Successive Surface Reactions on Hydrophilic Silica for Modified Magnetic Nanoparticle Attachment Probed by Sum-Frequency Generation Spectroscopy

Jeeranan Nonkumwong; Uriel Joseph Erasquin; Kurt Waldo Sy Piecco; Uvinduni I. Premadasa; Ahmed M. Aboelenen; Andrew Tangonan; Jixin Chen; David Ingram; Laongnuan Srisombat; Katherine Leslee Asetre Cimatu

doi:10.1021/acs.langmuir.8b01333

Successive Surface Reactions on Hydrophilic Silica for Modified Magnetic Nanoparticle Attachment Probed by Sum-Frequency Generation Spectroscopy

Jeeranan Nonkumwong, Uriel Joseph Erasquin, Kurt Waldo Sy Piecco, Uvinduni I. Premadasa, Ahmed M. Aboelenen, Andrew Tangonan, Jixin Chen, David Ingram, Laongnuan Srisombat, Katherine Leslee Asetre Cimatu

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16 Scopus citations

Abstract

Successive surface reactions on hydrophilic silica substrates were designed and performed to immobilize ethanolamine-modified magnetic ferrite-based nanoparticle (NP) for surface characterization. The various surfaces were monitored using sum-frequency generation (SFG) spectroscopy. The surface of the hydrophilic quartz substrate was first converted to a vinyl-terminated surface by utilizing a silanization reaction, and then, the surface functional groups were converted to carboxylic-terminated groups via a thiol-ene reaction. The appearance and disappearance of the vinyl (=CH₂) peak at ∼2990 cm^-1 in the SFG spectra were examined to confirm the success of the silanization and thiol-ene reactions, respectively. Acyl chloride (-COCl) formation from carboxy (-COOH) functional group was then performed for further attachment of magnetic amine-functionalized magnesium ferrite nanoparticles (NPs) via amide bond formation. The scattered NPs attached on the modified silica substrate was then used to study the changes in the spectral profile of the ethanolamine modifier of the NPs for in situ lead(II) (Pb²⁺) adsorption at the solid-liquid interface using SFG spectroscopy. However, due to the limited number of NPs attached and sensitivity of SFG spectroscopy toward expected change in the modifier spectroscopically, no significant change was observed in the SFG spectrum of the modified silica with magnetic NPs during exposure to Pb²⁺ solution. Nevertheless, SFG spectroscopy as a surface technique successfully monitored the modifications from a clean fused substrate to -COCl formation that was used to immobilize the decorated magnetic nanoparticles. The method developed in this study can provide a reference for many surface or interfacial studies important for selective attachment of adsorbed organic or inorganic materials or particles.

Original language	English
Pages (from-to)	12680-12693
Number of pages	14
Journal	Langmuir
Volume	34
Issue number	43
DOIs	https://doi.org/10.1021/acs.langmuir.8b01333
State	Published - Oct 30 2018
Externally published	Yes

Funding

The authors thank the National Science Foundation under Grant Nos. CHE-0947031 and CHE-1338000 for the acquisition of the femtosecond laser and nuclear magnetic spectrometer. The current work was also supported by the start-up fund provided by Ohio University. Additionally, the authors would like to thank the Nanoscale and Quantum Phenomena Institute and Condensed Matter and Surface Science for their additional financial support. The financial support for the preparation of nanoparticles was from the Center of Excellence in Materials Science and Technology, Chiang Mai University, under the administration of the Materials Science Research Center, Faculty of Science, Chiang Mai University. Jeeranan Nonkumwong would like to acknowledge the Science Achievement Scholarship of Thailand (SAST) for financial support for short-term research in the Cimatu research group, Department of Chemistry and Biochemistry, Ohio University. The authors thank the National Science Foundation under Grant Nos. CHE-0947031 and CHE-1338000 for the acquisition of the femtosecond laser and nuclear magnetic spectrometer. The current work was also supported by the start-up fund provided by Ohio University. Additionally the authors would like to thank the Nanoscale and Quantum Phenomena Institute and Condensed Matter and Surface Science for their additional financial support. The financial support for the preparation of nanoparticles was from the Center of Excellence in Materials Science and Technology Chiang Mai University, under the administration of the Materials Science Research Center, Faculty of Science, Chiang Mai University. Jeeranan Nonkumwong would like to acknowledge the Science Achievement Scholarship of Thailand (SAST) for financial support for short-term research in the Cimatu research group, Department of Chemistry and Biochemistry Ohio University.

Funders	Funder number
Center of Excellence in Materials Science and Technology, Chiang Mai University
Department of Chemistry and Biochemistry
Science Achievement Scholarship of Thailand
National Science Foundation
Ohio University
School of Aerospace Science and Technology
Faculty of Science, Chiang Mai University
National Science Foundation	CHE-0947031

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Nonkumwong, J., Erasquin, U. J., Sy Piecco, K. W., Premadasa, U. I., Aboelenen, A. M., Tangonan, A., Chen, J., Ingram, D., Srisombat, L., & Cimatu, K. L. A. (2018). Successive Surface Reactions on Hydrophilic Silica for Modified Magnetic Nanoparticle Attachment Probed by Sum-Frequency Generation Spectroscopy. Langmuir, 34(43), 12680-12693. https://doi.org/10.1021/acs.langmuir.8b01333

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title = "Successive Surface Reactions on Hydrophilic Silica for Modified Magnetic Nanoparticle Attachment Probed by Sum-Frequency Generation Spectroscopy",

abstract = "Successive surface reactions on hydrophilic silica substrates were designed and performed to immobilize ethanolamine-modified magnetic ferrite-based nanoparticle (NP) for surface characterization. The various surfaces were monitored using sum-frequency generation (SFG) spectroscopy. The surface of the hydrophilic quartz substrate was first converted to a vinyl-terminated surface by utilizing a silanization reaction, and then, the surface functional groups were converted to carboxylic-terminated groups via a thiol-ene reaction. The appearance and disappearance of the vinyl (=CH2) peak at ∼2990 cm-1 in the SFG spectra were examined to confirm the success of the silanization and thiol-ene reactions, respectively. Acyl chloride (-COCl) formation from carboxy (-COOH) functional group was then performed for further attachment of magnetic amine-functionalized magnesium ferrite nanoparticles (NPs) via amide bond formation. The scattered NPs attached on the modified silica substrate was then used to study the changes in the spectral profile of the ethanolamine modifier of the NPs for in situ lead(II) (Pb2+) adsorption at the solid-liquid interface using SFG spectroscopy. However, due to the limited number of NPs attached and sensitivity of SFG spectroscopy toward expected change in the modifier spectroscopically, no significant change was observed in the SFG spectrum of the modified silica with magnetic NPs during exposure to Pb2+ solution. Nevertheless, SFG spectroscopy as a surface technique successfully monitored the modifications from a clean fused substrate to -COCl formation that was used to immobilize the decorated magnetic nanoparticles. The method developed in this study can provide a reference for many surface or interfacial studies important for selective attachment of adsorbed organic or inorganic materials or particles.",

author = "Jeeranan Nonkumwong and Erasquin, {Uriel Joseph} and {Sy Piecco}, {Kurt Waldo} and Premadasa, {Uvinduni I.} and Aboelenen, {Ahmed M.} and Andrew Tangonan and Jixin Chen and David Ingram and Laongnuan Srisombat and Cimatu, {Katherine Leslee Asetre}",

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Nonkumwong, J, Erasquin, UJ, Sy Piecco, KW, Premadasa, UI, Aboelenen, AM, Tangonan, A, Chen, J, Ingram, D, Srisombat, L & Cimatu, KLA 2018, 'Successive Surface Reactions on Hydrophilic Silica for Modified Magnetic Nanoparticle Attachment Probed by Sum-Frequency Generation Spectroscopy', Langmuir, vol. 34, no. 43, pp. 12680-12693. https://doi.org/10.1021/acs.langmuir.8b01333

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T1 - Successive Surface Reactions on Hydrophilic Silica for Modified Magnetic Nanoparticle Attachment Probed by Sum-Frequency Generation Spectroscopy

AU - Nonkumwong, Jeeranan

AU - Erasquin, Uriel Joseph

AU - Sy Piecco, Kurt Waldo

AU - Premadasa, Uvinduni I.

AU - Aboelenen, Ahmed M.

AU - Tangonan, Andrew

AU - Chen, Jixin

AU - Ingram, David

AU - Srisombat, Laongnuan

AU - Cimatu, Katherine Leslee Asetre

PY - 2018/10/30

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N2 - Successive surface reactions on hydrophilic silica substrates were designed and performed to immobilize ethanolamine-modified magnetic ferrite-based nanoparticle (NP) for surface characterization. The various surfaces were monitored using sum-frequency generation (SFG) spectroscopy. The surface of the hydrophilic quartz substrate was first converted to a vinyl-terminated surface by utilizing a silanization reaction, and then, the surface functional groups were converted to carboxylic-terminated groups via a thiol-ene reaction. The appearance and disappearance of the vinyl (=CH2) peak at ∼2990 cm-1 in the SFG spectra were examined to confirm the success of the silanization and thiol-ene reactions, respectively. Acyl chloride (-COCl) formation from carboxy (-COOH) functional group was then performed for further attachment of magnetic amine-functionalized magnesium ferrite nanoparticles (NPs) via amide bond formation. The scattered NPs attached on the modified silica substrate was then used to study the changes in the spectral profile of the ethanolamine modifier of the NPs for in situ lead(II) (Pb2+) adsorption at the solid-liquid interface using SFG spectroscopy. However, due to the limited number of NPs attached and sensitivity of SFG spectroscopy toward expected change in the modifier spectroscopically, no significant change was observed in the SFG spectrum of the modified silica with magnetic NPs during exposure to Pb2+ solution. Nevertheless, SFG spectroscopy as a surface technique successfully monitored the modifications from a clean fused substrate to -COCl formation that was used to immobilize the decorated magnetic nanoparticles. The method developed in this study can provide a reference for many surface or interfacial studies important for selective attachment of adsorbed organic or inorganic materials or particles.

AB - Successive surface reactions on hydrophilic silica substrates were designed and performed to immobilize ethanolamine-modified magnetic ferrite-based nanoparticle (NP) for surface characterization. The various surfaces were monitored using sum-frequency generation (SFG) spectroscopy. The surface of the hydrophilic quartz substrate was first converted to a vinyl-terminated surface by utilizing a silanization reaction, and then, the surface functional groups were converted to carboxylic-terminated groups via a thiol-ene reaction. The appearance and disappearance of the vinyl (=CH2) peak at ∼2990 cm-1 in the SFG spectra were examined to confirm the success of the silanization and thiol-ene reactions, respectively. Acyl chloride (-COCl) formation from carboxy (-COOH) functional group was then performed for further attachment of magnetic amine-functionalized magnesium ferrite nanoparticles (NPs) via amide bond formation. The scattered NPs attached on the modified silica substrate was then used to study the changes in the spectral profile of the ethanolamine modifier of the NPs for in situ lead(II) (Pb2+) adsorption at the solid-liquid interface using SFG spectroscopy. However, due to the limited number of NPs attached and sensitivity of SFG spectroscopy toward expected change in the modifier spectroscopically, no significant change was observed in the SFG spectrum of the modified silica with magnetic NPs during exposure to Pb2+ solution. Nevertheless, SFG spectroscopy as a surface technique successfully monitored the modifications from a clean fused substrate to -COCl formation that was used to immobilize the decorated magnetic nanoparticles. The method developed in this study can provide a reference for many surface or interfacial studies important for selective attachment of adsorbed organic or inorganic materials or particles.

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Successive Surface Reactions on Hydrophilic Silica for Modified Magnetic Nanoparticle Attachment Probed by Sum-Frequency Generation Spectroscopy

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