Eunil Hahm

Glucose detection using 4-mercaptophenyl boronic acid-incorporated silver nanoparticles-embedded silica-coated graphene oxide as a SERS substrate

In this work, 4-mercaptophenyl boronic acid (4-MPBA) was self-assembled on the surface of silver nanoparticle-embedded silica-coated graphene oxide (GO@SiO2@Ag NPs@MPBA) to detect glucose by surface enhanced Raman scattering (SERS). The SERS intensity of 4-MPBA on the GO@SiO2@Ag NPs was 2.2-fold greater than that of GO@Ag NPs. Moreover, silica-coated GO exhibited lower background signals compared to GO. The SERS intensity of GO@SiO2@Ag NPs@MPBA peaked at 1 mM 4-MPBA. pH-dependent behavior of 4-MPBA on the GO@SiO2 @Ag NPs was investigated; the highest SERS signal intensity was detected at pH 3. The binding of glucose to 4-MPBA-incorporated GO@SiO2@Ag NPs increased the SERS signals at both 1,072 and 1,588 cm-1. The linear range was estimated from 2 to 20 mM glucose. These results provide insight into detection of glucose and the development of SERS-based biosensors using graphene oxide.

β-CD Dimer-immobilized Ag Assembly Embedded Silica Nanoparticles for Sensitive Detection of Polycyclic Aromatic Hydrocarbons.

We designed a β-CD dimer on silver nanoparticles embedded with silica nanoparticles (Ag@SiO2 NPs) structure to detect polycyclic aromatic hydrocarbons (PAHs). Silica NPs were utilized as a template for embedding silver NPs to create hot spot structures and enhance the surface-enhanced Raman scattering (SERS) signal, and a thioether-bridged dimeric β-CD was immobilized on Ag NPs to capture PAHs. The assembled Ag NPs on silica NPs were confirmed by TEM and the presence of β-CD dimer on Ag@SiO2 was confirmed by UV-vis and attenuated total reflection-Fourier transform infrared spectroscopy. The β-CD dimer@Ag@SiO2 NPs were used as SERS substrate for detecting perylene, a PAH, directly and in a wide linearity range of 10−7 M to 10−2 M with a low detection limit of 10−8 M. Also, the β-CD dimer@Ag@SiO2 NPs exhibited 1000-fold greater sensitivity than Ag@SiO2 NPs in terms of their perylene detection limit. Furthermore, we demonstrated the possibility of detecting various PAH compounds using the β-CD dimer@Ag@SiO2 NPs as a multiplex detection tool. Various PAH compounds with the NPs exhibited their distinct SERS bands by the ratio of each PAHs. This approach of utilizing the assembled structure and the ligands to recognize target has potential for use in sensitive analytical sensors.

Highly sensitive and reliable SERS probes based on nanogap control of a Au–Ag alloy on silica nanoparticles

We developed highly sensitive surface-enhanced Raman scattering (SERS) probes based on SiO2@Au@Ag nanoparticles (NPs) using the Ag growth onto Au NP seeds method. The SiO2@Au@Ag NPs were synthesized by reducing Ag ions under mild conditions (ascorbic acid) and using the structure-directing agent polyvinylpyrrolidone (PVP). SERS activities of the NPs were tuned by adjusting AgNO3 concentration, resulting in the growth of the Ag shell on the surface of the Au NP seeds and the formation of narrow gaps between two Ag NPs on the surface of the probes. The NPs exhibited strong Raman signals originating from a highly enhanced E-field at the gaps. The SiO2@Au@Ag NPs exhibited a low limit of detection (LOD) value of 2.4 nM for ATP, which proves that they are highly sensitive probes. Moreover, reproducible Raman signals of the SiO2@Au@Ag NPs toward ATP were obtained in batch-to-batch experiments which is very promising for potential use in on-site detection.

Silver Nanoparticle-Embedded Thin Silica-Coated Graphene Oxide as an SERS Substrate

A hybrid of Ag nanoparticle (NP)-embedded thin silica-coated graphene oxide (GO@SiO2@Ag NPs) was prepared as a surface-enhanced Raman scattering (SERS) substrate. A 6 nm layer of silica was successfully coated on the surface of GO by the physical adsorption of sodium silicate, followed by the hydrolysis of 3-mercaptopropyl trimethoxysilane. Ag NPs were introduced onto the thin silica-coated graphene oxide by the reduction of Ag+ to prepare GO@SiO2@Ag NPs. The GO@SiO2@Ag NPs exhibited a 1.8-fold enhanced Raman signal compared to GO without a silica coating. The GO@SiO2@Ag NPs showed a detection limit of 4-mercaptobenzoic acid (4-MBA) at 0.74 μM.

Adenosine Triphosphate-Encapsulated Liposomes with Plasmonic Nanoparticles for Surface Enhanced Raman Scattering-Based Immunoassays

In this study, we prepared adenosine triphosphate (ATP) encapsulated liposomes, and assessed their applicability for the surface enhanced Raman scattering (SERS)-based assays with gold-silver alloy (Au@Ag)-assembled silica nanoparticles (NPs; SiO2@Au@Ag). The liposomes were prepared by the thin film hydration method from a mixture of l-α-phosphatidylcholine, cholesterol, and PE-PEG2000 in chloroform; evaporating the solvent, followed by hydration of the resulting thin film with ATP in phosphate-buffered saline (PBS). Upon lysis of the liposome, the SERS intensity of the SiO2@Au@Ag NPs increased with the logarithm of number of ATP-encapsulated liposomes after lysis in the range of 8 × 106 to 8 × 1010. The detection limit of liposome was calculated to be 1.3 × 10−17 mol. The successful application of ATP-encapsulated liposomes to SiO2@Au@Ag NPs based SERS analysis has opened a new avenue for Raman label chemical (RCL)-encapsulated liposome-enhanced SERS-based immunoassays.

Thin silica shell coated Ag assembled nanostructures for expanding generality of SERS analytes

Surface-enhanced Raman scattering (SERS) provides a unique non-destructive spectroscopic fingerprint for chemical detection. However, intrinsic differences in affinity of analyte molecules to metal surface hinder SERS as a universal quantitative detection tool for various analyte molecules simultaneously. This must be overcome while keeping close proximity of analyte molecules to the metal surface. Moreover, assembled metal nanoparticles (NPs) structures might be beneficial for sensitive and reliable detection of chemicals than single NP structures. For this purpose, here we introduce thin silica-coated and assembled Ag NPs (SiO2@Ag@SiO2 NPs) for simultaneous and quantitative detection of chemicals that have different intrinsic affinities to silver metal. These SiO2@Ag@SiO2 NPs could detect each SERS peak of aniline or 4-aminothiophenol (4-ATP) from the mixture with limits of detection (LOD) of 93 ppm and 54 ppb, respectively. E-field distribution based on interparticle distance was simulated using discrete dipole approximation (DDA) calculation to gain insight into enhanced scattering of these thin silica coated Ag NP assemblies. These NPs were successfully applied to detect aniline in river water and tap water. Results suggest that SiO2@Ag@SiO2 NP-based SERS detection systems can be used as a simple and universal detection tool for environment pollutants and food safety.

Highly Sensitive Magnetic-SERS Dual-Function Silica Nanoprobes for Effective On-Site Organic Chemical Detection

We report magnetic silver nanoshells (M-AgNSs) that have both magnetic and SERS properties for SERS-based detection. The M-AgNSs are composed of hundreds of Fe3O4 nanoparticles for rapid accumulation and bumpy silver shell for sensitive SERS detection by near-infrared laser excitation. The intensity of the SERS signal from the M-AgNSs was strong enough to provide single particle-level detection. We obtained much stronger SERS signal intensity from the aggregated M-AgNSs than from the non-aggregated AgNSs. 4-Fluorothiophenol was detected at concentrations as low as 1 nM, which corresponds to 0.16 ppb. The limit of detection for tetramethylthiuram disulfide was 10 μM, which corresponds to 3 ppm. The M-AgNSs can be used to detect trace amounts of organic molecules using a portable Raman system.

SERS-Based Flavonoid Detection Using Ethylenediamine-β-Cyclodextrin as a Capturing Ligand

Ethylenediamine-modified β-cyclodextrin (Et-β-CD) was immobilized on aggregated silver nanoparticle (NP)-embedded silica NPs (SiO2@Ag@Et-β-CD NPs) for the effective detection of flavonoids. Silica NPs were used as the template for embedding silver NPs to create hot spots and enhance surface-enhanced Raman scattering (SERS) signals. Et-β-CD was immobilized on Ag NPs to capture flavonoids via host-guest inclusion complex formation, as indicated by enhanced ultraviolet absorption spectra. The resulting SiO2@Ag@Et-β-CD NPs were used as the SERS substrate for detecting flavonoids, such as hesperetin, naringenin, quercetin, and luteolin. In particular, luteolin was detected more strongly in the linear range 10−7 to 10−3 M than various organic molecules, namely ethylene glycol, β-estradiol, isopropyl alcohol, naphthalene, and toluene. In addition, the SERS signal for luteolin captured by the SiO2@Ag@Et-β-CD NPs remained even after repeated washing. These results indicated that the SiO2@Ag@Et-β-CD NPs can be used as a rapid, sensitive, and selective sensor for flavonoids.

Enzyme-catalyzed Ag Growth on Au Nanoparticle-assembled Structure for Highly Sensitive Colorimetric Immunoassay

We have developed a sensitive colorimetric immunoassay with broad dynamic range using enzyme-catalyzed Ag growth on gold nanoparticle (NP)-assembled silica (SiO2@Au@Ag). To reduce Ag+ ion content and promote Ag growth on the assembled Au NPs, alkaline phosphatase (AP)-based enzymatic amplification was incorporated, which considerably increased the colorimetric read-out. As a model study, sandwich enzyme-linked immunosorbent assay (ELISA) was used to quantify target IgG. The immune complexes capture the Ab-IgG-AP-labeled detection Ab and trigger the enzyme-catalyzed reaction to convert 2-phospho-L-ascorbic acid to ascorbic acid in the presence of the target IgG. Ascorbic acid reduced Ag+ to Ag, which formed Ag shells on the surface of SiO2@Au and enhanced the absorbance of the SiO2@Au@Ag solution. Plasmonic immunoassay showed a significant linear relationship between absorbance and the logarithm of IgG concentration in the range of ca. 7 × 10−13 M to 7 × 10−11 M. The detection limit was at 1.4 × 10−13 M, which is several hundred folds higher than that of any conventional colorimetric immunoassay. Thus, our novel approach of signal-amplification can be used for highly sensitive in vitro diagnostics and detection of target proteins with the naked eye without using any sophisticated instrument.

Assembly of Plasmonic and Magnetic Nanoparticles with Fluorescent Silica Shell Layer for Tri-functional SERS-Magnetic-Fluorescence Probes and Its Bioapplications

In this study, we report on the fabrication of multilayered tri-functional magnetic-SERS-fluorescence nanoprobes (MF-SERS particles) containing clustered superparamagnetic Fe3O4 nanoparticles (NPs), silver NPs, and a fluorescent silica layer. The MF-SERS particles exhibited strong SERS signals from the silver NPs as well as both superparamagnetism and fluorescence. MF–SERS particles were uptaken by cells, allowing successful separation using an external magnetic field. SERS and fluorescence signals could be detected from the NP-containing cells, and CD44 antibody-conjugated MF-SERS particles selectively targeted MDA-MB-231 cells. Based on these properties, MF-SERS particles proved to be a useful nanoprobe for multiplex detection and separation of cancer cells.