Surface composition of mixed self-assembled monolayers on Au by infrared attenuated total reflection spectroscopy

Angelo Tricase; Davide Blasi; Alessandro Favia; Angela Stefanachi; Francesco Leonetti; Giuseppe Colafemmina; Luisa Torsi; Gaetano Scamarcio

doi:10.1016/j.apsusc.2021.149883

Surface composition of mixed self-assembled monolayers on Au by infrared attenuated total reflection spectroscopy

Angelo Tricase, Davide Blasi, Alessandro Favia, Angela Stefanachi, Francesco Leonetti, Giuseppe Colafemmina, Luisa Torsi, Gaetano Scamarcio^*

^*Corresponding author for this work

Physics

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

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Abstract

Self-assembled monolayers (SAMs) of N-(2-hydroxyethyl)-3-mercaptopropanamide (NMPA) were synthesized directly on the surface of electron-beam evaporated Au films, starting from 3-mercaptopropionic acid (3MPA) via ethyl-3-(3-dimethylamino-propyl)carbodiimide/N-hydroxysulfosuccinimide sodium salt (EDC/NHSS) coupling with ethanolamine hydrochloride. The influence on the reaction yield of the acidity of EDC/NHSS solutions (pH = 5.6 or 4.8) was assessed by exploiting the high surface sensitivity of infrared attenuated total reflection spectroscopy. The light-matter interaction was modeled in the framework of a matrix formalism considering the complete multi-layer sample structure. A comparison between the relative intensity of the main absorption bands, associated with amide I and carbonyl stretching of carboxylic acid or amide II vibrations, with a calibration curve obtained from the measurement of mixed 3MPA/NMPA SAMs, show that the more acid solution is 16% more efficient. This is mostly due to the higher protonation of the 3MPA.

Original language	English
Article number	149883
Journal	Applied Surface Science
Volume	559
DOIs	https://doi.org/10.1016/j.apsusc.2021.149883
Publication status	Published - 1 Sept 2021
MoE publication type	A1 Journal article-refereed

Funding

This work was partly supported by the European Union's Horizon 2020 research and innovation programme SiMBiT [grant agreement No. 824946]; the Italian ministry MIUR [grants e-DESIGN (ARS01_01158); PMGB (ARS01_01195); IDF SHARID (ARS01_01270)]; the Academy of Finland [projects #316881, #316883, #332106]; ?bo Akademi University and CSGI (Consorzio Interuniversitario per lo Sviluppo dei Sistemi a Grandi Interfasi) This work was partly supported by the European Union’s Horizon 2020 research and innovation programme SiMBiT [grant agreement No. 824946]; the Italian ministry MIUR [grants e-DESIGN (ARS01_01158); PMGB (ARS01_01195); IDF SHARID (ARS01_01270)]; the Academy of Finland [projects #316881, #316883, #332106]; Åbo Akademi University and CSGI (Consorzio Interuniversitario per lo Sviluppo dei Sistemi a Grandi Interfasi)

Keywords

Attenuated total reflection spectroscopy
Biofunctionalized interfaces
Self-assembled monolayers

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10.1016/j.apsusc.2021.149883

1-s2.0-S0169433221009594-mainFinal published version, 1.72 MBLicence: CC BY-NC-ND

https://urn.fi/URN:NBN:fi-fe2022021118599

Cite this

@article{27703986be484e82ab07655e5bd48ae8,

title = "Surface composition of mixed self-assembled monolayers on Au by infrared attenuated total reflection spectroscopy",

abstract = "Self-assembled monolayers (SAMs) of N-(2-hydroxyethyl)-3-mercaptopropanamide (NMPA) were synthesized directly on the surface of electron-beam evaporated Au films, starting from 3-mercaptopropionic acid (3MPA) via ethyl-3-(3-dimethylamino-propyl)carbodiimide/N-hydroxysulfosuccinimide sodium salt (EDC/NHSS) coupling with ethanolamine hydrochloride. The influence on the reaction yield of the acidity of EDC/NHSS solutions (pH = 5.6 or 4.8) was assessed by exploiting the high surface sensitivity of infrared attenuated total reflection spectroscopy. The light-matter interaction was modeled in the framework of a matrix formalism considering the complete multi-layer sample structure. A comparison between the relative intensity of the main absorption bands, associated with amide I and carbonyl stretching of carboxylic acid or amide II vibrations, with a calibration curve obtained from the measurement of mixed 3MPA/NMPA SAMs, show that the more acid solution is 16\% more efficient. This is mostly due to the higher protonation of the 3MPA.",

keywords = "Attenuated total reflection spectroscopy, Biofunctionalized interfaces, Self-assembled monolayers",

author = "Angelo Tricase and Davide Blasi and Alessandro Favia and Angela Stefanachi and Francesco Leonetti and Giuseppe Colafemmina and Luisa Torsi and Gaetano Scamarcio",

note = "Funding Information: This work was partly supported by the European Union's Horizon 2020 research and innovation programme SiMBiT [grant agreement No. 824946]; the Italian ministry MIUR [grants e-DESIGN (ARS01\_01158); PMGB (ARS01\_01195); IDF SHARID (ARS01\_01270)]; the Academy of Finland [projects \#316881, \#316883, \#332106]; ?bo Akademi University and CSGI (Consorzio Interuniversitario per lo Sviluppo dei Sistemi a Grandi Interfasi) Funding Information: This work was partly supported by the European Union{\textquoteright}s Horizon 2020 research and innovation programme SiMBiT [grant agreement No. 824946]; the Italian ministry MIUR [grants e-DESIGN (ARS01\_01158); PMGB (ARS01\_01195); IDF SHARID (ARS01\_01270)]; the Academy of Finland [projects \#316881, \#316883, \#332106]; {\AA}bo Akademi University and CSGI (Consorzio Interuniversitario per lo Sviluppo dei Sistemi a Grandi Interfasi) Publisher Copyright: {\textcopyright} 2021 The Authors",

year = "2021",

month = sep,

day = "1",

doi = "10.1016/j.apsusc.2021.149883",

language = "English",

volume = "559",

journal = "Applied Surface Science",

issn = "0169-4332",

publisher = "Elsevier",

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T1 - Surface composition of mixed self-assembled monolayers on Au by infrared attenuated total reflection spectroscopy

AU - Tricase, Angelo

AU - Blasi, Davide

AU - Favia, Alessandro

AU - Stefanachi, Angela

AU - Leonetti, Francesco

AU - Colafemmina, Giuseppe

AU - Torsi, Luisa

AU - Scamarcio, Gaetano

N1 - Funding Information: This work was partly supported by the European Union's Horizon 2020 research and innovation programme SiMBiT [grant agreement No. 824946]; the Italian ministry MIUR [grants e-DESIGN (ARS01_01158); PMGB (ARS01_01195); IDF SHARID (ARS01_01270)]; the Academy of Finland [projects #316881, #316883, #332106]; ?bo Akademi University and CSGI (Consorzio Interuniversitario per lo Sviluppo dei Sistemi a Grandi Interfasi) Funding Information: This work was partly supported by the European Union’s Horizon 2020 research and innovation programme SiMBiT [grant agreement No. 824946]; the Italian ministry MIUR [grants e-DESIGN (ARS01_01158); PMGB (ARS01_01195); IDF SHARID (ARS01_01270)]; the Academy of Finland [projects #316881, #316883, #332106]; Åbo Akademi University and CSGI (Consorzio Interuniversitario per lo Sviluppo dei Sistemi a Grandi Interfasi) Publisher Copyright: © 2021 The Authors

PY - 2021/9/1

Y1 - 2021/9/1

N2 - Self-assembled monolayers (SAMs) of N-(2-hydroxyethyl)-3-mercaptopropanamide (NMPA) were synthesized directly on the surface of electron-beam evaporated Au films, starting from 3-mercaptopropionic acid (3MPA) via ethyl-3-(3-dimethylamino-propyl)carbodiimide/N-hydroxysulfosuccinimide sodium salt (EDC/NHSS) coupling with ethanolamine hydrochloride. The influence on the reaction yield of the acidity of EDC/NHSS solutions (pH = 5.6 or 4.8) was assessed by exploiting the high surface sensitivity of infrared attenuated total reflection spectroscopy. The light-matter interaction was modeled in the framework of a matrix formalism considering the complete multi-layer sample structure. A comparison between the relative intensity of the main absorption bands, associated with amide I and carbonyl stretching of carboxylic acid or amide II vibrations, with a calibration curve obtained from the measurement of mixed 3MPA/NMPA SAMs, show that the more acid solution is 16% more efficient. This is mostly due to the higher protonation of the 3MPA.

AB - Self-assembled monolayers (SAMs) of N-(2-hydroxyethyl)-3-mercaptopropanamide (NMPA) were synthesized directly on the surface of electron-beam evaporated Au films, starting from 3-mercaptopropionic acid (3MPA) via ethyl-3-(3-dimethylamino-propyl)carbodiimide/N-hydroxysulfosuccinimide sodium salt (EDC/NHSS) coupling with ethanolamine hydrochloride. The influence on the reaction yield of the acidity of EDC/NHSS solutions (pH = 5.6 or 4.8) was assessed by exploiting the high surface sensitivity of infrared attenuated total reflection spectroscopy. The light-matter interaction was modeled in the framework of a matrix formalism considering the complete multi-layer sample structure. A comparison between the relative intensity of the main absorption bands, associated with amide I and carbonyl stretching of carboxylic acid or amide II vibrations, with a calibration curve obtained from the measurement of mixed 3MPA/NMPA SAMs, show that the more acid solution is 16% more efficient. This is mostly due to the higher protonation of the 3MPA.

KW - Attenuated total reflection spectroscopy

KW - Biofunctionalized interfaces

KW - Self-assembled monolayers

UR - https://www.scopus.com/pages/publications/85110492846

U2 - 10.1016/j.apsusc.2021.149883

DO - 10.1016/j.apsusc.2021.149883

M3 - Article

AN - SCOPUS:85110492846

SN - 0169-4332

VL - 559

JO - Applied Surface Science

JF - Applied Surface Science

M1 - 149883

ER -

Surface composition of mixed self-assembled monolayers on Au by infrared attenuated total reflection spectroscopy

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