Investigations of polyelectrolyte adsorption at the solid/liquid interface by sum frequency spectroscopy

Evidence for long-range macromolecular alignment at highly charged quartz/water interfaces

Joonyeong Kim, Gibum Kim, Paul S. Cremer

Research output: Contribution to journalArticle

59 Citations (Scopus)

Abstract

IR-visible sum frequency spectroscopy (SFS) was employed to investigate the molecular level details of the adsorption of the positively charged polyelectrolyte, polydiallyldimethylammonium chloride (PDDA), at the quartz/water interface. Below pH 9.0, signal from the interfacial water structure was visible, but none from the adsorbed polymer could be detected. This indicated that the PDDA was not well enough aligned at the interface under these conditions to elicit a sum frequency response. At more basic pH values (ge;9.6), however, adsorbed PDDA molecules became well-ordered as indicated by the presence of CH stretch peaks from methylene and methyl groups. The intensities of the CH stretch modes were independent of the adsorbed amount of PDDA at pH 12.3 but decreased as the pH of the bulk solution was lowered. The conditions for polymer alignment fell outside the parameters where layer-by-layer growth of oppositely charged polyelectrolytes was possible because the net charge on the surface under high pH conditions remained negative.

Original languageEnglish (US)
Pages (from-to)8751-8756
Number of pages6
JournalJournal of the American Chemical Society
Volume124
Issue number29
DOIs
StatePublished - Jul 24 2002

Fingerprint

Quartz
Polyelectrolytes
Adsorption
Chlorides
Spectrum Analysis
Spectroscopy
Water
Liquids
Polymers
Frequency response
Molecules
Growth

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

@article{dbf3e8672d3445bab6b4df5dfcea485d,
title = "Investigations of polyelectrolyte adsorption at the solid/liquid interface by sum frequency spectroscopy: Evidence for long-range macromolecular alignment at highly charged quartz/water interfaces",
abstract = "IR-visible sum frequency spectroscopy (SFS) was employed to investigate the molecular level details of the adsorption of the positively charged polyelectrolyte, polydiallyldimethylammonium chloride (PDDA), at the quartz/water interface. Below pH 9.0, signal from the interfacial water structure was visible, but none from the adsorbed polymer could be detected. This indicated that the PDDA was not well enough aligned at the interface under these conditions to elicit a sum frequency response. At more basic pH values (ge;9.6), however, adsorbed PDDA molecules became well-ordered as indicated by the presence of CH stretch peaks from methylene and methyl groups. The intensities of the CH stretch modes were independent of the adsorbed amount of PDDA at pH 12.3 but decreased as the pH of the bulk solution was lowered. The conditions for polymer alignment fell outside the parameters where layer-by-layer growth of oppositely charged polyelectrolytes was possible because the net charge on the surface under high pH conditions remained negative.",
author = "Joonyeong Kim and Gibum Kim and Cremer, {Paul S.}",
year = "2002",
month = "7",
day = "24",
doi = "10.1021/ja0263036",
language = "English (US)",
volume = "124",
pages = "8751--8756",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "29",

}

TY - JOUR

T1 - Investigations of polyelectrolyte adsorption at the solid/liquid interface by sum frequency spectroscopy

T2 - Evidence for long-range macromolecular alignment at highly charged quartz/water interfaces

AU - Kim, Joonyeong

AU - Kim, Gibum

AU - Cremer, Paul S.

PY - 2002/7/24

Y1 - 2002/7/24

N2 - IR-visible sum frequency spectroscopy (SFS) was employed to investigate the molecular level details of the adsorption of the positively charged polyelectrolyte, polydiallyldimethylammonium chloride (PDDA), at the quartz/water interface. Below pH 9.0, signal from the interfacial water structure was visible, but none from the adsorbed polymer could be detected. This indicated that the PDDA was not well enough aligned at the interface under these conditions to elicit a sum frequency response. At more basic pH values (ge;9.6), however, adsorbed PDDA molecules became well-ordered as indicated by the presence of CH stretch peaks from methylene and methyl groups. The intensities of the CH stretch modes were independent of the adsorbed amount of PDDA at pH 12.3 but decreased as the pH of the bulk solution was lowered. The conditions for polymer alignment fell outside the parameters where layer-by-layer growth of oppositely charged polyelectrolytes was possible because the net charge on the surface under high pH conditions remained negative.

AB - IR-visible sum frequency spectroscopy (SFS) was employed to investigate the molecular level details of the adsorption of the positively charged polyelectrolyte, polydiallyldimethylammonium chloride (PDDA), at the quartz/water interface. Below pH 9.0, signal from the interfacial water structure was visible, but none from the adsorbed polymer could be detected. This indicated that the PDDA was not well enough aligned at the interface under these conditions to elicit a sum frequency response. At more basic pH values (ge;9.6), however, adsorbed PDDA molecules became well-ordered as indicated by the presence of CH stretch peaks from methylene and methyl groups. The intensities of the CH stretch modes were independent of the adsorbed amount of PDDA at pH 12.3 but decreased as the pH of the bulk solution was lowered. The conditions for polymer alignment fell outside the parameters where layer-by-layer growth of oppositely charged polyelectrolytes was possible because the net charge on the surface under high pH conditions remained negative.

UR - http://www.scopus.com/inward/record.url?scp=0037167006&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0037167006&partnerID=8YFLogxK

U2 - 10.1021/ja0263036

DO - 10.1021/ja0263036

M3 - Article

VL - 124

SP - 8751

EP - 8756

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 29

ER -