Viswanathan Kalpana, Ozhalici Hayriye, Elkins Casey L, Heisey Cheryl, Ward Thomas C, Long Timothy E
Department of Chemistry, Macromolecules and Interfaces Institute, Virginia Polytechnic Institute and State University, Blacksburg Virginia 24061, USA.
Langmuir. 2006 Jan 31;22(3):1099-105. doi: 10.1021/la052253h.
Specific and reversible adhesion of a terminal thymine-functionalized polystyrene (PS-thymine) was demonstrated for a silicon surface with complementary adenine recognition sites. A novel adenine-containing triethoxysilane (ADPTES), which was suitable for covalent attachment to silanol containing surfaces, was synthesized in one step from adenine and 3-isocyanatopropyl triethoxysilane (IPTES). 1H and 13C NMR spectroscopy and fast atom bombardment mass spectroscopy confirmed the chemical structure, and 29Si NMR spectroscopy indicated the absence of any premature hydrolysis of the alkoxysilane derivative. X-ray photoelectron spectroscopy (XPS) and water contact angle measurements indicated the attachment of PS-thymine to silicon surfaces that were modified with a mixture of ADPTES and 3-mercaptopropyl triethoxysilane (MPTES). PS-thymine attachment to surfaces that were modified with only MPTES was not observed. The exclusive attachment of PS-thymine to an ADPTES/MPTES-modified surface confirmed hydrogen bonding-mediated adenine-thymine association to silicon surfaces containing a sufficiently low concentration of adenine recognition sites. Although PS-thymine attachment to the ADPTES/MPTES-modified surfaces was insensitive to THF rinsing, the PS-thymine was completely removed from the surface upon DMSO rinsing because of the disruption of adenine-thymine hydrogen bonding with a more polar aprotic solvent. PS-thymine was successfully reattached to the ADPTES/MPTES-modified surface following the DMSO rinse, demonstrating the solvato-reversible nature of the adenine-thymine association.
已证明末端胸腺嘧啶功能化的聚苯乙烯（PS-胸腺嘧啶）能与具有互补腺嘌呤识别位点的硅表面发生特异性且可逆的粘附。一种新型的含腺嘌呤三乙氧基硅烷（ADPTES），它适合共价连接到含硅醇的表面，由腺嘌呤和3-异氰酸酯基丙基三乙氧基硅烷（IPTES）一步合成。1H和13C核磁共振光谱以及快原子轰击质谱证实了其化学结构，29Si核磁共振光谱表明烷氧基硅烷衍生物不存在任何过早水解的情况。X射线光电子能谱（XPS）和水接触角测量表明PS-胸腺嘧啶附着到了用ADPTES和3-巯基丙基三乙氧基硅烷（MPTES）混合物改性的硅表面。未观察到PS-胸腺嘧啶附着到仅用MPTES改性的表面。PS-胸腺嘧啶排他性地附着到ADPTES/MPTES改性表面，证实了氢键介导的腺嘌呤-胸腺嘧啶缔合到含足够低浓度腺嘌呤识别位点的硅表面。尽管PS-胸腺嘧啶附着到ADPTES/MPTES改性表面对四氢呋喃冲洗不敏感，但由于用极性更强的非质子溶剂破坏了腺嘌呤-胸腺嘧啶氢键，PS-胸腺嘧啶在二甲基亚砜冲洗后从表面完全去除。在二甲基亚砜冲洗后，PS-胸腺嘧啶成功重新附着到ADPTES/MPTES改性表面，证明了腺嘌呤-胸腺嘧啶缔合的溶剂化可逆性质。
