Adenine-containing block copolymers via ring-opening metathesis polymerization: Synthesis and self-assembly into rod morphologies
Adenine-containing block copolymers via ring-opening metathesis polymerization: Synthesis and self-assembly into rod morphologies
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DOI：
10.1021/ma025676o
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发表时间：
2002-12-17
期刊：
影响因子：
5.5
通讯作者：
Sleiman, HF
中科院分区：
文献类型：
--
作者：
Bazzi, HS;Sleiman, HF
近年来，合成聚合物中链-链缔合的控制一直是研究的热点。[1]为此，人们使用了许多非共价力，如货车范德华力、静电力和单点氢键相互作用。另一方面，生物大分子（如核酸）通过分子识别或通过多个氢键结合互补伙伴而获得了协同和选择性结合的显着能力。[2]因此，在聚合物相互作用的多样性中加入分子识别，可以赋予合成聚合物选择和结合其互补配偶体以及与生物系统有效界面的能力。3-7在过去的几年中，许多重要的贡献已经描述了含有分子识别单元的聚合物的合成及其选择性结合互补分子、聚合物和胶体金颗粒的能力。3-6在大多数这些先前的系统中，分子识别单元被并入通过常规自由基聚合产生的聚合物中或统计地连接到嵌段共聚物主链。3，4原子转移自由基聚合已被用于合成含有尿苷和腺苷单体的均聚物。6我们最近启动了一项研究计划，以检查使用开环易位聚合8，9来构建“DNA模拟”聚合物和含有区域规则聚合物主链的嵌段共聚物，这些聚合物主链被DNA碱基或类似物取代。10这些聚合物预期对其互补配偶体以及天然核酸显示出高结合亲和力和选择性，具有作为生物分子传感器和DNA递送剂的潜在应用。我们在这里报告的第一个合成含腺嘌呤的均聚物和嵌段共聚物通过控制开环易位聚合和这些氢键和自我互补的嵌段共聚物的能力，自组装成新的纳米级棒形态。使用呋喃-马来酸酐外加合物111作为起始材料12进行含腺嘌呤单体4的合成（方案1）。用3-溴丙胺氢溴酸盐处理该加合物导致酸酐开环，得到酰胺/酸产物2。在NaOAc/乙酸酐混合物中缩合成酰亚胺，得到溴化衍生物3。腺嘌呤与NaH在热DMF中反应，然后加入3，得到腺嘌呤取代的单体4。13
The control of strand-strand association in synthetic polymers has been the subject of intense investigation in recent years. 1 For this, a number of noncovalent forces, such as van der Waals, electrostatic, and singlepoint hydrogen-bonding interactions, have been used. 1 Biological macromolecules (eg, nucleic acids), on the other hand, derive their remarkable ability for cooperative and selective binding from molecular recognition or the association of complementary partners via multiple hydrogen bonds. 2 The addition of molecular recognition to the manifold of polymer interactions can thus endow synthetic polymers with the ability to select and bind their complementary partners as well as interface efficiently with biological systems. 3-7 In the past few years, a number of important contributions have described the synthesis of polymers containing molecular recognition units and their ability to selectively bind complementary molecules, polymers, and colloidal gold particles. 3-6 In most of these previous systems, molecular recognition units were incorporated into polymers generated by conventional free radical polymerization or statistically attached to a block copolymer backbone. 3, 4 Atom transfer radical polymerization has been used to synthesize homopolymers containing uridine and adenosine monomers. 6 We have recently initiated a research program to examine the use of the ring-opening metathesis polymerization8, 9 to construct “DNA-mimetic” polymers and block copolymers containing regioregular polymer backbones, which are substituted with DNA bases or analogues. 10 These polymers are expected to show high binding affinity and selectivity to their complementary partners, as well as to natural nucleic acids, with potential applications as biomolecule sensors and DNA-delivery agents. We here report the first synthesis of adenine-containing homopolymers and block copolymers via controlled ring-opening metathesis polymerization and the ability of these hydrogen-bonding and selfcomplementary block copolymers to self-assemble into novel nanoscale rod morphologies. The synthesis of adenine-containing monomer 4 was performed using the furan-maleic anhydride exo-adduct 111 as starting material12 (Scheme 1). Treatment of this adduct with 3-bromopropylamine hydrobromide resulted in ring-opening of the anhydride to yield the amide/acid product 2. Condensation to the imide in a NaOAc/acetic anhydride mixture yielded the bromoderivative 3. Reaction of adenine with NaH in hot DMF followed by addition of 3 gave adenine-substituted monomer 4. 13