Synthesis of a series of oligo(ethylene glycol)-terminated alkanethiol amides designed to address structure and stability of biosensing interfaces
Synthesis of a series of oligo(ethylene glycol)-terminated alkanethiol amides designed to address structure and stability of biosensing interfaces
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DOI：
10.1021/jo0012290
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发表时间：
2001-06-29
影响因子：
3.6
通讯作者：
Svensson, SCT
中科院分区：
文献类型：
--
作者：
Svedhem, S;Hollander, CÅ;Svensson, SCT
本文报道了一系列密切相关的低聚乙二醇封端的烷基乙酰胺（主要是HS（CH_2）（m）CONH（CH_2CH_2 O）（n）H; m = 2，5，11，15，n = 1，2，4，6，8，10，12）和类似酯的合成方法。这些化合物的制备是为了研究金表面自组装单分子膜的结构和稳定性，为设计新的生物传感界面提供前景。为此目的，制备了具有多达12个单元的单分散杂官能低聚（乙二醇）。使用银（I）氧化物进行对称的四-和六（乙二醇）二醛作为它们的甲磺酸酯的选择性单酰化。合成方法是基于各种低聚（乙二醇）衍生物通过末端氨基或羟基官能团与ω-（乙酰硫基）羧酸的碳二亚胺偶联。SAM：金上的结构进行了研究，相对于厚度，润湿性（水接触角类似于30度），和构象。得到了单层厚度（d）与低聚（乙二醇）链中的单元数（n）之间的关系的良好拟合：d = 2.8n + 21.8（埃）。有趣的是，相应的红外光谱分析表明，在构象的低聚物链从全反式（n = 4）到螺旋（n大于或等于6）构象的显着变化。当n > 6时，在自组装膜中观察到结晶螺旋结构.
A strategy for the synthesis of a series of closely related oligo(ethylene glycol)-terminated alkanethiol amides (principally HS(CH2)(m)CONH(CH2CH2O)(n)H; m = 2, 5, 11, 15, n = 1, 2, 4, 6, 8, 10, 12) and analogous esters has been developed. These compounds were made to study the structure and stability of self-assembled monolayers (SAMs) on gold in the prospect of designing new biosensing interfaces. For this purpose, monodisperse heterofunctional oligo(ethylene glycols) with up to 12 units were prepared. Selective monoacylation of the symmetrical tetra- and hexa(ethylene glycol) dials as their mesylates with the use of silver(I) oxide was performed. The synthetic approach was based an carbodiimide couplings of various oligo(ethylene glycol) derivatives to omega-(acetylthio) carboxylic acids via a terminal amino or hydroxyl function. SAM: structures on gold were studied with respect to thickness, wettability (water contact angles similar to 30 degrees), and conformation. A good fit was obtained for the relation between monolayer thickness (d) and the number of units in the oligo(ethylene glycol) chain (n): d = 2.8n + 21.8 (Angstrom). Interestingly, the corresponding infrared spectroscopy analysis showed a dramatic change in conformation of the oligomeric chains from all-trans (n = 4) to helical in (n greater than or equal to 6) conformation. A crystalline helical structure was observed in the SAMs for n > 6.