Hyejin Chang

Concave Rhombic Dodecahedral Au Nanocatalyst with Multiple High-Index Facets for CO2 Reduction

A concave rhombic dodecahedron (RD) gold nanoparticle was synthesized by adding 4-aminothiophenol (4-ATP) during growth from seeds. This shape is enclosed by stabilized facets of various high-indexes, such as (331), (221), and (553). Because it is driven thermodynamically and stabilized by 4-ATP ligands, the concave RD maintains its structure over a few months, even after rigorous electrochemical reactions. We discussed the mechanism of the shape evolution controlled by 4-ATP and found that both the binding energy of Au-S and the aromatic geometry of 4-ATP are major determinants of Au atom deposition during growth. As a possible application, we demonstrated that the concave RD exhibits superior electrocatalytic performance for the selective conversion of CO2 to CO in aqueous solution.

Fluorescence-Raman Dual Modal Endoscopic System for Multiplexed Molecular Diagnostics

Optical endoscopic imaging, which was recently equipped with bioluminescence, fluorescence, and Raman scattering, allows minimally invasive real-time detection of pathologies on the surface of hollow organs. To characterize pathologic lesions in a multiplexed way, we developed a dual modal fluorescence-Raman endomicroscopic system (FRES), which used fluorescence and surface-enhanced Raman scattering nanoprobes (F-SERS dots). Real-time, in vivo, and multiple target detection of a specific cancer was successful, based on the fast imaging capability of fluorescence signals and the multiplex capability of simultaneously detected SERS signals using an optical fiber bundle for intraoperative endoscopic system. Human epidermal growth factor receptor 2 (HER2) and epidermal growth factor receptor (EGFR) on the breast cancer xenografts in a mouse orthotopic model were successfully detected in a multiplexed way, illustrating the potential of FRES as a molecular diagnostic instrument that enables real-time tumor characterization of receptors during routine endoscopic procedures.

Spatial deformation of nanocellulose hydrogel enhances SERS

Bacterial cellulose hydrogels containing gold nanoparticles (AuNPs-BC) were prepared using a cost-effective and environment-friendly in situ synthesis method. Well-dispersed AuNPs were grown on the nanofiber surface of the BC hydrogel, forming substrates of surface-enhanced Raman spectroscopy (SERS). Increases in SERS-active sites in the AuNPs-BC hydrogel caused the enhancement of SERS intensity. The enhancement in SERS intensity of 4-fluorobenzenethiol and phenylacetic acid (PAA), used as test analytes, was compared with spatially-un-deformed AuNPs-BC hydrogels, as well as spatially-deformed AuNPs-BC hydrogels in which the BC layers had contracted during drying. Particularly noteworthy was the detection of PAA by the simple contraction of the substrate, despite a low affinity to surface gold.

Virus Templated Gold Nanocube Chain for SERS Nanoprobe

A M13 virus based SERS nanoprobe is presented. Gold nanocubes closely aligned into chains along the length of the virus intensify Raman signals of various reporter molecules serving as specific labels. An antibody is expressed at one end to detect the analyte. This new SERS nanoprobe holds promise for infinitesimal and multiplexed detection of any antigen.

Ag Shell−Au Satellite Hetero-Nanostructure for Ultra-Sensitive, Reproducible, and Homogeneous NIR SERS Activity

It is critical to create isotropic hot spots in developing a reproducible, homogeneous, and ultrasensitive SERS probe. Here, an Ag shell-Au satellite (Ag-Au SS) nanostructure composed of an Ag shell and surrounding Au nanoparticles was developed as a near-IR active SERS probe. The heterometallic shell-satellite structure based SERS probe produced intense and uniform SERS signals (SERS enhancement factor ∼1.4 × 10(6) with 11% relative standard deviation) with high detectability (100% under current measurement condition) by 785 nm photoexcitation. This signal enhancement was independent of the laser polarizations, which reflects the isotropic feature of the SERS activity of Ag-Au SS from the three-dimensional (3D) distribution of SERS hot spots between the shell and the surrounding satellite particles. The Ag-Au SS nanostructure shows a great potential as a reproducible and quantifiable NIR SERS probe for in vivo targets.

One-step synthesis of silver nanoshells with bumps for highly sensitive near-IR SERS nanoprobes

A seedless, one-step synthetic route to uniform bumpy silver nanoshells (AgNSs) as highly NIR sensitive SERS substrates is reported. These substrates can incorporate Raman label compounds and biocompatible polymers on their surface. AgNS based NIR-SERS probes are successfully applied to cell tracking in a live animal using a portable Raman system.

Direct Identification of On-Bead Peptides Using Surface-Enhanced Raman Spectroscopic Barcoding System for High-Throughput Bioanalysis

Recently, preparation and screening of compound libraries remain one of the most challenging tasks in drug discovery, biomarker detection, and biomolecular profiling processes. So far, several distinct encoding/decoding methods such as chemical encoding, graphical encoding, and optical encoding have been reported to identify those libraries. In this paper, a simple and efficient surface-enhanced Raman spectroscopic (SERS) barcoding method using highly sensitive SERS nanoparticles (SERS ID) is presented. The 44 kinds of SERS IDs were able to generate simple codes and could possibly generate more than one million kinds of codes by incorporating combinations of different SERS IDs. The barcoding method exhibited high stability and reliability under bioassay conditions. The SERS ID encoding based screening platform can identify the peptide ligand on the bead and also quantify its binding affinity for specific protein. We believe that our SERS barcoding technology is a promising method in the screening of one-bead-one-compound (OBOC) libraries for drug discovery.

A fast and reliable readout method for quantitative analysis of surface-enhanced Raman scattering nanoprobes on chip surface

Surface-enhanced Raman scattering techniques have been widely used for bioanalysis due to its high sensitivity and multiplex capacity. However, the point-scanning method using a micro-Raman system, which is the most common method in the literature, has a disadvantage of extremely long measurement time for on-chip immunoassay adopting a large chip area of approximately 1-mm scale and confocal beam point of ca. 1-μm size. Alternative methods such as sampled spot scan with high confocality and large-area scan method with enlarged field of view and low confocality have been utilized in order to minimize the measurement time practically. In this study, we analyzed the two methods in respect of signal-to-noise ratio and sampling-led signal fluctuations to obtain insights into a fast and reliable readout strategy. On this basis, we proposed a methodology for fast and reliable quantitative measurement of the whole chip area. The proposed method adopted a raster scan covering a full area of 100 μm × 100 μm region as a proof-of-concept experiment while accumulating signals in the CCD detector for single spectrum per frame. One single scan with 10 s over 100 μm × 100 μm area yielded much higher sensitivity compared to sampled spot scanning measurements and no signal fluctuations attributed to sampled spot scan. This readout method is able to serve as one of key technologies that will bring quantitative multiplexed detection and analysis into practice.

Ultrasensitive NIR‐SERRS Probes with Multiplexed Ratiometric Quantification for In Vivo Antibody Leads Validation

Immunotargeting ability of antibodies may show significant difference between in vitro and in vivo. To select antibody leads with high affinity and specificity, it is necessary to perform in vivo validation of antibody candidates following in vitro antibody screening. Herein, a robust in vivo validation of anti-tetraspanin-8 antibody candidates against human colon cancer using ratiometric quantification method is reported. The validation is performed on a single mouse and analyzed by multiplexed surface-enhanced Raman scattering using ultrasensitive and near infrared (NIR)-active surface-enhanced resonance Raman scattering nanoprobes (NIR-SERRS dots). The NIR-SERRS dots are composed of NIR-active labels and Au/Ag hollow-shell assembled silica nanospheres. A 93% of NIR-SERRS dots is detectable at a single-particle level and signal intensity is 100-fold stronger than that from nonresonant molecule-labeled spherical Au NPs (80 nm). The result of SERRS-based antibody validation is comparable to that of the conventional method using single-photon-emission computed tomography. The NIR-SERRS-based strategy is an alternate validation method which provides cost-effective and accurate multiplexing measurements for antibody-based drug development.

Corrigendum: Direct Identification of On-Bead Peptides Using Surface-Enhanced Raman Spectroscopic Barcoding System for High-Throughput Bioanalysis

Recently, preparation and screening of compound libraries remain one of the most challenging tasks in drug discovery, biomarker detection, and biomolecular profiling processes. So far, several distinct encoding/decoding methods such as chemical encoding, graphical encoding, and optical encoding have been reported to identify those libraries. In this paper, a simple and efficient surface-enhanced Raman spectroscopic (SERS) barcoding method using highly sensitive SERS nanoparticles (SERS ID) is presented. The 44 kinds of SERS IDs were able to generate simple codes and could possibly generate more than one million kinds of codes by incorporating combinations of different SERS IDs. The barcoding method exhibited high stability and reliability under bioassay conditions. The SERS ID encoding based screening platform can identify the peptide ligand on the bead and also quantify its binding affinity for specific protein. We believe that our SERS barcoding technology is a promising method in the screening of one-bead-one-compound (OBOC) libraries for drug discovery.