• Title/Summary/Keyword: Surface enhanced Raman scattering

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Tautomerism of Cytosine on Silver, Gold, and Copper: Raman Spectroscopy and Density Functional Theory Calculation Study

  • Cho, Kwang-Hwi;Joo, Sang-Woo
    • Bulletin of the Korean Chemical Society
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    • v.29 no.1
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    • pp.69-75
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    • 2008
  • Tautomerism of pyrimidine base cytosine has been comparatively examined on nanoparticle and roughened plate surfaces of silver, gold, and copper by surface-enhanced Raman scattering (SERS). The SERS spectrum was found to be different depending on the metals and their substrate conditions suggesting the dissimilar population of various tautomers of cytosine on the surfaces. The ab initio calculations were performed at the levels of B3LYP, HF, and MP2 levels of theory with the LanL2DZ basis set to estimate the energetic stability of the tautomers with the metal complexes as well as the gas phase state. The amino group and N3-coordinated tautomer was predicted to be more favorable for bonding to Au, whereas the hydroxyl and N1-coordinated zwitter ionic form is most stable with Ag and Cu as a bidentate form from the DFT calculation. The binding energy with the Ag atom is calculated to be smaller than those with the Au and Cu atoms in line with the temperature-dependent SERS spectra of cytosine.

Fabrication of shape-controlled Au nanoparticle arrays for SERS substrates

  • Shin, Seon Mi;Choi, Kyeong Woo;Ye, Seong Ji;Kim, Young Yun;Park, O Ok
    • Advances in materials Research
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    • v.3 no.3
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    • pp.139-149
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    • 2014
  • Surface enhanced Raman Scattering (SERS) has attracted attention because the technique enables detection of various chemicals, even down to single molecular scale. Among the diverse candidates for SERS substrates, Au nanoparticles are considered promising due to their fine optical properties, chemical stability and ease of surface modification. Therefore, the fabrication and optical characterization of gold particles on solid supports is highly desirable. Such structures have potential as SERS substrates because the localized surface plasmon resonance of gold nanoparticles is very sensitive to combined molecules and environments. In addition, it is well-known that the properties of Au nanoparticles are strongly dependent on their shape. In this work, arrays of shape-controlled Au nanoparticles were fabricated to exploit their enhanced and reproducible optical properties. First, shape-controlled Au nanoparticles were prepared via seed mediated solution-phase synthesis, including spheres, octahedra, and rhombic dodecahedra. Then, these shape-controlled Au nanoparticles were arranged on a PDMS substrate, which was nanopatterned using soft lithography of poly styrene particles. The Au nanoparticles were selectively located in a pattern of hexagonal spheres. In addition, the shape-controlled Au nanoparticles were arranged in various sizes of PDMS nanopatterns, which can be easily controlled by manipulating the size of polystyrene particles. Finally, the optical properties of the fabricated Au nanoparticle arrays were characterized by measuring surface enhanced Raman spectra with 4-nitrobenezenethiol.

SERS of Dithiocarbamate Pesticides Adsorbed on Silver Surface; Thiram

  • Kang, Jae-Soo;Hwang, Seon-Yeong;Lee, Chul-Jae;Lee, Mu-Sang
    • Bulletin of the Korean Chemical Society
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    • v.23 no.11
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    • pp.1604-1610
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    • 2002
  • In the present work, we studied thiram on silver surface by SERS. Investigations of disulfides with SERS revealed that the molecules undergo a surface reaction on silver, namely easy cleavage of the S-S bond. We believe that the two S atoms of resonance formed from the thiram may be chemisorbed strongly on Ag sol. This resonance form adheres perpendicularly to the Ag surface via the two S atoms, since the ${\delta}(CH3)$ and n (CN) mode perpendicular to the surface showed strong enhancement. The important roles of halide anion adsorption have been discussed and the pH effects of thiram on Ag sol in acidic, neutral, and alkaline conditions were examined.

SERS Analysis of CMC on Gold-Assembled Micelle

  • Jang, Nak-Han
    • Bulletin of the Korean Chemical Society
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    • v.25 no.9
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    • pp.1392-1396
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    • 2004
  • The micellization of dodecylpyridinum chloride (DPC) assembled on aqueous gold nanoparticles has been studied as a function of concentration using Surface-Enhanced Raman Scattering (SERS). At the low concentration, the strong SERS band of the benzene ring moiety was observed at 1025 $cm^{-1}$, and assigned to “trigonal ring breathing”. According to high concentration of DPC, a new strong band was also appeared at 1012 $cm^{-1}$, which was assigned to “totally symmetry ring breathing”. The difference of two spectra seems to ascribe to the geometry of polar head group, i.e., pyridinium cation. These geometry exist flat-down at low concentration, whereas standing-up or tilted geometry at high concentration. The critical micelle concentration (CMC) was first obtained from the ratio of intensities of the two bands related to the benzene ring moiety by vibrational spectroscopy, and was about 28 mM. After the CMC, the benzene ring moiety in the micelle state was more restricted than in monomer state because there is no more change of intensities at 1012 $cm^{-1}$. In addition, the size of gold-assembled micelle was estimated using light scattering and it was about 328.3 nm.

SERS Study of Bromothymol Blue Using the Silver Mirror substrate (Silver Mirror Substrate를 이용한 Bromothymol Blue의 SERS 연구)

  • Lee, Chul-Jae;Jung, Maeng-Joon;Kim, Dong-Yeub
    • Journal of the Korean Society of Industry Convergence
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    • v.15 no.2
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    • pp.43-47
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    • 2012
  • In this study, the experiments for surface enhancement of silver mirror substrate were done, where we checked the characteristics of silver mirror substrate made by Tollen's method. The surface enhancement of Bromothymol blue was analyzed by three kind of silver mirror substrates. The assignments of the vibrational bands shown in SERS spectra are given based on both literature and the semi-empirical calculations at the PM3 methods. Finally, we deduced that the adsorption orientation of bromothymol blue was little tilted flat to the silver mirror surfaces by using of the surface selection rules.

SERS Study of Eriochrome Black T Using the Silver Mirror Substrates (Silver Mirror Substrate를 이용한 Eriochrome Black T의 SERS 연구)

  • Lee, Chul-Jae;Jung, Maeng-Joon;Kim, Dong-Yeub
    • Journal of the Korean Society of Industry Convergence
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    • v.14 no.1
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    • pp.23-27
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    • 2011
  • In this study, the experiments for surface enhancement of silver mirror substrates were done, where we checked the characteristics of silver mirror substrate made by Tollen's method. The surface enhancement of Eriochrome Black T(EBT) was analyzed by silver mirror substrates. We observed the SERS spectra of EBT. The assignments of the vibrational bands shown in SERS spectra are given based on both literature and the semi-empirical calculations at the PM3 methods. Finally, we deduced that the adsorption orientation of EBT was little tilted perpendicular to the silver mirror surfaces by using of the surface selection rules.

Control of surface metal nanostructure with physical vapor deposition (물리기상증착을 이용한 금속표면 나노구조제어)

  • Jeong, Ji-Hye;Han, Min-A;Kim, Hyeon-Jong;Lee, Ho-Nyeon
    • Proceedings of the Korean Institute of Surface Engineering Conference
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    • 2015.11a
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    • pp.251-251
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    • 2015
  • 최근 질병 조기진단에 대한 사회적 요구가 높아짐에 따라 이에 대한 기술에 관심이 집중되고 있다. 그 중 표면증강라만산란(surface enhanced Raman scattering(SERS))을 이용하여 인체 내 소량의 바이오마커를 검출하는 연구가 활발히 진행중이다. 본 연구에서는 바이오마커의 검지감도를 최대치로 증가시키기 위해 SERS 기판의 나노구조를 최적화 하였다. SERS 기판 표면의 나노구조, 크기, 형상, 밀도 등에 따라 검지감도가 변화되기 때문에 이를 제어하기 위해 증착공정 변수에 변화를 주어 표면의 나노구조를 형성하였다. 이를 분석하기 위해 SEM, XRD를 사용하였으며 최적화된 SERS 기판을 활용하여 Rhodamine 6G의 신호가 $1{\times}10^5$ 이상의 enhancing factor를 확인하였다.

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Characterization of biotin-avidin recognition system constructed on the solid substrate

  • Lim, Jung-Hyurk
    • Analytical Science and Technology
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    • v.18 no.6
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    • pp.460-468
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    • 2005
  • The biotin-avidin complex, as a model recognition system, has been constructed through N-hydroxysuccinimide(NHS) reaction on a variety of substrates such as a smooth Au film, electrochemically roughened Au electrode and chemically modified mica. Stepwise self-assembled monolayers (SAMs) of biotin-avidin system were characterized by surface-enhanced resonance Raman scattering (SERRS) spectroscopy, atomic force microscopy (AFM) and surface plasmon resonance (SPR). A strong SERRS signal of rhodamine tags labeled in avidin from the SAMs on a roughened gold electrode indicated the successful complex formation of stepwise biotin-avidin recognition system. AFM images showed the circular shaped avidin aggregates (hexamer) with ca. $60{\AA}$ thick on the substrate, corresponding to one layer of avidin. The surface coverage and concentration of avidin molecules were estimated to be 90% and $7.5{\times}10^{-12}mol/cm^2$, respectively. SPR technique allowed one to monitor the surface reaction of the specific recognition with high sensitivity and precision.

Effect of Substrate Bias Voltage on DLC Films Prepared by ECR-PECVD (ECR-PECVD 방법으로 제작된 DLC 박막의 기판 Bias 전압 효과)

  • 손영호;정우철;정재인;박노길;김인수;김기홍;배인호
    • Journal of the Korean Vacuum Society
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    • v.9 no.4
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    • pp.328-334
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    • 2000
  • DLC (Diamond-Like Carbon) films were deposited by ECR-PECVD (electron cyclotron resonance plasma-enhanced chemical vapor deposition) method with the variation of substrate bias voltage under the others are constant except it. We have investigated the ion bombardment effect induced by the substrate bias voltage on films during the deposition of film. The characteristics of the film were analyzed using the Dektak surface profiler, SEM, FTIR spectroscopy, Raman spectroscopy and Nano Indentation tester. FTIR spectroscopy analysis shows that the amount of dehydrogenation in films was increased with the increase of substrate bias voltage and films thickness was decreased. Raman scattering analysis shows that integrated intensity ratio $(I_D /I_G)$ of the D and G peak was increased as the substrate bias voltage increased, and films hardness was increased. From these results, it can be concluded that films deposited at this experimental have the enhanced characteristics of DLC because of the ion bombardment effect on films during the deposition of film.

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Synthesis of Shape Controlled Pd Nanoparticles and Surface-Induced Photoreduction of 4-Nitrobenzenethiol on Pd (모양이 조절된 팔라듐 나노입자의 합성과 4-나이트로벤젠 사이올의 광환원 반응)

  • Lee, Young Wook;Shin, Tae Ho
    • Journal of the Korean Institute of Electrical and Electronic Material Engineers
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    • v.32 no.6
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    • pp.458-461
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    • 2019
  • The facile synthesis of shape-controlled Pd nanoparticles (PdNPs) with ascorbic acid as a reducing agent and cetyltrimethylammonium bromide (CTAB) as a capping agent is presented in this study. The synthesized PdNPs were characterized by UV-vis spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), and Raman Spectroscopy. The prepared PdNPs show efficient surface-enhanced Raman scattering (SERS) properties. SERS studies on the adsorption characteristics of 1,4-phenylene diisocyanide (1,4-PDI) on colloidal PdNPs have revealed that the relative peak intensity of the $(NC)_{free}$ and $(NC)_{bound}$ modes distinctly depends on the 1,4-PDI concentration as well as the shape of the PdNPs. Furthermore, we found that the PdNPs are also efficient photoelectron emitters such that the SERS spectrum of 4-nitrobenzenethiol (4-NBT) on PdNPs is readily converted to that of 4-aminobenzenethiol (4-ABT) under 632.8 nm radiation.