Reversible protection and reactive patterning of amine- and hydroxyl-terminated self-assembled monolayers on gold surfaces for the fabrication of biopolymer arrays
Reversible protection and reactive patterning of amine- and hydroxyl-terminated self-assembled monolayers on gold surfaces for the fabrication of biopolymer arrays
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DOI：
10.1021/la990718w
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发表时间：
2000-03-07
期刊：
影响因子：
3.9
通讯作者：
Corn, RM
中科院分区：
文献类型：
--
作者：
Frutos, AG;Brockman, JM;Corn, RM
本文描述了在金表面上使用碱不稳定保护基团9 - 芴甲氧羰基（Fmoc）和酸不稳定保护基团二甲氧基三苯甲基（DMT）对胺基和羟基封端的烷硫醇自组装单分子层（SAMs）进行可逆保护。当与紫外光图案化或微接触印刷技术结合使用时，这种可逆的SAM保护化学可用于控制表面不同部分的反应性和润湿性。这种空间控制被用于DNA阵列的制造中。具体而言，用胺基封端的烷硫醇11 - 巯基十一胺（MUAM）修饰的金表面与Fmoc的N - 羟基琥珀酰亚胺（NHS）酯衍生物反应，形成共价氨基甲酸酯键，将最初亲水的MUAM表面转变为疏水的、Fmoc封端的表面。当Fmoc修饰的表面暴露于仲胺溶液时，Fmoc被裂解，重新生成原始的亲水MUAM表面。Fmoc也被用作羟基保护基团，如Fmoc - Cl与11 - 巯基十一醇（MUD）单分子层的反应所示。疏水保护基团DMT与MUD和聚乙二醇封端的烷硫醇（PEG - SH）SAMs的ω - 羟基反应形成酸不稳定的醚键；通过将表面浸泡在3％三氟乙酸中去除DMT基团。采用偏振调制傅里叶变换红外反射吸收光谱（PM - FTIRRAS）、表面等离子体共振（SPR）和接触角测量相结合的方法来表征保护基团的附着和随后的去除。为了展示这种SAM保护化学和反应性图案化的一种应用，制造了一个DNA阵列，并将其用于错配结合蛋白MutS吸附的SPR成像测量。
The reversible protection of amine- and hydroxyl-terminated alkanethiol self-assembled monolayers (SAMs) on gold surfaces using the base-labile protecting group 9-fluorenylmethoxycarbonyl (Fmoc) and the acid-labile protecting group dimethoxytrityl (DMT) is described. When used in combination with UV photopatterning or mu-contact printing techniques, his reversible SAM protection chemistry can be used to control the reactivity and wettability of different portions of the surface. Such spatial control is utilized in the fabrication of DNA arrays. Specifically, gold surfaces modified with the amine-terminated alkanethiol 11-mercaptoundecylamine (MUAM) are reacted with an N-hydroxysuccinimide (NHS) ester derivative of Fmoc, forming a covalent urethane (carbamate) linkage and converting the initially hydrophilic MUAM surface to a hydrophobic, Fmoc-terminated surface. Upon exposure of the Fmoc-modified surface to a solution of a secondary amine, the Fmoc is cleaved, regenerating the original hydrophilic MUAM surface. Fmoc is also utilized as a hydroxyl protecting group, as demonstrated by the reaction of Fmoc-Cl with a monolayer of 11-mercaptoundecanol (MUD). The hydrophobic protecting group DMT is reacted with the w-hydroxyl groups of both MUD and poly(ethylene glycol)-terminated alkanethiol (PEG-SH) SAMs to form an acid labile ether bond; removal of the DMT group is accomplished by soaking the surface in 3% trifluoracetic acid. A combination of polarization-modulation Fourier transform infrared reflection absorption spectroscopy (PM-FTIRRAS), surface plasmon resonance (SPR), and contact angle measurements is used to characterize the attachment and subsequent removal of the protecting groups. To demonstrate one application of this SAM protection chemistry and reactive patterning, a DNA array is fabricated and used in an SPR imaging measurement of the adsorption of the mismatch binding protein MutS.