SERS Nanoparticles in Medicine: From Label-Free Detection to Spectroscopic Tagging

Lane, Lucas A.; Qian, Ximei; Nie, Shuai

doi:10.1021/acs.chemrev.5b00265

Cited by 774 publications

(616 citation statements)

References 485 publications

(825 reference statements)

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“…Spontaneous Raman microscopy probes vibrational transitions with much narrower resonances (peak width ~10 cm −1 ) and thus doesn’t suffer this problem, but its feeble signals make many demanding bio-imaging applications impossible. And while surface-enhanced Raman scattering offers remarkable sensitivity and multiplicity, it cannot be readily used to quantitatively image specific molecular targets inside live cells 9 . Here we show that carrying out stimulated Raman scattering under electronic pre-resonance conditions (epr-SRS) enables imaging with exquisite vibrational selectivity and sensitivity (down to 250 nM with 1-ms) in living cells.…”

mentioning

confidence: 99%

Super-multiplex vibrational imaging

Chen

Shi

et al. 2017

Nature

433

452

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The ability to directly visualize a large number of distinct molecular species inside cells is increasingly essential for understanding complex systems and processes. Even though existing methods have been used successfully to explore structural-functional relationships in nervous systems, profile RNA in situ, reveal tumor microenvironment heterogeneity or study dynamic macromolecular assembly1–4, it remains challenging to image many species with high selectivity and sensitivity under biological conditions. For instance, fluorescence microscopy faces a “color barrier” due to the intrinsically broad (~1500 cm−1) and featureless nature of fluorescence spectra5 that limits the number of resolvable colors to 2 to 5 (or 7-9 if using complicated instrumentation and analysis)6–8. Spontaneous Raman microscopy probes vibrational transitions with much narrower resonances (peak width ~10 cm−1) and thus doesn’t suffer this problem, but its feeble signals make many demanding bio-imaging applications impossible. And while surface-enhanced Raman scattering offers remarkable sensitivity and multiplicity, it cannot be readily used to quantitatively image specific molecular targets inside live cells9. Here we show that carrying out stimulated Raman scattering under electronic pre-resonance conditions (epr-SRS) enables imaging with exquisite vibrational selectivity and sensitivity (down to 250 nM with 1-ms) in living cells. We also create a palette of triple-bond-conjugated near-infrared dyes that each display a single epr-SRS peak in the cell-silent spectral window, and that with available fluorescent probes give 24 resolvable colors with potential for further expansion. Proof-of-principle experiments on neuronal co-cultures and brain tissues reveal cell-type dependent heterogeneities in DNA and protein metabolism under physiological and pathological conditions, underscoring the potential of this super-multiplex optical imaging approach for untangling intricate interactions in complex biological systems.

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mentioning

confidence: 99%

Super-multiplex vibrational imaging

Chen

Shi

et al. 2017

Nature

433

452

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“…1,2 As oscillation frequency is structure dependent, the SPR may be tuned by changing the size or shape of the nanoparticle (NP). 3−5 This tunability positions plasmonic metal NPs as highly attractive components in nanomedicine, 6−12 optoelectronics, 13−18 sensing, [6][7][8][9]13,18,19 and solar energy conversion. 20−24 In these applications, hollow metal nanostructures have distinct advantages over their solid metal counterparts including lower mass per particle for reduced material costs, higher surface-area-to-volume ratio for increased density of loading or catalytic sites, and enhanced plasmonic performance in applications like surface-enhanced Raman scattering (SERS), drug delivery, and catalysis.…”

Section: ■ Introductionmentioning

confidence: 99%

Highly Tunable Hollow Gold Nanospheres: Gaining Size Control and Uniform Galvanic Exchange of Sacrificial Cobalt Boride Scaffolds

Lindley

Cooper

Rojas‐Andrade

et al. 2018

ACS Appl. Mater. Interfaces

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In principle, the diameter and surface plasmon resonance (SPR) frequency of hollow metal nanostructures can be independently adjusted, allowing the formation of targeted photoactivated structures of specific size and optical functionality. Although tunable SPRs have been reported for various systems, the shift in SPR is usually concomitant with a change in particle size. As such, more advanced tunability, including constant diameter with varying SPR or constant SPR with varying diameter, has not been properly achieved experimentally. Herein, we demonstrate this advanced tunability with hollow gold nanospheres (HGNs). HGNs were synthesized through galvanic exchange using cobalt-based nanoparticles (NPs) as sacrificial scaffolds. Co 2 B NP scaffolds were prepared by sodium borohydride nucleation of aqueous cobalt chloride and characterized using UV−vis, dynamic light scattering, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy. Careful control over the size of the Co 2 B scaffold and its galvanic conversion is essential to realize fine control of the resultant HGN diameter and shell thickness. In pursuit of size control, we introduce B(OH) 4 − (the final product of NaBH 4 hydrolysis) as a growth agent to obtain hydrodynamic diameters ranging from ∼17−85 nm with relative standard deviation <3%. The highly monodisperse Co 2 B NPs were then used as scaffolds for the formation of HGNs. In controlling HGN shell thickness and uniformity, environmental oxygen was shown to affect both the structural and optical properties of the resultant gold shells. With careful control of these key factors, we demonstrate an HGN synthesis that enables independent variation of diameter and shell thickness, and thereby SPR, with unprecedented uniformity. The new synthesis method creates a truly tunable plasmonic nanostructure platform highly desirable for a wide range of applications, including sensing, catalysis, and photothermal therapy. KEYWORDS: cobalt boride, size control, sodium borohydride, galvanic exchange, hollow gold nanospheres, surface plasmon resonance ■ INTRODUCTIONPlasmonic metal nanostructures exhibit beneficial optical properties owing to their surface plasmon resonance (SPR), the collective oscillation of conduction band electrons that manifests as strong absorption, and/or scattering at the oscillation frequency.1,2 As oscillation frequency is structure dependent, the SPR may be tuned by changing the size or shape of the nanoparticle (NP). 3−5 This tunability positions plasmonic metal NPs as highly attractive components in nanomedicine, 6−12 optoelectronics, 13−18 sensing, [6][7][8][9]13,18,19 and solar energy conversion. 20−24 In these applications, hollow metal nanostructures have distinct advantages over their solid metal counterparts including lower mass per particle for reduced material costs, higher surface-area-to-volume ratio for increased density of loading or catalytic sites, and enhanced plasmonic performance in applications like surface-enhanced Raman scattering (SERS), drug ...

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“…Nanoplasmonics is an emerging area of scientific research with a variety of applications in spectroscopy, metamaterials engineering, biosensing, lasing, photocatalysis, nonlinear and quantum optics [1][2][3][4][5][6][7][8]. This discipline deals with the study of collective oscillations of conduction electrons at metal-dielectric interfaces, which can be resonantly excited upon external irradiation.…”

Section: Introductionmentioning

confidence: 99%

Engineering 3D Multi-Branched Nanostructures for Ultra- Sensing Applications

Chirumamilla¹,

Chirumamilla²,

Roberts³

et al. 2018

Raman Spectroscopy

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The fabrication of plasmonic nanostructures with sub-10 nm gaps supporting extremely large electric field enhancement (hot-spot) has attained great interest over the past years, especially in ultra-sensing applications. The "hot-spot" concept has been successfully implemented in surface-enhanced Raman spectroscopy (SERS) through the extensive exploitation of localized surface plasmon resonances. However, the detection of analyte molecules at ultra-low concentrations, i.e., down to the single/few molecule level, still remains an open challenge due to the poor localization of analyte molecules onto the hot-spot region. On the other hand, three-dimensional nanostructures with multiple branches have been recently introduced, demonstrating breakthrough performances in hot-spot-mediated ultra-sensitive detection. Multi-branched nanostructures support high hot-spot densities with large electromagnetic (EM) fields at the interparticle separations and sharp edges, and exhibit excellent uniformity and morphological homogeneity, thus allowing for unprecedented reproducibility in the SERS signals. 3D multi-branched nanostructures with various configurations are engineered for high hot-spot density SERS substrates, showing an enhancement factor of 10 11 with a low detection limit of 1 fM. In this view, multi-branched nanostructures assume enormous importance in analyte detection at ultra-low concentrations, where the superior hot-spot density can promote the identification of probe molecules with increased contrast and spatial resolution.

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SERS Nanoparticles in Medicine: From Label-Free Detection to Spectroscopic Tagging

Cited by 774 publications

References 485 publications

Super-multiplex vibrational imaging

Super-multiplex vibrational imaging

Highly Tunable Hollow Gold Nanospheres: Gaining Size Control and Uniform Galvanic Exchange of Sacrificial Cobalt Boride Scaffolds

Engineering 3D Multi-Branched Nanostructures for Ultra- Sensing Applications

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