Lee Lita, Leroux Yann R, Hapiot Philippe, Downard Alison J
†MacDiarmid Institute for Advanced Materials and Nanotechnology, Department of Chemistry, University of Canterbury, Private Bag 4800, Christchurch 8140, New Zealand.
‡Institut des Sciences Chimiques de Rennes (Equipe MaCSE), CNRS, UMR 6226, Université de Rennes 1, Campus de Beaulieu, Bat 10C, 35042 Rennes Cedex, France.
Langmuir. 2015 May 12;31(18):5071-7. doi: 10.1021/acs.langmuir.5b00730. Epub 2015 Apr 29.
Aminophenyl and aminomethylphenyl monolayers have been electrografted to glassy carbon and pyrolyzed photoresist film from the corresponding diazonium ions using a protection-deprotection strategy based on Boc (tert-butyloxycarbonyl) and Fmoc (fluorenylmethyloxycarbonyl) groups. After grafting and then deprotecting films of Boc-NH-Ar, Fmoc-NH-Ar, and Fmoc-NH-CH2-Ar, depth profiling by atomic force microscopy confirmed that the resulting amine-terminated films were monolayers. In contrast, after deprotection, Boc-NH-CH2-Ar gave a multilayer film. Electroactive carboxylic acid derivatives were coupled to the monolayers through amide linkages. Electrochemical measurements revealed that the deprotected Fmoc-NH-CH2-Ar monolayer gave the highest surface concentration of coupled nitrophenyl and ferrocenyl groups and DFT calculations established that this monolayer has the highest theoretical surface concentration of those examined.
采用基于叔丁氧羰基（Boc）和芴甲氧羰基（Fmoc）基团的保护-脱保护策略，已将氨基苯基和氨基甲基苯基单分子层从相应的重氮离子电接枝到玻碳和热解光刻胶膜上。在接枝然后脱保护Boc-NH-Ar、Fmoc-NH-Ar和Fmoc-NH-CH2-Ar膜后，通过原子力显微镜进行深度剖析证实，所得的胺端基膜为单分子层。相比之下，脱保护后，Boc-NH-CH2-Ar得到多层膜。通过酰胺键将电活性羧酸衍生物偶联到单分子层上。电化学测量表明，脱保护的Fmoc-NH-CH2-Ar单分子层给出了最高的偶联硝基苯基和二茂铁基表面浓度，密度泛函理论计算表明，该单分子层在所研究的单分子层中具有最高的理论表面浓度。
