Doping in poly( o-ethoxyaniline) nanostructured films studied with atomic force spectroscopy (AFS)
The study of intermolecular interactions at interfaces is essential for a number of applications, in addition to the understanding of mechanisms involved in sensing and biosensing with liquid samples. There are, however, only a few methods to probe such interfacial phenomena, one of which is the ato...
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| Published in: | Micron (Oxford, England : 1993) Vol. 39; no. 8; pp. 1119 - 1125 |
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| Main Authors: | , , , , , , |
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| Abstract | The study of intermolecular interactions at interfaces is essential for a number of applications, in addition to the understanding of mechanisms involved in sensing and biosensing with liquid samples. There are, however, only a few methods to probe such interfacial phenomena, one of which is the atomic force spectroscopy (AFS) where the force between an atomic force microscope tip and the sample surface is measured. In this study, we used AFS to estimate adhesion forces for a nanostructured film of poly(
o-ethoxyaniline) (POEA) doped with various acids, in measurements performed in air. The adhesion force was lower for POEA doped with inorganic acids, such as HCl and H
2SO
4, than with organic acids, because the counterions were screened by the ethoxy groups. Significantly, the morphology of POEA both in the film and in solution depends on the doping acid. Using small-angle X-ray scattering (SAXS) we observed that POEA dissolved in a mixture of dimethyl acetamide exhibits a more extended coil-like conformation, with smaller radius of gyration, than for POEA in water, as in the latter POEA solubility is lower. In AFS measurements in a liquid cell, the force curves for a POEA layer displayed an attractive region for pH
≥
5 due to van der Waals interactions, with no contribution from a double-layer since POEA was dedoped. In contrast, for pH
≤
3, POEA was doped and the repulsive double-layer force dominated. With AFS one is therefore able to correlate molecular-level interactions with doping and morphology of semiconducting polymers. |
|---|---|
| AbstractList | The study of intermolecular interactions at interfaces is essential for a number of applications, in addition to the understanding of mechanisms involved in sensing and biosensing with liquid samples. There are, however, only a few methods to probe such interfacial phenomena, one of which is the atomic force spectroscopy (AFS) where the force between an atomic force microscope tip and the sample surface is measured. In this study, we used AFS to estimate adhesion forces for a nanostructured film of poly(o-ethoxyaniline) (POEA) doped with various acids, in measurements performed in air. The adhesion force was lower for POEA doped with inorganic acids, such as HCl and H(2)SO(4), than with organic acids, because the counterions were screened by the ethoxy groups. Significantly, the morphology of POEA both in the film and in solution depends on the doping acid. Using small-angle X-ray scattering (SAXS) we observed that POEA dissolved in a mixture of dimethyl acetamide exhibits a more extended coil-like conformation, with smaller radius of gyration, than for POEA in water, as in the latter POEA solubility is lower. In AFS measurements in a liquid cell, the force curves for a POEA layer displayed an attractive region for pH>or=5 due to van der Waals interactions, with no contribution from a double-layer since POEA was dedoped. In contrast, for pH<or=3, POEA was doped and the repulsive double-layer force dominated. With AFS one is therefore able to correlate molecular-level interactions with doping and morphology of semiconducting polymers. The study of intermolecular interactions at interfaces is essential for a number of applications, in addition to the understanding of mechanisms involved in sensing and biosensing with liquid samples. There are, however, only a few methods to probe such interfacial phenomena, one of which is the atomic force spectroscopy (AFS) where the force between an atomic force microscope tip and the sample surface is measured. In this study, we used AFS to estimate adhesion forces for a nanostructured film of poly( o-ethoxyaniline) (POEA) doped with various acids, in measurements performed in air. The adhesion force was lower for POEA doped with inorganic acids, such as HCl and H 2SO 4, than with organic acids, because the counterions were screened by the ethoxy groups. Significantly, the morphology of POEA both in the film and in solution depends on the doping acid. Using small-angle X-ray scattering (SAXS) we observed that POEA dissolved in a mixture of dimethyl acetamide exhibits a more extended coil-like conformation, with smaller radius of gyration, than for POEA in water, as in the latter POEA solubility is lower. In AFS measurements in a liquid cell, the force curves for a POEA layer displayed an attractive region for pH ≥ 5 due to van der Waals interactions, with no contribution from a double-layer since POEA was dedoped. In contrast, for pH ≤ 3, POEA was doped and the repulsive double-layer force dominated. With AFS one is therefore able to correlate molecular-level interactions with doping and morphology of semiconducting polymers. The study of intermolecular interactions at interfaces is essential for a number of applications, in addition to the understanding of mechanisms involved in sensing and biosensing with liquid samples. There are, however, only a few methods to probe such interfacial phenomena, one of which is the atomic force spectroscopy (AFS) where the force between an atomic force microscope tip and the sample surface is measured. In this study, we used AFS to estimate adhesion forces for a nanostructured film of poly(o-ethoxyaniline) (POEA) doped with various acids, in measurements performed in air. The adhesion force was lower for POEA doped with inorganic acids, such as HCl and H(2)SO(4), than with organic acids, because the counterions were screened by the ethoxy groups. Significantly, the morphology of POEA both in the film and in solution depends on the doping acid. Using small-angle X-ray scattering (SAXS) we observed that POEA dissolved in a mixture of dimethyl acetamide exhibits a more extended coil-like conformation, with smaller radius of gyration, than for POEA in water, as in the latter POEA solubility is lower. In AFS measurements in a liquid cell, the force curves for a POEA layer displayed an attractive region for pH>or=5 due to van der Waals interactions, with no contribution from a double-layer since POEA was dedoped. In contrast, for pH<or=3, POEA was doped and the repulsive double-layer force dominated. With AFS one is therefore able to correlate molecular-level interactions with doping and morphology of semiconducting polymers. |
| Author | Alves, W.F. Mattoso, L.H.C. Neto, M. Oliveira Leite, F.L. Polikarpov, I. Herrmann, P.S.P. Oliveira Jr, O.N. |
| Author_xml | – sequence: 1 givenname: F.L. surname: Leite fullname: Leite, F.L. email: leite@cnpdia.embrapa.br, fabiolimaleite@gmail.com organization: Alan G. MacDiarmid Institute for Innovation and Business and National Nanotechnology Laboratory for Agribuseness (LNNA), Embrapa Agricultural Instrumentation, Rua XV de Novembro 1452, P.O. Box 741, CEP 13560-970 São Carlos, SP, Brazil – sequence: 2 givenname: W.F. surname: Alves fullname: Alves, W.F. organization: Alan G. MacDiarmid Institute for Innovation and Business and National Nanotechnology Laboratory for Agribuseness (LNNA), Embrapa Agricultural Instrumentation, Rua XV de Novembro 1452, P.O. Box 741, CEP 13560-970 São Carlos, SP, Brazil – sequence: 3 givenname: M. Oliveira surname: Neto fullname: Neto, M. Oliveira organization: Institute of Physics of São Carlos, University of São Paulo (USP), P.O. Box 369, CEP 13560-970 São Carlos, SP, Brazil – sequence: 4 givenname: I. surname: Polikarpov fullname: Polikarpov, I. organization: Institute of Physics of São Carlos, University of São Paulo (USP), P.O. Box 369, CEP 13560-970 São Carlos, SP, Brazil – sequence: 5 givenname: P.S.P. surname: Herrmann fullname: Herrmann, P.S.P. organization: Alan G. MacDiarmid Institute for Innovation and Business and National Nanotechnology Laboratory for Agribuseness (LNNA), Embrapa Agricultural Instrumentation, Rua XV de Novembro 1452, P.O. Box 741, CEP 13560-970 São Carlos, SP, Brazil – sequence: 6 givenname: L.H.C. surname: Mattoso fullname: Mattoso, L.H.C. organization: Alan G. MacDiarmid Institute for Innovation and Business and National Nanotechnology Laboratory for Agribuseness (LNNA), Embrapa Agricultural Instrumentation, Rua XV de Novembro 1452, P.O. Box 741, CEP 13560-970 São Carlos, SP, Brazil – sequence: 7 givenname: O.N. surname: Oliveira Jr fullname: Oliveira Jr, O.N. organization: Institute of Physics of São Carlos, University of São Paulo (USP), P.O. Box 369, CEP 13560-970 São Carlos, SP, Brazil |
| BackLink | https://www.ncbi.nlm.nih.gov/pubmed/18706822$$D View this record in MEDLINE/PubMed |
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| CitedBy_id | crossref_primary_10_3390_molecules27196326 crossref_primary_10_1002_sca_21109 crossref_primary_10_1016_j_molstruc_2017_09_084 crossref_primary_10_1155_2018_4782685 crossref_primary_10_1016_j_synthmet_2009_07_058 crossref_primary_10_1007_s13391_020_00242_z |
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| Keywords | Conducting polymers Atomic force microscopy Self-assembly Force curve Force spectroscopy Doping Adhesion forces Poly( o-ethoxyaniline) Layer-by-layer SAXS |
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