基于“点击化学”的功能糖分子构建与应用
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摘要
“点击化学(Click chemistry)"以其生成稳固的“碳-杂-碳(C-X-C)”连接核心为特色,从单个分子构建到组合化学,从结构的多样性到功能的多元化,它开辟出一套集实施简易、模块化、反应快速、收率高、立体选择性好以及对水氧不敏感等优点于一身的,具有广泛适用性和创造力的合成化学新方法。作为点击化学的杰出代表,一价铜离子催化的叠氮与炔的Huisgen1,3-偶极环加成(CuAAC)反应在糖类功能分子的合成中显示出巨大的优势。本论文研究工作以点击化学为合成基础,构建结构多样的“1,2,3-三氮唑型”功能糖分子。根据研究内容,分为以下三个部分：
第一部分(论文第2章)：
自然界的糖脂,囊括了一切以亲水的糖与疏水的脂通过不同方式连接而成、结构多样、功能复杂的两亲性分子。它们在作为生命体结构物质的同时,也担当信息和调控分子的角色,参与各种生物学过程。此外,种类繁多的糖脂天然产物以及通过化学合成手段获得的糖脂类化合物,具有抗癌、抗菌、免疫调节等广泛多样的生物活性,而出色的表面化学性能也使之在工业等领域得到广泛应用。
本部分研究工作经由简易的糖基和脂质配体合成策略,以CuAAC为连接手段,“点击”合成多系列、具有规律性结构变化的“1,2,3-三氮唑型”糖脂类似物,并进行了化合物库的体外生物活性和物理化学性质研究。在生物学活性研究中,系列Ⅰ、Ⅱ糖脂对多种人癌肿瘤细胞株表现出具一定“构效关系”规律的体外生长抑制活性；同时,系列Ⅱ糖脂在一定程度上显示了抗肿瘤活性的“类协同效应”现象；而系列Ⅰ糖脂则另表现出一定的抗菌活性规律。在物理化学性质研究中,系列Ⅰ、Ⅱ中部分化合物表现出有趣的“气-液界面”行为及性质规律；而在抗金属腐蚀性能方面,经过对系列Ⅰ、Ⅱ化合物初步抗腐蚀性质探索以及结构改进而得到的系列Ⅲ糖脂化合物,最终达到了提升其金属抗腐蚀性能的目的。
第二部分(论文第3章)：
自然界结构形式复杂的糖类与其受体蛋白之间的特异识别作用,构成了糖类生物学功能的基础。而多拷贝的糖链与簇集状受体的糖识别位点之间作用的“合力”,是实现这种生物学特异相互作用的有效方式,即所谓“多价效应”(或称“簇效应”)。许多人工合成糖簇及糖聚合物分子,也正是利用这一效应的结合力优势,实现对其特异受体出色的靶向或结合作用。
本部分研究工作以构建具有“多价糖基”的新型糖簇分子为主要目的,首先经多步反应合成以“肽氧键”串联、具“多价叠氮”修饰的非天然“氧肽”骨架,并选取具有重要生物学意义的单糖经简易合成得到糖炔,进而以CuAAC方法将二者相“点击”,得到“糖价态数”不等的“1,2,3-三氮唑”型“糖氨氧酸”及“糖氧肽”类化合物。所构建化合物具有可供方便修饰的氨基与羧基端头,利于进一步功能化应用：其多价GalNAc糖基使之具备潜在生物学靶向能力及类肿瘤疫苗的结构特征,在生物医学研究中颇具应用潜力。
第三部分(论文第4章)：
石墨烯这一新型二维纳米碳晶体的出现,引领纳米传感科学步入一个崭新的时代。它出色的光学、电学及结构学性质赋予其十分广阔的应用空间,而良好的生物相容度和低毒性也使它的生物医学应用优势巨大。自石墨烯出现以来不足10年的短暂过程中,以此二维平台为基础的新型纳米传感器的研究与应用被争相报道,并在物质探测和诊断学相关领域显示出尤为突出的应用价值。
本部分研究工作通过简洁高效的“点击化学”手段,将具有生物特异识别作用的单糖与荧光性质优良的罗丹明相连,合成结构简单的“糖-罗丹明”荧光物,并将其进一步与二维氧化态石墨烯材料以π-π作用相叠合,利用石墨烯-荧光团之间的"FRET效应”,搭建表面簇集糖荧光分子、“荧光关闭”的石墨烯纳米生物传感器。进而,我们通过糖-受体间特异识别、结合作用可干扰FRET过程这一原理,应用该传感体系成功实施了“糖特异凝集素”的“荧光启发式”检测,并首次将这一过程用于癌细胞表面糖蛋白受体的原位识别与荧光标记。该“荧光关开式”生物传感器构建简易、成本低廉、无毒,在生物学、医学诊断领域具有较强的实用价值。
"Click Chemistry" is characteristic of the formation of stable "C-X-C" bonding center. Ranging from unimolecule construction to combinational chemistry, from structural multiformity to functional diversification, click chemistry opens up a series of novel synthetic methods, which is widely applicable and highly creative, with the advantages of convenient implementation, modularization, fast reactivity, high yields, excellent stereoselectivity and insensitivity to water and oxygen. Prominent category as it is, copper(I) catalyzed Huisgen azide-alkyne1,3-dipolar cycloaddition (CuAAC) reaction shows great superiority in the synthesis of functionalized glycomolecules. In this dissertation,"1,2,3-riazole" linked glycomolecules with structural diversity and multifunction were fabricated on the basis of click chemistry, and the research content can be divided into3sections as follows:
Section One(Chapter2of the dissertation):
Glycolipids in nature include all amphiphilic compounds with diversified structures and complicated functions, which mainly consist of hydrophilic sugars and hydrophobic lipids connecting with each other in different ways. Besides the constructive roles in life, they functions as informational and regulating molecules, participating in various biological processes. Moreover, numerous natural and synthetic sugar-lipid derivatives possess comprehensive bioactivities such as anticancer, antibiosis and immunoregulating, and their remarkable surface chemical properties endow them with important applications in industry.
In our research, simple glycosyl and lipidic ligands were "clicked" together via CuAAC method to construct series of1,2,3-triazole linked glycolipids with regular changes in their structures. In the subsequent anticancer activity assessments,"structure-activity relationships" were partly displayed by compound series Ⅰ and Ⅱ, and "synergetic effect" was found in series Ⅱ. Besides, antibacteria results were acquired from series Ⅰ. In the physicochemical study, some interesting interfacial qualities were found on series Ⅰ and Ⅱ, and improved anticorrosion ability was achieved on series Ⅲ, whose structures were based on reformational modifications of series I and II compounds.
Section Two(Chapter3of the dissertation):
The specific recognition between multifarious sugars and their corresponding receptor proteins in nature layes the foundation of biological functions of sugars which can be effectively realized via the joint interactions between multicopied glycans and clustered receptors, namely "multivalent effect" or "clustered effect". A large amount of artificial glycoclusters and glycopolymers targeted their receptors successfully by utilizing the effect.
In this work, we aimed at constructing novel glycoclusters with multiple glycones. Unnatural "oxygen peptido-skeletons" with multiple azides were firstly concatenated by "peptidoxy" bonds. Glycosyl alkynes of biological importance were synthesized thereafter to "click" onto the skeletons via CuAAC in order to abtain1,2,3-triazolyl "glycosyl aminoxy acid" and "glycosyl oxygen peptides". These sugar derivatives possess modifiable carboxyl and amino groups that are convinent for further functionalization. The equipped GalNAc residues endow them with the biological targeting ability and features of tumor vaccine molecules, which is benefit for biological and medical applications.
Section Three(Chapter4of the dissertation):
On appearing of the new two dimensional nano material, graphene has been leading the way of sensing nanoscience into a brand-new era. Not only the splendid optical, electrical and structural properties endow it with wide utilizations, but the high biocompatibility and low toxicity also make it advantageous in biological and medical applicabilities. During the short10years since its appearance, innumerable new sensing nanoplatforms based on graphene have been competitively reported, which showed great applicable values in detection and diagnosis.
In this research, bio-recognizable sugars were connected with excellently fluorescent rhodamine group using click chemistry to get glycosyl rhodamine fluorophors which were stacked onto graphene oxide through π-π interaction in order to obtain clustered glycosyl fluorophors on the surface and FRET effect driving "light off" biological sensing platforms. Then, we conveniently conducted the "light on" detection of sugar specific lectins by the mechanism that sugar-protein interaction can impede the FRET effect. On the basis of this system, in suit recognition and fluorescent labeling of sugar receptors on cancer cell surface was successfully achieved for the first time. This fluorescent "OFF-ON" biosensing platform is simple, economical and non-toxic, which can be practically used in biological and medical diagnosis.
第一部分(论文第2章)：
自然界的糖脂,囊括了一切以亲水的糖与疏水的脂通过不同方式连接而成、结构多样、功能复杂的两亲性分子。它们在作为生命体结构物质的同时,也担当信息和调控分子的角色,参与各种生物学过程。此外,种类繁多的糖脂天然产物以及通过化学合成手段获得的糖脂类化合物,具有抗癌、抗菌、免疫调节等广泛多样的生物活性,而出色的表面化学性能也使之在工业等领域得到广泛应用。
本部分研究工作经由简易的糖基和脂质配体合成策略,以CuAAC为连接手段,“点击”合成多系列、具有规律性结构变化的“1,2,3-三氮唑型”糖脂类似物,并进行了化合物库的体外生物活性和物理化学性质研究。在生物学活性研究中,系列Ⅰ、Ⅱ糖脂对多种人癌肿瘤细胞株表现出具一定“构效关系”规律的体外生长抑制活性；同时,系列Ⅱ糖脂在一定程度上显示了抗肿瘤活性的“类协同效应”现象；而系列Ⅰ糖脂则另表现出一定的抗菌活性规律。在物理化学性质研究中,系列Ⅰ、Ⅱ中部分化合物表现出有趣的“气-液界面”行为及性质规律；而在抗金属腐蚀性能方面,经过对系列Ⅰ、Ⅱ化合物初步抗腐蚀性质探索以及结构改进而得到的系列Ⅲ糖脂化合物,最终达到了提升其金属抗腐蚀性能的目的。
第二部分(论文第3章)：
自然界结构形式复杂的糖类与其受体蛋白之间的特异识别作用,构成了糖类生物学功能的基础。而多拷贝的糖链与簇集状受体的糖识别位点之间作用的“合力”,是实现这种生物学特异相互作用的有效方式,即所谓“多价效应”(或称“簇效应”)。许多人工合成糖簇及糖聚合物分子,也正是利用这一效应的结合力优势,实现对其特异受体出色的靶向或结合作用。
本部分研究工作以构建具有“多价糖基”的新型糖簇分子为主要目的,首先经多步反应合成以“肽氧键”串联、具“多价叠氮”修饰的非天然“氧肽”骨架,并选取具有重要生物学意义的单糖经简易合成得到糖炔,进而以CuAAC方法将二者相“点击”,得到“糖价态数”不等的“1,2,3-三氮唑”型“糖氨氧酸”及“糖氧肽”类化合物。所构建化合物具有可供方便修饰的氨基与羧基端头,利于进一步功能化应用：其多价GalNAc糖基使之具备潜在生物学靶向能力及类肿瘤疫苗的结构特征,在生物医学研究中颇具应用潜力。
第三部分(论文第4章)：
石墨烯这一新型二维纳米碳晶体的出现,引领纳米传感科学步入一个崭新的时代。它出色的光学、电学及结构学性质赋予其十分广阔的应用空间,而良好的生物相容度和低毒性也使它的生物医学应用优势巨大。自石墨烯出现以来不足10年的短暂过程中,以此二维平台为基础的新型纳米传感器的研究与应用被争相报道,并在物质探测和诊断学相关领域显示出尤为突出的应用价值。
本部分研究工作通过简洁高效的“点击化学”手段,将具有生物特异识别作用的单糖与荧光性质优良的罗丹明相连,合成结构简单的“糖-罗丹明”荧光物,并将其进一步与二维氧化态石墨烯材料以π-π作用相叠合,利用石墨烯-荧光团之间的"FRET效应”,搭建表面簇集糖荧光分子、“荧光关闭”的石墨烯纳米生物传感器。进而,我们通过糖-受体间特异识别、结合作用可干扰FRET过程这一原理,应用该传感体系成功实施了“糖特异凝集素”的“荧光启发式”检测,并首次将这一过程用于癌细胞表面糖蛋白受体的原位识别与荧光标记。该“荧光关开式”生物传感器构建简易、成本低廉、无毒,在生物学、医学诊断领域具有较强的实用价值。
"Click Chemistry" is characteristic of the formation of stable "C-X-C" bonding center. Ranging from unimolecule construction to combinational chemistry, from structural multiformity to functional diversification, click chemistry opens up a series of novel synthetic methods, which is widely applicable and highly creative, with the advantages of convenient implementation, modularization, fast reactivity, high yields, excellent stereoselectivity and insensitivity to water and oxygen. Prominent category as it is, copper(I) catalyzed Huisgen azide-alkyne1,3-dipolar cycloaddition (CuAAC) reaction shows great superiority in the synthesis of functionalized glycomolecules. In this dissertation,"1,2,3-riazole" linked glycomolecules with structural diversity and multifunction were fabricated on the basis of click chemistry, and the research content can be divided into3sections as follows:
Section One(Chapter2of the dissertation):
Glycolipids in nature include all amphiphilic compounds with diversified structures and complicated functions, which mainly consist of hydrophilic sugars and hydrophobic lipids connecting with each other in different ways. Besides the constructive roles in life, they functions as informational and regulating molecules, participating in various biological processes. Moreover, numerous natural and synthetic sugar-lipid derivatives possess comprehensive bioactivities such as anticancer, antibiosis and immunoregulating, and their remarkable surface chemical properties endow them with important applications in industry.
In our research, simple glycosyl and lipidic ligands were "clicked" together via CuAAC method to construct series of1,2,3-triazole linked glycolipids with regular changes in their structures. In the subsequent anticancer activity assessments,"structure-activity relationships" were partly displayed by compound series Ⅰ and Ⅱ, and "synergetic effect" was found in series Ⅱ. Besides, antibacteria results were acquired from series Ⅰ. In the physicochemical study, some interesting interfacial qualities were found on series Ⅰ and Ⅱ, and improved anticorrosion ability was achieved on series Ⅲ, whose structures were based on reformational modifications of series I and II compounds.
Section Two(Chapter3of the dissertation):
The specific recognition between multifarious sugars and their corresponding receptor proteins in nature layes the foundation of biological functions of sugars which can be effectively realized via the joint interactions between multicopied glycans and clustered receptors, namely "multivalent effect" or "clustered effect". A large amount of artificial glycoclusters and glycopolymers targeted their receptors successfully by utilizing the effect.
In this work, we aimed at constructing novel glycoclusters with multiple glycones. Unnatural "oxygen peptido-skeletons" with multiple azides were firstly concatenated by "peptidoxy" bonds. Glycosyl alkynes of biological importance were synthesized thereafter to "click" onto the skeletons via CuAAC in order to abtain1,2,3-triazolyl "glycosyl aminoxy acid" and "glycosyl oxygen peptides". These sugar derivatives possess modifiable carboxyl and amino groups that are convinent for further functionalization. The equipped GalNAc residues endow them with the biological targeting ability and features of tumor vaccine molecules, which is benefit for biological and medical applications.
Section Three(Chapter4of the dissertation):
On appearing of the new two dimensional nano material, graphene has been leading the way of sensing nanoscience into a brand-new era. Not only the splendid optical, electrical and structural properties endow it with wide utilizations, but the high biocompatibility and low toxicity also make it advantageous in biological and medical applicabilities. During the short10years since its appearance, innumerable new sensing nanoplatforms based on graphene have been competitively reported, which showed great applicable values in detection and diagnosis.
In this research, bio-recognizable sugars were connected with excellently fluorescent rhodamine group using click chemistry to get glycosyl rhodamine fluorophors which were stacked onto graphene oxide through π-π interaction in order to obtain clustered glycosyl fluorophors on the surface and FRET effect driving "light off" biological sensing platforms. Then, we conveniently conducted the "light on" detection of sugar specific lectins by the mechanism that sugar-protein interaction can impede the FRET effect. On the basis of this system, in suit recognition and fluorescent labeling of sugar receptors on cancer cell surface was successfully achieved for the first time. This fluorescent "OFF-ON" biosensing platform is simple, economical and non-toxic, which can be practically used in biological and medical diagnosis.
引文
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