Vibrational spectroscopy for probing molecular-level interactions in organic films mimicking biointerfaces

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

Detection of trace levels of atrazine using surface-enhanced Raman scattering and information visualization

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

Mechanisms of SnO2 Nanoparticles Formation and Growth in Acid Ethanol Solution Derived from SAXS and Combined Raman-XAS Time-Resolved Studies

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Release of Cyanopyridine from a Ruthenium Complex Adsorbed on Gold: Surface-Enhanced Raman Scattering, Electrochemistry, and Density Functional Theory Analyses

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

Co-deposition of gold nanoparticles and metalloporphyrin using the langmuir-blodgett (LB) technique for Surface-Enhanced Raman Scattering (SERS)

The synergistic effect produced by metallic nanoparticles when incorporated into different systems empowers a research field that is growing rapidly. In addition, organometallic materials are at the center of intensive research with diverse applications such as light-emitting devices, transistors, solar cells, and sensors. The Langmuir-Blodgett (LB) technique has proven to be suitable to address challenges inherent to organic devices, since the film properties can be tuned at the molecular level. Here we report a strategy to incorporate gold nanoparticles (AuNPs) into the LB film by co-deposition in order to achieve surface-enhanced Raman scattering (SERS) of the zinc(II)-protoporphyrin (IX) dimethyl ester (ZnPPIX-DME). Prior to the LB co-deposition, the properties of the Langmuir monolayer of ZnPPIX-DME at the air-water interface, containing AuNPs in the subphase, are studied through the surface-pressure versus mean molecular area (π-A) isotherms. The ZnPPIX-DME+AuNPs π-A isotherm presented a significant shift to higher molecular area, suggesting an interaction between both ZnPPIX-DME molecules and AuNPs. Those interactions are a key factor allowing the co-deposition of both AuNPs and ZnPPIX-DME molecules onto a solid substrate, thus forming the LB film. SERS of ZnPPIX-DME was successfully attained, ensuring the spatial distribution of the AuNPs. Higher enhancement factors were found at AuNP aggregates, as a result of the intense local electromagnetic field found in the metal nanoparticle aggregates. The main vibrational bands observed in the SERS spectra suggest a physical adsorption of the ZnPPIX-DME onto the surface of AuNPs. The latter is not only in agreement with the interactions pointed out by the π-A isotherms but also suggests that this interaction is kept upon LB film co-deposition.

Silver-gold nanotubes containing hot spots on their surface: facile synthesis and surface-enhanced Raman scattering investigations

We report the synthesis of silver-gold nanotubes containing hot spots along their surface. The Ag-Au nanotubes exhibited exceptional SERS properties compared to silver nanowires, enabling the detection of crystal violet in the 10(-10) M regime, as well as 9-nitroanthracene and benzo[a] pyrene at 3.3 x 10(-7) M.

Vibrational spectroscopy on thermally and optically switchable spin crossover compounds

Oktaedrisch koordinierte Übergangsmetalle mit der Elektronenkonfiguration [Ar]3d4 - 3d7 können in zwei unterschiedlichen elektronischen Zuständen existieren: im High-Spin (HS) oder im Low-Spin (LS) Zustand. Zum Beispiel kann Fe(II) in 1A1g (LS) oder 5T2g (HS) Konfiguration auftreten.Besonderes Interesse besteht in der Aufklärung des Mechanismus der kooperativen Wechselwirkung, die den Spinübergang im Festkörper bestimmt. Hierzu müssen zunächst die internen Freiheitsgrade der molekularen Einheiten bekannt sein. Besonders der Beitrag der molekularen Schwingungen zur Entropiedifferenz, die die Triebkraft des Spinübergangs darstellt, ist von entscheidender Bedeutung. Bisher existieren nur wenige detaillierte Untersuchungen zu den Schwingungseigenschaften der Spincrossovermoleküle.In Rahmen der vorliegenden Arbeit wurden die Schwingungseigenschaften einiger Komplexverbindungen, die Spincrossover zeigen, im Detail untersucht. Dazu wurden temperaturabhängige Raman-, Fern- und Mittel-Infrarot-Spektroskopie, Isotopensubstitution und Normalkoordinatenanalysen (NKA) in Verbindung mit Dichtefunktional-Rechnungen (DFT) verwendet.Die gewonnenen Werte der zugeordneten Schwingungsfrequenzen und die bestimmten Kraftkonstantenänderungen können nun zur Verfeinerung von theoretischen Modellen zur Beschreibung des Spinübergangs verwendet werden.

MicroRaman Spectroscopy of Si Nanowires: Influence of Size

Si Nanowires (NWs) were studied by Raman microspectroscopy. The Raman spectrum of the NWs reveals important thermal effects, which broaden and shift the one phonon Raman bands. The low thermal conductivity of the NWs and the low thermal dissipation are responsible for the temperature enhancement in the NW under the excitation with the laser beam. We have modeled, using finite element methods, the interaction between the laser beam and the NWs. The Raman spectrum of Si NWs is interpreted in terms of the temperature induced by the laser beam excitation, in correlation with finite element methods (fem) for studying the interaction between the laser beam and the NWs.

Raman and infrared spectra of dimethyl ether 13C-isotopologue (CH3O13CH3) from a CCSD(T) potential energy surface

So far, no experimental data of the infrared and Raman spectra of 13C isotopologue of dimethyl ether are available. With the aim of providing some clues of its low-lying vibrational bands and with the hope of contributing in a next spectral analysis, a number of vibrational transition frequencies below 300 cm−1 of the infrared spectrum and around 400 cm−1 of the Raman spectrum have been predicted and their assignments were proposed. Calculations were carried out through an ab initio three dimensional potential energy surface based on a previously reported one for the most abundant dimethyl ether isotopologue (M. Villa et al., J. Phys. Chem. A 115 (2011) 13573). The potential function was vibrationally corrected and computed with a highly correlated CCSD(T) method involving the COC bending angle and the two large amplitude CH3 internal rotation degrees of freedom. Also, the Hamiltonian parameters could represent a support for the spectral characterization of this species. Although the computed vibrational term values are expected to be very accurate, an empirical adjustment of the Hamiltonian has been performed with the purpose of anticipating some workable corrections to any possible divergence of the vibrational frequencies. Also, the symmetry breaking derived from the isotopic substitution of 13C in the dimethyl ether was taken into account when the symmetrization procedure was applied.

Identification and relative quantification of tyrosine nitration in a model peptide using two-dimensional infrared spectroscopy

Nitration of tyrosine in proteins and peptides is a post-translational modification that occurs under conditions of oxidative stress. It is implicated in a variety of medical conditions, including neurodegenerative and cardiovascular diseases. However, monitoring tyrosine nitration and understanding its role in modifying biological function remains a major challenge. In this work, we investigate the use of electron-vibration-vibration (EVV) two-dimensional infrared (2DIR) spectroscopy for the study of tyrosine nitration in model peptides. We demonstrate the ability of EVV 2DIR spectroscopy to differentiate between the neutral and deprotonated states of 3-nitrotyrosine, and we characterize their spectral signatures using information obtained from quantum chemistry calculations and simulated EVV 2DIR spectra. To test the sensitivity of the technique, we use mixed-peptide samples containing various levels of tyrosine nitration, and we use mass spectrometry to independently verify the level of nitration. We conclude that EVV 2DIR spectroscopy is able to provide detailed spectroscopic information on peptide side-chain modifications and to detect nitration levels down to 1%. We further propose that lower nitration levels could be detected by introducing a resonant Raman probe step to increase the detection sensitivity of EVV 2DIR spectroscopy. (Graph Presented).

High-power widely tunable Raman fiber laser

Tunable Raman fiber lasers have attracted great interest owing to their high efficiency and reliability important for applications, such as optical fiber communications and sensing, spectroscopy, and instrument testing. Their tuning range is defined by the Raman gain bandwidth amounting to about 40 nm in telecom spectral range (∼1550 nm) for conventional silica single mode fibers (SMF). To increase the range, highly nonlinear fibers which broaden pump spectrum may be incorporated in the cavity of Raman fiber lasers, see e.g. [1]. Another approach is to involve Rayleigh scattering forming random distributed feedback in a relatively long fiber resulting in prominent flattening of the tuning curve [2]. In this paper we report on combination of these two techniques in tunable Raman fiber lasers thus providing great improvement of their output characteristics. © 2013 IEEE.

Use of time-resolved spectroscopy as a method to monitor carotenoids present in tomato extract obtained using ultrasound treatment

Introduction Compounds exhibiting antioxidant activity have received much interest in the food industry because of their potential health benefits. Carotenoids such as lycopene, which in the human diet mainly derives from tomatoes (Solanum lycopersicum), have attracted much attention in this aspect and the study of their extraction, processing and storage procedures is of importance. Optical techniques potentially offer advantageous non-invasive and specific methods to monitor them. Objectives To obtain both fluorescence and Raman information to ascertain if ultrasound assisted extraction from tomato pulp has a detrimental effect on lycopene. Method Use of time-resolved fluorescence spectroscopy to monitor carotenoids in a hexane extract obtained from tomato pulp with application of ultrasound treatment (583 kHz). The resultant spectra were a combination of scattering and fluorescence. Because of their different timescales, decay associated spectra could be used to separate fluorescence and Raman information. This simultaneous acquisition of two complementary techniques was coupled with a very high time-resolution fluorescence lifetime measurement of the lycopene. Results Spectroscopic data showed the presence of phytofluene and chlorophyll in addition to lycopene in the tomato extract. The time-resolved spectral measurement containing both fluorescence and Raman data, coupled with high resolution time-resolved measurements, where a lifetime of ~5 ps was attributed to lycopene, indicated lycopene appeared unaltered by ultrasound treatment. Detrimental changes were, however, observed in both chlorophyll and phytofluene contributions. Conclusion Extracted lycopene appeared unaffected by ultrasound treatment, while other constituents (chlorophyll and phytofluene) were degraded.

Comparative Study of Four Portuguese 16th Century Illuminated Manueline Charters based on Spectroscopy and Chemometrics Analysis

The comparative study based on spectroscopic analysis of the materials used to produce four sixteenth-century Manueline Charters (the Charters of Alcochete, Terena, Alandroal and Evora) was performed following a systematic analytical approach. SEM–EDS, l-Raman and l-FTIR analysis highlighted interesting features between them, namely the use of different pigments and colourants (such as different green and yellow pigments), the presence of pigments alterations and the use of a non-expected extemporaneous material (with the presence of titanium white in the Charter of Alcochete). Principal component analysis restricted to the C–H absorption region (3000–2840 cm-1) was applied to 36 infrared spectra of blue historical samples from the Charters of Alcochete,Terena, Alandroal and Évora, suggesting the use of a mixture of a triglyceride and polysaccharide as binder.

Advanced Spectroscopy for the Study of Colourants in Cultural Heritage

Colourants are substances used to change the colour of something, and are classified in three typology of colorants: a) pigments, b) dyes, and c) lakes and hybrid pigments. Their identification is very important when studying cultural heritage; it gives information about the artistic technique, can help in dating, and offers insights on the condition of the object. Besides, the study of the degradation phenomena constitutes a framework for the preventive conservation strategies, provides evidence of the object's original appearance, and contributes to the authentication of works of art. However, the complexity of these systems makes it impossible to achieve a complete understanding using a single technique, making necessary a multi-analytical approach. This work focuses on the set-up and application of advanced spectroscopic methods for the study of colourants in cultural heritage. The first chapter presents the identification of modern synthetic organic pigments using Metal Underlayer-ATR (MU-ATR), and the characterization of synthetic dyes extracted from wool fibres using a combination of Thin Layer Chromatography (TLC) coupled to MU-ATR using AgI@Au plates. The second chapter presents the study of the effect of metallic Ag in the photo-oxidation process of orpiment, and the influence of the different factors, such as light and relative humidity. We used a combination of vibrational and synchrotron radiation-based X-ray microspectroscopy techniques: µ-ATR-FT-IR, µ-Raman, SR-µ-XRF, µ-XANES at S K-, Ag L3- and As K-edges and SR-µ-XRD. The third chapter presents the study of metal carboxylates in paintings, specifically on the formation of Zn and Pb carboxylates in three different binders: stand linseed oil, whole egg, and beeswax. We used micro-ATR-FT-IR, macro FT-IR in total reflection (rMA-FT-IR), portable Near-Infrared spectroscopy (NIR), macro X-ray Powder Diffraction (MA-XRPD), XRPD, and Gas Chromatography Mass-Spectrometry (GC-MS). For the data processing, we explored the data from rMA-FT-IR and NIR with the Principal Component Analysis (PCA).