光谱法研究卟啉生物大分子在有序介质中的组装
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摘要
第一章 本章简要介绍了卟啉、环糊精、和杯芳烃化学性质及其结构特点以及在超分子化学中的研究现状。在对超分子组装概念介绍的基础上，简述了卟啉生物大分子在环糊精、DNA、和杯芳烃等有序介质中组装的历史和研究现状，并展望了其未来的发展趋势。
第二章 本章综述了以环糊精为主体分子对卟啉分子的包合作用，系统地概括了环糊精及其衍生物在与卟啉生物大分子相关领域的研究进展，包括生物模拟酶，光敏药物，分子识别用于气体分子和金属离子的测定以及超分子组装。
第三章 本章采用荧光光谱法、紫外可见分光光度法以及核磁共振技术研究了meso-四(对-羟基苯基)卟啉(THPP)在β-环糊精、羟丙基-β-环糊精和磺丁醚-β-环糊精三种环糊精介质中的组装。结果表明：THPP在环糊精介质中的组装具有选择性。修饰的β-环糊精比母体β-环糊精的选择性好，而且带有羟基的羟丙基-β-环糊精与THPP的强的组装作用可以将THPP的荧光强度提高300倍左右。同时通过调节溶液的pH考察了同一种环糊精与卟啉不同型体的相互作用，结果表明环糊精易与卟啉的中性型体作用。
第四章 本章采用荧光光谱法、紫外可见分光光度法以及核磁共振技术研究了meso-四(N-乙基吡啶基)卟啉(TEPyP)在β-环糊精、羟丙基-β-环糊精和磺丁醚-β-环糊精三种环糊精介质中的组装。结果表明：TEPyP在环糊精介质中的组装具有选择性。修饰的β-环糊精比母体β-环糊精的选择性好，而且带有负电荷的磺丁醚-β-环糊精与TEPyP具有强的组装作用，其结果归于带正电荷卟啉与带负电荷环糊精之间强的静电作用。同时通过调节溶液的pH考察了同一种环糊精与卟啉不同型体的相互作用，结果表明环糊精易与卟啉的中性型体作用。
第五章 本章采用荧光光谱法、紫外可见分光光度法以及共振光散射技术研究了meso-四(N-乙基吡啶基)卟啉(TEPyP)与小牛胸腺DNA(ctDNA)的相互作用。结果表明，两者主要是基于带正电荷卟啉与DNA外围的负电荷磷酸基间的静电作用，以外部组装的模式相互作用。在此研究的基础上探讨了环糊精的存在对卟啉与DNA相互作用的影响。结果表明，在三种环糊精存在下，TEPyP与DNA原有结合常数和结合位点都有不同程度的减小，即：环糊精和DNA在与卟啉作用过程中存在竞争。其中以磺丁醚-β-环糊精的影响最大，这进一步证明了卟啉与DNA间静电作用的模式。
第六章 本章采用荧光光谱法、紫外可见分光光度法研究了meso-四(N-乙基吡啶基)卟啉(TEPyP)与Calix[4]amne的组装过程。Calix[4]arene的加入，引起卟啉Soret吸收带的红移，并伴随着λ_(max)的减小。而TEPyP的荧光发射峰在CalixL4]arene存在下增强。采用非线性
山不诵大学2()04硕卜研究生学位论文
最小二乘法计算了叶琳与Cai议间的结合常数。结果表明，两者间是l:l的作用模式，结
合常数是1护石M，。详细讨论了PH值的影响，从pH值的影响曲线中可以得出结论:组
装的主要驱动力是带正电荷叶琳与带负电荷的Cai议之间强的静电作用。
Chapter 1 The chemical structure and characteristics of porphyrins, calixarenes, and cyclodextrins have been introduced in detail. The developments of these compounds in the supramolecular chemistry were also reviewed. The concept of self-assembly of supramolecular has been supplied. The history and the recent development of supramolecular assembly involved in the porphyrins, calixarenes, and cyclodextrins have been reviewed .
Chapter 2 The application and development of cyclodextrin and its derivatives in the fields related to porphyrin macrocyclic molecule are reviewed. It involves in biological artificial enzyme, photosensitized drugs, determination of gas molecule and metal ion by molecular recognition, and supramolecular assembly.
Chapter 3 meso-Tetrakis (4-hydroxylphenyl) prophyrin (THPP) is a photosensitizer offering a alternative approach to the treatment of cancer in the form of photodynamics therapy (PDT). The supramolecular system of THPP and β-cyclodextrin (β-CD), hydroxypropyl-β-cyclodextrin (HP-β-CD), and carboxymethyl-p-cyclodextrin (CM-β-CD), in aqueous solution has been studied by fluorescence and UV-Vis spectroscopy. The form of inclusion complexes has been observed on the basis of change in spectroscopic properties. It is noted that the addition of HP-β-CD leads to remarkably enhancement in fluorescence intensity (nearly 300 times) of THPP. THPP forms 1:1 inclusion complex with
β-CD and 1:2 inclusion complexes with the two other derivatives. Compared with β-CD and CM-β-CD, the strongest inclusion ability of HP-β-CD can be explained that the hydrogen bond plays an significant role in the inclusion process. In addition, the UV-Vis experiments showed that the cavity of HP-β-CD causes the transform of the state of THPP, which is in agreement with the effect of polarity of solvent Compared with the pure buffer solution, the distinct equilibrium, H4THPP2+(?)H2THPP, has been observed in the solution of HP-β-CD. It is certain that the fluorescence enhancement factor with nearly 300 presents a potential application in the detection of THPP in pharmacokinetics and biodistribution studies.
Chapter 4 5,10,15,20-tetrakis(4-N-ethylpyridiniurmyl)porphyrin (TEPyP) formed 1:1 stoichiometry inclusion complexes with β-cyclodextrin (β-CD) and its derivatives including hydroxypropyl- β-cyclodextrin (HP-β-CD), sulfobutylether-β-cyclodextrin (SBE-β-CD) in basic aqueous solution. The supramolecular system was investigated by the methods of fluorescence, UV-Vis absorption spectroscopy, nuclear magnetic resonance (NMR) technique. The inclusion ability of cyclodextrins exhibited remarkable difference for β-CD,
HP-β-CD and SBE-β-CD. A sociation constants as high as K=1.1×104 M-1 in the case of HP-β-CD/TEPyP and 2.0×105M-1 in the case of SBE-β-CD/TEPyP complexes were determined, whereas a lower value (K=550 M-1) was given in the case of β-CD/TEPyP. The results showed that hydrogen bond and charge attraction play important roles in the processes of host-guest interaction. The interaction mechanism of inclusion processes could be explained by the analysis of NMR spectroscopy. The supramolecular assembly was formed. β-CD and HP-β-CD approached from the primary face of cavities of CDs.
Chapter 5 The interaction model of meso-tetrakis (4-N-ethylpyridiumyl) porphyrin (TEPyP) and calf thymus DNA (ctDNA) was discussed based on the change in UV-Vis spectroscopy, fluorescence and Resonance Light-Scattering (RLS). The changed absorption spectral properties of TEPyP titrated with ctDNA were observed from red-shifted (△λ=14nm) and a large hypochromicity (42%). In fluorescence spectra, λexm,max of TEPyP shifted to longer wavelength (△λ,=13nm) and a decrease around 50% of the emission intensity was shown. The signal of resonance light-scattering was enhanced due to the presence of nucleic acid. In addition, comparative study on the interaction of TEPyP with ctDNA was further carried out in the presence of β-CD, HP-β-CD, and SBE-β-CD. The significant decrease of the binding constants an
第二章 本章综述了以环糊精为主体分子对卟啉分子的包合作用，系统地概括了环糊精及其衍生物在与卟啉生物大分子相关领域的研究进展，包括生物模拟酶，光敏药物，分子识别用于气体分子和金属离子的测定以及超分子组装。
第三章 本章采用荧光光谱法、紫外可见分光光度法以及核磁共振技术研究了meso-四(对-羟基苯基)卟啉(THPP)在β-环糊精、羟丙基-β-环糊精和磺丁醚-β-环糊精三种环糊精介质中的组装。结果表明：THPP在环糊精介质中的组装具有选择性。修饰的β-环糊精比母体β-环糊精的选择性好，而且带有羟基的羟丙基-β-环糊精与THPP的强的组装作用可以将THPP的荧光强度提高300倍左右。同时通过调节溶液的pH考察了同一种环糊精与卟啉不同型体的相互作用，结果表明环糊精易与卟啉的中性型体作用。
第四章 本章采用荧光光谱法、紫外可见分光光度法以及核磁共振技术研究了meso-四(N-乙基吡啶基)卟啉(TEPyP)在β-环糊精、羟丙基-β-环糊精和磺丁醚-β-环糊精三种环糊精介质中的组装。结果表明：TEPyP在环糊精介质中的组装具有选择性。修饰的β-环糊精比母体β-环糊精的选择性好，而且带有负电荷的磺丁醚-β-环糊精与TEPyP具有强的组装作用，其结果归于带正电荷卟啉与带负电荷环糊精之间强的静电作用。同时通过调节溶液的pH考察了同一种环糊精与卟啉不同型体的相互作用，结果表明环糊精易与卟啉的中性型体作用。
第五章 本章采用荧光光谱法、紫外可见分光光度法以及共振光散射技术研究了meso-四(N-乙基吡啶基)卟啉(TEPyP)与小牛胸腺DNA(ctDNA)的相互作用。结果表明，两者主要是基于带正电荷卟啉与DNA外围的负电荷磷酸基间的静电作用，以外部组装的模式相互作用。在此研究的基础上探讨了环糊精的存在对卟啉与DNA相互作用的影响。结果表明，在三种环糊精存在下，TEPyP与DNA原有结合常数和结合位点都有不同程度的减小，即：环糊精和DNA在与卟啉作用过程中存在竞争。其中以磺丁醚-β-环糊精的影响最大，这进一步证明了卟啉与DNA间静电作用的模式。
第六章 本章采用荧光光谱法、紫外可见分光光度法研究了meso-四(N-乙基吡啶基)卟啉(TEPyP)与Calix[4]amne的组装过程。Calix[4]arene的加入，引起卟啉Soret吸收带的红移，并伴随着λ_(max)的减小。而TEPyP的荧光发射峰在CalixL4]arene存在下增强。采用非线性
山不诵大学2()04硕卜研究生学位论文
最小二乘法计算了叶琳与Cai议间的结合常数。结果表明，两者间是l:l的作用模式，结
合常数是1护石M，。详细讨论了PH值的影响，从pH值的影响曲线中可以得出结论:组
装的主要驱动力是带正电荷叶琳与带负电荷的Cai议之间强的静电作用。
Chapter 1 The chemical structure and characteristics of porphyrins, calixarenes, and cyclodextrins have been introduced in detail. The developments of these compounds in the supramolecular chemistry were also reviewed. The concept of self-assembly of supramolecular has been supplied. The history and the recent development of supramolecular assembly involved in the porphyrins, calixarenes, and cyclodextrins have been reviewed .
Chapter 2 The application and development of cyclodextrin and its derivatives in the fields related to porphyrin macrocyclic molecule are reviewed. It involves in biological artificial enzyme, photosensitized drugs, determination of gas molecule and metal ion by molecular recognition, and supramolecular assembly.
Chapter 3 meso-Tetrakis (4-hydroxylphenyl) prophyrin (THPP) is a photosensitizer offering a alternative approach to the treatment of cancer in the form of photodynamics therapy (PDT). The supramolecular system of THPP and β-cyclodextrin (β-CD), hydroxypropyl-β-cyclodextrin (HP-β-CD), and carboxymethyl-p-cyclodextrin (CM-β-CD), in aqueous solution has been studied by fluorescence and UV-Vis spectroscopy. The form of inclusion complexes has been observed on the basis of change in spectroscopic properties. It is noted that the addition of HP-β-CD leads to remarkably enhancement in fluorescence intensity (nearly 300 times) of THPP. THPP forms 1:1 inclusion complex with
β-CD and 1:2 inclusion complexes with the two other derivatives. Compared with β-CD and CM-β-CD, the strongest inclusion ability of HP-β-CD can be explained that the hydrogen bond plays an significant role in the inclusion process. In addition, the UV-Vis experiments showed that the cavity of HP-β-CD causes the transform of the state of THPP, which is in agreement with the effect of polarity of solvent Compared with the pure buffer solution, the distinct equilibrium, H4THPP2+(?)H2THPP, has been observed in the solution of HP-β-CD. It is certain that the fluorescence enhancement factor with nearly 300 presents a potential application in the detection of THPP in pharmacokinetics and biodistribution studies.
Chapter 4 5,10,15,20-tetrakis(4-N-ethylpyridiniurmyl)porphyrin (TEPyP) formed 1:1 stoichiometry inclusion complexes with β-cyclodextrin (β-CD) and its derivatives including hydroxypropyl- β-cyclodextrin (HP-β-CD), sulfobutylether-β-cyclodextrin (SBE-β-CD) in basic aqueous solution. The supramolecular system was investigated by the methods of fluorescence, UV-Vis absorption spectroscopy, nuclear magnetic resonance (NMR) technique. The inclusion ability of cyclodextrins exhibited remarkable difference for β-CD,
HP-β-CD and SBE-β-CD. A sociation constants as high as K=1.1×104 M-1 in the case of HP-β-CD/TEPyP and 2.0×105M-1 in the case of SBE-β-CD/TEPyP complexes were determined, whereas a lower value (K=550 M-1) was given in the case of β-CD/TEPyP. The results showed that hydrogen bond and charge attraction play important roles in the processes of host-guest interaction. The interaction mechanism of inclusion processes could be explained by the analysis of NMR spectroscopy. The supramolecular assembly was formed. β-CD and HP-β-CD approached from the primary face of cavities of CDs.
Chapter 5 The interaction model of meso-tetrakis (4-N-ethylpyridiumyl) porphyrin (TEPyP) and calf thymus DNA (ctDNA) was discussed based on the change in UV-Vis spectroscopy, fluorescence and Resonance Light-Scattering (RLS). The changed absorption spectral properties of TEPyP titrated with ctDNA were observed from red-shifted (△λ=14nm) and a large hypochromicity (42%). In fluorescence spectra, λexm,max of TEPyP shifted to longer wavelength (△λ,=13nm) and a decrease around 50% of the emission intensity was shown. The signal of resonance light-scattering was enhanced due to the presence of nucleic acid. In addition, comparative study on the interaction of TEPyP with ctDNA was further carried out in the presence of β-CD, HP-β-CD, and SBE-β-CD. The significant decrease of the binding constants an
引文
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[2] 黄志镗．杨联明．化学进展．1994，6，173-177．
[3] Zinke A, Ziegler E. Ber.Dtsch.Chem.Ges., 1941,74B, 1729-1736; 1944,77B,264-267.
[4] Gutsche C.D, MuthukrishnanR. J.Org.Chem., 1978,43,4905-4906.
[5] Roltberg, A.E.; Holden, M.J.; Mayhew, M.P.; Kurnikov, I.; Beratan,D.N.; Vilker, V.L. J.Am. Chem. Soc., 1998,120,8927.
[6] Fleischer, E.B.; Cheung, S.K.; Hikita,M.; Matsuura,M.; Kurrihara, T.; Tajima, T.; Hattori,A., et al. Bull.Chem.Soc.Jpa. 1995,68,1959.
[7] Steinberg-Y frach, G.; Liddell,P.A.; Hung, S.C. Nature, 1997,385,239
[8] Nango, M.; Iida,K.; Yamaguch,M. Langmuir, 1996, 12,1981
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