Synthesis and characterization of bifunctional surfaces with tunable functional group pairs

John M. Galloway; Mayfair Kung; Harold H. Kung

doi:10.1016/j.susc.2015.10.004

Synthesis and characterization of bifunctional surfaces with tunable functional group pairs

John M. Galloway, Mayfair Kung, Harold H. Kung^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

6 Scopus citations

Abstract

Grafting of pairs of functional groups onto a silica surface was demonstrated by tethering both terminals of an organochlorosilane precursor molecule, Cl₂(CH₃)Si(CH₂)₄(CO)(OSi(i-Pr)₂)(CH₂)₂Si(CH₃)Cl₂, that possess a cleavable silyl ester bond, onto a silica surface. Hydrolytic cleavage of the silyl ester bond of the grafted molecule resulted in the generation of organized pairs of carboxylic acid and organosilanol groups. This organosilanol moiety was easily transformed into other functional groups through condensation reactions to form, together with the neighboring acid group, pairs such as carboxylic acid/secondary amine, carboxylic acid/pyridine, and carboxylic acid/phosphine. In the case of carboxylic acid/amine pairing, there was evidence of the formation of amide. A sample grafted with amine-carboxylic acid pairs was three times more active (per free amine) than a sample without such pairs for the nitroaldol condensation of 4-nitrobenzaldehyde and nitromethane.

Original language	English (US)
Pages (from-to)	284-290
Number of pages	7
Journal	Surface Science
Volume	648
DOIs	https://doi.org/10.1016/j.susc.2015.10.004
State	Published - Jun 1 2016

Funding

This work was supported by the Office of Basic Energy Sciences, US Department of Energy , DE-FG02-01ER15184 . Spectroscopic characterization was performed at the Integrated Molecular Structure Education and Research Center (IMSERC) supported in part by NSF CHE-1048773 and Int. Institute of Nanotechnology and NUANCE facilities at Northwestern University.

Keywords

Acyloxysilane
Bifunctional surface
Cooperative effect
Paired bifunctional groups
Surface modification

ASJC Scopus subject areas

Condensed Matter Physics
Surfaces and Interfaces
Surfaces, Coatings and Films
Materials Chemistry

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title = "Synthesis and characterization of bifunctional surfaces with tunable functional group pairs",

abstract = "Grafting of pairs of functional groups onto a silica surface was demonstrated by tethering both terminals of an organochlorosilane precursor molecule, Cl2(CH3)Si(CH2)4(CO)(OSi(i-Pr)2)(CH2)2Si(CH3)Cl2, that possess a cleavable silyl ester bond, onto a silica surface. Hydrolytic cleavage of the silyl ester bond of the grafted molecule resulted in the generation of organized pairs of carboxylic acid and organosilanol groups. This organosilanol moiety was easily transformed into other functional groups through condensation reactions to form, together with the neighboring acid group, pairs such as carboxylic acid/secondary amine, carboxylic acid/pyridine, and carboxylic acid/phosphine. In the case of carboxylic acid/amine pairing, there was evidence of the formation of amide. A sample grafted with amine-carboxylic acid pairs was three times more active (per free amine) than a sample without such pairs for the nitroaldol condensation of 4-nitrobenzaldehyde and nitromethane.",

keywords = "Acyloxysilane, Bifunctional surface, Cooperative effect, Paired bifunctional groups, Surface modification",

author = "Galloway, {John M.} and Mayfair Kung and Kung, {Harold H.}",

year = "2016",

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doi = "10.1016/j.susc.2015.10.004",

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journal = "Surface Science",

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T1 - Synthesis and characterization of bifunctional surfaces with tunable functional group pairs

AU - Galloway, John M.

AU - Kung, Mayfair

AU - Kung, Harold H.

PY - 2016/6/1

Y1 - 2016/6/1

N2 - Grafting of pairs of functional groups onto a silica surface was demonstrated by tethering both terminals of an organochlorosilane precursor molecule, Cl2(CH3)Si(CH2)4(CO)(OSi(i-Pr)2)(CH2)2Si(CH3)Cl2, that possess a cleavable silyl ester bond, onto a silica surface. Hydrolytic cleavage of the silyl ester bond of the grafted molecule resulted in the generation of organized pairs of carboxylic acid and organosilanol groups. This organosilanol moiety was easily transformed into other functional groups through condensation reactions to form, together with the neighboring acid group, pairs such as carboxylic acid/secondary amine, carboxylic acid/pyridine, and carboxylic acid/phosphine. In the case of carboxylic acid/amine pairing, there was evidence of the formation of amide. A sample grafted with amine-carboxylic acid pairs was three times more active (per free amine) than a sample without such pairs for the nitroaldol condensation of 4-nitrobenzaldehyde and nitromethane.

AB - Grafting of pairs of functional groups onto a silica surface was demonstrated by tethering both terminals of an organochlorosilane precursor molecule, Cl2(CH3)Si(CH2)4(CO)(OSi(i-Pr)2)(CH2)2Si(CH3)Cl2, that possess a cleavable silyl ester bond, onto a silica surface. Hydrolytic cleavage of the silyl ester bond of the grafted molecule resulted in the generation of organized pairs of carboxylic acid and organosilanol groups. This organosilanol moiety was easily transformed into other functional groups through condensation reactions to form, together with the neighboring acid group, pairs such as carboxylic acid/secondary amine, carboxylic acid/pyridine, and carboxylic acid/phosphine. In the case of carboxylic acid/amine pairing, there was evidence of the formation of amide. A sample grafted with amine-carboxylic acid pairs was three times more active (per free amine) than a sample without such pairs for the nitroaldol condensation of 4-nitrobenzaldehyde and nitromethane.

KW - Acyloxysilane

KW - Bifunctional surface

KW - Cooperative effect

KW - Paired bifunctional groups

KW - Surface modification

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JO - Surface Science

JF - Surface Science

ER -

Synthesis and characterization of bifunctional surfaces with tunable functional group pairs

Abstract

Funding

Keywords

ASJC Scopus subject areas

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