Investigation of the chemical origin and evidential value of differences in the SERS spectra of blue gel inks

Highly swellable polymer films doped with Ag nanoparticle aggregates (poly-SERS films) have been used to record very high signal:noise ratio, reproducible surface-enhanced (resonance) Raman (SER(R)S) spectra of in situ dried ink lines and their constituent dyes using both 633 and 785 nm excitation. These allowed the chemical origins of differences in the SERRS spectra of different inks to be determined. Initial investigation of pure samples of the 10 most common blue dyes showed that the dyes which had very similar chemical structures such as Patent Blue V and Patent Blue VF (which differ only by a single OH group) gave SERRS spectra in which the only indications that the dye structure had been changed were small differences in peak positions or relative intensities of the bands. SERRS studies of 13 gel pen inks were consistent with this observation. In some cases inks from different types of pens could be distinguished even though they were dominated by a single dye such as Victoria Blue B (Zebra Surari) or Victoria Blue BO (Pilot Acroball) because their predominant dye did not appear in other inks. Conversely, identical spectra were also recorded from different types of pens (Pilot G7, Zebra Z-grip) because they all had the same dominant Brilliant Blue G dye. Finally, some of the inks contained mixtures of dyes which could be separated by TLC and removed from the plate before being analysed with the same poly-SERS films. For example, the Pentel EnerGel ink pen was found to give TLC spots corresponding to Erioglaucine and Brilliant Blue G. Overall, this study has shown that the spectral differences between different inks which are based on chemically similar, but nonetheless distinct dyes, are extremely small, so very close matches between SERRS spectra are required for confident identification. Poly-SERS substrates can routinely provide the very stringent reproducibility and sensitivity levels required. This, coupled with the awareness of the reasons underlying the observed differences between similarly coloured inks allows a more confident assessment of the evidential value of inks SERS and should underpin adoption of this approach as a routine method for the forensic examination of inks.

Correlation between the photocatalysed oxidation of methylene blue in solution and the reduction of resazurin in a photocatalyst activity indicator ink (Rz Paii)

Multifunctional anthraquinone-based sensors: UV, O2and time

An anthraquinone dye, Remazol brilliant blue R, RBBR, is used to create an indicator which can function as: (i) a UV dosimeter, (ii) an O2 indicator and (iii) a ‘Consume within’ indicator, CWI, for fresh, refrigerated foods. The dye is encapsulated in an ink containing a polymer, glycerol and a UV-activated semiconductor photocatalyst, titanium dioxide. When cast as a film, the dye is readily reduced by the TiO2 photocatalyst nanoparticles, thereby changing the colour of the film from blue to yellow, via a transitional green colour. The RBBR indicator is appropriately formulated, and covered with a film of Sellotape, which acts as an O2 barrier, so as to act as a sunburn warning indicator for people with skin type II. In the absence of the layer of Sellotape the RBBR indicator is used as an, albeit slow, sensor for measuring ambient levels of O2. Finally, by keeping the Sellotape layer, a UV-activated, yellow-coloured, RBBR indicator film is found to take ca. 42 h at 5 °C in ambient air to attain a green colour, and, on this basis, it is demonstrated as a possible CWI for refrigerated fresh foods.