SERS tags based on silica microspheres with adsorbed gold nanostars

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Abstract

SERS tags are of great interest as bioanalysis platforms due to their combination of strong optical signal, photostability, and narrow spectral lines. Despite significant progress in the synthesis of new types of SERS tags based on gold nanoparticles, obtaining microparticles with a Raman scattering intensity sufficient for detection of a single tag using a conventional Raman microscope is not a trivial task. In this paper, hybrid colloidal nanocomposites based on silica microparticles and gold nanostars (AuNSTs) with the composition SiO2/AuNSTs/SiO2 were synthesized and characterized. Two types of gold nanostars, one with a plasmon resonance at 700 nm and the other with two maxima at 650 and 900 nm, were pre-synthesized and adsorbed on the surface of monodisperse colloidal silica particles with a diameter of 1.5 μm. Three types of thiolated aromatic molecules were used as Raman reporters: 4-nitrothiophenol, naphthalenethiol, and 1,4-benzenedithiol. The possibility of measuring the SERS signal from a single microparticle with an intensity variation of no more than 20% has been demonstrated, as well as the possibility of multiplex determination of various microparticles in one Raman image. A comprehensive assessment of the stability, including photostability, of the measured SERS signal over time was carried out when the physicochemical parameters of the microenvironment changed.

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About the authors

О. А. Inozemtseva

Саратовский государственный университет им. Н.Г. Чернышевского; Институт биохимии и физиологии растений и микроорганизмов Российской академии наук – обособленное структурное подразделение ФГБУН Федеральный исследовательский центр “Саратовский научный центр РАН”

Author for correspondence.
Email: Inozemtsevaoa@mail.ru
Russian Federation, ул. Астраханская, 83, Саратов, 410012; просп. Энтузиастов, 13, Саратов, 410049

E. S. Prikhozhdenko

Саратовский государственный университет им. Н.Г. Чернышевского

Email: Inozemtsevaoa@mail.ru
Russian Federation, ул. Астраханская, 83, Саратов, 410012

A. M. Kartashova

Саратовский государственный университет им. Н.Г. Чернышевского

Email: Inozemtsevaoa@mail.ru
Russian Federation, ул. Астраханская, 83, Саратов, 410012

Yu. A. Tyunina

Саратовский государственный университет им. Н.Г. Чернышевского; Институт биохимии и физиологии растений и микроорганизмов Российской академии наук – обособленное структурное подразделение ФГБУН Федеральный исследовательский центр “Саратовский научный центр РАН”

Email: Inozemtsevaoa@mail.ru
Russian Federation, ул. Астраханская, 83, Саратов, 410012; просп. Энтузиастов, 13, Саратов, 410049

A. M. Zakharevich

Саратовский государственный университет им. Н.Г. Чернышевского

Email: Inozemtsevaoa@mail.ru
Russian Federation, ул. Астраханская, 83, Саратов, 410012

A. M. Burov

Институт биохимии и физиологии растений и микроорганизмов Российской академии наук – обособленное структурное подразделение ФГБУН Федеральный исследовательский центр “Саратовский научный центр РАН”

Email: Inozemtsevaoa@mail.ru
Russian Federation, просп. Энтузиастов, 13, Саратов, 410049

B. N. Khlebtsov

Институт биохимии и физиологии растений и микроорганизмов Российской академии наук – обособленное структурное подразделение ФГБУН Федеральный исследовательский центр “Саратовский научный центр РАН”

Email: Inozemtsevaoa@mail.ru
Russian Federation, просп. Энтузиастов, 13, Саратов, 410049

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2. Fig. 1. Electron microscopic images of gold nanostars obtained by reducing ZXVC on the surface of 15 nm “seeds” with dimethylformamide (a) and ascorbic acid (b). The scale bar is 200 nm. Panel (c) shows the extinction spectra of the synthesized nanoparticles. Spectrum 1 is for the nanostars in panel (a), spectrum 2 is for the nanostars in panel (b).

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3. Fig. 2. Scanning electron microscopic image of silicate microparticles (a). Scale bar is 10 μm. The inset shows an enlarged image of individual particles. Scale bar is 1 μm. Histogram of the size distribution of silicate particles (b).

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4. Fig. 3. Electron microscopic images of two types of composite SERS labels with large (SiO2/NZB1) and small (SiO2/NZB2) stars on the surface of silicate microspheres (a). Scale bar is 1 μm. Extinction spectra of composite SERS labels (b). Spectrum 1 – for sample (SiO2/NZB1), spectrum 2 – for sample (SiO2/NZB2).

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5. Fig. 4. Electron microscopic images of two types of composite SERS labels: with large (SiO2/NZV1) (a, b) and small (SiO2/NZV2) stars (c, d) on the surface of silicate microspheres. Scale bars are 20 μm (a, c) and 1 μm (b, d).

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6. Fig. 5. SERS spectra from five single microparticles of SiO2@NZV1 (top), SiO2@NZV2 (middle), and SiO2@NZV1@SiO2 (a). Benzenedithiol was used as a reporter molecule. Microscopic image of single microparticles of SiO2@NZV1 (b). Numbers indicate the particles from which the SERS spectrum was obtained. The summarized data on the relative SERS intensity from single microparticles for two types of nanostars (NZV1 and NZV2) with and without a silicate shell, for three types of aromatic thiols (1,4-benzenedithiol (BDT), nitrobenzenethiol (NBT), and naphthalenethiol (NT)) are shown in panel (c).

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7. Fig. 6. SERS mapping of the region with the applied mixture of microparticles encoded by different aromatic thiols. The image is decoded by the intensity of the characteristic line of benzenedithiol at 1563 cm–1 (a), naphthalenethiol at 1385 cm–1 (b), nitrobenzenethiol at 1335 cm–1 (c). Panel (d) shows the optical microscopic image of the scanned region. Panel (e) shows typical SERS spectra of the studied microparticles and intensity variations (mean value and standard deviation) of the Raman lines.

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8. Fig. 7. Change in the intensity of Raman scattering from samples with adsorbed NZV1 (a) and NZV2 (b) for microparticles coated (dashed curve) and uncoated (solid curve) with a silicate shell, when irradiated with a laser for 300 seconds. Nitrobenzenethiol was used as a reporter molecule. The intensity of the line corresponding to the vibration of the nitro group was studied.

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9. Fig. 8. Change in the relative intensity of Raman scattering from samples with adsorbed NZV1 for microparticles uncoated (a) and coated (b) with a silicate shell during incubation in a medium with pH = 2 (circles), pH = 10 (squares) and in the DMEM cell culture medium (triangles). Nitrobenzenethiol was used as a reporter molecule. The intensity of the line corresponding to the vibration of the nitro group was studied.

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