Turning up the lights - fabrication of brighter SERRS nanotags

Brighter SERRS nanotags ideal for improved SERRS imaging were prepared by the controlled addition of electrolyte producing a dimer enriched solution, which was incubated with a Raman reporter before being stabilised by a polyethylene glycol (PEG) shell

Surface-enhanced spatially-offset raman spectroscopy (SESORS) in tissue analogs

Surface-enhanced, spatially-offset Raman spectroscopy (SESORS) combines the remarkable enhancements in sensitivity afforded by surface-enhanced Raman spectroscopy (SERS) with the non-invasive, sub-surface sampling capabilities of spatially-offset Raman spectroscopy (SORS). Taken together, these techniques show great promise for in vivo Raman measurements. Herein, we present a step forward for this technique, demonstrating SESORS through tissue analogs of six known and varied thickness, with a large number of distinct spatial offsets, in a back-scattering optical geometry. This is accomplished by spin-coating SERS-active nanoparticles (NPs) on glass slides, and monitoring the relative spectral contribution from the NPs and tissue sections, respectively, as a function of both tissue thickness and spatial offset of the collection probe. The results show that SESORS outperforms SERS alone for this purpose, NP signal is attainable at tissue thicknesses in excess of 6.75 mm, and that greater tissue thicknesses require greater spatial offsets to maximize NP signal, all with an optical geometry optimized for utility. This demonstration represents a step forward toward the implementation of SESORS for non-invasive, in vivo analysis

Detection of multiple nitroaromatic explosives via formation of a Janowsky complex and SERS

Military-grade explosives such as 2,4,6-trinitroluene (TNT) are still a major worldwide concern in terms of terror threat and environmental impact. The most common methods currently employed for the detection of explosives involve colorimetric tests, which are known to be rapid and portable; however, they often display false positives and lack sensitivity. Other methods used include ion mobility mass spectrometry, gas chromatography-mass spectrometry (GC-MS), and liquid chromatography-mass spectrometry (LC-MS), which despite producing more reliable results often require large, expensive instrumentation and specially trained staff. Here we demonstrate an alternative approach that utilizes the formation of a colored Janowsky complex with nitroaromatic explosives through reaction of the enolate ion of 3-mercapto-2-butanone. The colored complex is formed rapidly and can then be detected sensitively using surface-enhanced Raman scattering (SERS). We demonstrate that SERS can be used as a quick, sensitive, and selective technique for the detection of 2,4,6-trinitrotoluene (TNT), hexanitrostillbene (HNS), and 2,4,6-trinitrophenylmethylnitramine (tetryl) with a detection limit of 6.81 ng mL -1 achieved for TNT, 17.2 ng mL -1 for tetryl, and 135.1 ng mL -1 for HNS. This method of detection also requires minimal sample preparation, can be done in a solution-based format, and utilizes the same precursor reagents for complex formation with each of the explosives which can then be identified due to the specificity of the unique SERS response obtained. We demonstrate the ability to simultaneously identify three explosive compounds within a total analysis time of 10 min. This method of detection shows promise for the development of rapid and portable SERS-based assays which can be utilized in the field in order to achieve reliable and quantitative detection

Sensitive SERS nanotags for use with 1550 nm (retina-safe) laser excitation

Chalcogenopyrylium nanotags demonstrate an unprecedented SERS performance with a retina safe, 1550 nm laser excitation. These unique nanotags consisting of chalcogenopyrylium dyes and 100 nm gold nanoparticles produce exceptional SERS signals with picomolar detection limits obtained at this extremely red-shifted and eye-safe laser excitation

Sensitive SERS nanotags for use with a hand-held 1064 nm Raman spectrometer

This is the first report of the use of a hand-held 1064 nm Raman spectrometer combined with red shifted surface enhanced Raman scattering (SERS) nanotags to provide an unprecedented performance in the short-wave infrared (SWIR) region. A library consisting of 17 chalcogenopyrylium nanotags produce extraordinary SERS responses with femtomolar detection limits being obtained using the portable instrument. This is well beyond previous SERS detection limits at this far red shifted wavelength and opens up new options for SERS sensors in the SWIR region of the electromagnetic spectrum (between 950-1700 nm)

Detection of potentially toxic metals by SERS using salen complexes

Surfaced enhanced Raman scattering (SERS) can discriminate between metal complexes due to the characteristic “spectral fingerprints” obtained. As a result, SERS has the potential to develop relatively simple and sensitive methods of detecting and quantifying a range of metal ions in solution. This could be beneficial for the environmental monitoring of potentially toxic metals (PTMs). Here, salen (C16H16N2O2) was used as a ligand to form complexes of Ni(II), Cu(II), Mn(II) and Co(II) in solution. The SERS spectra showed characteristic spectral differences specific to each metal complex, thus allowing the identification of each of these metal ions. This method allows a number of metal ions to be detected using the same ligand and an identical preparation procedure. The limit of detection (LOD) was determined for each metal ion, and it was found that Ni(II), Cu(II) and Mn(II) could be detected below the WHO’s recommended limits in drinking water at 1, 2 and 2 µg L-1, respectively. Co(II) was found to have an LOD of 20 µg L-1, however no limit has been set for this ion by the WHO as the concentration of Co(II) in drinking water is generally <1-2 μg L-1. A contaminated water sample was also analysed where Mn(II) was detected at a level of 800 µg L-1

Ratiometric sensing of fluoride ions using Raman spectroscopy

Ratiometric Raman spectroscopy represents a novel sensing approach for the detection of fluoride anions based on alkyne desilylation chemistry. This method enables rapid, anion selective and highly sensitive detection of fluoride in a simple paper-based assay format using a portable Raman spectrometer

Surface science of soft scorpionates

The chemisorption of the soft scorpionate Li[PhTmMe] onto silver and gold surfaces is reported. Surface enhanced Raman spectroscopy in combination with the Raman analysis of suitable structural models, namely, [Cu(κ3-S,S,S-PhTmMe)(PCy3)], [Ag(κ3-S,S,S-PhTmMe)(PCy3)], [Ag(κ2-S,S-PhTmMe)(PEt3)], and [Au(κ1-S-PhTmMe)(PCy3)], are employed to identify the manner in which this potentially tridentate ligand binds to these surfaces. On colloidal silver surface-enhanced Raman spectroscopy (SERS) spectra are consistent with PhTmMe binding in a didentate fashion to the surface, holding the aryl group in close proximity to the surface. In contrast, on gold colloid, we observe that the species prefers a monodentate coordination in which the aryl group is not in close proximity to the surface

Resonance Raman detection of antioxidants using an iron oxide nanoparticle catalysed decolourisation assay

Nanozymes are metal nanoparticles with catalytic properties that can be used to oxidise peroxidase substrates giving a colorimetric response which can be detected using UV-vis, and recently, Raman spectroscopy. Due to their ease of synthesis and increased stability, nanozymes are being increasing investigated to replace conventional enzymes for the detection of biomolecules. Here we exploit the catalytic activity of iron oxide (Fe2O3) nanoparticles combined with the substrate 2,2-Azinobis(3-ethyl-benzothiazoline-6-sulfonic acid) (ABTS) in a decolourisation assay for the detection of antioxidants. Fe2O3 nanoparticles were used to catalyse the oxidation of ABTS to its green radical cation which, upon the addition of an antioxidant, resulted in a decolourisation due to the reduction of the radical cation caused by the hydrogen donating antioxidant. The assay was applied for the detection of multiple antioxidants (glutathione, chlorogenic acid and ascorbic acid), and was followed by monitoring the resonance Raman scattering from the ABTS solution using a portable Raman system with 785 nm laser excitation. This novel assay has the potential to be optimised to detect antioxidant activity in body fluid with low limits of detection with point of use monitoring

Data processing of three-dimensional vibrational spectroscopic chemical images for pharmaceutical applications

Vibrational spectroscopic chemical imaging is a powerful tool in the pharmaceutical industry to assess the spatial distribution of components within pharmaceutical samples. Recently, the combination of vibrational spectroscopic chemical mapping with serial sectioning has provided a means to visualise the three-dimensional (3D) structure of a tablet matrix. There are recognised knowledge gaps in current tablet manufacturing processes, particularly regarding the size, shape and distribution of components within the final drug product. The performance of pharmaceutical tablets is known to be primarily influenced by the physical and chemical properties of the formulation. Here, we describe the data processing methods required to extract quantitative domain size and spatial distribution statistics from 3D vibrational spectroscopic chemical images. This provides a means to quantitatively describe the microstructure of a tablet matrix and is a powerful tool to overcome knowledge gaps in current tablet manufacturing processes, optimising formulation development