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Nano Materials for Sensing

A large number of modern artists use commercial pens for their productions. Because such pens easily fade a large proportion of art works produced since 1950 is already in need of some form of conservation. The first step of any conservation action requires identification of ink mixtures. Such identification is challenging because ink formulations are often protected by patent, novel formulations are periodically introduced in the market and a comprehensive data base does not exist.

Surface Enhanced Raman Scattering (SERS) has been identified as suitable tool for the identification of dye mixtures in commercial inks used in modern artworks as it is a potentially non-invasive technique providing fingerprints of analytes. Therefore, SERS could constitute a novel, safe and easy-to-use analytical tool for paper conservators towards more effective preservation and conservation of modern paper artworks.

We have developed a range of nanomaterial formulations for both ex-situ and in situ SERS analysis of inks and have tested them with a blue BIC ballpoint pen and several Stabilo felt tip pen colors. The use of gold nanorod aqueous suspensions in combination with thin layer chromatography (TLC) has allowed identification of phtalocyanine and crystal violet dyes in the BIC pen. In addition, gold nanorod arrays were used for trace identification of inks (< 10 nM). Due to their high degree of geometrical order, such SERS substrates provided high reproducibility and analysis and allowed quantitative measurements.

Metal nanoinks based on silver nanoparticles and metal nanorods were used for Pen-On-Paper (POP) fabrication of SERS diagnostic paper substrates. SERS spectra of single and crossed BIC ballpoint pen lines were easily obtained and distinguished. Metal nanoinks were also used to “write” SERS active areas on paper surfaces in order to acquire SERS spectra directly from felt-tip pens colored paper samples. Rodhamine6G, tartrazine and phtalocyanine were found as main components of red/pink, yellow and blue colored areas, respectively.

a) Photograph of silver POP with BIC pen crossed lines; b) Photograph of silver nanoink used for fabrication of a); c) SERS spectra of single and crossed BIC pen lines shown in a); d) Raman and SERS spectra of Stabilo pink colored paper (shown in the inset).

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