Arsenic (As) undergoes extensive metabolism in biological systems involving numerous metabolites with varying toxicities. It is important to obtain reliable information on arsenic speciation for understanding toxicity and relevant modes of action. Currently, popular arsenic speciation techniques, such as chromatographic/electrophoretic separation following extraction of biological samples, may induce the alternation of arsenic species during sample preparation. The present study was aimed to develop novel arsenic speciation methods for biological matrices using surface-enhanced Raman spectroscopy (SERS), which, as a rapid and non-destructive photon scattering technique. The use of silver nanoparticles with different surface coating molecules as SERS substrates permits the measurement of four common arsenicals, including arsenite (AsIII), arsenate (AsV), monomethylarsonic acid (MMAV) and dimethylarsinic acid (DMAV). This speciation was successfully carried out using positively charged nanoparticles, and simultaneous detection of arsenicals was achieved. Secondly, arsenic speciation using coffee ring effect-based separation and SERS detection was explored on a silver nanofilm (AgNF), which was prepared by close packing of silver nanoparticles (AgNPs) on a glass substrate surface. Although arsenic separation using the conventional coffee ring effect is difficult because of the limited migration distance, a halo coffee ring was successfully developed through addition of surfactants, and was shown to be capable of arsenicals separation. The surfactants introduced in the sample solution reduce the surface tension of the droplet and generate strong capillary action. Consequently, solvent in the droplet migrated into the peripheral regions and the solvated arsenicals to migrated varying distances due to their differential affinity to AgNF, resulting in a separation of arsenicals in the peripheral region of the coffee ring. Finaly, a method combining experimental Raman spectra measurements and theoretical Raman spectra simulations was developed and employed to obtain Raman spectra of important and emerging arsenic metabolites. These arsenicals include monomethylarsonous acid (MMAIII), dimethylarsinous acid (DMAIII), dimethylmonothioarinic acid (DMMTAV), dimethyldithioarsinic acid (DMDTAV), S-(Dimethylarsenic) cysteine (DMAIIICys) and dimethylarsinous glutathione (DMAIIIGS). The fingerprint vibrational frequencies obtained here for various arsenicals, some of which have not reported previously, provide valuable information for future SERS detection of arsenicals.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-04-27T14:25:47Z No. of bitstreams: 1 dhienifferferreiradecarvalho.pdf: 5689053 bytes, checksum: fec45b3ef7e9df5f96e4b20d31f2177e (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-05-13T13:02:17Z (GMT) No. of bitstreams: 1 dhienifferferreiradecarvalho.pdf: 5689053 bytes, checksum: fec45b3ef7e9df5f96e4b20d31f2177e (MD5) / Made available in DSpace on 2017-05-13T13:02:17Z (GMT). No. of bitstreams: 1 dhienifferferreiradecarvalho.pdf: 5689053 bytes, checksum: fec45b3ef7e9df5f96e4b20d31f2177e (MD5) Previous issue date: 2011-12-14 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Nesta dissertação foi utilizada a espectroscopia Raman intensificado por superfície (Surface Enhanced Raman Scattering – SERS) para monitorar a adsorção de moléculas de interesse biológico em superfície metálica de ouro ou cobre. Foram sintetizadas diferentes nanopartículas metálicas de ouro, variando-se a concentração, a ordem de adição dos reagentes e a temperatura em que as sínteses foram feitas. Através dos espectros de extinção dos coloides metálicos foi possível estimar a distribuição de tamanhos obtida em cada uma das sínteses, e as amostras foram também analisadas por medidas de microscopia eletrônica de varredura e espalhamento dinâmico de luz. As nanopartículas de cobre foram obtidas em meio aquoso, sofrendo oxidação da superfície com formação de óxido de cobre (II), cuja cinética foi acompanhada por espectros de extinção. Quando um adsorbato com caráter redutor foi adicionado à superfície metálica, houve redução do óxido de cobre, presente na superfície da nanopartícula, permitindo a obtenção do espectro SERS da forma oxidada da espécie adsorvida. A molécula que possibilitou o estudo deste mecanismo redox foi a p fenilenodiamina, sendo obtido o espectro SERS da espécie oxidada radical cátion. Serotonina, adrenalina, L-carnosina, melatonina, rifampicina e albumina sérica bovina foram os adsorbatos utilizados para a obtenção dos espectros SERS em coloide de ouro. Estas moléculas apresentam anéis aromáticos, que contribuem para uma elevada polarizabilidade molecular e por isso se espera elevado sinal SERS. Estas espécies também possuem átomos de nitrogênio e oxigênio, os quais estão disponíveis como sítios de coordenação para a interação com a superfície metálica. Para obtenção dos espectros SERS foram utilizadas diferentes radiações excitantes, na busca da ressonância com as transições do plasmon de superfície localizado das nanopartículas de ouro. Foi ainda realizado o cálculo teórico vibracional para cada um dos adsorbatos estudados, isolados ou coordenados a um ou mais átomos de ouro ou cobre, através dos quais foi realizada a atribuição dos espectros Raman e SERS dos sólidos e dos complexos de superfície formados, respectivamente. Através desta atribuição e das regras de seleção de superfície foi possível determinar a geometria de adsorção da biomolécula à superfície da nanopartícula metálica. / In this dissertation the Surface Enhanced Raman Scattering (SERS) spectroscopy was used to monitor molecules with biological interest adsorbed on gold or copper metallic surfaces. Different gold metallic nanoparticles were synthesized varing the concentration, the addition order of the reagents and the temperature in which the syntheses were made. The size distributions were estimated for each colloid synthesis by the extinction spectra of the suspensions, and the samples were also analyzed by scanning electronic microscopy and dynamic light scattering techniques. Copper nanoparticles were obtained in aqueous media, undergoing surface oxidation with the formation of Cu(II) oxide, whose kinetic was followed by extinction spectra. When a reducer adsorbate was added to the nanoparticle suspension, the copper oxide, present in the metallic surfaces, undergoing reduction, allowing the achievement of SERS spectrum of the adsorbate in the oxidized form. The molecule which allowed the study of this redox mechanism was p-phenylenediamine, and the SERS spectrum was obtained from the radical cation species. Serotonin, adrenaline, L-carnosine, melatonin, rifampicin and bovine serum albumin were the adsorbates selected to obtain the SERS spectra in gold colloids. These molecules exhibit aromatic rings, whose is expected high contribution for the molecular polarizability, and in consequence of this a great SERS signal. Such species also have nitrogen and oxygen atoms, which are available coordination sites for interaction with the metallic surface. Different exciting radiations were used for searching of the resonance with the localized surface plasmon transitions of the gold nanoparticles. It was made the vibrational theoretical calculations for each studied adsorbate, isolated and coordinated to one or more gold or copper atoms, that were used for the assignment of Raman and SERS spectra of the solid and the surface complex, respectively. Through such assignment and the surface selection rules it was possible to determinate the adsorption geometry of biomolecule on the metallic surface.

Benzodiazepines are among the most prescribed compounds for anti-anxiety and are present in many toxicological screens. These drugs are also prominent in the commission of drug facilitated sexual assaults due their effects on the central nervous system. Due to their potency, a low dose of these compounds is often administered to victims; therefore, the target detection limit for these compounds in biological samples is 10 ng/mL. Currently these compounds are predominantly analyzed using immunoassay techniques; however more specific screening methods are needed. The goal of this dissertation was to develop a rapid, specific screening technique for benzodiazepines in urine samples utilizing surface-enhanced Raman spectroscopy (SERS), which has previously been shown be capable of to detect trace quantities of pharmaceutical compounds in aqueous solutions. Surface enhanced Raman spectroscopy has the advantage of overcoming the low sensitivity and fluorescence effects seen with conventional Raman spectroscopy. The spectra are obtained by applying an analyte onto a SERS-active metal substrate such as colloidal metal particles. SERS signals can be further increased with the addition of aggregate solutions. These agents cause the nanoparticles to amass and form hot-spots which increase the signal intensity. In this work, the colloidal particles are spherical gold nanoparticles in aqueous solution with an average size of approximately 30 nm. The optimum aggregating agent for the detection of benzodiazepines was determined to be 16.7 mM MgCl2, providing the highest signal intensities at the lowest drug concentrations with limits of detection between 0.5 and 127 ng/mL. A supported liquid extraction technique was utilized as a rapid clean extraction for benzodiazepines from urine at a pH of 5.0, allowing for clean extraction with limits of detection between 6 and 640 ng/mL. It was shown that at this pH other drugs that are prevalent in urine samples can be removed providing the selective detection of the benzodiazepine of interest. This technique has been shown to provide rapid (less than twenty minutes), sensitive, and specific detection of benzodiazepines at low concentrations in urine. It provides the forensic community with a sensitive and specific screening technique for the detection of benzodiazepines in drug facilitated assault cases.

Owing to their increasing application and potential toxicity, engineered nanoparticles (ENPs) have been considered as a potential agricultural contaminant that may pose unknown risk to human beings. However, many techniques require invasive and complicated sample preparation procedures to detect and characterize engineered nanomaterials in complex matrices. In the first part of this thesis, we present a non-destructive and label-free approach based on surface enhanced Raman spectroscopic (SERS) mapping technique to qualitatively detect and characterize gold nanoparticles (AuNPs), on and in spinach leaves in situ. We were able to detect the clearly enhanced signals from AuNPs at 15 to 125 nm on and in spinach leaves. Peak characterizations revealed the aggregation status of Au NPs and their interactions with plant biomolecules, such as chlorophylls and carotenoids. This developed approach will open a new analytical platform for various researches on studying ENPs' adhesion and accumulation. The second part focuses on investigating the interaction between AgNPs and plant leaves using surface enhanced Raman spectroscopy. AgNPs of different surface coating (citrate, CIT and polyvinylpyrrolidone, PVP) and size (40 and 100 nm), were deposited onto spinach leaves. SERS signals produced from all kinds of AgNPs exhibited a unique C-S stretching peak at 650-680 cm-1. In vitro study indicates this peak may originate from the interaction between AgNPs and cysteine-like compounds based on the peak pattern recognition. The interaction between AgNPs and the cysteine-like compounds happened as soon as 0.5 h after AgNPs exposure. The in situ replacement of the CIT with the cysteine-like compounds on the AgNP surfaces was faster compared to that of the PVP. Based on the mapping of the highest C-S peak, we observed the CIT-AgNPs penetrated faster in spinach leaves than the PVP-AgNPs, although the penetration profile for both of them is similar after 48 h (P ˂ 0.05). The 40 nm CIT-AgNPs was able to penetrate deeper (to the depth of 183 ± 38 µm) than the 100 nm CIT-AgNPs (to the depth of 90 ± 51 µm) after 48 h. The results obtained here demonstrate the size of AgNPs is the main factor that affects the penetration depth, and the surface coating mainly affects the initial speed of interaction and penetration. This study helps us to better understand the distribution and biotransformation of AgNPs in plants. In the third part, the removal efficiency of postharvest washing on AgNPs that had accumulated on fresh produce was evaluated. Ten µL commercially available 40 nm citrate coated AgNPs (0.4 mg L-1) were dropped to a (1×1 cm2) spot on spinach leaves, followed by washing with deionized water (DI water), Tsunami® 100 (80 mg L-1) or Clorox® bleach (200 mg L-1). Then, AgNPs removal efficiency of the three treatments was evaluated by surface enhanced Raman spectroscopy (SERS), scanning electron microscopy (SEM)-energy dispersive spectrometer (EDS), and inductively coupled plasma mass spectrometry (ICP-MS). ICP-MS results showed that deionized water removed statistically insignificant amounts of total Ag, whereas Tsunami® 100 and Clorox® bleach yielded 21% and 10% decreases in total Ag, respectively (P < 0.05). The increased removal efficiency resulted from Ag NPs dissolution and Ag+ release upon contact with the oxidizing agents in Tsunami® 100 (peroxyacetic acid, hydrogen peroxide) and Clorox® bleach (sodium hypochlorite). According to the SERS results, the deionized water and Tsunami® 100 treatments removed nonsignificant amounts of AgNPs. Clorox® bleach decreased Ag NPs by more than 90% (P < 0.05), however, SEM-EDS images revealed the formation of large silver chloride (AgCl) crystals (162 ± 51 nm) on the leaf, which explained low total Ag removal from ICP-MS. This study indicates current factory washing methods for fresh produce may not be effective in reducing AgNPs (by water and Tsunami® 100) and total Ag (by all three means). This highlights the necessity to develop an efficient washing method for NP removal from food surfaces in the future.

The presented thesis deals with preparation of GaN nanocrystals with a metal core. In the theoretical part of the thesis GaN with its properties and applications is introduced. Further, some of the preparation methods of GaN are presented, mainly focusing on MBE growth. Deposition of metal NPs from colloidal solution and the state of the art approaches to enhance luminescence of GaN based structures is discussed. The experimental part follows three steps of preparation of GaN crystals with the Ag core. In the first step the Ag NPs are deposited on the Si(111) substrate. In the second step the Ga deposition process is optimized and in the third step the deposited Ga is transformed into GaN. After the Ga deposition the samples were analyzed by SEM/EDX and SAM/AES. The properties of prepared GaN crystals with the Ag core were studied by XPS, photoluminescence and Raman spectroscopy.

Presented thesis is focused on the study of properties of Ga and GaN nanostructures on graphene. In the theoretical part of the thesis a problematics of graphene and GaN fabrication is discussed with a focus on the relation of Ga and GaN to graphene. The experimental part of the thesis deals with the depositions of Ga on transferred CVD-graphene on SiO2. The samples are analyzed by various methods (XPS, AFM, SEM, Raman spectroscopy, EDX). The properties of Ga on graphene are discussed with a focus on the surface enhanced Raman scattering effect. Furthermore, a deposition of Ga on exfoliated graphene and on graphene on a copper foil is described. GaN is fabricated by nitridation of the Ga structures on graphene. This process is illustrated by the XPS measurements of a distinct Ga peak and the graphene valence band during the process of nitridation.

Optical sensors based on Surface-enhanced Raman scattering (SERS) effect are among the most versatile sensors due to their ability to characterize samples in various states of matter. The appeal of the SERS sensors lies in the molecular “fingerprint” specificity, sensitivity, and the non-invasive nature of the analysis. Although the current state of art SERS sensors have advanced toward ultrasensitivity with single-molecule detection limit, ultrafast analysis at femtosecond and sub-nanometer resolution, the application of these innovations in the industrial settings is still limited by the complexity of the substrate fabrication and the reproducibility of the SERS measurements. In this context, a study on the SERS sensors fabrication strategies and reliability of the SERS analysis is essential. This dissertation investigates various hybrids of noble metal and semiconductor materials and surface modifications to improve the stability and reliability of SERS measurement. Different industrial applications, including detection of petrochemical organic compounds and sensitive biochemical samples, were conducted to evaluate the performance of different SERS sensor designs. Evaluation of the morphology and surface functionalization of the substrate was accomplished to optimize the performance and stability of the collected signal. Together with the separately performed studies on Raman signal processing and interpretation, the proposed SERS sensor fabrication and signal analysis approach was successfully applied to detect and quantify organic isomers compounds and mutation point in peptides. The findings presented in this thesis offer rational SERS substrate designs and detection approaches that can advance the future commercialization of SERS sensors.

There has been a notable rise in the alternative protein market in the recent years which promotes an interest in the research of both animal and plant proteins to establish better structure-function relationships. Over the years many analytical tools have been used to study proteins and compare them, however Raman Spectroscopy and Surface Enhanced Raman Spectroscopy (SERS) have not been as much used for this application. SERS consolidates Raman Spectroscopy that primarily measures molecular vibrations and nanostructures that enhance the weak Raman signals. The objective of this study is to explore the capability of the Raman instrumentation in combination with different substrates for spectroscopic analysis of 3 animal proteins viz. whey, k-casein and albumin from chicken egg white and 4 plant proteins namely mung bean, soy, pea and faba bean. Herein, we firstly established a method that could be applied to all proteins to detect characteristic peaks that are related to their structure. Of all the methods, SERS with silver dendrites was the most promising method that detected protein characteristic peaks, particularly the shifts around 700-900 cm-1 attributed to the CN stretch and tryptophan groups. Although different proteins exhibit similar spectral characteristics, they were discriminated using principal component analysis. Then we explored the optimal method to study the effect of different environmental conditions including pH and salt concentration on the protein spectroscopic analysis. The limitations of the substrates were better understood during this process as Ag dendrites failed to provide a spectrum in the high pH range but was compatible with different salt concentrations. The peaks in the Amide-I region were vi used as a marker to study the effect of change in pH and salt. Most proteins showing a shift in the band suggesting a transition from α-sheet to a random coil conformation. The acquired spectra and subsequent PCA results depicted that pea protein was the most susceptible to change in pH amongst other proteins whereas faba bean was susceptible to a change in salt concentration. Finally, these learnings were applied to analyze a real-world food product to compare its spectroscopic characteristic with the standards we have. In conclusion, we demonstrated that Raman Spectroscopy and SERS was able to provide distinct spectroscopic characteristics of plant and animal proteins that may be used to facilitate the quality control or product development of novel plant-based food products. Future work will investigate the relationship between the spectroscopic characteristics and the structural function of proteins.

Raman spectroscopy is among the most widely employed methods to investigate the properties of materials in several fields of study. Evolution in materials science allowed us to fabricate suitable substrates, at the nanoscale, capable to enhance the electromagnetic field of the signals coming from the samples which at this range turn out to be in most cases singles or a few molecules. This particular variation of the classical technique is called SERS (Surface Enanched Raman Spectroscopy). In this work, the enhancement of the electromagnetic field is obtained by manipulation of the optical properties of metals with respect to their size. By using electroless deposition (bottom up technique), gold and silver nanoparticles were deposited in nanostructured patterns obtained on silicon wafers by means of electron beam lithography (top down technique). Rhodamine 6G in aqueous solution at extremely low concentration (10-8 M) was absorbed on the resultant dimers and the collection of the Raman spectra demonstrated the high efficiency of the substrates.

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