TIME-RESOLVED RESONANCE RAMAN-SPECTROSCOPY OF TRIPLET-STATE METALATED AND FREE-BASE TETRAARYLPORPHYRINS

Resonance Raman spectra of the T-1 excited states of Zn and free-base tetra-4-sulfonatophenylporphyrin (TPPS) have been recorded at room temperature in aqueous solution using two-colour time-resolved methods. The spectra of both sulfonated molecules are very similar to their tetraphenylporphyrin (TPP) analogues, which have been recorded in THF solution using the same pump-probe conditions, but they have higher signal-to-noise ratios because interference from strong solvent bands is reduced. Although two different T-1 spectra of Zn(TPP) have been reported these spectra differ slightly from each other and from the spectrum reported here, which has band positions very close (+/-6 cm(-1)) to those of Zn(TPPS). The high S/N ratios obtainable for the water-soluble porphyrins have allowed reliable polarization data to be recorded for their S-0 and T-1 states. This data set allows a realistic comparison of the changes in bonding associated with excitation of both free-base and Zn tetraarylporphyrins to the T-1 state.

Local probing of ferroelectric and ferroelastic switching through stress-mediated piezoelectric spectroscopy

Strain effects have a significant role in mediating classic ferroelectric behavior such as polarization switching and domain wall dynamics. These effects are of critical relevance if the ferroelectric order parameter is coupled to strain and is therefore, also ferroelastic. Here, switching spectroscopy piezoresponse force microscopy (SS-PFM) is combined with control of applied tip pressure to exert direct control over the ferroelastic and ferroelectric switching events, a modality otherwise unattainable in traditional PFM. As a proof of concept, stress-mediated SS-PFM is applied toward the study of polarization switching events in a lead zirconate titanate thin film, with a composition near the morphotropic phase boundary with co-existing rhombohedral and tetragonal phases. Under increasing applied pressure, shape modification of local hysteresis loops is observed, consistent with a reduction in the ferroelastic domain variants under increased pressure. These experimental results are further validated by phase field simulations. The technique can be expanded to explore more complex electromechanical responses under applied local pressure, such as probing ferroelectric and ferroelastic piezoelectric nonlinearity as a function of applied pressure, and electro-chemo-mechanical response through electrochemical strain microscopy.

A time-resolved electron paramagnetic resonance spectroscopy study of paramagnetic porphyrins /

There is considerable interest in intramolecular energy transfer, especially in complexes which absorb visible light, because it is crucial to the better understanding of photoharvesting systems in photosynthetic organisms and for utilizing solar energy as well. Porphyrin dimers represent one of the best systems for the exploration of light-induced intramolecular energy transfer. Many kinds of porphyrins and porphyrin dimers have been studied over the past decade, however little attention has been paid to the influence of paramagnetic metals on the behavior of their excited states. In this thesis, Electron Paramagnetic Resonance Spectroscopy (EPR) is used to study such compounds. After light irradiation, porphyrins easily produce a variety of excited states, which are spin polarized and can be detected by the time-resolved (TR) EPR technique. The spin polarized results for vanadyl porphyrins, their electrostatically-coupled dimers, a covalently-linked copper porphyrin-free base porphyrin dimer, and free base porphyrins are presented in this thesis. From these results we can conclude that the spin polarization patterns of vanadyl porphyrins come primarily from the trip-quartet state generated by intersystem crossing (lSC) from the excited sing-doublet state through the trip-doublet state. The spin polarization pattern of electrostatically-coupled vanadyl porphyrin-free base porphyrin dimer is produced by the triplet state of the free base porphyrin half which is coupled to the unpaired electron on the vanadyl ion.

Deriving the magnitude of niobium off-center displacement in ferroelectric niobates from infrared spectroscopy

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Corrosion of the component phases presents in high copper dental amalgams. Application of electrochemical impedance spectroscopy and electrochemical noise analysis

The corrosion resistance of three of the constituent phases in high copper dental amalgams has been investigated by electrochemical methods in 0.9% NaCl solution. Polarization curves show corrosion potentials most positive for gamma(1)-Ag2Hg3, followed by Ag-Cu, and gamma-Ag3Sn in agreement with the order of corrosion resistance deduced from the corrosion currents. Complex plane impedance plots at the open circuit potential showed distorted semicircles with diffusional components at low frequency for Ag-Hg and Ag-Cu, while for gamma-Ag3Sn a layer of corrosion products is formed, partially or completely covering the surface of the electrode. Impedance and noise spectra have been compared in the frequency domain, and show good agreement. (C) 2004 Elsevier Ltd. All rights reserved.

Ferroelectric fatigue endurance of Bi4-xLaxTi3O12 thin films explained in terms of x-ray photoelectron spectroscopy

The nature of defects in polycrystalline Bi4-xLaxTi3O12 (BLT) thin films with x=0.00, 0.25, 0.50, and 0.75 was evaluated by x-ray photoemission spectroscopy measurements. The influence of oxygen vacancies and substitution of Bi for La atoms were discussed. In the BLT thin films, it was found that the oxygen ions at the metal-oxygen octahedral were much more stable than those at the [Bi2O2] layers. on the other hand, for Bi4Ti3O12 (BIT) thin film, oxygen vacancies could be induced both at the titanium-oxygen octahedral and at the [Bi2O2] layers. The oxygen-vacancy defect pairs determined in BIT and Bi3.75La0.25Ti3O12 (BLT025) can pin the polarization of surrounding lattices leading to fatigue of capacitors. Meanwhile, the concentration of similar defect pairs is relatively low in heavily doped BIT films and then good fatigue resistance is observed.

Dielectric Spectroscopy Analyses of SrBi4Ti4O15 Films Obtained from Soft Chemical Solution

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

Infrared and far-infrared spectroscopy of (CH3OH)-C-13: TeraHertz laser lines and assignments

We use a (CO2)-C-13 laser as optical pumping source to search for new THz laser lines generated from (CH3OH)-C-13. Nineteen new THz laser lines (also identified as far-infrared, FIR) ranging from 42.3 mu m (7.1 THz) to 717.7 mu m (0.42 THz) are reported. They are characterized in wavelength, offset, relative polarization, relative intensity, and optimum working pressure. We have assigned eight laser lines to specific rotational energy levels in the excited state associated with the C-O stretching mode. (c) 2006 Elsevier B.V. All rights reserved.

Electrochemical impedance spectroscopy characterization of passive film formed on implant Ti-6Al-7Nb alloy in Hank's solution

The influence of potential on electrochemical behavior of Ti-6Al-7Nb alloy under simulate physiological conditions was investigated by electrochemical impedance spectroscopy (EIS). The experimental results were compared with those obtained by potentiodynamic polarization curves. All measurements were carried out in Hank's aerated solution at 25degreesC, at pH 7.8 and at different potentials (corrosion potential, 0 mV(SCE), 1000 mV(SCE), and 2000 mV(SCE)). The EIS spectra exhibited a two-step or a two-time constant system, suggesting the formation of a two-layer oxide film on the metal surface. The high corrosion resistance, displayed by this alloy in electrochemical polarization tests, is due to the dense inner layer, while its osseointegration ability can be ascribed to the presence of the outer porous layer. (C) 2004 Kluwer Academic Publishers.

Capacitance Spectroscopy: A Versatile Approach To Resolving the Redox Density of States and Kinetics in Redox-Active Self-Assembled Monolayers

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

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

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

Application of Mossbauer spectroscopy to the study of corrosion resistance in NaCl solution of plasma nitrided AISI 316L stainless steel

Corrosion research in steels is one of the areas in which Mossbauer spectroscopy has become a required analytical technique, since it is a powerful tool for both identifying and quantifying distinctive phases (which contain Fe) with accuracy. In this manuscript, this technique was used to the study of corrosion resistance of plasma nitrided AISI 316L samples in the presence of chloride anions. Plasma nitriding has been carried out using dc glow-discharge, nitriding treatments, in medium of 80 vol.% H-2 and 20 vol.% N-2, at 673 K, and at different time intervals: 2, 4, and 7 h. Treated samples were characterized by means of phase composition and morphological analysis, and electrochemical tests in NaCl aerated solution in order to investigate the influence of treatment time on the microstructure and the corrosion resistance, proved by conversion electron Mossbauer spectroscopy (CEMS), glancing angle X-ray diffraction (GAXRD), scanning electron microscopy (SEM) and potentiodynamic polarization. A modified layer of about 8 gin was observed for all the nitrided samples, independently of the nitriding time. A metastable phase, S phase or gamma(N), was produced. It seems to be correlated with gamma`-Fe-4 N phase. If the gamma(N) fraction decreases, the gamma` fraction increases. The gamma(N) magnetic nature was analyzed. When the nitriding time increases, the results indicate that there is a significant reduction in the relative fraction of the magnetic gamma(N) (in) phase. In contrast, the paramagnetic gamma(N) (p) phase increases. The GAXRD analysis confirms the Mossbauer results, and it also indicates CrN traces for the sample nitrided for 7 h. Corrosion results demonstrate that time in the plasma nitriding treatment plays an important role for the corrosion resistance. The sample treated for 4 h showed the best result of corrosion resistance. It seems that the epsilon/gamma` fraction ratio plays an important role in thin corrosion resistance since this sample shows the maximum value for this ratio. (c) 2008 Published by Elsevier B.V.

Grating coupled surface plasmon enhanced fluorescence spectroscopy

Over the last three decades, sensors based on the phenomenon of surface plasmon resonance have proven particularly suitable for real time thin film characterization, gas detection, biomolecular interaction examination and to supplement electrochemical methods. Systems based on prism coupling have been combined with fluorescence detection under the name of surface plasmon fluorescence spectroscopy to increase sensitivity even further. Alternatively, metal gratings can be employed to match photons for plasmon resonance. The real time monitoring of binding reactions not yet been reported in the combination of fluorescence detection and grating coupling. Grating-based systems promise more competitive products, because of reduced operating costs, and offer benefits for device engineering. This thesis is comprised of a comprehensive study of the suitability of grating coupling for fluorescence based analyte detection. Fundamental properties of grating coupled surface plasmon fluorescence spectroscopy are described, as well as issues related to the commercial realization of the method. Several new experimental techniques are introduced and demonstrated in order to optimize performance in certain areas and improve upon capabilities in respect to prism-based systems. Holographically fabricated gratings are characterized by atomic force microscopy and optical methods, aided by simulations and profile parameters responsible for efficient coupling are analyzed. The directional emission of fluorophores immobilized on a grating surface is studied in detail, including the magnitude and geometry of the fluorescence emission pattern for different grating constants and polarizations. Additionally, the separation between the minimum of the reflected intensity and the maximum fluorescence excitation position is examined. One of the key requirements for the commercial feasibility of grating coupling is the cheap and faithful mass production of disposable samples from a given master grating. The replication of gratings is demonstrated by a simple hot embossing method with good reproducibility to address this matter. The in-situ fluorescence detection of analyte immobilization and affinity measurements using grating coupling are described for the first time. The physical factors related to the sensitivity of the technique are assessed and the lower limit of detection of the technique is determined for an exemplary assay. Particular attention is paid to the contribution of bulk fluorophores to the total signal in terms of magnitude and polarization of incident and emitted light. Emission from the bulk can be a limiting factor for experiments with certain assay formats. For that reason, a novel optical method, based on the modulation of both polarization and intensity of the incident beam, is introduced and demonstrated to be capable of eliminating this contribution.

NMR spectroscopy and imaging of hyperpolarized gases

Since the discovery of the nuclear magnetic resonance (NMR) phenomenon, countless NMR techniques have been developed that are today indispensable tools in physics, chemistry, biology, and medicine. As one of the main obstacles in NMR is its notorious lack of sensitivity, different hyperpolarization (HP) methods have been established to increase signals up to several orders of magnitude. In this work, different aspects of magnetic resonance, using HP noble gases, are studied, hereby combining different disciplines of research. The first part examines new fundamental effects in NMR of HP gases, in theory and experiment. The spin echo phenomenon, which provides the basis of numerous modern experiments, is studied in detail in the gas phase. The changes of the echo signal in terms of amplitude, shape, and position, due to the fast translational motion, are described by an extension of the existing theory and computer simulations. With this knowledge as a prerequisite, the detection of intermolecular double-quantum coherences was accomplished for the first time in the gas phase. The second part of this thesis focuses on the development of a practical method to enhance the dissolution process of HP 129Xe, without loss of polarization or shortening of T1. Two different setups for application in NMR spectroscopy and magnetic resonance imaging (MRI) are presented. The continuous operation allows biological and multidimensional spectroscopy in solutions. Also, first in vitro MRI images with dissolved HP 129Xe as contrast agent were obtained at a clinical scanner.

Assessing the functional structure of molecular transporters by EPR spectroscopy

In this thesis, the self-assembled functional structure of a broad range of amphiphilic molecular transporters is studied. By employing paramagnetic probe molecules and ions, continuous-wave and pulse electron paramagnetic resonance spectroscopy reveal information about the local structure of these materials from the perspective of incorporated guest molecules. First, the transport function of human serum albumin for fatty acids is in the focus. As suggested by the crystal structure, the anchor points for the fatty acids are distributed asymmetrically in the protein. In contrast to the crystallographic findings, a remarkably symmetric entry point distribution of the fatty acid binding channels is found, which may facilitate the uptake and release of the guest molecules. Further, the metal binding of 1,2,3-triazole modified star-shaped cholic acid oligomers is studied. These biomimetic molecules are able to include and transport molecules in solvents of different polarity. A pre-arrangement of the triazole groups induces a strong chelate-like binding and close contact between guest molecule and metal ion. In absence of a preordering, each triazole moiety acts as a single entity and the binding affinity for metal ions is strongly decreased. Hydrogels based on N-isopropylacrylamide phase separate from water above a certain temperature. The macroscopic thermal collapse of these hydrogels is utilized as a tool for dynamic nuclear polarization. It is shown that a radical-free hyperpolarized solution can be achieved with a spin-labeled gel as separable matrix. On the nanoscale, these hydrogels form static heterogeneities in both structure and function. Collapsed regions protect the spin probes from a chemical decay while open, water-swollen regions act as catalytic centers. Similarly, thermoresponsive dendronized polymers form structural heterogeneities, which are, however, highly dynamic. At the critical temperature, they trigger the aggregation of the polymer into mesoglobules. The dehydration of these aggregates is a molecularly controlled non-equilibrium process that is facilitated by a hydrophobic dendritic core. Further, a slow heating rate results in a kinetically entrapped non-equilibrium state due to the formation of an impermeable dense polymeric layer at the periphery of the mesoglobule.