Research Article
An Enhanced GC/MS Procedure for the Identification of
Proteins in Paint Microsamples
D. Fico ,
1
E. Margapoti ,
2
A. Pennetta ,
1
and G. E. De Benedetto
1,2
1
Laboratorio di Spettrometria di Massa Analitica ed Isotopica, Dipartimento di Beni Culturali, Universit` a del Salento,
73100 Lecce, Italy
2
IBAM-CNR, Sede di Lecce, Via per Monteroni, 73100 Lecce, Italy
CorrespondenceshouldbeaddressedtoA.Pennetta;antonio.pennetta@unisalento.it
Received 28 August 2017; Revised 30 November 2017; Accepted 22 January 2018; Published 1 April 2018
AcademicEditor:ErwinRosenberg
Copyright©2018D.Ficoetal.isisanopenaccessarticledistributedundertheCreativeCommonsAttributionLicense,which
permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
echemicalcharacterizationofmaterialsusedinworksofartisextremelyusefulforgainingabetterknowledgeoftheartistic
heritageandtoguaranteeitspreservation.AderivatizationGC/MSprocedurefortheidentificationofproteinsinamicrosample
frompaintedworksofarthasbeenoptimized.eaminoacidfractionisderivatizedusinganhydrousdimethylformamide(DMF)
assolventinsteadofpyridine(Py),commonlyusedtofacilitatethereaction.Althoughpyridineisoftenconsideredasilylation
catalyst,therearemanyinstancesinwhichsilylationreactionsactuallyareslowerinpyridinethanothersolvents.Inaddition,
pyridine also may have other undesirable effects such as the promotion of secondary products and other chromatographic
anomalies.UsingDMF,theformationofartifactsislimitedandthederivatizationyieldofhydrophilicaminoacidssuchasproline
andhydroxyprolinehasimproved,thusmakingtheidentificationoforganicpaintmediamorestraightforward.emethodhas
been validated and successfully applied to identify the binder of the sample taken from the pictorial cycle of the 12th century
monastery of Santa Maria delle Cerrate (Lecce, Italy), thus highlighting the use of eggs as a binding medium.
1. Introduction
Proteinaceouspaintmedia,especiallythosebasedoneggand
milk, have been used over the centuries by painters, due to
excellent optical features and stability of the paint films ob-
tained[1,2].echemicalcharacterizationofmaterialsusedis
extremely useful for surveying historical treatments and for
gainingabetterknowledgeoftheartisticheritage.isstudy
entails investigating the original constituent materials and
thosebecomeanintegralpartoftheworkofartitselfasaneffect
ofagingandrestorations.Assessingthestateofconservationof
a painting is fundamental when choosing a conservative
strategy based on both prevention and intervention. De-
velopinganalyticaltechniquesforunderstandingthechemical
composition of painting materials and for studying the deg-
radationprocessisthusofgreatimportance.
In the conservation of paintings, a special care and at-
tentiontoorganicmaterialsisnecessary,duetotheirrelatively
increased tendency to undergo degradation, transformation,
andoxidationprocess[2].Infact,thepaintlayersmayexhibit
cracking, darkening, yellowing, and loss of stability and co-
hesion.Milkorcasein,animalglue,egg,dryingoils(walnut,
linseed, and poppy seed oils), plant resins (e.g., sandarac,
mastic,andcolophony),animalresins,andwaxesarethemost
common organic materials historically used in the Mediter-
ranean area and in Europe. e chemical composition and
physical properties of these organic materials (mixtures of
organic species consisting of proteins, triglycerides, terpene
compounds,sterols,esters,alcohols,hydrocarbons,freeacid,
etc.) are considerably influenced by environment and aging
[1,2].Awiderangeofnaturalandsyntheticorganicmaterials
was used for consolidation and restoration [1]. Organic ma-
terialswereusedasbinderstodispersepigmentsandtoapply
themonallthesupports,therebygeneratinganadherentand
elasticfilm.Proteinaceousmaterialswerethusemployedinthe
temperatechnique,dryingoilintheoiltechnique,andbeeswax
in encaustic painting [1, 2]. e precise study of organic
materials in cultural heritage works was investigated on
Hindawi
Journal of Analytical Methods in Chemistry
Volume 2018, Article ID 6032084, 8 pages
https://doi.org/10.1155/2018/6032084