两亲嵌段共聚物的功能化研究
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摘要
近年来,由于两亲嵌段共聚物在许多研究热点如仿生矿化、纳米材料(L-B膜)、生物材料、药物控制释放载体、基因运输体系等领域有着广泛的应用前景,人们对其分子设计、合成和自组装行为控制进行了深入的研究。通过分子设计和对其溶液中外部环境的控制,几乎能得到任意的自组装形态。在这个基础上,人们开始了对其在不同方面应用的探索。基于两亲嵌段共聚物这样的背景,本论文的工作主要是合成了含温敏和pH敏感的两亲嵌段共聚物,并对其功能化进行了研究,具体内容摘要如下：
1、初步改善了氧阴离子聚合方法。通常,人们以萘钾的悬浊液为引发剂,因为难以准确计量,不利于大规模地工业化应用。本论文以固体形态的叔丁醇钾来替代萘钾,前者是固体,容易计量,并且在适当的条件下更容易保存。
2、通过氧阴离子聚合方法我们得到了带氨基的两嵌段共聚物,之后通过与活化了的生物素(Biotin)反应将生物素接上去,这样就得到了带生物素为官能团的两亲嵌段共聚物。我们表征了其在水溶液中的自组装行为。因为生物素和亲和素(Avidin)具有很强的非化学作用,如果将药物包裹在带生物素的胶束中,就能靶向输送到含有Avidin的组织上。
3、设计合成了BAB型的嵌段共聚物,其中B链段为DMAEMA或DEAEMA链段,A为PEO链段。对此BAB嵌段共聚物在水溶液中的自组装行为随温度和pH值的影响我们进行了详细的研究,以期对两亲嵌段共聚物的自组装行为的研究作出自己的贡献。
4、另外,本课题组长期从事催化剂的研究。所以,我们就有一个设想,嵌段共聚物是否有一种新的用途：与金属离子一起作为一种高效、易分离、可回收的非均相催化剂。我们应用BAB三嵌段共聚物首先和盐酸反应生成聚电解质。然后聚电解质和氯化铜一起作为催化剂,在三甲酚(TMP)氧化成三甲醌(TMBQ)的空气氧化反应中起到了显著的效果,不但催化效率高,而且易回收套用。概括起来,本论文在以下三个方面具有创新性：
一、基于改进了的氧阴离子聚合法,合成了温敏和pH敏感的BAB型两亲嵌段共聚物PDMAEMA-PEG-PDMAEMA,并表征了其自组装行为。
二、首次将生物素连接到温敏和pH敏感的两亲嵌段共聚物,得到功能化了的AB型两亲嵌段共聚物,并对其溶液中的自组装行为进行了研究。
三、成功地以PDMAEMA-PEG-PDMAEMA与氯化铜络合,使两亲嵌段共聚物功能化为高分子催化剂,应用在三甲酚空气氧化成三甲醌上,得到了不亚于单体的催化效率和可接受的回收套用次数。
Recent years, amphiphilic block copolymers have numerous application possibilities in many hot research areas like biomimetic mineralization, nanomaterials (L-B membranes), biomaterials, drug/gene delivery system and so on. Thus, the molecular design, synthesis, and self-assembly behavior have been deeply researched. By molecular design and controlling of the external environment, nearly each self-assembled mophorlogy can be got. Based on this, the applications are important topics. In this thesis, temperature and pH sensitive amphiphilic block copolymers have been synthesized and the functionalization is researched. The relatively detailed summaries were as follows.
1. The synthesis of the amphiphilic block copolymers has been preliminarily improved. Normaly, the suspension of potassium naphthalene was used to initiate the synthesis. This is not easy to quantitatively determined, and is not good to be applicated in industry. This thesis replaced potassium naphthalene with solide potassium t-butoxide. Thus, the amount could be conveniently fixed and could also be conveniently stored.
2. We obtained AB type amphiphilic block copolymers with tert-amino group through the oxygen cationic polymerization method. Afterwards, functionalized block copolymers with a biotin end group were obtained by reacted with activated biotin, which was biotin-NHS. The self-assembly behavior in water was characterized. Since Biotin has very strong specific interaction with avidin, once the medicine has been bundled in the fuctionalized micelle with biotin group, it could be easily targeted to the organization with avidin.
3. We also designed the BAB type block copolymer, in which "B" referred to DMAEMA or DEAEMA segment, and "A" referred to PEO segment. The self-assembly behavior was carefully discussed, since the polymers were thermo-and pH-sensitive.
4. Besides, our group has a long time interest in the catalyst. This thesis supposed that block copolymers have a new application:as a highly effective, easily separated, and recyclable heterogeneous catalyst. The copolymer was complexed with CuCl2, and was used in the aero-oxidation of TMP to TMBQ.
The synthesis of PDMAEMA-PEG-PDMAEMA diblock copolymers by oxygen anion polymerization, the synthesis of biotin-PEG-PDMAEMA, and the functionalization of PDMEMA-PEG-PDMAEMA to be used as a highly effective, easily separated, and recyclable heterogeneous catalyst in the aero oxidation of TMP to TMBQ, to our best knowledge, are unprecedented.
1、初步改善了氧阴离子聚合方法。通常,人们以萘钾的悬浊液为引发剂,因为难以准确计量,不利于大规模地工业化应用。本论文以固体形态的叔丁醇钾来替代萘钾,前者是固体,容易计量,并且在适当的条件下更容易保存。
2、通过氧阴离子聚合方法我们得到了带氨基的两嵌段共聚物,之后通过与活化了的生物素(Biotin)反应将生物素接上去,这样就得到了带生物素为官能团的两亲嵌段共聚物。我们表征了其在水溶液中的自组装行为。因为生物素和亲和素(Avidin)具有很强的非化学作用,如果将药物包裹在带生物素的胶束中,就能靶向输送到含有Avidin的组织上。
3、设计合成了BAB型的嵌段共聚物,其中B链段为DMAEMA或DEAEMA链段,A为PEO链段。对此BAB嵌段共聚物在水溶液中的自组装行为随温度和pH值的影响我们进行了详细的研究,以期对两亲嵌段共聚物的自组装行为的研究作出自己的贡献。
4、另外,本课题组长期从事催化剂的研究。所以,我们就有一个设想,嵌段共聚物是否有一种新的用途：与金属离子一起作为一种高效、易分离、可回收的非均相催化剂。我们应用BAB三嵌段共聚物首先和盐酸反应生成聚电解质。然后聚电解质和氯化铜一起作为催化剂,在三甲酚(TMP)氧化成三甲醌(TMBQ)的空气氧化反应中起到了显著的效果,不但催化效率高,而且易回收套用。概括起来,本论文在以下三个方面具有创新性：
一、基于改进了的氧阴离子聚合法,合成了温敏和pH敏感的BAB型两亲嵌段共聚物PDMAEMA-PEG-PDMAEMA,并表征了其自组装行为。
二、首次将生物素连接到温敏和pH敏感的两亲嵌段共聚物,得到功能化了的AB型两亲嵌段共聚物,并对其溶液中的自组装行为进行了研究。
三、成功地以PDMAEMA-PEG-PDMAEMA与氯化铜络合,使两亲嵌段共聚物功能化为高分子催化剂,应用在三甲酚空气氧化成三甲醌上,得到了不亚于单体的催化效率和可接受的回收套用次数。
Recent years, amphiphilic block copolymers have numerous application possibilities in many hot research areas like biomimetic mineralization, nanomaterials (L-B membranes), biomaterials, drug/gene delivery system and so on. Thus, the molecular design, synthesis, and self-assembly behavior have been deeply researched. By molecular design and controlling of the external environment, nearly each self-assembled mophorlogy can be got. Based on this, the applications are important topics. In this thesis, temperature and pH sensitive amphiphilic block copolymers have been synthesized and the functionalization is researched. The relatively detailed summaries were as follows.
1. The synthesis of the amphiphilic block copolymers has been preliminarily improved. Normaly, the suspension of potassium naphthalene was used to initiate the synthesis. This is not easy to quantitatively determined, and is not good to be applicated in industry. This thesis replaced potassium naphthalene with solide potassium t-butoxide. Thus, the amount could be conveniently fixed and could also be conveniently stored.
2. We obtained AB type amphiphilic block copolymers with tert-amino group through the oxygen cationic polymerization method. Afterwards, functionalized block copolymers with a biotin end group were obtained by reacted with activated biotin, which was biotin-NHS. The self-assembly behavior in water was characterized. Since Biotin has very strong specific interaction with avidin, once the medicine has been bundled in the fuctionalized micelle with biotin group, it could be easily targeted to the organization with avidin.
3. We also designed the BAB type block copolymer, in which "B" referred to DMAEMA or DEAEMA segment, and "A" referred to PEO segment. The self-assembly behavior was carefully discussed, since the polymers were thermo-and pH-sensitive.
4. Besides, our group has a long time interest in the catalyst. This thesis supposed that block copolymers have a new application:as a highly effective, easily separated, and recyclable heterogeneous catalyst. The copolymer was complexed with CuCl2, and was used in the aero-oxidation of TMP to TMBQ.
The synthesis of PDMAEMA-PEG-PDMAEMA diblock copolymers by oxygen anion polymerization, the synthesis of biotin-PEG-PDMAEMA, and the functionalization of PDMEMA-PEG-PDMAEMA to be used as a highly effective, easily separated, and recyclable heterogeneous catalyst in the aero oxidation of TMP to TMBQ, to our best knowledge, are unprecedented.
引文
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