Vibrational Sum-Frequency Generation Activity of a 2,4-Dinitrophenyl Phospholipid Hybrid Bilayer: Retrieving Orientational Parameters from a DFT Analysis of Experimental Data

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Résumé

The vibrational nonlinear activity of films of 2,4-dinitrophenyl phospholipid (DNP) at the solid interface is measured by sum-frequency generation spectroscopy (SFG). Hybrid bilayers are formed by a Langmuir-Schaefer approach in which the lipid layer is physisorbed on top of a self-assembled monolayer of dodecanethiol on Pt with the polar heads pointing out from the surface. The SFG response is investigated in two vibrational frequency domains, namely, 3050-2750 and 1375-1240 cm. The first region probes the CH stretching modes of DNP films, and the latter explores the vibrational nonlinear activity of the 2,4-dinitroaniline moiety of the polar head of the lipid. Analysis of the CH stretching vibrations suggests substantial conformational order of the aliphatic chains with only a few gauche defects. To reliably assign the detected SFG signals to specific molecular vibrations, DFT calculations of the IR and Raman activities of molecular models are performed and compared to experimental solid-state spectra. This allows unambiguous assignment of the observed SFG vibrations to molecular modes localized on the 2,4-dinitroaniline moiety of the polar head of DNP. Then, SFG spectra of DNP in the 1375-1240 cm frequency range are simulated and compared with experimental ones, and thus the 1,4-axis of the 2,4-dinitrophenyl head is estimated to have tilt and rotation angles of 45±5° and 0±30°, respectively. Nonlinear vibrational response of a hybrid bilayer of 2,4-dinitrophenyl phospholipid (DNP) supported on a Pt surface is interpreted qualitatively and quantitatively by sum-frequency generation spectroscopy and density functional theory calculations. Spectral simulations also reveal the orientation of the 2,4-dinitrophenyl polar head of DNP, which is estimated to have tilt and rotation angles of 45±5° and 0±30°, respectively (see picture).
langue originaleAnglais
Pages (de - à)1227-1236
Nombre de pages10
journalChemPhysChem
Volume14
Numéro de publication6
Date de mise en ligne précoce3 avr. 2013
Les DOIs
étatPublié - 15 avr. 2013

Empreinte digitale

Vibrational spectra
Discrete Fourier transforms
Phospholipids
Spectroscopy
spectroscopy
Stretching
vibration
lipids
Molecular vibrations
Lipids
methylidyne
Self assembled monolayers
Density functional theory
frequency ranges
Defects
density functional theory
solid state
probes
defects
simulation

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@article{b93350732b3d4f84a415b3ac48c74464,
title = "Vibrational Sum-Frequency Generation Activity of a 2,4-Dinitrophenyl Phospholipid Hybrid Bilayer: Retrieving Orientational Parameters from a DFT Analysis of Experimental Data",
abstract = "The vibrational nonlinear activity of films of 2,4-dinitrophenyl phospholipid (DNP) at the solid interface is measured by sum-frequency generation spectroscopy (SFG). Hybrid bilayers are formed by a Langmuir-Schaefer approach in which the lipid layer is physisorbed on top of a self-assembled monolayer of dodecanethiol on Pt with the polar heads pointing out from the surface. The SFG response is investigated in two vibrational frequency domains, namely, 3050-2750 and 1375-1240 cm. The first region probes the CH stretching modes of DNP films, and the latter explores the vibrational nonlinear activity of the 2,4-dinitroaniline moiety of the polar head of the lipid. Analysis of the CH stretching vibrations suggests substantial conformational order of the aliphatic chains with only a few gauche defects. To reliably assign the detected SFG signals to specific molecular vibrations, DFT calculations of the IR and Raman activities of molecular models are performed and compared to experimental solid-state spectra. This allows unambiguous assignment of the observed SFG vibrations to molecular modes localized on the 2,4-dinitroaniline moiety of the polar head of DNP. Then, SFG spectra of DNP in the 1375-1240 cm frequency range are simulated and compared with experimental ones, and thus the 1,4-axis of the 2,4-dinitrophenyl head is estimated to have tilt and rotation angles of 45±5° and 0±30°, respectively. Nonlinear vibrational response of a hybrid bilayer of 2,4-dinitrophenyl phospholipid (DNP) supported on a Pt surface is interpreted qualitatively and quantitatively by sum-frequency generation spectroscopy and density functional theory calculations. Spectral simulations also reveal the orientation of the 2,4-dinitrophenyl polar head of DNP, which is estimated to have tilt and rotation angles of 45±5° and 0±30°, respectively (see picture).",
author = "D. Lis and J. Guthmuller and B. Champagne and C. Humbert and B. Busson and A. Peremans and F. Cecchet",
year = "2013",
month = "4",
day = "15",
doi = "10.1002/cphc.201201063",
language = "English",
volume = "14",
pages = "1227--1236",
journal = "ChemPhysChem",
issn = "1439-4235",
publisher = "Wiley-VCH Verlag",
number = "6",

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TY - JOUR

T1 - Vibrational Sum-Frequency Generation Activity of a 2,4-Dinitrophenyl Phospholipid Hybrid Bilayer: Retrieving Orientational Parameters from a DFT Analysis of Experimental Data

AU - Lis, D.

AU - Guthmuller, J.

AU - Champagne, B.

AU - Humbert, C.

AU - Busson, B.

AU - Peremans, A.

AU - Cecchet, F.

PY - 2013/4/15

Y1 - 2013/4/15

N2 - The vibrational nonlinear activity of films of 2,4-dinitrophenyl phospholipid (DNP) at the solid interface is measured by sum-frequency generation spectroscopy (SFG). Hybrid bilayers are formed by a Langmuir-Schaefer approach in which the lipid layer is physisorbed on top of a self-assembled monolayer of dodecanethiol on Pt with the polar heads pointing out from the surface. The SFG response is investigated in two vibrational frequency domains, namely, 3050-2750 and 1375-1240 cm. The first region probes the CH stretching modes of DNP films, and the latter explores the vibrational nonlinear activity of the 2,4-dinitroaniline moiety of the polar head of the lipid. Analysis of the CH stretching vibrations suggests substantial conformational order of the aliphatic chains with only a few gauche defects. To reliably assign the detected SFG signals to specific molecular vibrations, DFT calculations of the IR and Raman activities of molecular models are performed and compared to experimental solid-state spectra. This allows unambiguous assignment of the observed SFG vibrations to molecular modes localized on the 2,4-dinitroaniline moiety of the polar head of DNP. Then, SFG spectra of DNP in the 1375-1240 cm frequency range are simulated and compared with experimental ones, and thus the 1,4-axis of the 2,4-dinitrophenyl head is estimated to have tilt and rotation angles of 45±5° and 0±30°, respectively. Nonlinear vibrational response of a hybrid bilayer of 2,4-dinitrophenyl phospholipid (DNP) supported on a Pt surface is interpreted qualitatively and quantitatively by sum-frequency generation spectroscopy and density functional theory calculations. Spectral simulations also reveal the orientation of the 2,4-dinitrophenyl polar head of DNP, which is estimated to have tilt and rotation angles of 45±5° and 0±30°, respectively (see picture).

AB - The vibrational nonlinear activity of films of 2,4-dinitrophenyl phospholipid (DNP) at the solid interface is measured by sum-frequency generation spectroscopy (SFG). Hybrid bilayers are formed by a Langmuir-Schaefer approach in which the lipid layer is physisorbed on top of a self-assembled monolayer of dodecanethiol on Pt with the polar heads pointing out from the surface. The SFG response is investigated in two vibrational frequency domains, namely, 3050-2750 and 1375-1240 cm. The first region probes the CH stretching modes of DNP films, and the latter explores the vibrational nonlinear activity of the 2,4-dinitroaniline moiety of the polar head of the lipid. Analysis of the CH stretching vibrations suggests substantial conformational order of the aliphatic chains with only a few gauche defects. To reliably assign the detected SFG signals to specific molecular vibrations, DFT calculations of the IR and Raman activities of molecular models are performed and compared to experimental solid-state spectra. This allows unambiguous assignment of the observed SFG vibrations to molecular modes localized on the 2,4-dinitroaniline moiety of the polar head of DNP. Then, SFG spectra of DNP in the 1375-1240 cm frequency range are simulated and compared with experimental ones, and thus the 1,4-axis of the 2,4-dinitrophenyl head is estimated to have tilt and rotation angles of 45±5° and 0±30°, respectively. Nonlinear vibrational response of a hybrid bilayer of 2,4-dinitrophenyl phospholipid (DNP) supported on a Pt surface is interpreted qualitatively and quantitatively by sum-frequency generation spectroscopy and density functional theory calculations. Spectral simulations also reveal the orientation of the 2,4-dinitrophenyl polar head of DNP, which is estimated to have tilt and rotation angles of 45±5° and 0±30°, respectively (see picture).

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U2 - 10.1002/cphc.201201063

DO - 10.1002/cphc.201201063

M3 - Article

AN - SCOPUS:84876017863

VL - 14

SP - 1227

EP - 1236

JO - ChemPhysChem

JF - ChemPhysChem

SN - 1439-4235

IS - 6

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