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

Kearns, Hayleigh; Bedics, Matthew A.; Shand, Neil C.; Faulds, Karen; Detty, Michael R.; Graham, Duncan

doi:10.1039/c5an02662h

Cited by 20 publications

(32 citation statements)

References 25 publications

(41 reference statements)

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“…We have previously reported the use of red-shifted chalcogenpyrylium based Raman reporters for both SERS 1,28,26 and surface enhanced spatially offset Raman spectroscopy (SESORS) applications using NIR Raman excitation. 22 By controlling the length of the number of sp 2 carbons in the aliphatic backbone and the choice of chalcogen atoms in the ring system, it is possible to tune the absorption maximum of the Raman reporter into the near infrared (NIR).…”

Section: Resultsmentioning

confidence: 99%

“…Raman spectroscopy provides sensitive, molecularly specific vibrational information, however it is an inherently weak scattering process. 1 Through the use of molecularly specific Raman reporters adsorbed on the surface of metallic nanostructures, e.g. gold nanoparticles (AuNPs), surface enhanced Raman scattering (SERS) provides a means of enhancing the Raman scattering process by several orders of magnitude.…”

Section: Introductionmentioning

confidence: 99%

“…gold nanoparticles (AuNPs), surface enhanced Raman scattering (SERS) provides a means of enhancing the Raman scattering process by several orders of magnitude. 1 Moreover, by utilising a laser that corresponds to an electronic transition of the analyte, further enhancement can be achieved by surface enhanced resonance Raman scattering (SERRS). Not only has SERRS been reported to produce vibrational fingerprint spectra with enhancements up to 10 14 , the nanoparticles can also quench the fluorescence that can be an issue with resonant enhancement.…”

Section: Introductionmentioning

confidence: 99%

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Surface enhanced resonance Raman spectroscopy (SERRS) for probing through plastic and tissue barriers using a handheld spectrometer

Nicolson

Jamieson

Mabbott

et al. 2018

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The ability to probe through barriers and tissue non-invasively is an urgent unmet need in both the security and biomedical imaging fields. Surface enhanced Raman spectroscopy (SERS) has been shown to yield superior enhancement in signal over conventional Raman techniques. Furthermore, by utilising a resonant Raman reporter to produce surface enhanced resonance Raman spectroscopy (SERRS), even greater enhancement in chemical signal can be generated. Here we show the benefit of using red-shifted chalcogenpyrylium based Raman reporters for probing through large thicknesses of plastic and tissue barriers using a conventional Raman instrument. In addition, the benefit of using a resonant Raman reporter for superior levels of through barrier detection is demonstrated, and we aim to show the advantage of using resonant nanotags in combination with conventional Raman spectroscopy to probe through plastic and tissue barriers. Raman signals were collected from SERRS active nanotags through plastic thicknesses of up to 20 mm, as well as the detection of the same SERRS nanotags through up to 10 mm of tissue sections using a handheld conventional Raman spectrometer. The ability to detect SERRS-active nanotags taken up into ex vivo tumour models known as multicellular tumour spheroids (MTS), through depths of 5 mm of tissue is also shown. The advantages of applying multivariate analysis for through barrier detection when discriminating analytes with similar spectral features as the barrier is also clearly demonstrated. To the best of our knowledge, this is the first report of the assessment of the maximum level of through barrier detection using a conventional handheld Raman instrument for SERS applications as well as demonstration of the power of resonant nanotags for probing through barriers using conventional Raman spectroscopy.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Surface enhanced resonance Raman spectroscopy (SERRS) for probing through plastic and tissue barriers using a handheld spectrometer

Nicolson

Jamieson

Mabbott

et al. 2018

Analyst

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“…Further complicating this matter is the presence of auto-fluorescence from biological components and poor tissue penetration depth of visible excitation wavelengths. Accordingly, many SERS measurements are now being performed with near-IR (NIR) wavelength excitation (30)(31)(32), which may help to mitigate fluorescence and increase tissue penetration in future applications.…”

Section: Instrumental Considerationsmentioning

confidence: 99%

Bioanalytical Measurements Enabled by Surface-Enhanced Raman Scattering (SERS) Probes

Jamieson

Asiala

Gracie

et al. 2017

Annual Rev. Anal. Chem.

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Since its discovery in 1974, surface-enhanced Raman scattering (SERS) has gained momentum as an important tool in analytical chemistry. SERS is used widely for analysis of biological samples, ranging from in vitro cell culture models, to ex vivo tissue and blood samples, and direct in vivo application. New insights have been gained into biochemistry, with an emphasis on biomolecule detection, from small molecules such as glucose and amino acids to larger biomolecules such as DNA, proteins, and lipids. These measurements have increased our understanding of biological systems, and significantly, they have improved diagnostic capabilities. SERS probes display unique advantages in their detection sensitivity and multiplexing capability. We highlight key considerations that are required when performing bioanalytical SERS measurements, including sample preparation, probe selection, instrumental configuration, and data analysis. Some of the key bioanalytical measurements enabled by SERS probes with application to in vitro, ex vivo, and in vivo biological environments are discussed.

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“…More recent work describes two new chalcogenopyrilium dyes with absorption maxima at 959 and 986 nm, which, when used with 100 nm AuNPs and excited at 1550 nm, gave intense SERS spectra with detection limits of 50.6 ± 4.6 and 62.9 ± 4.8 pM, respectively. 107 Achieving such sensitivity using a retina-safe laser is particularly impressive since Raman scattering is inherently weak in this NIR region, yet is advantageous for biomedical applications.…”

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Surface-enhanced Raman spectroscopy for in vivo biosensing

et al. 2017

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| Surface enhanced Raman scattering (SERS) is of interest for biomedical analysis and imaging due to its sensitivity, specificity and multiplexing capabilities. The successful application of SERS for in vivo biosensing necessitates probes to be biocompatible and procedures to be minimally invasive, challenges that have respectively been met by the design of nanoprobes and instrumentation. This Review presents recent developments in these areas, describing case studies in which sensors have been implemented, as well as outlining shortcomings that have to be addressed before SERS sees clinical use.In 1928, C. V. Raman first reported the scattering phenomenon that now bears his name.1,2 Raman scattering has since become a powerful analytical technique, including for biomedical applications, 3 where label-free and objective tissue diagnostics 4-6 ex vivo and in vivo, as well as drug-cell interaction studies in vitro have been conducted. [7][8][9] The majority of incident photons experience elastic (Rayleigh) scattering, with only about 1 in 10 7 photons undergoing inelastic (Raman) scattering. 10 In 1974, Fleischmann and co-workers described a phenomenon that would later become known as surface enhanced Raman scattering (SERS) 11 . They observed a large enhancement in inelastic scattering from pyridine when the analyte was adsorbed onto a Ag electrode, an effect that had previously been mentioned by the team of A. J. McQuillan in 1973, 12 with Van Duyne later attributing the signal enhancement to the roughened metal surface via the physical phenomenon he coined SERS.13 Unlike conventional Raman spectroscopy, SERS analyses require samples to be labelled, a disadvantage offset by the large intensity enhancement that makes SERS an important analytical tool with high sensitivity and low detection limits.14,15 The exact mechanism of SERS is not fully understood but an electromagnetic enhancement factor plays the major role 16 , whereby free electrons in a metal nanoparticle (NP) encounter applied radiation whose electromagnetic field varies at a frequency matching the oscillation frequency of electrons in the NPs. Such plasmon resonance at the NP surface arises from an intense electric field, which intensifies Raman modes arising from molecules near or attached to the NP surface. The Raman signals can also be enhanced due to the formation of chargetransfer complexes between the roughened metal surface and molecules bound to it. We now leave our discussion of the SERS mechanism, but refer readers interested in these fundamental principles to some comprehensive articles on the subject. [17][18][19] Well-known selection rules allow for one to predict if a given vibrational mode is infrared-and/or Raman-active. Indeed, by considering the magnitude of the change in dipole moment or polarizability associated with a vibration, one can rationalize infrared or Raman data, respectively. Compared to Raman spectroscopy, SERS involves analyte molecules interacting with a roughened metal substrate, such that the symmetry ...

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

Cited by 20 publications

References 25 publications

Surface enhanced resonance Raman spectroscopy (SERRS) for probing through plastic and tissue barriers using a handheld spectrometer

Surface enhanced resonance Raman spectroscopy (SERRS) for probing through plastic and tissue barriers using a handheld spectrometer

Bioanalytical Measurements Enabled by Surface-Enhanced Raman Scattering (SERS) Probes

Surface-enhanced Raman spectroscopy for in vivo biosensing

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