《本科毕业设计---二氢卟吩类新型光敏剂的制备与光敏性质研究.doc》由会员分享，可在线阅读，更多相关《本科毕业设计---二氢卟吩类新型光敏剂的制备与光敏性质研究.doc（83页珍藏版）》请在金锄头文库上搜索。
1、新一代二氢卟吩类光敏剂的制备与性质研究分类号： 学校代码： 10574 密级： 学号：2007021203South China Normal University硕士学位论文题目：二氢卟吩类新型光敏剂的制备与光敏性质研究学位申请人： 王 君 专业名称： 材料物理与化学 研究方向： 功能材料 所在院系： 化学与环境学院 导师姓名及职称： 罗一帆 教授 论文提交日期： 2010年6月 I二氢卟吩类新型光敏剂的制备与光敏性质研究二氢卟吩类新型光敏剂的制备与光敏性质研究专业：材料物理与化学 申请者：王君 导师：罗一帆 教授摘 要本文以我国特有的廉价蚕沙叶绿素为原料开展了二氢卟吩e6、二氢卟吩e4、U
2、F(UF是应用二氢卟吩e6和e4及其他物质组合得到光敏特性较好的一种复合新型光敏剂)三种二氢卟吩类新型光敏剂抗肿瘤新药的制备与光敏性质研究工作。主要内容与结论归纳如下：1. 以色谱PLATISIL ODS (5m ,250mm4.6mm)对二氢卟吩e6和e4进行高效液相色谱法（HPLC）检测研究。得到二氢卟吩e6的HPLC检测的最佳色谱条件： 以pH 3.2 0.01 mol/L的醋酸铵甲醇溶液作为流动相；梯度洗脱条件：甲醇85%（0.5%/min）100%；流速：1.0 mLmin-1；检测波长：407 nm。并对上述方法进行了方法学考察，测定二氢卟吩e6在0.32.0mg/ml范围内线性良
3、好，r=0.99953，方法日内稳定性的相对标准偏差为10.77%，方法精密度的相对标准偏差为0.65%。二氢卟吩e4的HPLC检测的最佳色谱条件：以pH 3.2 0.01 mol/L的醋酸铵甲醇溶液作为流动相；梯度洗脱条件：甲醇85%（0.5%/min）100%；流速：1.0 mLmin-1；检测波长：400 nm。并对上述方法进行了方法学考察，测定二氢卟吩e4在0.11.0 mg/ml范围内线性良好，r=0.99918，方法日内稳定性的相对标准偏差为7.59%，方法精密度的相对标准偏差为0.41%。2. 以二氢卟吩e6合成的最佳条件：反应体系需隔绝氧气，并通入氮气，于140回流25min为
4、基础，成功地进行了二氢卟吩e6的增量化合成和纯化实验。得到的产物经纯化后，二氢卟吩e6的含量均80%；筛选出了最佳萃取条件：萃取时间为40min，萃取物与萃取剂用量比为1：40；研究了无毒制备二氢卟吩e6的新方法：除去了反应中有毒的试剂吡啶和丙酮，用无毒的溶剂乙醇代替了有毒溶剂甲醇。经纯化后二氢卟吩e6含量80%。通过正交实验法对二氢卟吩e4合成条件进行研究，初步得出了最佳合成条件：160、20min。同时成功地进行了二氢卟吩e4的增量化合成实验。以萃取时间为40min，萃取物与萃取剂用量比为1：40，萃取次数为3次对合成产物进行萃取，使二氢卟吩e4粗品纯度提高到82.62%。3. 针对国内外
5、尚无明确报道的二氢卟吩e4及UF的光敏性及光漂白特性进行了分析讨论。研究了6个不同浓度条件下，二氢卟吩e4的光谱特性和光漂白特性：二氢卟吩e4在不同浓度的溶液中以单体形式存在；二氢卟吩e4的光漂白特性为光学修饰型，二氢卟吩e4的漂白半衰期大于80min，在肿瘤治疗过程中，有利于光进入更深层次，增加了治疗深度，有利于PDT治疗。分别对UF粉末及UF液体的稳定性进行了实验研究。结果表明，在低温（04）、避光条件下UF粉末的贮存期限应在在210天内；在低温（04）、避光条件下UF液体的贮存期限应在30天内。研究了6个不同浓度的UF在进行不同时间的垂直照射光照后的吸收光谱的变化。通过吸收光谱变化对UF
6、的光漂白特性进行了评价，UF的光漂白属于光学修饰型 ，UF的漂白半衰期远大于90min，因而有利于PDT治疗。关键词：二氢卟吩e6；二氢卟吩e4；UF； HPLC； 光谱；光敏性；光漂白SYNTHESIS AND PHOTOSENSITIVENESS OF NOVEL CHLORIN PHOTOSENSITIZERSMajor: Materials Physics and Chemistry Name: Jun WangSupervisor: Professor Yifan LuoABSTRACTThis paper discussed the novel antitumor drugchlo
7、rin e6, chlorin e4 and UF (UF is an advanced composite photosensitizer which is synthetised by chlorin e6 , chlorin e4 and other compounds)photosensitizer which is based on silkworm excrement proper to our country as material. Some new experiment results are obtained and illustrated as following:1.
8、Study on PLATISIL ODS 5m (250mm4.6mm) column in chlorin e6 and chlorin e4 is carry out high performance liquid chromatography(HPLC) detection. Optimum analysis conditions of chlorin e6 providing the best resolution of analytes was performed by gradient elution with mobile phases of 0.01 molL-1 ammon
9、ium acetate solution and methanol. Reversed-phase conditions: 85%（0.5%/min）100% ; flow rate: 1.0 mLmin-1; detection wavelength: 407nm. The peak area of chlorin e6 and concentration achieved good linear relation ranged from 0.3 to 2.0mg/ml, r=0.99953, the stability(RSD)was 10.77%, the precision (RSD)
10、 was 0.65%.Optimum analysis conditions of chlorin e4 providing the best resolution of analytes was performed by gradient elution with mobile phases of 0.01 molL-1 ammonium acetate solution and methanol. Reversed-phase conditions: 85%（0.5%/min）100% ; flow rate: 1.0 mLmin-1; detection wavelength: 400n
11、m. The peak area of chlorin e6 and concentration achieved good linear relation ranged from 0.1 to 1.0mg/ml, r=0.99918, the stability(RSD)was 7.59%, the precision (RSD) was 0.41%.2. According to the best synthesis condition of chlorin e6: reaction system to be isolated from oxygen and nitrogen access
12、, at 140 returning 25min, we succeed in incremental synthesis and refining of chlorin e6. And have made the products purity upgrade to 80%. Screen out optimum extraction method: extraction time 40min, the ratio of extractive and extraction agent is 1:40; study out a innoxious method of synthesis chl
13、orin e6: removal of the toxic reagents pyridine and acetone, replaced the noxious methyl alcohol with innoxious reagents alcohol. After extraction the product of new synthesis method could surpass 80%.Orthogonal test to optimize the best method of synthesis of chlorin e4 is used. Optimum synthesis c
14、ondition is 160, 20min. At the same time, succeed in incremental synthesis and refining of chlorin e4. Take the extraction time as 40min, the ratio of extractive and extraction agent is 1:40, leaching for 3 times. This improved the purity crude chlorin e4 product to 82.62%.3. To the question that le
15、ck of analysis of spectrum properties and the photobleaching of chlorin e4 and UF both in abroad and at home, we discussed these properties above.Study the properties and the photobleaching of chlorin e4 under 6 different concentrations. The experimental result show that chlorin e4 is present as monomers in different concentration and its photobleaching is photology modified. The photobleaching experimental of chlorin e4 also show that the half lifetime of photosensitizer chlorin e4 is
