=27℃)；K_A=5.38×10~5，n=1.3，r=3.81(t=37℃)；K_A=5.67×10~5，n=1.4，r=4.38(t=47℃)。粉防己碱与牛血清白蛋白之间的K_A=1.52×10~5，n=1.2，r=2.34(t=27℃)；K_A=2.03×10~5，n=1.3，r=2.48(t=37℃)；K_A=2.89×10~5，n=1.4，r=2.71(t=47℃)。粉防己碱与人血清白蛋白之间的K_A=4.02×10~5，n=1.0，r=3.00(t=27℃)；K_A=4.76×10~5，n=1.2，r=3.14(t=37℃)；K_A=4.98×10~5，n=1.3，r=3.39(t=47℃)。并根据热力学数据确定了它们之间的主要作用力类型，同时用同步荧光光谱和三维荧光光谱探讨了防己诺林碱和粉防己碱对血清白蛋白构象的影响。
(7)利用荧光光谱和紫外光谱法研究了槲皮素与牛血清白蛋白之间的相互作用。结果表明，静态猝灭和非辐射能量转移是导致槲皮素对BSA荧光猝灭的两大原因，槲皮素与BSA的结合常数K_A为2.8×10~8(26℃)和3.1×10~8(36℃)，结合位点数为1.76±0.01，根据F(?)rster非辐射能量转移理论得到槲皮素与BSA之间的结合距离为3.25 nm(26℃)和3.30 nm(36℃)，表明槲皮素的部分片段可以插入BSA分子内部。通过计算热力学参数，可知该药物与蛋白的相互作用是一个熵增加和吉布斯自由能降低的自发过程，并由此推断槲皮素与BSA之间的作用力是以疏水相互作用为主。
(8)应用荧光光谱和紫外光谱法研究了卡马西平(CBZ)与牛血清白蛋白的结合反应，实验结果表明，卡马西平可以插入BSA分子内部形成CBZ-BSA复合物而产生荧光猝灭。研究表明静态猝灭和非辐射能量转移是导致卡马西平对BSA荧光猝灭的两大原因。求得CBZ与BSA之间的结合常数K_A分别为1.8×10~4(27℃)；2.8×10~4(37℃)和结合位点数n：0.97(27℃)；1.01(37℃)。根据F(?)rster非辐射能量转移理论求出了卡马西平与BSA之间的结合距离为3.6 nm(27℃)和3.4 nm(37℃)。CBZ与BSA的结合过程是熵增大，吉布斯自由能减小的过程，反应自发进行，它们之间主要靠疏水作用力结合。
In the thesis, CE was combined with on-line sweeping and hollow fiber-basedliquid-phase microextraction technique. Efficient and sensitive methods were developedfor the determination of Strychnos alkaloids, carbamazepine in Chinese herbal medicinesand biological samples. The interactions of Strychnos alkaloids, fangchinoline,tetrandrine and carbamazepine with serum albumin were studied by fluorescencequenching spectra, synchronous fluorescence spectra, three-dimensional fluorescencespectra and ultra-violet spectra. This thesis is mainly concerned with the followingaspects:
(1) The investigation of an on-line sweeping preconcentration method in micellarelectrokinetic chromatography (MEKC) for the determination of Strychnos alkaloids,namely strychnine and brucine.
After experimental optimizations, the best separation was achieved in 50 mmol L~(-1)H_3PO_4 (pH 2.0) containing 100 mmol L~(-1) SDS and acetonitrile in a ratio of 4:1 (v/v),with an applied voltage of -20 kV at 20℃. The sample matrix consisted of 100 mmol L~(-1)H_3PO_4 (pH 2.0), and sample introduction was performed at 0.5 psi for 270 s, withphotodiode array detection at 203 nm. Compared with the conventional MEKC injectionmethod, up to 100-fold improvement in concentration sensitivity was achieved in termsof peak height by using this sweeping injection technique. In the method, the compoundberberine was used as the internal standard for the improvement of the experimentalreproducibility. The calibration curve was linear over a range of 0.5-15μg mL~(-1) for bothstrychnine and brucine, with a correlation coefficient of 0.998 and 0.997, respectively.The detection limits (S/N=3:1) for strychnine and brucine were 0.05μg mL~(-1) and 0.07μg mL~(-1), respectively. The Sweeping-MEKC method has been successfully applied to theanalysis of strychnine and brucine in Strychnos nux-vomica L and its Chinese medicinalpreparations.
(2) The establishment of a new method for the enrichment of Strychnos alkaloids inbiological samples via liquid-phase mieroextraction (LPME) based on porous polypropylene hollow fibers combined with on-line sweeping in micellar electrokineticchromatography (MEKC).
Strychnos alkaloids were first extracted from urine sample, in which the concentrationof NaOH was 0.5 mmol L~(-1). The unionized analytes were subsequently extracted into1-octanol impregnated in the pores of hollow fibers, and then into 100 mmol L~(-1) H_3PO_4inside the hollow fiber. The extract was analyzed directly by on-line sweeping in micellarelectrokinetic chromatography (MEKC). In the method, the compound berberine wasused as the internal standard for the improvement of the experimental reproducibility.The calibration curve was linear over a range of 20-200 ng mL~(-1) for both strychnine andbrucine in human urine sample, with a correlation coefficient of 0.996 and 0.997,respectively. The detection limits (S/N=3:1) for strychnine and brucine were 1 ng ml~(-1)and 2 ng mL~(-1), respectively. The LPME-sweeping method has been successfully appliedto the analysis of strychnine and brucine in real urine sample, indicating thatLPME-sweeping-MEKC is a promising combination for the analysis of basic drugspresent at low levels in some biological matrices.
(3) The development of a sensitive and simple micellar electrokinetic chromatography(MEKC) method for the determination of antiepileptic drug, Carbamazepine(CBZ), usingsweeping on-line concentration method with photodiode array detection.
The effect of pH, concentration of the running buffer solution, organic modifier,voltage and injection time on the concentration efficiency was investigated. An untreatedfused-silica capillary was used (50 cm; effective length, 40 cm, 75μm i.d.) for theanalysis. The background solution (BGS) was 50 mmol L~(-1) NaH_2PO_4 (pH 3.0) and 100mmol L~(-1) SDS containing 20％acetonitrile with an applied voltage of -20 kV at 25℃.Sample introduction was performed at 0.5 psi for 90 s with diode array detection at 214nm. In the method validation, the calibration curve was linear over a range of 0.5-40μgmL~(-1) for CBZ with a correlation coefficient of 0.998. The detection limit (S/N=3:1) ofCBZ was 0.10μg mL~(-1). About 100-fold improvement in concentration sensitivity wasachieved in terms of peak height by the sweeping method compared to conventionalinjection method. The Sweeping-MEKC method has been successfully applied to theanalysis of CBZ in tablet and human serum.
(4) The development of a simple capillary zone electrophoresis method for thedetermination of levodopa and methyldopa in human serum.
The influence of pH, concentration of the running buffer solution, voltage andinjection time was investigated. The best separation was obtained with a fused-silicacapillary column(50 cm×75μm I. D.) in a running buffer of 40 mmol L~(-1) sodiumtetraborate (pH=9.5), with an applied voltage of 22 kV at 25℃. Sample introductionwas performed at 0.5 psi for 7 s combined with diode array detection at 200 nm. Thelinear range of methyldopa and levodopa were 0.001～0.064 mg mL~(-1) (r=0.9998) and 0.001～0.071 mg/mL (r=0.9994) respectively, the detection limit (S/N=3:1) ofmethyldopa and levodopa were 0.6μg mL~(-1) and 0.8μg mL~(-1).
(5) The study on the interaction between brucine and bovine serum albumin (BSA)using fluorescence spectroscopy (FS) and ultraviolet spectroscopy (UV).
The experimental results showed that brucine could quench the intrinsic fluorescenceof BSA. It was found that static quenching and non-radiation energy transfer were themain reasons leading to the fluorescence quenching. The apparent binding constants (K_A)between brucine and BSA were 6.3×10~3 (27℃) and 7.7×10~3 (37℃) and the bindingsites (n) were 0.94 (27℃) and 0.97 (37℃). According to the F(?)rster theory ofnon-radiation energy transfer, the binding distances (r) were also obtained. The processof binding was a spontaneous molecular interaction in which entropy increased andGibbs free energy decreased, which indicated that the interaction between brucine andBSA was driven mainly by hydrophobic force.
(6) The study on the interaction of fangchinoline and tetrandrine with bovine serumalbumin and human serum albumin (HSA) under different temperatures by fluorescencequenching spectra, synchronous fluorescence spectra, three-dimensional fluorescencespectra and ultra-violet spectra.
It was shown that fangchinoline and tetrandrine had a quite strong ability to quenchthe intrinsic fluorescence of BSA or HSA. The Stem-Volmer curve on the fluorescence ofBSA or HSA quenched by fangchinoline and tetrandrine indicated the quenchingmechanism between fangchinoline or tetrandrine and BSA or HSA was a staticquenching. According to the F(?)rster theory of non-radiation energy transfer, the bindingdistances (r), the binding constants (K_A) and the binding sites (n) were obtained. Forfangchinoline and BSA: K_A=1.05×10~5, n=1.4, r=2.53 (t=27℃); K_A=3.31×10~5,n=1.3, r=2.70(t=37℃); K_A=7.24×10~5, n=1.2, r=2.92 (t=47℃)。Forfangchinoline and HSA: K_A=5.04×10~5, n=1.2, r=3.52 (t=27℃); K_A=5.38×10~5,n=1.3, r=3.81 (t=37℃); KA=5.67×10~5, n=1.4, r=4.38 (t=47℃)。For tetrandrineandBSA:K_A=1.52×10~5, n=1.2, r=2.34(t=27℃); K_A=2.03×10~5, n=1.3, r=2.48 (t=37℃); K_A=2.89×10~5, n=1.4, r=2.71 (t=47℃)。For tetrandrine and HSA:K_A=4.02×10~5, n=1.0, r=3.00(t=27℃); K_A=4.76×10~5, n=1.2, r=3.14(t=37℃); K_A=4.98×10~5, n=1.3, r=3.39(t=47℃)。The thermodynamic parametersshowed that the interaction between fangchinoline or tetrandrine and BSA or HSA wasdriven mainly by hydrophobic force. Synchronous spectrum and three- dimensionalfluorescence spectrum were used to investigate the structural changes of BSA and HSA.
(7) The investigation of interaction between quercetin and bovine serum albumin usingfluorescence spectroscopy and ultraviolet spectroscopy.
The apparent binding constants (KA) between quercetin and BSA were 2.8×10~8 (26℃)and 3.1×10~8 (36℃) and the binding sites (n) were 1.7±0.02. According to the F(?)rster theory of non- radiation energy transfer, the binding distances (r) were also obtained. Theexperimental results showed that the quercetin could quenching the intrinsic fluorescenceof BSA by forming the quercetin-BSA complex. It was found that both static quenchingand non-radiation energy transfer were the main reasons leading to the fluorescencequenching. The process of binding was a spontaneous molecular interaction in whichentropy increased while Gibbs free energy decreased, which indicated that the interactionbetween quercetin and BSA was driven mainly by hydrophobic force.
(8) The investigation of the interaction between bovine serum albumin and CBZusing fluorescence spectroscopy and ultraviolet spectroscopy.
The experimental results showed that the CBZ could insert into the BSA molecular,quenching the intrinsic fluorescence of BSA by forming the CBZ-BSA complex. It wasfound that both static quenching and non-radiation energy transfer were the main reasonsleading to the fluorescence quenching. The apparent binding constants (KA) betweenCBZ and BSA were determined to 1.8×10~4 (27℃) and 2.8×10~4 (37℃). The bindingsites values (n) were 0.97 (27℃) and 1.01 (37℃), respectively. According to the F(?)rstertheory of non-radiation energy transfer, the binding distances (r) between BSA and CBZwere 3.6 nm (27℃) and 3.4 nm (37℃) respectively. The process of the binding was amolecular interaction in which entropy and Gibbs free energy both decreased, whichindicated that the interaction between CBZ and BSA was mainly driven by hydrogenbond and Vander Waals force.
(1)采用在线推扫预富集—胶束毛细管电泳法建立了测定中草药中马钱子生物碱的新方法。经过实验优化，最佳分离条件为：分离缓冲溶液为50 mmol L~(-1) H_3PO_4(pH 2.0)，100 mmol L~(-1) SDS，20％乙腈(v／v)，分离电压-20 kV，在0.5 psi下进样270 s，检测波长为203 nm。与传统MEKC方法相比较，灵敏度提高了100倍(以峰高计)。以小檗碱为内标，士的宁与马钱子碱的浓度在0.5～15μg／mL范围内与其峰面积与内标峰面积的比值呈良好的线性关系，线性相关系数分别为0.998和0.997，检出限分别为0.05μg／mL和0.07μg／mL。本方法应用于测定中草药马钱子和中药制剂伸筋活络丸中马钱子碱的含量，获得满意结果。
(2)首次将中空纤维液相微萃取(HF-LPME)与在线推扫富集胶束电动色谱法相结合，建立了测定尿样中马钱子生物碱的新方法。以小檗碱为内标，士的宁、马钱子碱与内标峰面积的比值与分析物浓度在20～200 ng／mL范围内呈良好的线性关系，线性相关系数分别为0.996和0.997，士的宁与马钱子碱的检出限分别为1ng／mL和2 ng／mL(S／N=3∶1)。
(3)建立了在线推扫富集毛细管电泳紫外检测测定药物和人血清中卡马西平浓度的方法。以pH=3.0的50 mmol L~(-1) NaH_2PO_4，100 mmol L~(-1) SDS，20％乙腈为分离缓冲溶液，在0.5 psi下进样90 s，检测波长214 nm，分离电压为-20 kV。卡马西平浓度在0.5-40μg／mL范围内与其峰面积呈良好的线性关系，线性相关系数为0.998，检出限为0.1μg／mL(S／N=3∶1)。
(4)建立了毛细管区带电泳紫外检测测定血清中左旋多巴和甲基多巴的新方法，以pH=9.5的40 mmol L~(-1)硼砂为分离缓冲溶液，在0.5 psi压力下进样7 s，分离电压22 kV，检测波长200 nm，检测温度25℃的条件下进行测定，甲基多巴和左旋多巴浓度分别在0.001～0.064 mg／mL和0.001～0.071 mg／mL范围内与峰面积呈良好线性关系，线性相关系数分别为0.9998和0.9994，检出限分别为0.6μg／mL和0.8μg／mL(信噪比为3∶1)，已用于血清中甲基多巴和左旋多巴的测定。
(5)应用荧光光谱和紫外光谱法研究了马钱子碱与牛血清白蛋白(BSA)的结合反应，求得它们之间的结合常数K_A和结合位点数n，分别为K_A=6,3×10~3，n=0.94(27℃)；KA=7.7×10~3，n=0.97(37℃)。根据F(?)rster非辐射能量转移理论求出了马钱子碱与BSA之间的结合距离为3.99 nm(27℃)和4.21 nm(37℃)。探讨了马钱子碱的荧光猝灭机理，结果表明马钱子碱能够插入BSA内部形成基态复合物导致其内源荧光猝灭，猝灭机理主要是静态猝灭和非辐射能量转移。根据热力学参数确定了马钱子碱与BSA之间的作用力类型主要为疏水性相互作用。
(6)在不同温度下，用荧光猝灭光谱、同步荧光光谱、三维荧光光谱和紫外．可见吸收光谱，研究了防己诺林碱和粉防己碱与牛血清白蛋白和人血清白蛋白(HSA)之间的相互作用。结果表明，防己诺林碱和粉防己碱对血清白蛋白有较强的荧光猝灭作用，根据不同温度下防己诺林碱和粉防己碱对血清白蛋白的荧光猝灭作用，确定他们对血清白蛋白的荧光猝灭作用属于静态猝灭。并根据F(?)rster非辐射能量转移理论计算出防己诺林碱和粉防己碱与血清白蛋白间的结合距离r、结合常数K_A和结合位点数n。防己诺林碱与牛血清白蛋白之间的K_A=1.05×10~5，n=1.4，r=2.53(t=27℃)；K_A=3.31×10~5，n=1.3，r=2.70(t=37℃)；K_A=7.24×10~5，n=1.2，r=2.92(t=47℃)。防己诺林碱与人血清白蛋白之间的K_A=5.04×10~5，n=1.2，r=3.52(t=27℃)；K_A=5.38×10~5，n=1.3，r=3.81(t=37℃)；K_A=5.67×10~5，n=1.4，r=4.38(t=47℃)。粉防己碱与牛血清白蛋白之间的K_A=1.52×10~5，n=1.2，r=2.34(t=27℃)；K_A=2.03×10~5，n=1.3，r=2.48(t=37℃)；K_A=2.89×10~5，n=1.4，r=2.71(t=47℃)。粉防己碱与人血清白蛋白之间的K_A=4.02×10~5，n=1.0，r=3.00(t=27℃)；K_A=4.76×10~5，n=1.2，r=3.14(t=37℃)；K_A=4.98×10~5，n=1.3，r=3.39(t=47℃)。并根据热力学数据确定了它们之间的主要作用力类型，同时用同步荧光光谱和三维荧光光谱探讨了防己诺林碱和粉防己碱对血清白蛋白构象的影响。
(7)利用荧光光谱和紫外光谱法研究了槲皮素与牛血清白蛋白之间的相互作用。结果表明，静态猝灭和非辐射能量转移是导致槲皮素对BSA荧光猝灭的两大原因，槲皮素与BSA的结合常数K_A为2.8×10~8(26℃)和3.1×10~8(36℃)，结合位点数为1.76±0.01，根据F(?)rster非辐射能量转移理论得到槲皮素与BSA之间的结合距离为3.25 nm(26℃)和3.30 nm(36℃)，表明槲皮素的部分片段可以插入BSA分子内部。通过计算热力学参数，可知该药物与蛋白的相互作用是一个熵增加和吉布斯自由能降低的自发过程，并由此推断槲皮素与BSA之间的作用力是以疏水相互作用为主。
(8)应用荧光光谱和紫外光谱法研究了卡马西平(CBZ)与牛血清白蛋白的结合反应，实验结果表明，卡马西平可以插入BSA分子内部形成CBZ-BSA复合物而产生荧光猝灭。研究表明静态猝灭和非辐射能量转移是导致卡马西平对BSA荧光猝灭的两大原因。求得CBZ与BSA之间的结合常数K_A分别为1.8×10~4(27℃)；2.8×10~4(37℃)和结合位点数n：0.97(27℃)；1.01(37℃)。根据F(?)rster非辐射能量转移理论求出了卡马西平与BSA之间的结合距离为3.6 nm(27℃)和3.4 nm(37℃)。CBZ与BSA的结合过程是熵增大，吉布斯自由能减小的过程，反应自发进行，它们之间主要靠疏水作用力结合。
In the thesis, CE was combined with on-line sweeping and hollow fiber-basedliquid-phase microextraction technique. Efficient and sensitive methods were developedfor the determination of Strychnos alkaloids, carbamazepine in Chinese herbal medicinesand biological samples. The interactions of Strychnos alkaloids, fangchinoline,tetrandrine and carbamazepine with serum albumin were studied by fluorescencequenching spectra, synchronous fluorescence spectra, three-dimensional fluorescencespectra and ultra-violet spectra. This thesis is mainly concerned with the followingaspects:
(1) The investigation of an on-line sweeping preconcentration method in micellarelectrokinetic chromatography (MEKC) for the determination of Strychnos alkaloids,namely strychnine and brucine.
After experimental optimizations, the best separation was achieved in 50 mmol L~(-1)H_3PO_4 (pH 2.0) containing 100 mmol L~(-1) SDS and acetonitrile in a ratio of 4:1 (v/v),with an applied voltage of -20 kV at 20℃. The sample matrix consisted of 100 mmol L~(-1)H_3PO_4 (pH 2.0), and sample introduction was performed at 0.5 psi for 270 s, withphotodiode array detection at 203 nm. Compared with the conventional MEKC injectionmethod, up to 100-fold improvement in concentration sensitivity was achieved in termsof peak height by using this sweeping injection technique. In the method, the compoundberberine was used as the internal standard for the improvement of the experimentalreproducibility. The calibration curve was linear over a range of 0.5-15μg mL~(-1) for bothstrychnine and brucine, with a correlation coefficient of 0.998 and 0.997, respectively.The detection limits (S/N=3:1) for strychnine and brucine were 0.05μg mL~(-1) and 0.07μg mL~(-1), respectively. The Sweeping-MEKC method has been successfully applied to theanalysis of strychnine and brucine in Strychnos nux-vomica L and its Chinese medicinalpreparations.
(2) The establishment of a new method for the enrichment of Strychnos alkaloids inbiological samples via liquid-phase mieroextraction (LPME) based on porous polypropylene hollow fibers combined with on-line sweeping in micellar electrokineticchromatography (MEKC).
Strychnos alkaloids were first extracted from urine sample, in which the concentrationof NaOH was 0.5 mmol L~(-1). The unionized analytes were subsequently extracted into1-octanol impregnated in the pores of hollow fibers, and then into 100 mmol L~(-1) H_3PO_4inside the hollow fiber. The extract was analyzed directly by on-line sweeping in micellarelectrokinetic chromatography (MEKC). In the method, the compound berberine wasused as the internal standard for the improvement of the experimental reproducibility.The calibration curve was linear over a range of 20-200 ng mL~(-1) for both strychnine andbrucine in human urine sample, with a correlation coefficient of 0.996 and 0.997,respectively. The detection limits (S/N=3:1) for strychnine and brucine were 1 ng ml~(-1)and 2 ng mL~(-1), respectively. The LPME-sweeping method has been successfully appliedto the analysis of strychnine and brucine in real urine sample, indicating thatLPME-sweeping-MEKC is a promising combination for the analysis of basic drugspresent at low levels in some biological matrices.
(3) The development of a sensitive and simple micellar electrokinetic chromatography(MEKC) method for the determination of antiepileptic drug, Carbamazepine(CBZ), usingsweeping on-line concentration method with photodiode array detection.
The effect of pH, concentration of the running buffer solution, organic modifier,voltage and injection time on the concentration efficiency was investigated. An untreatedfused-silica capillary was used (50 cm; effective length, 40 cm, 75μm i.d.) for theanalysis. The background solution (BGS) was 50 mmol L~(-1) NaH_2PO_4 (pH 3.0) and 100mmol L~(-1) SDS containing 20％acetonitrile with an applied voltage of -20 kV at 25℃.Sample introduction was performed at 0.5 psi for 90 s with diode array detection at 214nm. In the method validation, the calibration curve was linear over a range of 0.5-40μgmL~(-1) for CBZ with a correlation coefficient of 0.998. The detection limit (S/N=3:1) ofCBZ was 0.10μg mL~(-1). About 100-fold improvement in concentration sensitivity wasachieved in terms of peak height by the sweeping method compared to conventionalinjection method. The Sweeping-MEKC method has been successfully applied to theanalysis of CBZ in tablet and human serum.
(4) The development of a simple capillary zone electrophoresis method for thedetermination of levodopa and methyldopa in human serum.
The influence of pH, concentration of the running buffer solution, voltage andinjection time was investigated. The best separation was obtained with a fused-silicacapillary column(50 cm×75μm I. D.) in a running buffer of 40 mmol L~(-1) sodiumtetraborate (pH=9.5), with an applied voltage of 22 kV at 25℃. Sample introductionwas performed at 0.5 psi for 7 s combined with diode array detection at 200 nm. Thelinear range of methyldopa and levodopa were 0.001～0.064 mg mL~(-1) (r=0.9998) and 0.001～0.071 mg/mL (r=0.9994) respectively, the detection limit (S/N=3:1) ofmethyldopa and levodopa were 0.6μg mL~(-1) and 0.8μg mL~(-1).
(5) The study on the interaction between brucine and bovine serum albumin (BSA)using fluorescence spectroscopy (FS) and ultraviolet spectroscopy (UV).
The experimental results showed that brucine could quench the intrinsic fluorescenceof BSA. It was found that static quenching and non-radiation energy transfer were themain reasons leading to the fluorescence quenching. The apparent binding constants (K_A)between brucine and BSA were 6.3×10~3 (27℃) and 7.7×10~3 (37℃) and the bindingsites (n) were 0.94 (27℃) and 0.97 (37℃). According to the F(?)rster theory ofnon-radiation energy transfer, the binding distances (r) were also obtained. The processof binding was a spontaneous molecular interaction in which entropy increased andGibbs free energy decreased, which indicated that the interaction between brucine andBSA was driven mainly by hydrophobic force.
(6) The study on the interaction of fangchinoline and tetrandrine with bovine serumalbumin and human serum albumin (HSA) under different temperatures by fluorescencequenching spectra, synchronous fluorescence spectra, three-dimensional fluorescencespectra and ultra-violet spectra.
It was shown that fangchinoline and tetrandrine had a quite strong ability to quenchthe intrinsic fluorescence of BSA or HSA. The Stem-Volmer curve on the fluorescence ofBSA or HSA quenched by fangchinoline and tetrandrine indicated the quenchingmechanism between fangchinoline or tetrandrine and BSA or HSA was a staticquenching. According to the F(?)rster theory of non-radiation energy transfer, the bindingdistances (r), the binding constants (K_A) and the binding sites (n) were obtained. Forfangchinoline and BSA: K_A=1.05×10~5, n=1.4, r=2.53 (t=27℃); K_A=3.31×10~5,n=1.3, r=2.70(t=37℃); K_A=7.24×10~5, n=1.2, r=2.92 (t=47℃)。Forfangchinoline and HSA: K_A=5.04×10~5, n=1.2, r=3.52 (t=27℃); K_A=5.38×10~5,n=1.3, r=3.81 (t=37℃); KA=5.67×10~5, n=1.4, r=4.38 (t=47℃)。For tetrandrineandBSA:K_A=1.52×10~5, n=1.2, r=2.34(t=27℃); K_A=2.03×10~5, n=1.3, r=2.48 (t=37℃); K_A=2.89×10~5, n=1.4, r=2.71 (t=47℃)。For tetrandrine and HSA:K_A=4.02×10~5, n=1.0, r=3.00(t=27℃); K_A=4.76×10~5, n=1.2, r=3.14(t=37℃); K_A=4.98×10~5, n=1.3, r=3.39(t=47℃)。The thermodynamic parametersshowed that the interaction between fangchinoline or tetrandrine and BSA or HSA wasdriven mainly by hydrophobic force. Synchronous spectrum and three- dimensionalfluorescence spectrum were used to investigate the structural changes of BSA and HSA.
(7) The investigation of interaction between quercetin and bovine serum albumin usingfluorescence spectroscopy and ultraviolet spectroscopy.
The apparent binding constants (KA) between quercetin and BSA were 2.8×10~8 (26℃)and 3.1×10~8 (36℃) and the binding sites (n) were 1.7±0.02. According to the F(?)rster theory of non- radiation energy transfer, the binding distances (r) were also obtained. Theexperimental results showed that the quercetin could quenching the intrinsic fluorescenceof BSA by forming the quercetin-BSA complex. It was found that both static quenchingand non-radiation energy transfer were the main reasons leading to the fluorescencequenching. The process of binding was a spontaneous molecular interaction in whichentropy increased while Gibbs free energy decreased, which indicated that the interactionbetween quercetin and BSA was driven mainly by hydrophobic force.
(8) The investigation of the interaction between bovine serum albumin and CBZusing fluorescence spectroscopy and ultraviolet spectroscopy.
The experimental results showed that the CBZ could insert into the BSA molecular,quenching the intrinsic fluorescence of BSA by forming the CBZ-BSA complex. It wasfound that both static quenching and non-radiation energy transfer were the main reasonsleading to the fluorescence quenching. The apparent binding constants (KA) betweenCBZ and BSA were determined to 1.8×10~4 (27℃) and 2.8×10~4 (37℃). The bindingsites values (n) were 0.97 (27℃) and 1.01 (37℃), respectively. According to the F(?)rstertheory of non-radiation energy transfer, the binding distances (r) between BSA and CBZwere 3.6 nm (27℃) and 3.4 nm (37℃) respectively. The process of the binding was amolecular interaction in which entropy and Gibbs free energy both decreased, whichindicated that the interaction between CBZ and BSA was mainly driven by hydrogenbond and Vander Waals force.
引文
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