Alkylierung von porösem Silicium durch direkte Umsetzung mit Alkenen und Alkinen

Bateman, J.E.; Eagling, Robert; Worrall, David R.; Horrocks, Benjamin R.; Houlton, Andrew

doi:10.1002/(sici)1521-3757(19981002)110:19<2829::aid-ange2829>3.0.co;2-5

Cited by 7 publications

(3 citation statements)

References 19 publications

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“…Our preferred method is thermal hydrosilation of alkenyl/alkynyl derivatives due to its functional group tolerance 71. 72 Alkylation of hydrogen‐terminated Si<111> ( Si‐H ) with 4,4′‐dimethoxytrityl‐protected ω ‐undecenol provides modified silicon surfaces ( Si‐C 11 ‐ODMT ) which, after detritylation, present a primary alcohol group suitable for on‐chip DNA synthesis 5. As a phosphoramidite, 1 was incorporated at the electrode surface as a monomer ( Si‐1 ) and into growing oligonucleotides ( Si‐1‐ODN ), as shown in Scheme .…”

Section: Resultsmentioning

confidence: 99%

Ferrocenyl‐Modified DNA: Synthesis, Characterization and Integration with Semiconductor Electrodes

Pike

Ryder

Horrocks

et al. 2004

Chemistry A European J

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The ferrocenyl-nucleoside, 5-ethynylferrocenyl-2'-deoxycytidine (1) has been prepared by Pd-catalyzed cross-coupling between ethynylferrocene and 5-iodo-2'-deoxycytidine and incorporated into oligonucleotides by using automated solid-phase synthesis at both silica supports (CPG) and modified single-crystal silicon electrodes. Analysis of DNA oligonucleotides prepared and cleaved from conventional solid supports confirms that the ferrocenyl-nucleoside remains intact during synthesis and deprotection and that the resulting strands may be oxidised and reduced in a chemically reversible manner. Melting curve data show that the ferrocenyl-modified oligonucleotides form duplex structures with native complementary strands. The redox potential of fully solvated ferrocenyl 12-mers, 350 mV versus SCE, was shifted by +40 mV to a more positive potential upon treatment with the complement contrary to the anticipated negative shift based on a simple electrostatic basis. Automated solid-phase methods were also used to synthesise 12-mer ferrocenyl-containing oligonucleotides directly at chemically modified silicon <111> electrodes. Hybridisation to the surface-bound ferrocenyl-DNA caused a shift in the reduction potential of +34 mV to more positive values, indicating that, even when a ferrocenyl nucleoside is contained in a film, the increased density of anions from the phosphate backbone of the complement is still dominated by other factors, for example, the hydrophobic environment of the ferrocene moiety in the duplex or changes in the ferrocene-phosphate distances. The reduction potential is shifted >100 mV after hybridisation when the aqueous electrolyte is replaced by THF/LiClO(4), a solvent of much lower dielectric constant; this is consistent with an explanation based on conformation-induced changes in ferrocene-phosphate distances.

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Section: Resultsmentioning

confidence: 99%

Ferrocenyl‐Modified DNA: Synthesis, Characterization and Integration with Semiconductor Electrodes

Pike

Ryder

Horrocks

et al. 2004

Chemistry A European J

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“…Hydrogen‐terminated surfaces represent the initial state from which silicon semiconductor devices are fabricated 11. Chidsey and co‐workers first demonstrated that such single‐crystal surfaces12 react with alkenes to give chemically robust Si−C‐bonded monolayers, and further advances have shown the applicability of this chemistry to porous silicon 13–15. The reaction may be driven by thermal, catalytic, electrochemical, and photochemical methods,13, 16 and patterning of the monolayers, for example, by using photolithographic techniques, is possible.…”

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confidence: 99%

“…The reaction may be driven by thermal, catalytic, electrochemical, and photochemical methods,13, 16 and patterning of the monolayers, for example, by using photolithographic techniques, is possible. We have used a simple protecting group method to produce monolayers with terminal OH groups (Figure 1); hydrogen‐terminated silicon surfaces of oriented (111) single‐crystal and porous silicon were alkylated with 4,4′‐dimethoxytrityl‐protected ω ‐undecenol (trityl=triphenylmethyl) by refluxing it in toluene; this is a previously established method to form robust Si−C‐bonded monolayers 15, 17. The 17‐mer oligonucleotides where then synthesized at these modified surfaces with UltraMILD base phosphoramidites (Glen Research, VA, USA) by using a DNA synthesizer and a column assembly modified to accept approximately 1‐cm 2 Si chips.…”

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confidence: 99%

DNA On Silicon Devices: On-Chip Synthesis, Hybridization, and Charge Transfer

et al. 2002

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Surface-immobilized DNA has an increasing number of roles in science and technology because of the ease with which it can be manipulated chemically and enzymatically in a highly controlled manner. Complex DNA architectures [1] and the use of DNA as a scaffold for making electronic connections [2] have been reported, and the use of DNA as a component in so-called molecular electronics has been frequently advocated. [3] Applications also include DNA microarrays [4] for sequencing through hybridization, the study of gene expression, and even for prototype computing devices which utilize the fidelity of the hybridization reaction. [5±7] In most cases, the DNA is immobilized on glass, oxidized silicon wafers, or other insulating supports. Methods for combining DNA with electronic materials are anticipated to be increasingly important in light of the considerable interest in DNAbased nanotechnology, [1] DNA-mediated charge transfer, [8] and DNA-based wires. [2] For substrates such as gold [9] or Si, [10] where there is the possibility of charge transfer through the DNA to the surface, immobilization has relied upon the attachment of presynthesized strands. However, to date there has been no demonstration of the use of automated solidphase DNA synthesis nor charge transfer through DNAbased assemblies at a semiconductor. For many proposed applications the ability to combine microelectronic processing techniques, [11] for example, photolithography and micromachining, with automated chemical synthesis has clear advantages. Herein we outline a method that enables the straightforward integration of DNA technology with microelectronics.Hydrogen-terminated surfaces represent the initial state from which silicon semiconductor devices are fabricated. [11] Chidsey and co-workers first demonstrated that such singlecrystal surfaces [12] react with alkenes to give chemically robust Si À C-bonded monolayers, and further advances have shown the applicability of this chemistry to porous silicon. [13±15] The reaction may be driven by thermal, catalytic, electrochemical, and photochemical methods, [13,16] and patterning of the monolayers, for example, by using photolithographic techniques, is possible. We have used a simple protecting group method to produce monolayers with terminal OH groups ( Figure 1); hydrogen-terminated silicon surfaces of oriented (111) single-crystal and porous silicon were alkylated with 4,4'-dimethoxytrityl-protected w-undecenol (trityl triphenylmethyl) by refluxing it in toluene; this is a previously

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