On the quantitative adsorption behavior of multi-zwitterionic end-functionalized polymers onto gold surfaces

Mi Kyoung Park; Giorgos Sakellariou; Stergios Pispas; Nikos Hadjichristidis; Rigoberto Advincula

doi:10.1016/j.colsurfa.2008.05.034

On the quantitative adsorption behavior of multi-zwitterionic end-functionalized polymers onto gold surfaces

Mi Kyoung Park, Giorgos Sakellariou, Stergios Pispas, Nikos Hadjichristidis, Rigoberto Advincula^*

^*Corresponding author for this work

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

3 Scopus citations

Abstract

We investigate the adsorption behavior of polystyrene (PS) chains end-functionalized with one, two, and three zwitterionic groups onto gold surfaces using the quartz crystal microbalance (QCM) method. The grafting density of the adsorbed chains was found to have a scaling behavior with respect to molecular weight and number of functional zwitterionic arms. The addition of more sulfobetaine zwitterionic end-group increases the adsorption onto the gold surface, resulting in higher grafting density and closer interchain spacing between the brushes. However, when the polymer brushes became too dense (the conformation ratio, γ < 0.4) the kinetic process becomes the limiting process, due to the strong repulsion between the existing polymer brushes, in which case the number of zwitterionic groups becomes the more dominant component. The experimental data of interchain spacing, s, was found to be directly related to the scaling relationship (N_s/Δ)^3/5, in which N_s is the degree of polymerization of PS and Δk_BT is the sticking energy, which follows the theoretical prediction as previously reported. The advantages of using the current model polymers and method include: neutrality and small size of the sulfobetaine anchoring group, fast time scale kinetics, and direct quantitative behavior by which adsorption phenomenon is observed in situ using the QCM.

Original language	English (US)
Pages (from-to)	115-121
Number of pages	7
Journal	Colloids and Surfaces A: Physicochemical and Engineering Aspects
Volume	326
Issue number	3
DOIs	https://doi.org/10.1016/j.colsurfa.2008.05.034
State	Published - Sep 1 2008
Externally published	Yes

Bibliographical note

Funding Information:
The Research Committee of the University of Athens and the financial support of the Ministry of Education through the PYTHAGORAS postdoctoral program: “Support of the research groups in the Universities,” cofinanced from the Operational Programme and Initial Educational Vocational Training—EPEAEK and the European Social Funds, are greatly appreciated. In addition, we thank the U.S. National Science Foundation for support through its Collaborative Research in Chemistry Program (CRC-CHEM 0304807) and DMR-0315565. We also acknowledge technical support from Maxtek Inc. and Mr. Yushin Park.

Keywords

Adsorption
Polybutadiene
Polystyrene
QCM
SPR
Scaling parameter
Zwitterionic

ASJC Scopus subject areas

Surfaces and Interfaces
Physical and Theoretical Chemistry
Colloid and Surface Chemistry

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10.1016/j.colsurfa.2008.05.034

Cite this

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title = "On the quantitative adsorption behavior of multi-zwitterionic end-functionalized polymers onto gold surfaces",

abstract = "We investigate the adsorption behavior of polystyrene (PS) chains end-functionalized with one, two, and three zwitterionic groups onto gold surfaces using the quartz crystal microbalance (QCM) method. The grafting density of the adsorbed chains was found to have a scaling behavior with respect to molecular weight and number of functional zwitterionic arms. The addition of more sulfobetaine zwitterionic end-group increases the adsorption onto the gold surface, resulting in higher grafting density and closer interchain spacing between the brushes. However, when the polymer brushes became too dense (the conformation ratio, γ < 0.4) the kinetic process becomes the limiting process, due to the strong repulsion between the existing polymer brushes, in which case the number of zwitterionic groups becomes the more dominant component. The experimental data of interchain spacing, s, was found to be directly related to the scaling relationship (Ns/Δ)3/5, in which Ns is the degree of polymerization of PS and ΔkBT is the sticking energy, which follows the theoretical prediction as previously reported. The advantages of using the current model polymers and method include: neutrality and small size of the sulfobetaine anchoring group, fast time scale kinetics, and direct quantitative behavior by which adsorption phenomenon is observed in situ using the QCM.",

keywords = "Adsorption, Polybutadiene, Polystyrene, QCM, SPR, Scaling parameter, Zwitterionic",

author = "Park, {Mi Kyoung} and Giorgos Sakellariou and Stergios Pispas and Nikos Hadjichristidis and Rigoberto Advincula",

note = "Funding Information: The Research Committee of the University of Athens and the financial support of the Ministry of Education through the PYTHAGORAS postdoctoral program: “Support of the research groups in the Universities,” cofinanced from the Operational Programme and Initial Educational Vocational Training—EPEAEK and the European Social Funds, are greatly appreciated. In addition, we thank the U.S. National Science Foundation for support through its Collaborative Research in Chemistry Program (CRC-CHEM 0304807) and DMR-0315565. We also acknowledge technical support from Maxtek Inc. and Mr. Yushin Park. ",

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AU - Sakellariou, Giorgos

AU - Pispas, Stergios

AU - Hadjichristidis, Nikos

AU - Advincula, Rigoberto

N1 - Funding Information: The Research Committee of the University of Athens and the financial support of the Ministry of Education through the PYTHAGORAS postdoctoral program: “Support of the research groups in the Universities,” cofinanced from the Operational Programme and Initial Educational Vocational Training—EPEAEK and the European Social Funds, are greatly appreciated. In addition, we thank the U.S. National Science Foundation for support through its Collaborative Research in Chemistry Program (CRC-CHEM 0304807) and DMR-0315565. We also acknowledge technical support from Maxtek Inc. and Mr. Yushin Park.

PY - 2008/9/1

Y1 - 2008/9/1

N2 - We investigate the adsorption behavior of polystyrene (PS) chains end-functionalized with one, two, and three zwitterionic groups onto gold surfaces using the quartz crystal microbalance (QCM) method. The grafting density of the adsorbed chains was found to have a scaling behavior with respect to molecular weight and number of functional zwitterionic arms. The addition of more sulfobetaine zwitterionic end-group increases the adsorption onto the gold surface, resulting in higher grafting density and closer interchain spacing between the brushes. However, when the polymer brushes became too dense (the conformation ratio, γ < 0.4) the kinetic process becomes the limiting process, due to the strong repulsion between the existing polymer brushes, in which case the number of zwitterionic groups becomes the more dominant component. The experimental data of interchain spacing, s, was found to be directly related to the scaling relationship (Ns/Δ)3/5, in which Ns is the degree of polymerization of PS and ΔkBT is the sticking energy, which follows the theoretical prediction as previously reported. The advantages of using the current model polymers and method include: neutrality and small size of the sulfobetaine anchoring group, fast time scale kinetics, and direct quantitative behavior by which adsorption phenomenon is observed in situ using the QCM.

AB - We investigate the adsorption behavior of polystyrene (PS) chains end-functionalized with one, two, and three zwitterionic groups onto gold surfaces using the quartz crystal microbalance (QCM) method. The grafting density of the adsorbed chains was found to have a scaling behavior with respect to molecular weight and number of functional zwitterionic arms. The addition of more sulfobetaine zwitterionic end-group increases the adsorption onto the gold surface, resulting in higher grafting density and closer interchain spacing between the brushes. However, when the polymer brushes became too dense (the conformation ratio, γ < 0.4) the kinetic process becomes the limiting process, due to the strong repulsion between the existing polymer brushes, in which case the number of zwitterionic groups becomes the more dominant component. The experimental data of interchain spacing, s, was found to be directly related to the scaling relationship (Ns/Δ)3/5, in which Ns is the degree of polymerization of PS and ΔkBT is the sticking energy, which follows the theoretical prediction as previously reported. The advantages of using the current model polymers and method include: neutrality and small size of the sulfobetaine anchoring group, fast time scale kinetics, and direct quantitative behavior by which adsorption phenomenon is observed in situ using the QCM.

KW - Adsorption

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KW - SPR

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JO - Colloids and Surfaces A: Physicochemical and Engineering Aspects

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ER -

On the quantitative adsorption behavior of multi-zwitterionic end-functionalized polymers onto gold surfaces

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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