The Surface Plasmon Resonance of Supported Noble Metal Nanoparticles: Characterization, Laser Tailoring, and SERS Application

This work deals with the optical properties of supported noble metal nanoparticles, which are dominated by the so-called Mie resonance and are strongly dependent on the particles’ morphology. For this reason, characterization and control of the dimension of these systems are desired in order to optimize their applications. Gold and silver nanoparticles have been produced on dielectric supports like quartz glass, sapphire and rutile, by the technique of vapor deposition under ultra-high vacuum conditions. During the preparation, coalescence is observed as an important mechanism of cluster growth. The particles have been studied in situ by optical transmission spectroscopy and ex situ by atomic force microscopy. It is shown that the morphology of the aggregates can be regarded as oblate spheroids. A theoretical treatment of their optical properties, based on the quasistatic approximation, and its combination with results obtained by atomic force microscopy give a detailed characterization of the nanoparticles. This method has been compared with transmission electron microscopy and the results are in excellent agreement. Tailoring of the clusters’ dimensions by irradiation with nanosecond-pulsed laser light has been investigated. Selected particles are heated within the ensemble by excitation of the Mie resonance under irradiation with a tunable laser source. Laser-induced coalescence prevents strongly tailoring of the particle size. Nevertheless, control of the particle shape is possible. Laser-tailored ensembles have been tested as substrates for surface-enhanced Raman spectroscopy (SERS), leading to an improvement of the results. Moreover, they constitute reproducible, robust and tunable SERS-substrates with a high potential for specific applications, in the present case focused on environmental protection. Thereby, these SERS-substrates are ideally suited for routine measurements.

Synthesis, spectroscopy and spectroelectrochemistry of chlorocarbonyl {1,2-bis[(2,6-diisopropylphenyl)imino]-acenaphthene-kappa(2)-N,N '}rhodium (I)

Reaction of the dinuclear complex [{Rh(CO)(2)}(2) (mu-Cl)(2)]with an alpha-diimine ligand, 1,2- bis[(2,6-diisopropylphenyl) imino] acenaphthene (iPr(2)Ph-bian), produces square-planar [RhCl(CO)(iPr(2)Ph-bian)]. For the first time, 2: 1 and 1: 1 alpha-diimine/dimer reactions yielded the same product. The rigidity of iPr(2)Ph-bian together with its flexible electronic properties and steric requirements of the 2,6-diisopropyl substituents on the benzene rings allow rapid closure of a chelate bond and replacement of a CO ligand instead of chloride. A resonance Raman study of [RhCl(CO)(iPr(2)Ph-bian)] has revealed a predominant Rh-to-bian charge transfer (MLCT) character of electronic transitions in the visible spectral region. The stabilisation of [RhCl(CO)(iPr(2)Ph-bian)] in lower oxidation states by the pi-acceptor iPr(2)Ph-bian ligand was investigated in situ by UV-VIS, IR and EPR spectroelectrochemistry at variable temperatures. The construction of the novel UV-VIS-NIR-IR low-temperature OTTLE cell used in these studies is described in the last part of the paper.

Fano resonance in heavily doped porous silicon

Unexpectedly, the Fano resonance caused by the interference of continuum electron excitations with the longitudinal optical (LO) phonons was observed in random porous Si by Raman scattering. The analysis of the experimental data shows that the electron states trapped at the Si-SiO(2) interface dominate in the observed Raman scattering. The gap energy associated with the interface states was determined. Copyright (C) 2011 John Wiley & Sons, Ltd.

Raman, IR, UV-vis and EPR characterization of two copper dioxolene complexes derived from L-dopa and dopamine

The anionic complexes [Cu(L(1-))(3)](1-), L(-) = dopasemiquinone or L-dopasemiqui none, were prepared and characterized. The complexes are stable in aqueous solution showing intense absorption bands at ca. 605 nm for Cu(II)-L-dopasemiquinone and at ca. 595 nm for Cu(II)-dopasemiquinone in the UV-vis spectra, that can be assigned to intraligand transitions. Noradrenaline and adrenaline, under the same reaction conditions, did not yield Cu-complexes, despite the bands in the UV region showing that noradrenaline and adrenaline were oxidized during the process. The complexes display a resonance Raman effect, and the most enhanced bands involve ring modes and particularly the vCC + vCO stretching mode at ca. 1384 cm(-1). The free radical nature of the ligands and the oxidation state of the Cu(II) were confirmed by the EPR spectra that display absorptions assigned to organic radicals with g= 2.0005 and g = 2.0923, and for Cu(II) with g = 2.008 and g = 2.0897 for L-dopasemiquinone and dopasemiquinone, respectively. The possibility that dopamine and L-dopa can form stable and aqueous-soluble copper complexes at neutral pH, whereas noradrenaline and adrenaline cannot, may be important in understanding how Cu(II)-dopamine crosses the cellular membrane as proposed in the literature to explain the role of copper in Wilson disease. (c) 2008 Elsevier B.V. All rights reserved.

Reaction of a model siderophore with Ni(II), Co(II) and Zn(II) in aqueous solution: Kinetics and spectroscopy

A spectroscopic study was performed showing that the [Fe(III)(L(2-))(2)](1-) (L(2-) = dopacatecholate) complex reacts with Ni(II), Co(II) and Zn(II) in an aqueous solution containing S(2)O(3)(2-) resulting in the soluble [M(L(1-))(3)](1-) (L(1-) = dopasemiquinone; M = Ni(II), Co(II) or Zn(II) complex species. The Raman and IR spectra of the [CTA][M(L(1-))(3)] complexes, CTA hexadecyltrimethylammonium cation, in the solid state were obtained. The kinetic constants for the metal substitution reactions were determined at four different temperatures, providing values for Delta W(not equal) Delta S(not equal) and Delta G(not equal). The reactions were slow (k = 10(-1)1 M s(-1)) and endothermic. The system investigated can be considered as a simplified model to explain some aspects of siderophore chemistry. (c) 2007 Elsevier Inc. All rights reserved.

Surface-enhanced Raman study of electrochemical and photocatalytic degradation of the azo dye Janus Green B

The photocatalytic degradation of Janus Green B azo dye over silver modified titanium dioxide films was investigated by surface-enhanced Raman spectroscopy (SERS). An optimized SERS-active substrate was employed to study the photodegradation reaction of Janus Green B. Considering that photocatalytic degradation processes of organic molecules adsorbed on TiO2 might involve either their oxidation or reduction reaction, the vibrational spectroelectrochemical study of the dye was also performed, in order to clarify the transformations involved in initial steps of its photochemical decomposition. In order to understand the changes in Raman spectra of Janus Green B after photodegradation and/or electrochemical processes, a vibrational assignment of the main Raman active modes of the dye was carried out, based on a detailed resonance Raman profile. Products formed by electrochemical and photochemical degradation processes were compared. The obtained results revealed that the first steps of the degradation process of Janus Green B involve a reductive mechanism. (C) 2007 Published by Elsevier B.V.

The role of cross-linking structures to the formation of one-dimensional nano-organized polyaniline and their Raman fingerprint

In the present work. the resonance Raman. UV-vis-NIR and scanning electron microscopic (SEM) data of nanorods (about similar to 300 rim in diameter) and nanofibers (about similar to 93 nm in diameter) of PANI are presented and compared. The PANI samples were synthesized in aqueous media with dodecybenzenesulfonic acid (DBSA) and beta-naphtalenesulfonic acid (beta-NSA) as dopants, respectively. The presence of hands at 578, 1400 and 1632cm(-1) in the Raman spectra of PANI-NSA and PANI-DBSA shows that the formation of cross-linking structures is a general feature of the PANI chains prepared in micellar media. It is proposed that these structures are responsible for the one-dimensional PANI morphology formation. In addition, the Raman band at 609cm(-1) of PANI fibers is correlated with the extended PANI chain coil formation. (C) 2008 Elsevier B.V. All rights reserved.

Surface-enhanced Raman scattering and micro-Raman imaging of Langmuir-Blodgett films of rhodium phthalocyanine

Rhodium phthalocyanine (RhPc) was synthesized and ultra thin Langmuir-Blodgett (LB) films of RhPc were successfully fabricated. The LB film characterization was carried out using both UV-vis absorption spectra and Raman scattering. The Raman spectroscopy was carried out using 633 and 780 nm laser lines. LB films were deposited onto Ag nanoparticles to achieve the surface-enhanced pre-resonance Raman scattering (pre-SERRS) and surface-enhanced Raman scattering (SERS) for both laser lines, respectively, which allowed the characterization of the RhPc ultra thin films. The morphology of the LB RhPc neat film is extracted from micro-Raman imaging. (C) 2003 Elsevier B.V. All rights reserved.

Incorporation of Ag nanoparticles into membrane mimetic systems composed by phospholipid layer-by-layer (LbL) films to achieve surface-enhanced Raman scattering as a tool in drug interaction studies

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

V(2)O(5)/TiO(2) catalytic xerogels raman and EPR studies

Raman spectroscopy and Electron Paramagnetic Resonance (EPR) studies were performed on a series of V(2)O(5)/TiO(2) catalysts prepared by a modified sol-gel method in order to identify the vanadium species. Two species of surface vanadium were identified by Raman measurements, monomeric vanadyls and polymeric vanadates. Monomeric vanadyls are characterized by a narrow Raman band at 1030 cm(-1) and polymeric vanadates by two broad bands in the region from 900 to 960 cm(-1) and 770 to 850 cm(-1). The Raman spectra do not exhibit characteristic peaks of crystalline V(2)O(5). These results are in agreement with those of X-ray Diffractometry (XRD) and Fourier Transform Infrared (FT-IR) previously reported (C.B. Rodella et al., J. Sol-Gel Sci. Techn., submitted). At least three families of V(4+) ions were identified by EPR investigations. The analysis of the EPR spectra suggests that isolated V(4+) ions are located in sites with octahedral symmetry substituting for Ti(4+) ions in the rutile structure. Magnetically interacting V(4+) ions are also present as pairs or clusters giving rise to a broad and structureless EPR line. At higher concentration of V(2)O(5), a partial oxidation of V(4+) to V(5+) is apparent from the EPR results.

Structural study of thin films prepared from tungstate glass matrix by Raman and X-ray absorption spectroscopy

Thin films were prepared using glass precursors obtained in the ternary system NaPO(3)-BaF(2)-WO(3) and the binary system NaPO(3)-WO(3) with high concentrations of WO(3) (above 40% molar). Vitreous samples have been used as a target to prepare thin films. Such films were deposited using the electron beam evaporation method onto soda-lime glass substrates. Several structural characterizations were performed by Raman spectroscopy and X-ray Absorption Near Edge Spectroscopy (XANES) at the tungsten L(I) and L(III) absorption edges. XANES investigations showed that tungsten atoms are only sixfold coordinated (octahedral WO(6)) and that these films are free of tungstate tetrahedral units (WO(4)). In addition, Raman spectroscopy allowed identifying a break in the linear phosphate chains as the amount of WO(3) increases and the formation of P-O-W bonds in the films network indicating the intermediary behavior of WO(6) octahedra in the film network. Based on XANES data, we suggested a new attribution of several Raman absorption bands which allowed identifying the presence of W-O and W=O terminal bonds and a progressive apparition of W-O-W bridging bonds for the most WO(3) concentrated samples (above 40% molar) attributed to the formation of WO(6) clusters. (C) 2008 Elsevier B.V. All rights reserved.

Structural study of tungstate fluorophosphate glasses by Raman and X-ray absorption spectroscopy

Transparent glasses were synthesized in the NaPO3-BaF2 WO3 tertiary system and several structural characterizations were performed by X-ray absorption spectroscopy (XANES) at the tungsten L-I and L-III absorption edges and by Raman spectroscopy. Special attention was paid to the coordination state of tungsten atoms in the vitreous network.XANES investigations showed that tungsten atoms are only six-fold coordinated (octahedra WO6) and that these glasses are free of tungstate tetrahedra (WO4).In addition, Raman spectroscopy allowed to identify a break in the linear phosphate chains as the amount of WO3 increases and the formation of P-O-W bonds in the vitreous network indicating the modifier behavior of WO6 octahedra in the glass network. Based on XANES data, we suggested a new attribution of several Raman absorption bands which allowed to identify the presence of W-O- and W=O terminal bonds and a progressive apparition of W-O-W bridging bonds for the most WO3 concentrated samples (≥ 30% molar) due to the formation of WO6 clusters. © 2004 Elsevier B.V. All rights reserved.

Metal-Organic Semiconductor Nanostructures for Surface-Enhanced Raman Scattering

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Large-Area Plasmonic Substrate of Silver-Coated Iron Oxide Nanorod Arrays for Plasmon-Enhanced Spectroscopy

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Substrato flexível portátil para detecção e análises químicas usando fenômenos de amplificação sers e serrs por espectroscopia micro-raman e processo de obtenção do dito substrato

É descrita a invenção de um substrato flexível portátil para detecção e análises químicas usando fenômenos de amplificação sers e serrs por espectroscopia micro-raman e processo de obtenção do dito substrato. É descrita a invenção de um substrato flexível portátil para detecção e análises químicas usando fenômenos de amplificação sers (surface enhanced raman spectroscopy) e serrs (surface-enhanced resonance spectroscopy) por espectroscopia micro-raman e respectivo processo de obtenção do dito substrato que provê um substrato de borracha natural impregnando com nanopartículas de ouro.