scispace - formally typeset
Search or ask a question
Journal ArticleDOI

A combined Surface Enhanced Raman Spectroscopy (SERS)/UV-vis approach for the investigation of dye content in commercial felt tip pens inks.

TL;DR: Surface Enhanced Raman Scattering (SERS) and UV-vis spectroscopy were used for the first time for the systematic identification of dye composition in commercial felt tip pens to support the development of conservation protocols for the long term preservation of modern art collections.
About: This article is published in Talanta.The article was published on 2018-05-01 and is currently open access. It has received 17 citations till now.

Summary (2 min read)

1. Introduction

  • Artists have always tried to test new materials and techniques to create original and innovative artistic forms.
  • The preservation of such produced artworks presents significant conservation challenges, as the fast color fading of constituting inks can result in severe deterioration and changes in appearance in short timeframes [3].
  • Germinario et al. used a combination of spectroscopic techniques and chromatographic techniques for the identification of dye and binder components in commercial felt tip pens [10].
  • The use of SERS for heritage applications started in the late 1980's [16–18] when this spectroscopic technique was applied to the identification of dyes in a variety of artistic media.

2.1. Materials

  • Silver nitrate, trisodium citrate, ascorbic acid and reference dyes (Amaranth, Auramine O, Basic Red 9, Blue 38, Crystal Violet, Copper Phthalocyanine, Eosin Y, Erioglaucine, Green S, Methyl Blue, Poinceau 4R, Rhodamine B, Rhodamine 6G, Tartrazine, Victoria Blue B) were purchased from Sigma-Aldrich and used without any further purification.
  • All glassware was cleaned with aqua regia and deionized water prior nanoparticle synthesis.
  • Felt-tip pens from Tombow, Stabilo, Giotto, Caran D’Ache and Carioca brands were purchased from art supplies in Ireland.
  • The complete list of all analyzed felt tip pens is shown in Table 1.

2.3. UV–vis analysis

  • In order to obtain spectra from felt tip pens an extraction procedure was applied whereby colored paper squares (3 cm2) were placed in two glass vials (30min) containing 1.5mL of H2O and MeOH, respectively.
  • The resulting colored solution was measured by UV–vis.

2.5. Optical microscopy

  • White light optical microscopy images of colored paper were acquired with an Axioskop II, Carl Zeiss Ltd.
  • Microscope equipped with a halogen lamp and a charge-coupled detector camera (CCD; Coolsnap CF, Photometrics).

3. Results and discussion

  • Ag nanoinks used for SERS analysis were synthesized according to a method developed by Polavaru et al. which consisted into decreasing the volume of Ag nanoparticles obtained by the classical method of Lee and Meisel by two orders of magnitude [28,29].
  • Rhodamine 6G and Tartrazine were identified in yellow Giotto color (Fig. 3d).
  • In order to carry out a more complete identification and to narrow down the number of uncertain assignations, complementary spectral analysis was carried out whereby UV–vis spectra of the ink extracted from felt tip pen colored drawings was compared to UV–vis spectra of reference dyes.
  • The collection of UV–vis spectra for all analyzed colors also supported the data shown in Fig. 2 and helped to understand the origin of the observed differences between NR and SERS spectra among the different colors.

4. Conclusions

  • This work presents the results of the first systematic identification of dye content in commercial felt tip pens.
  • A total of thirty pens from six colors and five different brands were analyzed by a combined SERS/ UV–vis approach.
  • At the selected excitation wavelength of 514 nm SERS showed to be highly effective in quenching the strong fluorescence backgrounds for all examined colors, generating diagnostic spectra otherwise not observable by NR spectroscopy.
  • Complementary UV–vis analysis was carried out in order complement and extends the identification made by SERS.
  • This work represents a substantial step beyond the state of the art in the field of modern conservation science as it presents an analytical approach suitable for the reliable and sensitive investigation of industrially produced dyes constituting the core colorant components of a large number of artwork produced since 1950's.

Did you find this useful? Give us your feedback

Figures (6)
Citations
More filters
Journal ArticleDOI
02 Mar 2020-Analyst
TL;DR: The proposed dual-channel assay could serve as a simple and rapid method for sensing CBZ in tap water, cauliflower, and pear juice within 30 min and showed effective sensitivity toward CBZ with limit of detection and limit of quantitation values of 37 and 122 ppb.
Abstract: In this study, a 4-aminobenzenethiol-functionalized core-shell silver-coated gold nanoparticle (Au@Ag-4ABT NP) system was designed for the rapid sensing of carbendazim (CBZ) using a combination of naked-eye colorimetry and surface-enhanced Raman spectroscopy (SERS) dual-channel approach. Under alkaline conditions, the deprotonated CBZ species could interact with Ag surfaces via the N-Ag-O and N-Ag-N bonds. As a result, the neighboring Au@Ag-4ABT NPs would come closer through π-π interactions inducing the aggregation of Au@Ag-4ABT NPs. The aggregation of nanoparticles caused changes in the optical properties of the colloidal system, allowing observation with naked eyes, while the generation of more localized surface plasmon resonance "hotspots" between the adjacent Au@Ag nanoparticles permitted monitoring by the SERS technique. The proposed method showed effective sensitivity toward CBZ with limit of detection and limit of quantitation values of 37 and 122 ppb, respectively. In addition, the proposed dual-channel assay could serve as a simple and rapid method for sensing CBZ in tap water, cauliflower, and pear juice within 30 min.

61 citations

Journal ArticleDOI
TL;DR: A facile replacement reduction method to directly deposit the large-scale Ag nanoparticles on a silicon substrate at the room temperature and short reaction time (3 min) was reported in this paper.

28 citations

Journal ArticleDOI
TL;DR: A method based on Boundary Element Method (BEM) simulation is used to accurately predict the colloidal SERS EFs of gold nanoparticle (AuNP) aggregates, and it was found that larger aggregates do not exhibit stronger hot spots, but rather higher amounts of them, influencing the overall predicted EFs, which well reflect the results obtained experimentally.
Abstract: Colloidal gold nanostructures are nowadays widely involved in sensor applications. One of the most interesting techniques that takes advantage of them is certainly the Surface Enhanced Raman Scattering (SERS) effect, even if it is often considered a tricky technique due to structural constraints required by the nanostructured substrates to obtain high enhancement factors (EFs), i.e. the presence of hot spots. Because of the easy preparation and high number of hot spots, aggregated gold nanospheres seem to be the most efficient through the SERS colloids, but their characteristic high disorder makes them unpredictable and difficult to compare between different batches. For this reason, less SERS effective, but more regular and organized substrates are usually preferred. In this study, a method based on Boundary Element Method (BEM) simulation is used to accurately predict the colloidal SERS EFs of gold nanoparticle (AuNP) aggregates, starting from their experimental extinction spectra. Surprisingly, it was found that larger aggregates do not exhibit stronger hot spots, but rather higher amounts of them, influencing the overall predicted EFs, which well reflect the results obtained experimentally.

25 citations

References
More filters
Journal ArticleDOI
TL;DR: This review describes recent fundamental spectroscopic studies that reveal key relationships governing the LSPR spectral location and its sensitivity to the local environment, including nanoparticle shape and size and introduces a new form of L SPR spectroscopy, involving the coupling between nanoparticle plasmon resonances and adsorbate molecular resonances.
Abstract: Localized surface plasmon resonance (LSPR) spectroscopy of metallic nanoparticles is a powerful technique for chemical and biological sensing experiments. Moreover, the LSPR is responsible for the electromagnetic-field enhancement that leads to surface-enhanced Raman scattering (SERS) and other surface-enhanced spectroscopic processes. This review describes recent fundamental spectroscopic studies that reveal key relationships governing the LSPR spectral location and its sensitivity to the local environment, including nanoparticle shape and size. We also describe studies on the distance dependence of the enhanced electromagnetic field and the relationship between the plasmon resonance and the Raman excitation energy. Lastly, we introduce a new form of LSPR spectroscopy, involving the coupling between nanoparticle plasmon resonances and adsorbate molecular resonances. The results from these fundamental studies guide the design of new sensing experiments, illustrated through applications in which researchers use both LSPR wavelength-shift sensing and SERS to detect molecules of chemical and biological relevance.

5,444 citations

Journal ArticleDOI
TL;DR: Surface enhanced Raman spectroscopy (SERS) is a powerful vibrational spectrograph that allows for highly sensitive structural detection of low concentration analytes through the amplification of electromagnetic fields generated by the excitation of localized surface plasmons.

1,793 citations

Journal ArticleDOI
TL;DR: An earlier library of Raman spectra compiled using visible excitation has been extended by the addition of 22 further reference spectra obtained with 780.0, 647.1, 632.8 and/or 514.5 nm excitation.

884 citations

Journal ArticleDOI
TL;DR: The calculated resonance enhancements are found to be on the order of 10(5), which indicates that a surface enhancement factor of about 10(10) would be required in SERS in order to achieve single-molecule detection of R6G.
Abstract: In this work, we present the first calculation of the resonance Raman scattering (RRS) spectrum of rhodamine 6G (R6G) which is a prototype molecule in surface-enhanced Raman scattering (SERS). The calculation is done using a recently developed time-dependent density functional theory (TDDFT) method, which uses a short-time approximation to evaluate the Raman scattering cross section. The normal Raman spectrum calculated with this method is in good agreement with experimental results. The calculated RRS spectrum shows qualitative agreement with SERS results at a wavelength that corresponds to excitation of the S(1) state, but there are significant differences with the measured RRS spectrum at wavelengths that correspond to excitation of the vibronic sideband of S(1). Although the agreement with the experiments is not perfect, the results provide insight into the RRS spectrum of R6G at wavelengths close to the absorption maximum where experiments are hindered due to strong fluorescence. The calculated resonance enhancements are found to be on the order of 10(5). This indicates that a surface enhancement factor of about 10(10) would be required in SERS in order to achieve single-molecule detection of R6G.

344 citations


"A combined Surface Enhanced Raman S..." refers background in this paper

  • ...Eosin Y [19,30], Rhodamine B [31] and Rhodamine 6G [32]were unequivocally identified as the main dye components in Red Tombow, pink Caran D’Ache and Orange Giotto Turbocolor colors, respectively (Fig....

    [...]

Frequently Asked Questions (1)
Q1. What are the contributions mentioned in the paper "A combined surface enhanced raman spectroscopy (sers)/uv–vis approach for the investigation of dye content in commercial felt tip pens inks" ?

In this work Surface Enhanced Raman Scattering ( SERS ) and UV–vis spectroscopy were used for the first time for the systematic identification of dye composition in commercial felt tip pens. The spectral data of all felt tip pens collected through this work were assembled in a database format.