Transferência de energia entre corantes catiônicos em sistemas homogêneos

In this work, the energy transfer by dipole-dipole interaction between cationic dyes in n-alcohols (methanol, ethanol, 1-propanol and 1-butanol) is studied by time resolved and steady state fluorescence measurements. The critical radii of energy transfer were determined by three independent methods; the spectral overlap, fluorescence decay profiles, and relative intensity measurements. In all solvents, R0 values of the dye pairs obtained from spectral overlap were between 40 to 90 Å. Steady state and time resolved fluorescence measurements resulted in values of R0 in the range of 50 - 80 Å, with good correlation of values.

Óxido misto de ítrio-alumínio dopado com Eu(III)

In this work, we report the synthesis and the photoluminescence features of Eu(III)-doped yttrium-aluminium oxide obtained by non-hydrolytic sol-gel routes. After heating the powders above 600 ºC the XRD patterns show the presence of the Y4Al2O9 (YAM) and Y3Al5O12 (YAG) phases. At 800 and at 1500 ºC the PL spectra display the Eu(III) lines characteristic of the YAM monoclinic phase. The 5D0->7F2 transition is favored relatively to the 5D0->7F1 lines. However, at 1100 ºC the cubic YAG is the preferential phase and the 5D0->7F1 transition dominates the spectrum. The Eu(III) ions lie in a centrosymmetrical site. The different solvents used in the sol-gel synthesis also change the relative proportion between these two phases. This is monitored analyzing the modifications in the relative intensity between the 5D0->7F2 and the 5D0->7F1 transitions.

Comparaison des réponses physiologiques lors d’un exercice incrémental maximal sur vélo immergé et sur terrain sec : aspects biomécaniques, cardiopulmonaires et hémodynamiques.

L’exercice en immersion dans l'eau peut générer des réponses hémodynamiques et cardiorespiratoires différentes à celles de l’exercice sur terraine sec. Cependant, aucune étude n’a comparé ces réponses sur vélo aquatique (VA) à celles sur vélo sur terrain sec (VS) à une même puissance mécanique externe (Pext). À cet égard, le premier travail de cette thèse visait, d’abord, à trouver les équivalences de Pext lors du pédalage sur VA en immersion à la poitrine par rapport au VS au laboratoire, en considérant que cela restait non déterminé à ce jour. Une équation de mécanique des fluides fut utilisée pour calculer la force déployée pour le système de pédalage (pales, leviers, pédales) et des jambes à chaque tour de pédale. Ensuite, cette force totale a été multipliée par la vitesse de pédalage pour estimer la Pext sur VA. Ayant trouvé les équivalences de Pext sur VA et VS, nous nous sommes fixés comme objectif dans la deuxième étude de comparer les réponses hémodynamiques et cardiorespiratoires lors d'un exercice maximal progressif sur VS par rapport au VA à une même Pext. Les résultats ont montré que le VO2 (p<0.0001) et la différence artério-veineuse (C(a-v)O2) (p<0.0001) étaient diminués lors de l’exercice sur VA comparativement à celui sur VS. Parmi les variables hémodynamiques, le volume d’éjection systolique (VES) (p˂0.05) et le débit cardiaque (Qc) (p˂0.05) étaient plus élevés sur VA. En plus, on nota une diminution significative de la fréquence cardiaque (FC) (p˂0.05). Étant donné qu’à une même Pext les réponses physiologiques sont différentes sur VA par rapport à celles sur VS, nous avons effectué une troisième étude pour établir la relation entre les différentes expressions de l'intensité relative de l'exercice (% du VO2max,% de la FCmax,% du VO2 de réserve (% de VO2R) et % de la FC réserve (% FCR)). Les résultats ont démontré que la relation % FCR vs % VO2R était la plus corrélée (régression linéaire) et la plus proche de la ligne d’identité. Ces résultats pourraient aider à mieux prescrire et contrôler l’intensité de l'exercice sur VA pour des sujets sains. Finalement, une dernière étude comparant la réactivation parasympathique après un exercice maximal incrémental effectué sur VA et VS en immersion au niveau de la poitrine a montré que la réactivation parasympathique à court terme était plus prédominante sur VA (i,e. t, delta 10 à delta 60 et T30, p<0.05). Cela suggérait, qu’après un exercice maximal sur VA, la réactivation parasympathique à court terme était accélérée par rapport à celle après l'effort maximal sur VS chez de jeunes sujets sains. En conclusion, nous proposons une méthode de calcul de la puissance mécanique externe sur VA en fonction de la cadence de pédalage. Nous avons démontré que pendant l’exercice sur VA les réponses hémodynamiques et cardiorespiratoires sont différentes de celles sur VS à une même Pext et nous proposons des équations pour le calcul du VO2 dans l’eau ainsi qu’une méthode pour la prescription et le contrôle de l’exercice sur VA. Finalement, la réactivation parasympathique à court terme s’est trouvée accélérée après un effort maximal incrémental sur VA comparativement à celle sur VS.

Absorptionsspektrometrie in der Kavität eines Halbleiterlasers unter Ausnutzung der Modenkonkurrenz zwischen zwei Moden

Motivation dieser Arbeit ist die Idee, ein höchst sensitives und selektives Spektroskop, welches gleichzeitig robust ist, auf Basis von Halbleiterlasern zum Einsatz in der Atemgasdiagnostik zu entwickeln. Technische Grundlage ist die Idee, die Probe innerhalb des Laserresonators zu vermessen (sogenannte intra cavity absorption spectroscopy, ICAS). Im speziellen soll durch die Verwendung des relativen Intensitätsrauschens zur Messwertbestimmung und die Verwendung von nur zwei Moden statt der sonst für ICAS verwendeten multimodigen Laser, die Empfindlichkeit erhöht, sowie die Messwerterfassung vereinfacht werden. Die Probe im Laserresonator zu Messen, hat den Vorteil, dass durch die multiple Hin­ und Rückreflektion die wirksame Pfadlänge durch die Probe vervielfacht wird. Dabei werden Verluste an den Resonatorspiegeln durch die Verstärkung der aktiven Zone des Lasers kompensiert. Außerdem wird durch die Konkurrenz der Moden um die idealerweise homogen verbreiterte Verstärkung im Laser die Empfindlichkeit noch einmal bedeutend erhöht. Schon eine geringe Absorption bei einer bestimmten Wellenlänge wird die Intensität des betroffenen Modes zugunsten der anderen Moden verringern. Die Arbeit beschäftigt sich zum einen mit der spektroskopischen Untersuchung zwei- er für die Atemgasdiagnostik relevanter Stoffe, Aceton und das in der Anästhesie häufig eingesetzte Propofol, um das Umfeld, in dem der Laser Verwendung finden soll, zu beleuchten. Diese Untersuchungen flossen in die Entwicklung des später zum Sensor auszubauenden Lasers ein. Für den Laser wurden in der Telekommunikation übliche, glasfaserbasierte, robuste Standardbauteile wie ein optischer Halbleiterverstärker (semiconductor optical amplifier, SOA), Faserkoppler und Faser­Bragg­Gitter verwendet. Die Bauteile wurden charakterisiert. Teilaspekte des Aufbaus wurden mit der Software CAMFR simuliert. Schließlich wurde der Laser als solcher aufgebaut und charakterisiert. Das Ziel der Zweimodigkeit, in einem Intervall von 2 nm durchstimmbar, konnte erreicht werden. An einem vom Heinrich­Hertz­Institut in Berlin entwickelten zweimodigen Halbleiterlasers wurden Untersuchungen der Idee zur Vereinfachung der Messwerterfassung mittels relativen Intensitätsrauschens (relative intensity noise, RIN) durchgeführt. Als Messgröße stellt das RIN die Amplituden der Intensitätsschwankungen des Lasers gegen die Frequenzen der Intensitätsschwankungen als Rauschspektrum dar. Es konnte nachgewiesen werden, dass das Rauschspektrum charakteristisch für das Oszillationsverhalten des Lasers ist.

Theoretical and experimental study of intracavity laser absorption spectroscopy

In this thesis, a dual mode tunable gas sensor based on intracavity laser absorption spectroscopy (ICLAS) principle is investigated, both, numerically and experimentally. In order to minimize the cost and size of the gas sensor, relative intensity noise (RIN) is implemented as a detection parameter. Investigation is performed to determine the effect of injection current, operating temperature, mode spacing, and cavity length on RIN. It has been found that it is best to operate the gas sensor at smaller mode spacing and near the threshold current or at larger mode spacing and far above the threshold current for the use of RIN as the readout parameter.

Remote gas detection and quantitative analysis from infrared emission spectra obtained by Fourier transform infrared spectroscopy

Techniques for obtaining quantitative values of the temperatures and concentrations of remote hot gaseous effluents from their measured passive emission spectra have been examined in laboratory experiments. The high sensitivity of the spectrometer in the vicinity of the 2397 cm-1 band head region of CO2 has allowed the gas temperature to be calculated from the relative intensity of the observed rotational lines. The spatial distribution of the CO2 in a methane flame has been reconstructed tomographically using a matrix inversion technique. The spectrometer has been calibrated against a black body source at different temperatures and a self absorption correction has been applied to the data avoiding the need to measure the transmission directly. Reconstruction artifacts have been reduced by applying a smoothing routine to the inversion matrix.

Wave-breaking characteristics of Northern Hemisphere winter blocking: a two-dimensional approach

This paper generalises and applies recently developed blocking diagnostics in a two- dimensional latitude-longitude context, which takes into consideration both mid- and high-latitude blocking. These diagnostics identify characteristics of the associated wave-breaking as seen in the potential temperature (θ) on the dynamical tropopause, in particular the cyclonic or anticyclonic Direction of wave-Breaking (DB index), and the Relative Intensity (RI index) of the air masses that contribute to blocking formation. The methodology is extended to a 2-D domain and a cluster technique is deployed to classify mid- and high-latitude blocking according to the wave-breaking characteristics. Mid-latitude blocking is observed over Europe and Asia, where the meridional gradient of θ is generally weak, whereas high-latitude blocking is mainly present over the oceans, to the north of the jet-stream, where the meridional gradient of θ is much stronger. They occur respectively on the equatorward and poleward flank of the jet- stream, where the horizontal shear ∂u/∂y is positive in the first case and negative in the second case. A regional analysis is also conducted. It is found that cold-anticyclonic and cyclonic blocking divert the storm-track respectively to the south and to the north over the East Atlantic and western Europe. Furthermore, warm-cyclonic blocking over the Pacific and cold-anticyclonic blocking over Europe are identified as the most persistent types and are associated with large amplitude anomalies in temperature and precipitation. Finally, the high-latitude, cyclonic events seem to correlate well with low- frequency modes of variability over the Pacific and Atlantic Ocean.

Characterization and antimicrobial efficacy against E. coli of a helium/air plasma at atmospheric pressure created in a plastic package

A plasma source, sustained by the application of a floating high voltage (±15 kV) to parallel-plate electrodes at 50 Hz, has been achieved in a helium/air mixture at atmospheric pressure (P = 105 Pa) contained in a zip-locked plastic package placed in the electrode gap. Some of the physical and antimicrobial properties of this apparatus were established with a view to ascertain its performance as a prototype for the disinfection of fresh produce. The current–voltage (I–V) and charge–voltage (Q–V) characteristics of the system were measured as a function of gap distance d, in the range (3 × 103 ≤ Pd ≤ 1.0 × 104 Pa m). The electrical measurements showed this plasma source to exhibit the characteristic behaviour of a dielectric barrier discharge in the filamentary mode and its properties could be accurately interpreted by the two-capacitance in series model. The power consumed by the discharge and the reduced field strength were found to decrease quadratically from 12.0 W to 4.5 W and linearly from 140 Td to 50 Td, respectively, in the range studied. Emission spectra of the discharge were recorded on a relative intensity scale and the dominant spectral features could be assigned to strong vibrational bands in the 2+ and 1− systems of N2 and ${\rm N}_2^+$ , respectively, with other weak signatures from the NO and OH radicals and the N+, He and O atomic species. Absolute spectral intensities were also recorded and interpreted by comparison with the non-equilibrium synthetic spectra generated by the computer code SPECAIR. At an inter-electrode gap of 0.04 m, this comparison yielded typical values for the electron, vibrational and translational (gas) temperatures of (4980 ± 100) K, (2700 ± 200) K and (300 ± 100) K, respectively and an electron density of 1.0 × 1017 m−3. A Boltzmann plot also provided a value of (3200 ± 200 K) for the vibrational temperature. The antimicrobial efficacy was assessed by studying the resistance of both Escherichia coli K12 its isogenic mutants in soxR, soxS, oxyR, rpoS and dnaK selected to identify possible cellular responses and targets related with 5 min exposure to the active gas in proximity of, but not directly in, the path of the discharge filaments. Both the parent strain and mutants populations were significantly reduced by more than 1.5 log cycles in these conditions, showing the potential of the system. Post-treatment storage studies showed that some transcription regulators and specific genes related to oxidative stress play an important role in the E. coli repair mechanism and that plasma exposure affects specific cell regulator systems.

Biomineralisation by earthworms: an investigation into the stability and distribution of amorphous calcium carbonate

Background Many biominerals form from amorphous calcium carbonate (ACC), but this phase is highly unstable when synthesised in its pure form inorganically. Several species of earthworm secrete calcium carbonate granules which contain highly stable ACC. We analysed the milky fluid from which granules form and solid granules for amino acid (by liquid chromatography) and functional group (by Fourier transform infrared (FTIR) spectroscopy) compositions. Granule elemental composition was determined using inductively coupled plasma-optical emission spectroscopy (ICP-OES) and electron microprobe analysis (EMPA). Mass of ACC present in solid granules was quantified using FTIR and compared to granule elemental and amino acid compositions. Bulk analysis of granules was of powdered bulk material. Spatially resolved analysis was of thin sections of granules using synchrotron-based μ-FTIR and EMPA electron microprobe analysis. Results The milky fluid from which granules form is amino acid-rich (≤ 136 ± 3 nmol mg−1 (n = 3; ± std dev) per individual amino acid); the CaCO3 phase present is ACC. Even four years after production, granules contain ACC. No correlation exists between mass of ACC present and granule elemental composition. Granule amino acid concentrations correlate well with ACC content (r ≥ 0.7, p ≤ 0.05) consistent with a role for amino acids (or the proteins they make up) in ACC stabilisation. Intra-granule variation in ACC (RSD = 16%) and amino acid concentration (RSD = 22–35%) was high for granules produced by the same earthworm. Maps of ACC distribution produced using synchrotron-based μ-FTIR mapping of granule thin sections and the relative intensity of the ν2: ν4 peak ratio, cluster analysis and component regression using ACC and calcite standards showed similar spatial distributions of likely ACC-rich and calcite-rich areas. We could not identify organic peaks in the μ-FTIR spectra and thus could not determine whether ACC-rich domains also had relatively high amino acid concentrations. No correlation exists between ACC distribution and elemental concentrations determined by EMPA. Conclusions ACC present in earthworm CaCO3 granules is highly stable. Our results suggest a role for amino acids (or proteins) in this stability. We see no evidence for stabilisation of ACC by incorporation of inorganic components.

EPR in the Characterization of the Shade Effect on Translucence, Remaining Free Radicals, and Polymerization Depth of Commercially Available Resin Composites

The aim of this study was to assess the relation between the number of free radicals generated and the polymerization depth in two different commercial brands of resin composites with different colors and translucence. Electron paramagnetic resonance quantified the radical populations through relative intensity (I (r)) of free radicals generated, and radical decay was monitored. Sample translucence and the classical polymerization depth were measured. The analysis indicated that resin with more color pigments (MA4, I (r) = 0.73 a.u) or more opacity components (ODA2, I (r) = 0.84 a.u) generated smaller populations of free radicals and have the lower polymerization depth than clearer (M, I (r) = 1.20 a.u and MA2, I (r) = 1.02) or more translucent (OEA2, I (r) = 1.00 a.u) composites for the same light-curing time. It seems that irradiation doses have to be adequate to more colored and less translucent resins.

Intralamellar structural modifications related to the proton exchanging in K(4)Nb(6)O(17) layered phase

Basic structural aspects about the layered hexaniobate of K(4)Nb(6)O(17) composition and its proton-exchanged form were investigated mainly by spectroscopic techniques. Raman spectra of hydrous K(4)Nb(6)O(17) and H(2)K(2)Nb(6)O(17)center dot H(2)O show significant modifications in the 950-800 cm(-1) region (Nb-O stretching mode of highly distorted NbO(6) octahedra). The band at 900 cm(-1) shifts to 940 cm(-1) after the replacement of K(+) ion by proton. Raman spectra of the original materials and the related deuterated samples are similar suggesting that no isotopic effect occurs. Major modifications were observed when H(2)K(2)Nb(6)O(17) was dehydrated: the relative intensity of the band at 940 cm(-1) decreases and new bands seems to be present at about 860-890 cm(-1). The H(+) ions should be shielded by the hydration sphere what preclude the interaction with the layers. Removing the water molecules, H(+) ions can establish a strong interaction with oxygen atoms, decreasing the bond order of Nb-O linkage. X-ray absorption near edge structure studies performed at Nb K-edge indicate that the niobium coordination number and oxidation state remain identical after the replacement of potassium by proton. From the refinement of the fine structure, it appears that the Nb-Nb coordination shell is divided into two main contributions of about 0.33 and 0.39 nm, and interestingly the population, i.e., the number of backscattering atoms is inversed between the two hexaniobate materials. 2009 Elsevier Ltd. All rights reserved.

FT-Raman investigation of biodegradable polymers: Poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

This work presents a FT-Raman study (lambda(0) = 1064 nm) of naturally occurring polyester poly[(R)-3-hydroxybutyrate] (PHB) and its copolymer poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyvalerate] (PHBV) with 5,8 and 12 mol % of HV (hydroxyvalerate). The FT-Raman spectra of films indicate that full width at half height of the band centered at 1725 cm(-1) and relative intensity of bands at 1443 and 1458 cm(-1) can be use to estimate the crystalline degree in film samples. The similarity between Raman spectra of molten PHB and PHBV and theirs CDCl(3) solutions suggested that molten polymers present similar conformation than polymers in solution. Raman data of these samples showed that bands at 1220, 1402, 1725, 2998 and 3009 cm(-1) are due to crystalline helical structure and the bands at 1453, 1740, 2881, 2938 and 2990 cm(-1) are originated from disordered domains. It is shown that composition of PHBV samples can be estimated by analyzing the ratio of the intensity of the bands at 2938 cm(-1) (nu C-H) and 1740 cm(-1) (nu C=O) in the spectra of solutions and of bands at 1354 (wCH(2)) and 1740 cm(-1) (nu C=O) in spectra of molten polymers. (C) 2010 Elsevier B.V. All rights reserved.

On the Phase Transformation in Mechanically Alloyed Ni-Nb and Ni-Ta and Ni-Nb-Ta Powders

This paper reports on the phase transformation during the preparation of Ni-25Nb, Ni-25Ta, Ni-20Nb-5Ta and Ni-15Nb-10Ta (at-%) powders by high-energy ball milling from elemental powders. The milling process was performed in a planetary ball milling using stainless steel balls and vials, rotary speed of 300rpm, and a ball-to-powder of 10:1. To minimize contamination and spontaneous ignition the powders were handled under argon atmosphere in a glove box. The milled powders were characterized by means of X-ray diffraction techniques. Results indicated that the Ni atoms were preferentially dissolved into the Nb (and/or Ta) lattice at the initial milling times, which contributed to change the relative intensity on the diffraction peaks. After the dissolution of Nb (and/or Ta) into the Ni lattice, the Ni peaks were moved to the direction of lower diffraction angles in Ni-25Nb, Ni-25Ta, Ni-20Nb-5Ta, Ni-15Nb-10Ta powders, indicating that the mechanical alloying was achieved.

The vinyl bromide optically pumped far infrared laser: New large offset emissions

We present the results of a study on vinyl bromide for the search for new far infrared (FIR) laser lines. As the pump source, we use a CW waveguide CO2 laser with a tunability of 290 MHz around each line in order to pump large offset vibrational transitions. As a consequence, we obtained 28 new FIR laser emissions; 24 of them have wavelengths greater than 500 mum and are, therefore, suitable to be used in high-field EPR spectroscopy, For each of the new lines, we give the wavelength, the offset of the pumping transition with respect to the center Frequency of the CO2 emission, the polarization relative to that of the pumping laser line, the operating pressure, and the relative intensity. We also present a catalog including data of all of the FIR laser lines observed from this molecule up to now.

DCOOD optically pumped by a (CO2)-C-13 laser: new terahertz laser lines

In this work we report on new optically pumped THz laser lines from deuterated formic acid (DCOOD). An isotopic (CO2)-C-13 laser was used for the first time as a pump source for this molecule, and a Fabry-Perot cavity was used as a THz laser resonator. Optoacoustic absorption spectra were used as a guide to search for new THz laser lines. We could observe six new laser lines in the range from 303.8 mu m (0.987 THz) to 725.1 mu m (0.413 THz). The lines were characterized according to wavelength, relative polarization, relative intensity, and optimum working pressure. The transferred lamb-dip technique was used to measure the frequency absorption transition for both of these laser lines. Furthermore, we also present a catalogue of all THz laser lines generated from DCOOD.