【作者】 单旭峰；

【导师】 王正平；

【作者基本信息】 哈尔滨工程大学 ， 应用化学， 2004， 硕士

【摘要】 吡咯化合物是一类很重要的化合物，多吡咯衍生物广泛存在于自然界中，如血红蛋白、维生素B₁₂及胆色素等吡咯衍生物在动植物生理和生命活动中起到非常重要的作用。例如吡咯希夫碱、卟啉光敏剂、叶绿素铜钠盐等都是吡咯的衍生物。本论文对吡咯衍生物的自组装、两种卟啉光敏剂的光物理性质以及叶绿素铜钠盐的抗自由基和应用进行了研究。 超分子化学由诺贝尔奖得者J-M.Lehn于1987年提出，它是研究超分子或分子超结构的形成、性质及应用的化学。超分子的形成是通过分子组装来实现的，分子自组装是在一定条件下主体分子和配体分子构筑成一定结构的超分子化学行为。利用金属离子与配体进行自组装研究，近年来已成为一个重要课题。在诸多配体中，Lehn等发现的吡啶类化合物具有很有意义的自组装行为。但它有一个问题，即吡啶类化合物与金属离子络合后为了维持其电中性，要求所形成的超分子必须有负离子。这就会造成晶格混乱，并且影响它的纯化，性质和应用。与吡啶类化合物不同，吡咯类化合物由于有着独特的化学结构，被发现是一类理想的自组装配体。吡咯氮上的氢可以被除去而形成单阴离子的共振稳定的配体，同金属离子形成中性的络合物，而不需要反离子，产物很容易分离和纯化。第二章中合成了一种四吡咯镍超分子化合物、三种吡咯希夫碱镍和一种吡咯希夫碱银的超分子化合物，均得到了单晶，利用X—ray测定了晶体的结构，对每个晶体的结构进行了分析和研究，并对四吡咯镍化合物的傅立叶变换红外和拉曼光谱进行了分析和讨论。其中银超分子化合物中吡咯环的C-N部分以di-η²方式配位于Ag（Ⅰ），这种情况在以往的文献中未见报道，是第一个Ag（Ⅰ）与吡咯C-N键的，π电子络合的超分子。此反应为设计合成新型配体并用于Ag（Ⅰ）-π超分子络合物的组装提供了一个新途径。 光动力治疗的目的在于有效地消除人体病灶组织的同时尽可能地不损伤正常组织。光物理过程是光动力过程中非常重要的一个过程．在这一过程中，处于激发态的光敏剂经系间窜越，转变为三重态，这是自旋禁阻的过程，因而三重态的寿命较长（微秒数量级），能有机会与附近的分子发生能量（类型Ⅱ）或电子转移（类型Ⅰ）。由于光敏作用必须通过光敏剂的三重态进行，所以研究光敏剂的光物理性质显得尤其重要，特别是三重态光物理性质。在第三章中对两种二氢卟酚光敏剂的光物理性质进行研究。研究结果发现这两种哈尔滨工程大学硕士学位论文光敏剂具有较长的荧光寿命、三重态寿命，较高的三重态量子产率。光物理性质的研究，以及本实验室在光化学和光生物性质上的研究都表明这两种光敏剂是优良的光敏剂。 香烟烟气含有大量有毒物质，而对自由基毒性的研究较少，只是近几年自由基对人体的危害才引起科研工作者的关心。在香烟过滤嘴中加入自由基清除剂，无疑会减少自由基对人体的危害。我们利用叶琳的一种衍生物一叶绿素，利用化学方法将其修饰成更加稳定的水溶性的叶绿素铜钠盐。叶绿素铜钠盐广泛地用于食品、化妆品和医药工业，而对香烟烟气中自由基的清除作用过去研究很少。我们首先在实验室条件下对叶绿素铜钠盐制备工艺条件进行了改进研究，然后利用顺磁共振技术对香烟烟气中的烷氧基、烷基自由基的清除效果进行了研究。发现其对烷氧基、烷氧自由基有较好的清除效果，清除率为20%以上。叶绿素铜钠盐具有较低的生产成本、无毒、水溶性好、工艺简单等优点，再结合其它类型清除剂一并使用，有望在卷烟工业中实现工业化，生产低毒卷烟。关键词:毗咯衍生物;自组装;二苯基叶酚;光物理性质;叶绿素铜钠盐;自由基清除剂更多还原

【Abstract】 Pyrrole is a kind of very important chemical compound, most of whose derivatives extensively exist in nature, such as hemoglobin, vitamin B12 and bilirubin. Pyrrole derivatives in the physiology and life of animal and plant play very important roles. Other compounds, for example, pyrrole Schiff base, porphyrin photosensitizers and sodium copper chlorophyll in, are also pyrrole derivatives. In this paper the assembly of pyrrole derivatives, the physical properities of two kind of photosensitizer porphyrins and anti-freeradical property and application of sodium copper chlorophyllin are investigated.J M Lehn, a Noble Prizer, bought forward the concept of supramolecular in 1987,which study on thechemistry of supramolecular or formation, character and application of molecular suprastructure. The formation of supramolecular implement by molecular assembly, the concept of which is that in a certain condition ligand molecular and host molecular build up a special construction supramolecular. It is very important to construct complicated molecular, biological molecular especially. The use of metal ions and ligands in supramolecular assemblies has been extensively studied in recent years. Among many ligands designed by chemists, the polybipyridine ligands developed by Lehn and his colleagues are particularly interesting. Due to the nature of the ligands (neutral), these complexes are charged species. Therefore, counterions must be used to generate neutral compounds. This may result in competitive binding between the counterion and the ligand, which is usually overcome by the use of specific noncoordinating counterions. Unfortunately, this type of counterion often gives rise to considerable disorder in the solid state. In contrast to pyridine, pyrroles were recently found to be ideal building blocks for supramolecular assemblies. In pyrroles, the hydrogen at the N-H group can be removed and the resulting mono-anionic species is a resonance stabilized ligand. The complexes generated by pyrroles and metal ions are neutral species. Therefore, counterions are not needed. Consequently, it is particularly convenient to purify the complexes by column chromatography since they are not charged and are generally the least polar component in the reaction mixtures. In the second chapter a tetrapyrrole nickel complex, three pyrrole Schiff base nickel complex and a silver pyrrole complex are synthesized and crystals of them are obtained. We use X-ray method to determine and analyze the structure of these crystals. The Fourier-transform Raman (FT-Raman) and infrared (FT-IR) absorption spectra of the tetrapyrrole nickel complex have been investigated. This paperreports the first silver network polymer formed through the self-assembly of bis (pyrrol-2-yl- methyleneamine) with silver nitrate, in which the silver centers are bonded to the C-N bonds of pyrrole ring in r|2 fashion. This provides a new approach to design and synthesis new ligands and use these ligands to form Ag( I)- it supramolecular self-assembly.The aim of photodynamic therapy is to eliminate the focus tissue in human body and not damage the normal tissue. In photodynamic therapy process photophysical process is very important, excited photosensitizer reach the triplet state by intersystem crossing, which is spin-banning process. So the lifetime of triple state is longer and photosensitizer in triplet state has chance to exchange the energy with neighour molecular (type II) or electron transfer (type I). Because photosensitizing effect must do through triplet state of photosensitizer, it is very important to investigate its photophysical properties physical propertise the triple state especially. In the third chapter photophysical properities of two kinds of chlorin photosensitizer is investigated. The results show that both of them have higher triple state quantum yield and longer fluorescence lifetime and triple state lifetime. The result of these investigation and study on the properties of photochemistry and photobiology prove that two photosensitizer are high quality ones.T更多还原