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Systems redox biology analysis of cancerJohnston, Hannah Elizabeth January 2018 (has links)
The Warburg effect describes the survival advantage of cancer cells in that they can proliferate under low oxygen/hypoxic conditions via a less efficient pathway known as glycolysis. It has not yet been documented at which point, in an oxygen gradient, phenotypic changes occur. Measuring the intracellular redox potential (IRP) and its impact on cellular dynamics would provide greater insight into how disruption of redox homeostasis caused by changes in oxygen concentration leads to aberrant cell signalling and diseases such as cancer. Current techniques in measuring IRP include redox-sensitive fluorescent proteins such as roGFP which is glutathione-specific. Measuring the concentration of one redox couple is, however, not an accurate representation of IRP as it does not necessarily inform about the state of other redox couples. Furthermore, fluorescent biosensors can suffer from photobleaching and may interact with other oxidants. The IRP was measured, in this work, using our newly developed novel-class of surface enhanced Raman scattering nanoparticles which can quantitatively measure the redox potential of cells in vitro. A 'homemade' device was created to keep the cells under fixed pO2 whilst obtaining measurements. The IRP was correlated with the transcriptomic and downstream metabolic profiles of MCF7 breast cancer cells, under perturbed pO2, using 1H NMR spectroscopy (NMR), mass spectrometry (MS) and RNA-sequencing. Discriminatory metabolites were all associated with energy and glucose metabolism. Discriminatory microRNAs were all affiliated with the hallmarks of cancer; the regulation of some is controlled by transcription factors containing redox-sensitive motifs in their DNA binding domains. Multivariate analysis techniques were used to analyse the different data streams in a holistic way that allows the correlation of redox potential, metabolism and transcription.
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Advanced SERS Sensing System With Magneto-Controlled Manipulation Of Plasmonic NanoprobesKhoury, Christopher G. January 2012 (has links)
<p>There is an urgent need to develop practical and effective systems to detect diseases, such as cancer, infectious diseases and cardiovascular diseases.</p><p>Nanotechnology is a new, maturing field that employs specialized techniques to detect and diagnose infectious diseases. To this end, there have been a wealth of techniques that have shown promising results, with fluorescence and surface-enhanced Raman scattering being two important optical modalities that are utilized extensively. The progress in this specialized niche is staggering and many research groups in academia, as well as governmental and corporate organizations, are avidly pursuing leads which have demonstrated optimistic results.</p><p>Although much fundamental science is still in the pipeline under the guise of both ex-vivo and in-vivo testing, it is ultimately necessary to develop diagnostic devices that are able to impact the greatest number of people possible, in a given population. Such systems make state-of-the-art technology platforms accessible to a large population pool. The development of such technologies provide opportunities for better screening of at-risk patients, more efficient monitoring of disease treatment and tighter surveillance of recurrence. These technologies are also intrinsically low cost, facilitating the large scale screening for disease prevention.</p><p>Fluorescence has long been established as the optical transduction method of choice, because of its wealth of available dyes, simple optical system, and long heritage from pathology. The intrinsic limitations of this technique, however, have given rise to a complementary, and more recent, modality: surface-enhanced Raman scattering (SERS). There has been an explosive interest in this technique for the wealth of information it provides without compromising its narrow spectral width.</p><p>A number of novel studies and advances are successively presented throughout this study, which culminate to an advanced SERS-based platform in the last chapter.</p><p>The finite element method algorithm is critically evaluated against analytical solutions as a potential tool for the numerical modeling of complex, three-dimensional nanostructured geometries. When compared to both the multipole expansion for plane wave excitation, and the Mie-theory with dipole excitation, this algorithm proves to provide more spatially and spectrally accurate results than its alternative, the finite-difference time domain algorithm.</p><p>Extensive studies, both experimental and numerical, on the gold nanostar and Nanowave substrate for determining their potential as SERS substrates, constituted the second part of this thesis. The tuning of the gold nanostar geometry and plasmon band to optimize its SERS properties were demonstrated, and significant 3-D modeling was performed on this exotic shape to correlate its geometry to the solution's exhibited plasmon band peak position and large FWHM. The Nanowave substrate was experimentally revived and its periodic array of E-field hotspots, which was until recently only inferred, was finally demonstrated via complex modeling.</p><p>Novel gold- and silver- coated magnetic nanoparticles were synthesized after extensive tinkering of the experimental conditions. These plasmonics-active magnetic nanoparticles were small and displayed high stability, were easy to synthesize, exhibited a homogeneous distribution, and were easily functionalizable with Raman dye or thiolated molecules.</p><p>Finally, bowtie-shaped cobalt micromagnets were designed, modeled and fabricated to allow the controllable and reproducible concentrating of plasmonics-active magnetic nanoparticles. The external application of an oscillating magnetic field was accompanied by a cycling of the detected SERS signal as the nanoparticles were concentrated and re-dispersed in the laser focal spot. This constituted the first demonstration of magnetic-field modulated SERS; its simplicity of design, fabrication and operation opens doors for its integration into diagnostic devices, such as a digital microfluidic platform, which is another novel concept that is touched upon as the final section of this thesis.</p> / Dissertation
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Engineering Gold Nanorod-Based Plasmonic Nanocrystals for Optical ApplicationsHuang, Jianfeng 09 1900 (has links)
Plasmonic nanocrystals have a unique ability to support localized surface plasmon resonances and exhibit rich and intriguing optical properties. Engineering plasmonic nanocrystals can maximize their potentials for specific applications. In this dissertation, we developed three unprecedented Au nanorod-based plasmonic nanocrystals through rational design of the crystal shape and/or composition, and successfully demonstrated their applications in light condensation, photothermal conversion, and surface-enhanced Raman spectroscopy (SERS). The “Au nanorod-Au nanosphere dimer” nanocrystal was synthesized via the ligand-induced asymmetric growth of a Au nanosphere on a Au nanorod. This dimeric nanostructure features an extraordinary broadband optical absorption in the range of 400‒1400nm, and it proved to be an ideal black-body material for light condensation and an efficient solar-light harvester for photothermal conversion. The “Au nanorod (core) @ AuAg alloy (shell)” nanocrystal was built through the epitaxial growth of homogeneously alloyed AuAg shells on Au nanorods by precisely controlled synthesis. The resulting core-shell structured, bimetallic nanorods integrate the merits of the AuAg alloy with the advantages of anisotropic nanorods, exhibiting strong, stable and tunable surface plasmon resonances that are essential for SERS applications in a corrosive environment. The “high-index faceted Au nanorod (core) @ AuPd alloy (shell)” nanocrystal was produced via site-specific epitaxial growth of AuPd alloyed horns at the ends of Au nanorods. The AuPd alloyed horns are bound with high-index side facets, while the Au nanorod concentrates an intensive electric field at each end. This unique configuration unites highly active catalytic sites with strong SERS sites into a single entity and was demonstrated to be ideal for in situ monitoring of Pd-catalyzed reactions by SERS. The synthetic strategies developed here are promising towards the fabrication of novel plasmonic nanocrystals with fascinating properties for nanoplasmonics and nanophotonics.
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Label-free plasmonic detection using nanogratings fabricated by laser interference lithographyHong, Koh Yiin 02 January 2017 (has links)
Plasmonics techniques, such as surface plasmon resonance (SPR) and surface-enhanced Raman scattering (SERS), have been widely used for chemical and biochemical sensing applications. One approach to excite surface plasmons is through the coupling of light into metallic grating nanostructures. Those grating nanostructures can be fabricated using state-of-the-art nanofabrication methods. Laser interference lithography (LIL) is one of those methods that allow the rapid fabrication of nanostructures with a high-throughput. In this thesis, LIL was combined with other microfabrication techniques, such as photolithography and template stripping, to fabricate different types of plasmonic sensors. Firstly, template stripping was applied to transfer LIL-fabricated patterns of one-dimensional nanogratings onto planar supports (e.g., glass slides and plane-cut optical fiber tips). A thin adhesive layer of epoxy resin was used to facilitate the transfer. The UV-Vis spectroscopic response of the nanogratings supported on glass slides demonstrated a strong dependency on the polarization of the incident light. The bulk refractive index sensitivities of the glass-supported nanogratings were dependent on the type of metal (Ag or Au) and the thickness of the metal film. The described methodology provided an efficient low-cost fabrication alternative to produce metallic nanostructures for plasmonic chemical sensing applications. Secondly, we demonstrated a versatile procedure (LIL either alone or combined with traditional laser photolithography) to prepare both large area (i.e. one inch2) and microarrays (μarrays) of metallic gratings structures capable of supporting SPR excitation (and SERS). The fabrication procedure was simple, high-throughput, and reproducible, with less than 5 % array-to-array variations in geometrical properties. The nanostructured gold μarrays were integrated on a chip for SERS detection of ppm-level of 8-quinolinol, an emerging water-borne pharmaceutical contaminant. Lastly, the LIL-fabricated large area nanogratings have been applied for SERS detection of the mixtures of quinolone antibiotics, enrofloxacin, an approved veterinary antibiotic, and one of its active metabolite, ciprofloxacin. The quantification of these analytes (enrofloxacin and ciprofloxacin) in aqueous mixtures were achieved by employing chemometric analysis. The limit of quantification of the method described in this work is in the ppm-level, with <10 % SERS spatial variation. Isotope-edited internal calibration method was attempted to improve the accuracy and reproducibility of the SERS methodology. / Graduate / 2018-02-17
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Preparation And Surface Modification Of Noble Metal Nanoparticles With Tunable Optical Properties For Sers ApplicationsKaya, Murat 01 April 2011 (has links) (PDF)
Metal nanostructures exhibit a wide variety of interesting physical and chemical properties, which can be tailored by altering their size, morphology, composition, and environment. Gold and silver nanostructures have received considerable attention for many decades because of their widespread use in applications such as catalysis, photonics, electronics, optoelectronics, information storage, chemical and biological sensing, surface plasmon resonance and surface-enhanced Raman scattering (SERS) detection.
This thesis is composed of three main parts about the synthesis, characterization and SERS applications of shape-controlled and surface modified noble metal nanoparticles. The first part is related to a simple synthesis of shape controlled solid gold, hollow gold, silver, gold-silver core-shell, hollow gold-silver double-shell nanoparticles by applying aqueous solution chemistry. Nanoparticles obtained were used for SERS detection of dye molecules like brilliant cresyl blue (BCB) and crystal violet (CV) in aqueous system.
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The second part involves the synthesis of surface modified silver nanoparticles for the detection of dopamine (DA) molecules. Determination of a dopamine molecule attached to a iron-nitrilotriaceticacid modified silver (Ag-Fe(NTA)) nanoparticles by using surface-enhanced resonance Raman scattering (SERRS) was achieved. The Ag-Fe (NTA) substrate provided reproducibility and excellent sensitivity. Experimental results showed that DA was detected quickly and accurately without any pretreatment in nM levels with excellent discrimination against ascorbic acid (AA) (which was among the lowest value reported in direct SERS detection of DA).
In the third part, a lanthanide series ion (Eu3+) containing silver nanoparticle was prepared for constructing a molecular recognition SERS substrate for the first time. The procedure reported herein, provides a simple way of achieving reproducible and sensitive SERS spectroscopy for organophosphates (OPP) detection. The sensing of the target species was confirmed by the appearance of an intense SERS signal of the methyl phosphonic acid (MPA), a model compound for nonvolatile organophosphate nerve agents, which bound to the surface of the Ag-Eu3+ nanostructure. The simplicity and low cost of the overall process makes this procedure a potential candidate for analytical control processes of nerve agents.
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Application Of Surface-enhanced Raman Scattering (sers) Method For Genetic AnalysesKarabicak, Seher 01 March 2011 (has links) (PDF)
Raman spectroscopy offers much better spectral selectivity but its usage has been limited by its poor sensitivity. The discovery of surface-enhanced Raman scattering (SERS) effect, which results in increased sensitivities of up to 108-fold for some compounds, has eliminated this drawback.
A new SERS active substrate was developed in this study. Silver nanoparticle-doped polyvinyl alcohol (PVA) coated SERS substrate prepared through chemical and electrochemical reduction of silver particles dispersed in the polymer matrix. Performances of the substrates were evaluated with some biologically important compounds.
The specific detection of DNA has gained significance in recent years since increasingly DNA sequences of different organisms are being assigned. Such sequence knowledge can be employed for identification of the genes of microorganisms or diseases. In this study, specific proteasome gene sequences were detected both label free spectrophotometric detection and SERS detection. In label free spectrophotometic detection, proteasome gene probe and complementary target gene sequence were attached to the gold nanoparticles separately. Then, the target and probe oligonucleotide-modified gold solutions were mixed for hybridization and the shift in the surface plasmon absorption band of gold nanoparticles were followed.
SERS detection of specific nucleic acid sequences are mainly based on hybridization of DNA targets to complementary probe sequences, which are labelled with SERS active dyes. In this study, to show correlation between circulating proteasome levels and disease state we suggest a Raman spectroscopic technique that uses SERGen probes. This novel approach deals with specific detection of elevated or decreased levels of proteasome genes&rsquo / transcription in patients as an alternative to available enzyme activity measurement methods. First, SERGen probes were prepared using SERS active labels and specific proteasome gene sequences. Then DNA targets to complementary SERGen probe sequences were hybridized and SERS active label peak was followed.
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High Sensitivity Surface Enhanced Raman Scattering Detection of TryptophanKandakkathara, Archana A Unknown Date
No description available.
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Adsorção molecular em metais de transição (ferro, cobalto e níquel) monitorada pela técnica de espalhamento Raman intensificado pela superfície: diferentes tipos de substratos metálicos / Molecular adsorption on transition metals (iron, cobalt and nickel) monitored by the surface-enhanced Raman scattering technique: several metallic substratesAndrade, Gustavo Fernandes Souza 24 September 2007 (has links)
Nesta tese de doutorado foram desenvolvidas metodologias para obter espectros Raman intensificados pela superficie de adsorbatos orgânicos em eletrodos de Fe, Co e Ni, que são metais que apresentam baixo fator de intensificação SERS. Foram desenvolvidos procedimentos de ativação eletroquímica para eletrodos puros dos três metais. Os protocolos de ativação eletroquímica foram utilizados para obter espectros SERS de piridina, 1,10-fenantrolina e 2- e 4-aminopiridina. O fator de intensificação determinado para o três metais, da ordem de 102-103 vezes, depende fortemente do modo vibracional do adsorbato. Os espectros SERS da piridina nos metais de transição, quando comparados com os cálculos de espectros vibracionais de cluster da piridina com átomos metálicos por DFT mostram que a formação do radical α-piridil com a adsorção nos metais de transição, proposta na literatura, não ocorre. Os perfis de excitação SERS calculados pelo modelo de transferência de carga da piridina apresentaram boa correlação com os dados experimentais. Os resultados SERS para a 1,10-fenantrolina mostraram que a espécie que adsorve é a molécula livre, com a espécie adsorvida semelhante ao complexo sintetizado. A dependência das intensidades relativas com o potencial nos espectros SERS é diferente da observada para os espectros Raman ressonante dos complexos da phen com metais de transição, mostrando que o estado excitado monitorado pelas duas técnicas é diferente. O monitoramento da adsorção das 2-aminopiridinas nos metais de transição permitiu sugerir a adsorção pelo anel piridínico para potenciais menos negativos e através dos nitrogênios piridínico e amínico para potenciais mais negativos em eletrodos de Co e Ni, e para o Fe adsorve apenas pelo nitrogênio piridínico. Em solução eletrolítica 0,1 mol.L-1 KCl, a 4-aminopiridina passa de fracamente ligada para um complexo de superficie semelhante ao complexo sintetizado para potenciais mais negativos. Utilizando a solução eletrolítica 0,1 mol.L-1 KI, as duas espécies são observadas para um intervalo maior de potenciais. No eletrodo de Ni, observa-se 4-aminopiridina protonada para E = -0,7 V; para potenciais mais negativos um complexo de superficie semelhante ao complexo sintetizado é observado. Os filmes eletrodepositados de Co e Ni em eletrodos de Ag ativado eletroquimicamente permitiram a obtenção de espectros SERS da py com alto fator de intensificação. Os filmes com espessuras maiores que 2 monocamadas de Co ou Ni apresentaram bandas intensas da piridina adsorvida nestes metais, sem bandas da piridina adsorvida em Ag, indicando que os filmes não apresentam pinholes, com intensidade SERS 100 vezes maior do que os metais puros. As intensidades relativas dos espectros SERS são similares à obtidas nos espectros SERS da piridina nos metais puros para filmes finos mais espessos do que 7 monocamadas. Foram construídos substratos de Au SERS-ativos com alto desempenho e reprodutibilidade por eletrodeposição sobre uma máscara de microesferas de poliestireno. Os espectros SERS da 4-mercaptopiridina adsorvida nos substratos otimizados apresentaram intensidade 2 vezes maior do que o eletrodo de Au ativado eletroquimicamente. A reprodutibilidade do sinal SERS para estes substratos foi de ± 15 %, indicando que estes substratos podem ser utilizados como sensores para sistemas de interesse analítico. / Surface-enhanced Raman spectra of organic adsorbates on Fe, Co and Ni electrodes were acquired after the development of specific methodologies described in this PhD thesis. Electrochemical activation procedures were developed for the three bare metaIs electrodes. The electrochemical activation protocols were applied for the acquisition of SERS spectra of pyridine, 1,10-phenanthroline and 2- and 4-aminopyridine on Fe, Co e Ni electrodes. The total and relative intensities changes of SERS bands with the applied potentials were explained by the charge transfer mechanism, which had a large contribution in the SERS enhancement for these metaIs. The enhancement factor determined for the three metaIs, on the 102-103 times range, strongly depends on the adsorbate\' s vibrational modes. The SERS spectra of pyridine on the transition metals and vibrational spectra calculations of pyridine with metallic atoms showed that the formation of α-pyridil in the adsorption on transition metaIs, suggested in the literature, didn\'t occur. The calculated pyridine SERS excitation profiles present reasonable correlaton with the experimental data. The SERS results for 1,10-phenanthroline showed that the free molecule was the adsorbing species. The potential dependence of the SERS relative intensities was different from those of the resonance Raman spectra of 1,10-phenanthroline complexes with transition metal ions, indicating that different excited states were probed by the two techniques. 2-aminopyridine adsorbed through the pyridinic ring at less negative potentials and through both pyridinic and aminic nitrogens at more negative potentials on Co and Ni electrodes, but for Fe electrode it adsorbed exclusively through the pyridinic nitrogen. 4-aminopyridine adsorbed perpendicularly to the electrode. In 0,1 mol.L-1 KCl electrolytic solution, 4-aminopyridine changed from weak1y bound to a surface complex similar to the synthesized complex at more negative potentials. In 0,1 mol.L-1 KI electrolytic solution, both species were observed in a larger potential interval. On the Ni electrode, protonated 4aminopyridine was observed for V = -0.7 V, and for more negative potentials a surface complex, similar to the synthesized one, was observed. The electrodeposition of ultrathin film of Co and Ni on electrochemically-activated Ag electrodes allowed obtaining SERS spectra of pyridine with high enhancement factors. The SERS spectra of py for films thickness higher than 2 monolayers of Co or Ni presented intense bands of pyridine adsorbed on these metals, and no bands of pyridine adsorbed on Ag were observed, indicanting the absence of pinholes in the films. The relative intensities of SERS spectra on the thin films were similar to those obtained for the SERS of pyridine on the bare metaIs electrodes for films thicker than 7 monolayers, but with SERS intensity 100 times higher. The SERS activity and signal strength reproducibility of Au nanostructured substrates obtained by electrodeposition on a polystyrene masking were evaluated. The SERS spectra of 4-mercaptopyridine adsorbed on optimized electrodes presented intensities 2 times greater than those of the electrochemically activated Au electrode. The SERS intensity reproducibility for these substrates was ± 15%, indicating the potential use of such substrates as sensors.
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Nanostructured Assemblies Based On Metal Colloids And Monolayers: Preparation, Characterisation And Studies Towards Novel ApplicationsDevarajan, Supriya 07 1900 (has links)
Nanoscience dominates virtually every field of science and technology in the 21st century. Nanoparticles are of fundamental interest since they possess unique size- dependent properties (optical, electrical, mechanical, chemical, magnetic etc.), which are quite different from the bulk and the atomic state. Bimetallic nanoparticles are of particular interest since they combine the advantages of the individual monometallic counterparts.
The present study focuses on bimetallic nanoparticles containing gold as one of the constituents. Au-Pd, Au-Pt and Au-Ag bimetallic/alloy nanoparticles have been prepared by four different synthetic methods, and characterised by a variety of techniques, with an emphasis on Au-Ag alloy systems in the solution phase as well as in the form of nanostructured films on solid substrates. Au- Ag alloy nanoparticles have been used to demonstrate two different applications. The first is the use of Au-Ag monolayer protected alloy clusters in demonstrating single electron charging events in the solution phase as well as in the dry state. Single electron transfer events involving nanosized particles are being probed extensively due to their potential applications in the field of electronics. The second is an analytical application, involving the use of trisodium citrate capped Au-Ag alloy hydrosols as substrates for surface enhanced Raman and resonance Raman scattering [SE(R)RS] studies. The sols have been used for single molecule detection purposes.
Various organic molecules such as quinones, phthalocyanines and methyl violet have been self- assembled in a stepwise manner on the nanoparticulate as well as bulk Au, Ag and Au-Ag surfaces, and characterised extensively by spectroscopic, electrochemical and spectroelectrochemical techniques.
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Adsorção molecular em metais de transição (ferro, cobalto e níquel) monitorada pela técnica de espalhamento Raman intensificado pela superfície: diferentes tipos de substratos metálicos / Molecular adsorption on transition metals (iron, cobalt and nickel) monitored by the surface-enhanced Raman scattering technique: several metallic substratesGustavo Fernandes Souza Andrade 24 September 2007 (has links)
Nesta tese de doutorado foram desenvolvidas metodologias para obter espectros Raman intensificados pela superficie de adsorbatos orgânicos em eletrodos de Fe, Co e Ni, que são metais que apresentam baixo fator de intensificação SERS. Foram desenvolvidos procedimentos de ativação eletroquímica para eletrodos puros dos três metais. Os protocolos de ativação eletroquímica foram utilizados para obter espectros SERS de piridina, 1,10-fenantrolina e 2- e 4-aminopiridina. O fator de intensificação determinado para o três metais, da ordem de 102-103 vezes, depende fortemente do modo vibracional do adsorbato. Os espectros SERS da piridina nos metais de transição, quando comparados com os cálculos de espectros vibracionais de cluster da piridina com átomos metálicos por DFT mostram que a formação do radical α-piridil com a adsorção nos metais de transição, proposta na literatura, não ocorre. Os perfis de excitação SERS calculados pelo modelo de transferência de carga da piridina apresentaram boa correlação com os dados experimentais. Os resultados SERS para a 1,10-fenantrolina mostraram que a espécie que adsorve é a molécula livre, com a espécie adsorvida semelhante ao complexo sintetizado. A dependência das intensidades relativas com o potencial nos espectros SERS é diferente da observada para os espectros Raman ressonante dos complexos da phen com metais de transição, mostrando que o estado excitado monitorado pelas duas técnicas é diferente. O monitoramento da adsorção das 2-aminopiridinas nos metais de transição permitiu sugerir a adsorção pelo anel piridínico para potenciais menos negativos e através dos nitrogênios piridínico e amínico para potenciais mais negativos em eletrodos de Co e Ni, e para o Fe adsorve apenas pelo nitrogênio piridínico. Em solução eletrolítica 0,1 mol.L-1 KCl, a 4-aminopiridina passa de fracamente ligada para um complexo de superficie semelhante ao complexo sintetizado para potenciais mais negativos. Utilizando a solução eletrolítica 0,1 mol.L-1 KI, as duas espécies são observadas para um intervalo maior de potenciais. No eletrodo de Ni, observa-se 4-aminopiridina protonada para E = -0,7 V; para potenciais mais negativos um complexo de superficie semelhante ao complexo sintetizado é observado. Os filmes eletrodepositados de Co e Ni em eletrodos de Ag ativado eletroquimicamente permitiram a obtenção de espectros SERS da py com alto fator de intensificação. Os filmes com espessuras maiores que 2 monocamadas de Co ou Ni apresentaram bandas intensas da piridina adsorvida nestes metais, sem bandas da piridina adsorvida em Ag, indicando que os filmes não apresentam pinholes, com intensidade SERS 100 vezes maior do que os metais puros. As intensidades relativas dos espectros SERS são similares à obtidas nos espectros SERS da piridina nos metais puros para filmes finos mais espessos do que 7 monocamadas. Foram construídos substratos de Au SERS-ativos com alto desempenho e reprodutibilidade por eletrodeposição sobre uma máscara de microesferas de poliestireno. Os espectros SERS da 4-mercaptopiridina adsorvida nos substratos otimizados apresentaram intensidade 2 vezes maior do que o eletrodo de Au ativado eletroquimicamente. A reprodutibilidade do sinal SERS para estes substratos foi de ± 15 %, indicando que estes substratos podem ser utilizados como sensores para sistemas de interesse analítico. / Surface-enhanced Raman spectra of organic adsorbates on Fe, Co and Ni electrodes were acquired after the development of specific methodologies described in this PhD thesis. Electrochemical activation procedures were developed for the three bare metaIs electrodes. The electrochemical activation protocols were applied for the acquisition of SERS spectra of pyridine, 1,10-phenanthroline and 2- and 4-aminopyridine on Fe, Co e Ni electrodes. The total and relative intensities changes of SERS bands with the applied potentials were explained by the charge transfer mechanism, which had a large contribution in the SERS enhancement for these metaIs. The enhancement factor determined for the three metaIs, on the 102-103 times range, strongly depends on the adsorbate\' s vibrational modes. The SERS spectra of pyridine on the transition metals and vibrational spectra calculations of pyridine with metallic atoms showed that the formation of α-pyridil in the adsorption on transition metaIs, suggested in the literature, didn\'t occur. The calculated pyridine SERS excitation profiles present reasonable correlaton with the experimental data. The SERS results for 1,10-phenanthroline showed that the free molecule was the adsorbing species. The potential dependence of the SERS relative intensities was different from those of the resonance Raman spectra of 1,10-phenanthroline complexes with transition metal ions, indicating that different excited states were probed by the two techniques. 2-aminopyridine adsorbed through the pyridinic ring at less negative potentials and through both pyridinic and aminic nitrogens at more negative potentials on Co and Ni electrodes, but for Fe electrode it adsorbed exclusively through the pyridinic nitrogen. 4-aminopyridine adsorbed perpendicularly to the electrode. In 0,1 mol.L-1 KCl electrolytic solution, 4-aminopyridine changed from weak1y bound to a surface complex similar to the synthesized complex at more negative potentials. In 0,1 mol.L-1 KI electrolytic solution, both species were observed in a larger potential interval. On the Ni electrode, protonated 4aminopyridine was observed for V = -0.7 V, and for more negative potentials a surface complex, similar to the synthesized one, was observed. The electrodeposition of ultrathin film of Co and Ni on electrochemically-activated Ag electrodes allowed obtaining SERS spectra of pyridine with high enhancement factors. The SERS spectra of py for films thickness higher than 2 monolayers of Co or Ni presented intense bands of pyridine adsorbed on these metals, and no bands of pyridine adsorbed on Ag were observed, indicanting the absence of pinholes in the films. The relative intensities of SERS spectra on the thin films were similar to those obtained for the SERS of pyridine on the bare metaIs electrodes for films thicker than 7 monolayers, but with SERS intensity 100 times higher. The SERS activity and signal strength reproducibility of Au nanostructured substrates obtained by electrodeposition on a polystyrene masking were evaluated. The SERS spectra of 4-mercaptopyridine adsorbed on optimized electrodes presented intensities 2 times greater than those of the electrochemically activated Au electrode. The SERS intensity reproducibility for these substrates was ± 15%, indicating the potential use of such substrates as sensors.
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