Photonic crystals in biology

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Poster Session, Tuesday, June 15 Synthesis of Pyrogallol-Formaldehyde Nano Resin and Usage as an Adsorbent Mustafa Can 1 *, Emrah Bulut 2 and Mahmut Özacar 2 1 Sakarya University, Institute of Sciences and Technology , 54187 Sakarya, Turkey 2 Sakarya University, Department of Chemistry, 54187 Sakarya, Turkey Theme A1 - B702 Abstract- Pyrogallol (PG) and formaldehyde condensation reaction was carried out to prepare the pyrogallol-formaldehyde nano resin (PGNR). Polymerization of formaldehyde with PG was performed at optimal conditions obtained from literature to establish the nano resin formulation. Obtained nano resin was used as adsorbent for adsorption of rhodium (III) ions from solutions. PGNR was characterized by SEM, EDS and FTIR-ATR spectroscopy, respectively. Conventional syntheses of polyphenol resins are classified into chemical and enzymatic methods. In the chemical methods, phenol reacts with formaldehyde in acidic or alkaline media, forming novolac and resol resins. These polymers characteristically possess high mechanical strength, durability to chemicals, and insulation properties, and thus have applications in the automobile and electrical industries. The phenol unit in polyphenol as an electron donor is oxidized to quinone, and the nobel metal ions accept electrons from the polyphenol, generating nobel metal particles. Nobel metal particle growth via electrontransfer reactions between organic molecules and metal ions has been used in the field of nanobiotechnology to develop novel bioelectronics and biosensor systems [1]. Pyrogallol (PG) consist of an aromatic ring bearing three adjacent hydroxyl groups (position 1,2 and 3), leaving three free sites on the ring. Reactivity considerations show that the hydroxyl functions enhance the reactivity of positions 4 and 6. The remaining position (5) whould have the same degree of activation as phenol. These three possible reactive sites permit the eventual formation of a tridimensional network during polymerization as in the case of phenol. Thus, we decided to study the reactivity of PG in the synthesis of PGNR [2]. Alkaline-catalyzed PGNR are prepared similar to phenolformaldehyde resins. There are two steps leading to formation of PGNR: methylolation and condensation reactions. Adsorption capacity of PGNR was found to be 32 mg/g Rh (III) from Langmuir isotherm. The morphology and size of PGNR was investigated using SEM and the SEM image was showed in Fig. 1. The FTIR spectra analysis of PG, PGNR and Rh adsorbed PGNR were caried out [2, 3]. Figure 2 represent the FTIR-ATR spectra of PG, PGNR and Rh adsorbed PGNR. The main bands and their assigments in PG are as follows: stretching vibrations of the aromatic ring (C-C)/(C=C) at 1620, 1518, 1483, 1361 cm -1 , stretching vibrations of the phenolic group (C-OH) at 1518, 1313, 1286, 1242, 996 cm -1 , bending vibrations of the phenolic group (C-OH) at 1483, 1362, 1186, 1156 cm-1 and bending (C-H) at 1138, 1061 cm -1 . Formation of PGR leads to obvious changes in FTIR spectra: complete disappearance of the bands at 1518, 1362, 847 to 762 cm -1 , shiff of the band at 1043 to 996 cm -1 . The band intensities between 1314 and 1061 cm -1 are reduced and some of them are combined in the spectrum of the PGNR. This situation may be attributed to the phenolic –OH groups. Also, the formation of –CH 2 – O – CH 2 – linkage appeared at 1198 cm -1 . The peak intensities at 1517 and 1483 cm -1 is reduced due to the formation of – CH 2 – linkage [4-6]. When the spectra Figure 1. SEM image of PGNR Figure 2. FTIR spectra of PG, PGNR and Rh adsorbed PGNR of Rh adsorbed PGNR were compared with the spectrum of the PGNR, the small peak serias at 1294 and 1043 cm -1 are combined and reduced peak intensities, because of PGNR-Rh complex formation between Rh and some phenolic groups of PGNR [4-6]. This study was supported by the Scientific Research Projects Commission of Sakarya University (Project number: 2009 50 02 005). *Corresponding author: 0Tmstfacan@gmail.com [1] K. Hamamoto, H. Kawakita, K. Ohto, and K. Inoue, React. Funct. Polym. 69, 694 (2009). [2] J. M. Garro-Galvez and B. Riedl, J. Appl. Polym. Sci. 65, 399 (1997). [3] S. Kim and H.J. Kim, J. Appl. Polym. Sci. 17, 1369 (2003). [4] Y.K. Lee, H.J. Kim, M. Rafailovich and J. Sokolov, Int. J. Adhes. 22, 375 (2002). [5] M. Özacar, C. Soykan 102, 786 (2006). [6] I. Mohammed-Ziegler and F. Billes, J. Mol. Struct. 618, 259 (2002). 6th Nanoscience and Nanotechnology Conference, zmir, 2010 230
Poster Session, Tuesday, June 15 Theme A1 - B702 Inve stigation of SERS of orga nic molecule bridge d go ld nanoparticles: Synthesis and charac terization Remziye Gü zel 1 *, , 2 3 and Ali Osman Solak 3 1 2 Dum 3 Ankara University, Faculty of Science, Department of Chemistry, Ankara, Turkey Abstract -We describe the short range SERS effect of AuNP by bridging them with an organic molecule, HS(CH 2 ) 2 CONHPhSH, which has very low inherent sensitivity of Raman scattering. The nanoparticles are contacted by S(CH 2 ) 2 CONHPhS- linker bridges in which presence of different heteroatoms and functionalities makes it interesting for characterization by XPS, UV, RAIRS, EIS, TEM, Fluorescence microscopy and SERS. In recent years, investigation of nanomaterials, especially metal nanoparticles, has attracted much importance, because of their interesting chemical, mechanical and physical properties and potential applications in nanoelectronic and optoelectronic devices. Nowadays, much effort has been committed to fabrication of metal nanocomposites, including alloys, core-shell and mixed particles, due to their valuable non-linear optical properties in optical switches [1,2], in catalysis [3,4] and in surface-enhanced Raman scattering (SERS) [5]. Nanostructured materials that can be tailored to achieve greater mechanical properties along with their electrical, optical, thermal and other functional properties are essential for future applications in many industry sectors. The electronic conduction of many different metal/organic/metal systems has been studied experimentally [6]. The thiol group forms a strong chemical bond to the gold surface. In the case of physisorption, the molecule is bound to the surface by weak Van der Waals forces [7]. In this work, we describe the short range SERS effect of AuNP by bridging with an organic molecule, HS(CH 2 ) 2 CONHPhSH, which has very low inherent sensitivity of Raman scattering. We construct the AuS(CH 2 ) 2 CONHPhSAu assembly in a step by step fashion which allows us to follow the route of synthesis spectroscopically and to investigate the individual SERS effects of mono nanoparticles on the organic bridge. To achieve this goal, firstly we describe the monolayer attachment of mercaptopropionic acid (MPA) to the AuNPs to construct MPA self assembled gold nanoparticles, AuS(CH 2 ) 2 COOH. In the second step, the carboxylic acid terminated self assembled monolayer (SAM) film surrounding the AuNPs is activated with N-(3- dimethylaminopropyl)-N-ethylcarbodiimide hydrochloride (EDC) to bind 4-aminothiophenol (ATP) to the AuS(CH 2 ) 2 COOH forming a dithiol terminated protective organic film (AuS(CH 2 ) 2 CONHPhSH). Lastly, Au nanoparticles are bridged to this structure through the terminal SH groups to construct the organic film bridged AuS(CH2) 2 CONHPhSAu assembly. Then, we have investigated the enhancement of the Raman signals of the organic wire between metal nanoparticles by the accumulation of the MPCs and assemblies on the glassy carbon (GC) surface. The nanoparticles are contacted by - S(CH 2 ) 2 CONHPhS- linker bridges in which presence of different heteroatoms and functionalities makes it interesting for characterization by XPS, UV-Vis, RAIRS, EIS, Fluorescence microscopy and SERS. We emphasize the effect of plasmon coupling on the S(CH 2 ) 2 CONHPhS- bridge between Au and Au nanoparticles. This effect can be exploited to build new nanostructure architectures in the fabrication of single molecule detection biosensors. Formula Structure AuS(CH 2 ) 2 COOH O S OH AuS(CH 2 ) 2 CONHPhSH O S NH AuS(CH 2 ) 2 CONHPhSAu O S NH Figure 1. Formula and structures of MPCs and nanoparticle-organic molecule assembly forms [1]. I would like to thank Prof. Dr. Ali Osman SOLAK who presenting us his research laboratory for our experiments *Corresponding author: 0Tguzel.remziye@gmail.com [1] Twardowski, M., Nuzzo, R- G., 2002. Chemically mediated grain growth in nanotextured Au and Au/Cu thin films: Novel substrates for the formation of self-assembled monolayers, Langmuir, 18: 5529-5538. [2] Lal, S., Taylor, R-N., Jackson, J-B., Westcott, S-L., Nordlander, P., Halas, N-J., 2002. Light interaction between gold nanoshells plasmon resonance and planar optical waveguides, J. Phys. Chem. B 106: 5609-5612. [3] Tsai, S-H., Liu, Y-H., Wu, P-L., Yeh, C-S., 2003. Preparation of Au-Ag-Pd trimetallic nanop articles and their application as catalysts, J. Mater. Chem. 13: 978-980. [4] Wang, A-Q., Liu, J-H., Lin, S-D., Lin, T-S., Mou, C-Y., 2005. A novel efficient Au-Ag alloy catalyst systems: preparation, activity, and characterization, J. Catal. 233: 186-190. [5] Lu, L., Zhang, H., Sun, G., Xi, S., Wang, H., 2003. Aggregation-based fabrication and assembly of roughened composite metallic nanoshells: Application in surface-enhanced raman scattering, Langmuir 19: 9490-9493. [6] Reed M.A., Zhou, C., Muller, C-J., Burgin, T-P., Tour, J-M., 1997. Conductance of a molecular junction, Science, 278: 252-254. [7] Mujica, V., Kemp, M., Ratner, M.A., 1994. Electron conduction in moleculer wires. I.A scattering formalism, J. Chem. Phys. 101: 6849-6856. S SH 6th Nanoscience and Nanotechnology Conference, zmir, 2010 231
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