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Title: Reaction of Pb(II) and Zn(II) with Ethyl Linoleate To Form Structured Hybrid Inorganic–Organic Complexes: A Model for Degradation in Historic Paint Films

Abstract

To investigate soap formation in drying oils in historic paints, the reaction between metal acetates (K+, Zn2+, Pb2+) and ethyl linoleate (EL) was studied using optical microscopy, X-ray powder diffraction, and electron microscopy. Pb(II) and Zn(II) react rapidly with EL to form highly structured, spherulitic, luminescent crystallites that aggregate. Evidence from Fourier transform infrared (FTIR) and scanning electron microscopy/energy dispersive X-ray analysis and high-resolution synchrotron powder X-ray diffraction indicates that these are organic-inorganic hybrid complexes or coordination polymers. FTIR absorbance peaks at ca. 1540 cm-1 for Pb(II) and ca. 1580 cm-1 for Zn(II) are consistent with the formation of carboxylate complexes. The complexes formed offer insight into the degradation processes observed in oil paint films, suggesting that soap formation is rapid when metal ions are solubilized and can occur with unsaturated fatty acids that are present in fresh oils. Finally, these complexes may account for the atypical luminescence observed in lead-containing cured oil paint films.

Authors:
 [1];  [1];  [2];  [1]
  1. Scientific Research Department, Conservation Division, National Gallery of Art, 2000B South Club Drive, Landover, Maryland 20785, United States
  2. CNRS, University of Bordeaux, ICMCB, 87 Avenue du Docteur A. Schweitzer, UPR 9048, 33608 Pessac Cedex, France
Publication Date:
Research Org.:
National Gallery of Art, Landover, MD (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Gallery of Art (United States)
Contributing Org.:
Univ. of Bordeaux (France)
OSTI Identifier:
1321031
Alternate Identifier(s):
OSTI ID: 1329023
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Published Article
Journal Name:
ACS Omega
Additional Journal Information:
Journal Name: ACS Omega Journal Volume: 1 Journal Issue: 3; Journal ID: ISSN 2470-1343
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

MacDonald, Margaret G., Palmer, Michael R., Suchomel, Matthew R., and Berrie, Barbara H. Reaction of Pb(II) and Zn(II) with Ethyl Linoleate To Form Structured Hybrid Inorganic–Organic Complexes: A Model for Degradation in Historic Paint Films. United States: N. p., 2016. Web. doi:10.1021/acsomega.6b00075.
MacDonald, Margaret G., Palmer, Michael R., Suchomel, Matthew R., & Berrie, Barbara H. Reaction of Pb(II) and Zn(II) with Ethyl Linoleate To Form Structured Hybrid Inorganic–Organic Complexes: A Model for Degradation in Historic Paint Films. United States. https://doi.org/10.1021/acsomega.6b00075
MacDonald, Margaret G., Palmer, Michael R., Suchomel, Matthew R., and Berrie, Barbara H. Wed . "Reaction of Pb(II) and Zn(II) with Ethyl Linoleate To Form Structured Hybrid Inorganic–Organic Complexes: A Model for Degradation in Historic Paint Films". United States. https://doi.org/10.1021/acsomega.6b00075.
@article{osti_1321031,
title = {Reaction of Pb(II) and Zn(II) with Ethyl Linoleate To Form Structured Hybrid Inorganic–Organic Complexes: A Model for Degradation in Historic Paint Films},
author = {MacDonald, Margaret G. and Palmer, Michael R. and Suchomel, Matthew R. and Berrie, Barbara H.},
abstractNote = {To investigate soap formation in drying oils in historic paints, the reaction between metal acetates (K+, Zn2+, Pb2+) and ethyl linoleate (EL) was studied using optical microscopy, X-ray powder diffraction, and electron microscopy. Pb(II) and Zn(II) react rapidly with EL to form highly structured, spherulitic, luminescent crystallites that aggregate. Evidence from Fourier transform infrared (FTIR) and scanning electron microscopy/energy dispersive X-ray analysis and high-resolution synchrotron powder X-ray diffraction indicates that these are organic-inorganic hybrid complexes or coordination polymers. FTIR absorbance peaks at ca. 1540 cm-1 for Pb(II) and ca. 1580 cm-1 for Zn(II) are consistent with the formation of carboxylate complexes. The complexes formed offer insight into the degradation processes observed in oil paint films, suggesting that soap formation is rapid when metal ions are solubilized and can occur with unsaturated fatty acids that are present in fresh oils. Finally, these complexes may account for the atypical luminescence observed in lead-containing cured oil paint films.},
doi = {10.1021/acsomega.6b00075},
journal = {ACS Omega},
number = 3,
volume = 1,
place = {United States},
year = {Wed Sep 07 00:00:00 EDT 2016},
month = {Wed Sep 07 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acsomega.6b00075

Citation Metrics:
Cited by: 12 works
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Works referenced in this record:

A twelve-analyzer detector system for high-resolution powder diffraction
journal, July 2008

  • Lee, Peter L.; Shu, Deming; Ramanathan, Mohan
  • Journal of Synchrotron Radiation, Vol. 15, Issue 5
  • DOI: 10.1107/S0909049508018438

Characterisation of metal carboxylates by Raman and infrared spectroscopy in works of art: Characterisation of metal carboxylates by Raman and infrared spectroscopy in works of art
journal, July 2014

  • Otero, Vanessa; Sanches, Diogo; Montagner, Cristina
  • Journal of Raman Spectroscopy, Vol. 45, Issue 11-12
  • DOI: 10.1002/jrs.4520

X-ray powder diffraction data for selected metal soaps
journal, March 2002

  • Corbeil, Marie-Claude; Robinet, Laurianne
  • Powder Diffraction, Vol. 17, Issue 1
  • DOI: 10.1154/1.1431950

Modular Chemistry: Secondary Building Units as a Basis for the Design of Highly Porous and Robust Metal−Organic Carboxylate Frameworks
journal, April 2001

  • Eddaoudi, Mohamed; Moler, David B.; Li, Hailian
  • Accounts of Chemical Research, Vol. 34, Issue 4, p. 319-330
  • DOI: 10.1021/ar000034b

Luminescent lead(ii) complexes: new three-dimensional mixed ligand MOFs
journal, January 2012

  • Martínez Casado, Francisco Javier; Cañadillas-Delgado, Laura; Cucinotta, Fabio
  • CrystEngComm, Vol. 14, Issue 8
  • DOI: 10.1039/c2ce06546k

Novel Colloidal Interactions in Anisotropic Fluids
journal, March 1997


Theories and experimental investigations of the structural and thermotropic mesomorphic phase behaviors of metal carboxylates
journal, May 2014


The characterisation of lead fatty acid soaps in ‘protrusions’ in aged traditional oil paint
journal, November 2003


The molecular structure of three types of long-chain zinc(II) alkanoates for the study of oil paint degradation
journal, October 2014


Synthesis of various metal stearates and the corresponding monodisperse metal oxide nanoparticles
journal, November 2016


Metal–carboxylate interactions in metal–alginate complexes studied with FTIR spectroscopy
journal, February 2010

  • Papageorgiou, Sergios K.; Kouvelos, Evangelos P.; Favvas, Evangelos P.
  • Carbohydrate Research, Vol. 345, Issue 4
  • DOI: 10.1016/j.carres.2009.12.010

Analytical Imaging Studies of Cross-Sections of Paintings Affected by Lead Soap Aggregate Formation
journal, September 2007


Structural diversity and chemical trends in hybrid inorganic–organic framework materials
journal, January 2006

  • Cheetham, Anthony K.; Rao, C. N. R.; Feller, Russell K.
  • Chem. Commun., Issue 46
  • DOI: 10.1039/B610264F

Thermotropic Phase Transitions in Some Lead(II) Carboxylates
journal, September 1986


Nuclear Magnetic Resonance Spectra and 207 Pb Chemical-Shift Tensors of Lead Carboxylates Relevant to Soap Formation in Oil Paintings
journal, March 2014

  • Catalano, Jaclyn; Yao, Yao; Murphy, Anna
  • Applied Spectroscopy, Vol. 68, Issue 3
  • DOI: 10.1366/13-07209

Lead(II) carboxylate supramolecular compounds: Coordination modes, structures and nano-structures aspects
journal, December 2011

  • Hu, Mao-Lin; Morsali, Ali; Aboutorabi, Leila
  • Coordination Chemistry Reviews, Vol. 255, Issue 23-24
  • DOI: 10.1016/j.ccr.2011.05.019

Short lead( ii ) soaps: from weakly fluorescent crystals to strongly phosphorescent and structurally varied vitreous phases. A thermal, structural and spectroscopic study
journal, January 2014

  • Martínez-Casado, Francisco J.; Ramos-Riesco, Miguel; Rodríguez-Cheda, José A.
  • J. Mater. Chem. C, Vol. 2, Issue 44
  • DOI: 10.1039/C4TC01645A

The Characterization of Metal Soaps
journal, January 2003


Luminescent metal–organic frameworks
journal, January 2009

  • Allendorf, M. D.; Bauer, C. A.; Bhakta, R. K.
  • Chemical Society Reviews, Vol. 38, Issue 5
  • DOI: 10.1039/b802352m

Structure and Mesomorphism of Neodymium(III) Alkanoates
journal, December 2000

  • Binnemans, Koen; Jongen, Liesbet; Bromant, Claudia
  • Inorganic Chemistry, Vol. 39, Issue 26
  • DOI: 10.1021/ic000470u

The luminescence of lead(II) decanoate
journal, March 1988


Short chain lead (II) alkanoates as ionic liquids and glass formers: A d.s.c., X-ray diffraction and FTIR spectroscopy study
journal, March 2007

  • Casado, F. J. Martínez; Sánchez Arenas, A.; García Pérez, M. V.
  • The Journal of Chemical Thermodynamics, Vol. 39, Issue 3
  • DOI: 10.1016/j.jct.2006.07.023

The interaction of long chain sodium carboxylates and sodium dodecylsulfate with lead(II) ions in aqueous solutions
journal, January 2014

  • Pereira, Rui F. P.; Valente, Artur J. M.; Burrows, Hugh D.
  • Journal of Colloid and Interface Science, Vol. 414
  • DOI: 10.1016/j.jcis.2013.09.051