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      • Coating gold nanoparticles to a glass substrate by spin-coat method as a surface-enhanced raman spectroscopy (SERS) plasmonic sensor to detect molecular vibrations of bisphenol-a (BPA)

        Eskandari, Vahid,Hadi, Amin,Sahbafar, Hossein Techno-Press 2022 Advances in nano research Vol.13 No.5

        Bisphenol A (BPA) is one of the chemicals used in monomer epoxy resins and polycarbonate plastics. The surface-enhanced Raman spectroscopy (SERS) method is precise for identifying biological materials and chemicals at considerably low concentrations. In the present article, the substrates coated with gold nanoparticles have been studied to identify BPA and control the diseases caused by this chemical. Gold nanoparticles were made by a simple chemical method and by applying gold salt and trisodium citrate dihydrate reductant and were coated on glass substrates by a spin-coat approach. Finally, using these SERS substrates as plasmonic sensors and Raman spectroscopy, the Raman signal enhancement of molecular vibrations of BPA was investigated. Then, the molecular vibrations of BPA in some consumer goods were identified by applying SERS substrates as plasmonic sensors and Raman spectroscopy. The fabricated gold nanoparticles are spherical and quasi-spherical nanoparticles that confirm the formation of gold nanoparticles by observing the plasmon resonance peak at 517 nm. Active SERS substrates have been coated with nanoparticles, which improve the Raman signal. The enhancement of the Raman signal is due to the resonance of the surface plasmons of the nanoparticles. Active SERS substrates, gold nanoparticles deposited on a glass substrate, were fabricated for the detection of BPA; a detection limit of 10-9 M and a relative standard deviation (RSD) equal to 4.17% were obtained for ten repeated measurements in the concentration of 10-9 M. Hence, the Raman results indicate that the active SERS substrates, gold nanoparticles for the detection of BPA along with the developed methods, show promising results for SERS-based studies and can lead to the development of microsensors. In Raman spectroscopy, SERS active substrate coated with gold nanoparticles are of interest, which is larger than gold particles due to the resonance of the surface plasmons of gold nanoparticles and the scattering of light from gold particles since the Raman signal amplifies the molecular vibrations of BPA. By decreasing the concentration of BPA deposited on the active SERS substrates, the Raman signal is also weakened due to the reduction of molecular vibrations. By increasing the surface roughness of the active SERS substrates, the Raman signal can be enhanced due to increased light scattering from rough centers, which are the same as the larger particles created throughout the deposition by the spin-coat method, and as a result, they enhance the signal by increasing the scattering of light. Then, the molecular vibrations of BPA were identified in some consumer goods by SERS substrates as plasmonic sensors and Raman spectroscopy.

      • SCISCIESCOPUS

        Development of SERS substrate using phage-based magnetic template for triplex assay in sepsis diagnosis

        Nguyen, A.H.,Shin, Y.,Sim, S.J. Elsevier Applied Science 2016 Biosensors & bioelectronics Vol.85 No.-

        Development of a new substrate for surface-enhanced Raman scattering (SERS) is one area of interest for the improvement of SERS performance. Herein, we introduce a new method for developing new mesoporous SERS substrates using M13 phages that display cysteine-rich peptides on the pVIII major units, which is an alternative for thiol donor using chemical modifications. Together with the SERS substrate development, and the use of the SERS technique for sepsis diagnostics is a new approach in clinical settings. The substrates were characterized and magnetized with magnetic immuno colloids made of gold-coated magnetic nanoparticles and specific antibodies. Conventionally, the SERS-tags are prepared by using gold nanoparticles and are modified with Raman dyes to immobilize specific antibodies to capture the biomarkers in the serum samples. However, in this method the SERS-tags are bound to the mesoporous substrate via antibody/antigen interactions to form clusters or layer-by-layer assemblies of SERS-tags for Raman signal enhancement. The SERS spectra showed distinct peaks for tags corresponding to three typical sepsis-specific biomarkers for diagnostics with the limit of detection values of 27 pM, 103 pM, and 78 pM for C-reactive protein (CRP), procalcitonin (PCT), and soluble triggering receptor expressed on myeloid cells-1 (sTREM-1), respectively. With such an approach, SERS can be used for clinical purposes and can be improved by phage display modification rather than chemical alternatives.

      • Fabrication of Multi-functional Surface Enhanced Raman Scattering (SERS) Nanoprobes for Various Applications

        김형모,전봉현 한국공업화학회 2018 한국공업화학회 연구논문 초록집 Vol.2018 No.0

        In this study, we present two different hybrid nanoprobes having both magnetic and surface enhanced Raman scattering (SERS) properties for SERS-based detection using the magnetic silver nanoshells (M-AgNSs) and the multi-layered tri-functional magnetic-SERS-fluorescence particles (MF-SERS Particles). We obtained much stronger SERS signal intensity from the aggregated M-AgNSs than from the non-aggregated AgNSs, and the limit of detection for tetramethylthiram disulfide was 10 μM, which corresponds to 3 ppm. Also, 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 antibody-conjugated MF-SERS Particles selectively targeted cells. Based on these properties, both hybrid nanomaterials were proved to be a useful nanoprobes.

      • SERS study of Ag/FeS/4-MBA interface based on the SPR effect

        Ma, Ning,Zhang, Xin-Yuan,Fan, Wenyue,Guo, Shuang,Zhang, Yongjun,Liu, Yang,Chen, Lei,Jung, Young Mee Elsevier 2019 Spectrochimica acta. Part A, Molecular and biomole Vol.219 No.-

        <P><B>Abstract</B></P> <P>In this work, an ordered metal-semiconductor molecular system was introduced, and 4-mercaptobenzoic acid (4-MBA) was employed to study the charge transfer (CT) at the metal-semiconductor interface based on surface-enhanced Raman scattering (SERS) spectra. The thickness of the sputtered FeS was controlled so that the surface plasmon resonance (SPR) of Ag underwent a displacement change, and the contribution of the SPR to the CT was studied through surface plasmon (SP) absorption. Furthermore, SERS spectra obtained at different excitation wavelengths were used to calculate the degree of CT in the layer-by-layer sputtering system. When Ag was irradiated with incident light, the strong SPR of Ag was excited, generating an increased electromagnetic field (EM). This amplified EM generated hot electrons at the interface between the FeS and Ag, and then the hot electrons were rearranged. Therefore, we established a simple and effective method for studying the impact of SPR on interfacial CT and analyzed the SERS spectra in accordance with Lombardi's basic theory and the physical effects associated with SPR. This theory is in good agreement with the experimental results. On this basis, we also proposed a mechanism by which SPR impacts the CT, which is beneficial for studying interfacial CT and obtaining an in-depth understanding of the CT mechanism in SERS. This work also enables the expansion of the applications of the SERS technique in the field of nanomaterials.</P> <P><B>Highlights</B></P> <P> <UL> <LI> SERS substrate was designed based on the layer-by-layer sputtering of Ag/FeS. </LI> <LI> 4-MBA was employed to study the CT at the metal-semiconductor interface. </LI> <LI> The SPR of Ag promotes the electron transfer process of the Ag/FeS/4-MBA system. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>In this paper, we designed a layer-by-layer sputtering of Ag and FeS on the PS template. FeS, as an ultranarrow bandgap semiconductor with a bandgap width of only 0.1 eV, exhibited different properties for SERS. The SPR of Ag can be tuned by controlling the FeS film thickness, which is beneficial for studying interface CT and obtaining an in-depth understanding of the CT mechanism in SERS.</P> <P>[DISPLAY OMISSION]</P>

      • SCISCIESCOPUS

        A low-cost, monometallic, surface-enhanced Raman scattering-functionalized paper platform for spot-on bioassays

        Kim, Wan-Sun,Shin, Jae-Ho,Park, Hun-Kuk,Choi, Samjin Elsevier 2016 Sensors and actuators. B Chemical Vol.222 No.-

        <P><B>Abstract</B></P> <P>We demonstrate the fabrication and spot-on bioassay application of a low-cost, monometallic, surface-enhanced Raman scattering (SERS) paper platform using gold nanoparticle (AuNP)-loaded screen printing inks. The AuNPs were used to enhance the Raman intensity through a surface plasmon resonance (SPR)-driven optical property and sodium carboxymethylcellulose (CMC) was used as a viscous ink to create uniform distribution of the AuNPs on the paper substrate. To minimize the coffee ring effect and uniformly disperse the nanoparticles, the size of citrate-capped AuNPs, the CMC concentration, the volume ratio of CMC solution and AuNPs, and the printing cycles were optimized. Two printing cycles of optimized ink with a 7:1 mixture of 2-wt% CMC and AuNPs produced the strongest SERS effect and an enhancement factor of 1.8×10<SUP>4</SUP> with a SERS paper platform based on a Rhodamine B probe molecule. The platform exhibited high reproducibility, with less than 5% spot-to-spot variation in Raman intensity. Furthermore, the SERS spectra of normal and two virus-infected tear biofluids were comparable to the SERS spectral findings of gold-deposited SERS substrates. The enhanced SERS activity and high reproducibility of a low-cost, flexible, portable, and lightweight paper platform suggest the potential of point-of-care applications of biofluids in fields ranging from clinical analysis to industry.</P> <P><B>Highlights</B></P> <P> <UL> <LI> A simple and facile SERS-functionalized paper platform was designed for POC diagnostics of biofluids. </LI> <LI> The optical property of surface plasmon resonance was implemented using monometallic gold NPs. </LI> <LI> The viscous property of a sodium CMC solution was used to improve the uniformity and reproducibility of SERS. </LI> <LI> The low-cost SERS paper sensor showed an effective signature for classifying adenoviral and herpes simplex conjunctivitis. </LI> </UL> </P>

      • Systematic study of single-step synthesis of SERS tags

        이은진,이윤식 한국공업화학회 2015 한국공업화학회 연구논문 초록집 Vol.2015 No.1

        As a novel optical nanoprobe, surface-enhanced Raman scattering (SERS) tags have drawn growing interests in chemical and biological sensing, environmental monitoring, and bioimaging fields. Ideally, a SERS tag should provide uniform and stable SERS signals via SERS-active hot spots in SERS tag nanostructures. Furthermore, Raman reporters on metal nanostructures should be adsorbed firmly and remained stable over time, which are still challenging. Herein, we present a single-step synthesis strategy for Ag nano-gap bumpy shell (Ag NBS) SERS tag. The SERS tags showed 2-nm sized gap, which can generate a strong EM filed enhancement, eventually leading to highly enhanced Raman signals. The SERS signals exhibited long-term stability. The mechanism for the formation of Ag NBS was also systematically studied.

      • KCI등재

        Charge transfer study for semiconductor and semiconductor/ metal composites based on surface‐enhanced Raman scattering

        Yang Bo,Wang Ye,Guo Shuang,진실아,Park Eungyeong,Chen Lei,Jung Young Mee 대한화학회 2021 Bulletin of the Korean Chemical Society Vol.42 No.11

        With the development of the surface-enhanced Raman scattering (SERS) technique, new multipurpose and multiperformance SERS-active substrates have been developed. Semiconductor and semiconductor/metal composites show versatility and SERS activity for theoretical and practical applications. Semiconductor-based SERS substrates with different microstructures, materials and compositions have been prepared to explore the enhancement effect on Raman signals. The discovery of the SERS enhancement effect of semiconductors makes up for the gap that SERS development is limited to metal-based materials. Semiconductor/metal composite substrates have established preparation technology that is compatible with the characteristics of different materials to form a stable and solid substrate that can regulate the SERS enhancement mechanism. These composites establish a good model for the theoretical research of SERS, which is of great significance to explore its enhancement mechanism. In this review, various semiconductor materials are introduced as SERS-active substrates. Versatile applications of semiconductorbased SERS and its enhancement mechanism are also presented

      • Highly-sensitive SERS-based immunoassay platform prepared on silver nanoparticle-decorated electrospun polymeric fibers

        Yun, Byung Ju,Koh, Won-Gun Elsevier 2020 Journal of industrial and engineering chemistry Vol.82 No.-

        <P><B>Abstract</B></P> <P>A new, highly sensitive surface enhanced Raman scattering (SERS)-based immunoassay platform was prepared using silver nanoparticle (AgNP)-decorated electrospun fibers as the capture substrate. We used electrospinning and silver mirror reaction to generate AgNP-decorated polycaprolactone (PCL) fiber matrix (Ag-PCL). The resultant capture substrates obtained were bi-directionally porous, free-standing, and flexible. AgNP formation on the PCL fibers was confirmed via SEM, AFM, XPS, and TGA analysis. In addition, gold nanoparticles immobilized with a Raman reporter, 4-mercaptobenzoic acid (4-MBA), were prepared as the SERS tag. This tag could significantly enhance the SERS signal via generation of additional hot spots between AgNPs on fibers and AuNPs. For a model immunoassay to detect prostate specific antigen (PSA), PSA antibodies were immobilized on both Ag-PCL and AuNP SERS tags. The large surface area of fiber substrates allowed the immobilization of large amounts of antibodies and their porous structures facilitated the assessment of the target antigen to immobilized antibodies. Binding of PSA between antibodies on AgNPs and AuNPs led to formation of a sandwich structure by the two metal nanostructures, and consequently, highly sensitive detection of PSA was possible up to a detection limit of 1pg/mL within 1h of reaction time. The developed SERS-based immunoassay platform produced uniform and reproducible SERS signals over the entire substrate area and from different samples.</P> <P><B>Highlights</B></P> <P> <UL> <LI> SERS-based immunoassay was carried out using AgNP-decorated electrospun fibers as capture substrate. </LI> <LI> SERS signal was greatly amplified by the generation of hot spots between AgNPs on fibers and AuNP-based SERS tag. </LI> <LI> Fast and sensitive detection of PSA was possible due to the large surface area and porous structure of fibrous substrate. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

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        A label-free cellulose SERS biosensor chip with improvement of nanoparticle-enhanced LSPR effects for early diagnosis of subarachnoid hemorrhage-induced complications

        Kim, Wansun,Lee, Sung Ho,Ahn, Yong Jin,Lee, Seung Ho,Ryu, Jiwook,Choi, Seok Keun,Choi, Samjin Elsevier 2018 Biosensors & bioelectronics Vol.111 No.-

        <P><B>Abstract</B></P> <P>It is very difficult to predict some complications after subarachnoid hemorrhage (SAH), despite rapid advances in medical science. Herein, we introduce a label-free cellulose surface-enhanced Raman spectroscopy (SERS) biosensor chip with pH-functionalized, gold nanoparticle (AuNP)-enhanced localized surface plasmon resonance (LSPR) effects for identification of SAH-induced cerebral vasospasm and hydrocephalus caused by cerebrospinal fluid (CSF). The SERS biosensor chip was implemented by the synthesis reaction of the AuNPs, which were charged positively through pH level adjustment, onto a negatively-charged cellulose substrate with <I>ξ = </I>–30.7 mV. The zeta potential, nanostructural properties, nanocrystallinity, and computational calculation-based electric field distributions of the cellulose-originated AuNPs were optimized to maximize LSPR phenomena and then characterized. Additionally, the performance of the SERS biosensor was compared under two representative excitation laser sources in the visible region (532 nm) and near-infrared region (785 nm). The Raman activities of our SERS biosensor chip were evaluated by trace small molecules (crystal violet, 2 µL), and the biosensor achieved an enhancement factor of 3.29 × 10<SUP>9</SUP> for the analytic concept with an excellent reproducibility of 8.5% relative standard deviation and a detection limit of 0.74 pM. Furthermore, the experimental results revealed that the five proposed SERS-based biomarkers could provide important information for identifying and predicting SAH-induced cerebral vasospasm and hydrocephalus complications (91.1% reliability and 19.3% reproducibility). Therefore, this facile and effective principle of our SERS biosensor chip may inspire the basis and strategies for the development of sensing platforms to predict critical complications in various neurosurgical diagnoses.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Bare cellulose at pH 3 showed the lowest negative electric potential, <I>ξ = </I>–30.7 mV. </LI> <LI> A pH adjustment led to improved SERS performance of the cellulose biosensor chip. </LI> <LI> Five SERS-based biomarkers were proposed to predict SAH-induced complications. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

      • Multilayer Ag-Embedded Silica Nanostructure as a Surface-Enhanced Raman Scattering-Based Chemical Sensor with Dual-Function Internal Standards

        Hahm, Eunil,Cha, Myeong Geun,Kang, Eun Ji,Pham, Xuan-Hung,Lee, Sang Hun,Kim, Hyung-Mo,Kim, Dong-Eun,Lee, Yoon-Sik,Jeong, Dae-Hong,Jun, Bong-Hyun American Chemical Society 2018 ACS APPLIED MATERIALS & INTERFACES Vol.10 No.47

        <P>Surface-enhanced Raman scattering (SERS) spectroscopy is attractive in various detection analysis fields. However, the quantitative method using SERS spectroscopy remains as an area to be developed. The key issues in developing quantitative analysis methods by using SERS spectroscopy are the fabrication of reliable SERS-active materials such as nanoparticle-based structures and the acquisition of the SERS signal without any disturbance that may change the SERS signal intensity and frequency. Here, the fabrication of seamless multilayered core-shell nanoparticles with an embedded Raman label compound as an internal standard (ML<SUB>RLC</SUB> dots) for quantitative SERS analysis is reported. The embedded Raman label compound in the nanostructure provides a reference value for calibrating the SERS signals. By using the ML<SUB>RLC</SUB> dots, it is possible to gain target analyte signals of different concentrations while retaining the Raman signal of the internal standard. The ML<SUB>4-BBT</SUB> dots, containing 4-bromobenzenethiol (4-BBT) as an internal standard, are successfully applied in the quantitative analysis of 4-fluorobenzenethiol and thiram, a model pesticide. Additionally, ratiometric analysis was proved practical through normalization of the relative SERS intensity. The ratiometric strategy could be applied to various SERS substrates for quantitative detection of a wide variety of targets.</P> [FIG OMISSION]</BR>

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