Experimental and Theoretical Study on the One- and Two-Photon Absorption Properties of Novel Organic Molecules Based on Phenylacetylene and Azoaromatic Moieties

This Article reports a combined experimental and theoretical analysis on the one and two-photon absorption properties of a novel class of organic molecules with a pi-conjugated backbone based on phenylacetylene (JCM874, FD43, and FD48) and azoaromatic (YB3p2S) moieties. Linear optical properties show that the phenylacetylene-based compounds exhibit strong molar absorptivity in the UV and high fluorescence quantum yield with lifetimes of approximately 2.0 ns, while the azoaromatic-compound has a strong absorption in the visible region with very low fluorescence quantum yield. The two-photon absorption was investigated employing nonlinear optical techniques and quantum chemical calculations based on the response functions formalism within the density functional theory framework. The experimental data revealed well-defined 2PA spectra with reasonable cross-section values in the visible and IR. Along the nonlinear spectra we observed two 2PA allowed bands, as well as the resonance enhancement effect due to the presence of one intermediate one-photon allowed state. Quantum chemical calculations revealed that the 2PA allowed bands correspond to transitions to states that are also one-photon allowed, indicating the relaxation of the electric-dipole selection rules. Moreover, using the theoretical results, we were able to interpret the experimental trends of the 2PA spectra. Finally, using a few-energy-level diagram, within the sum-over-essential states approach, we observed strong qualitative and quantitative correlation between experimental and theoretical results.

Effect of Solvent-Induced Coil to Helix Conformational Change on the Two-Photon Absorption Spectrum of Poly(3,6-phenanthrene)

This paper investigates the effect of solvent-induced conformational changes of poly(3,6-phenanthrene) on their two-photon absorption (2PA). Such effect was studied employing the wavelength-tunable femtosecond Z-scan technique and modeled using the sum-over-essential states approach. We observed a strong reduction of the 2PA cross-section when the sample was prepared in hexane (poor solvent) in comparison to chloroform (good solvent), which is related to the conformation adopted by the polymer in each case. In chloroform it adopts a random coil conformation, as opposed to the one-handed helix conformation in hexane. Our results pointed out that the coil to helix conformation change decreases the degree of molecular planarity of the polymer pi-conjugated backbone, which is primarily responsible for their optical nonlinearity, contributing to diminishing the effective transition dipole moments and, consequently, the 2PA cross-section. Moreover, by studying the nonlinear response with different light polarization, we showed that, although the solvent-induced conformational change does not alter the molecular symmetry of the polymer, it modifies considerably the direction of the transition dipole moments between the excited states.

Levothyroxine Absorption in Morbidly Obese Patients Before and After Roux-En-Y Gastric Bypass (RYGB) Surgery

Roux-en-Y gastric bypass (RYGB) modifies the anatomical structure of the upper intestine tract, reduces gastric acid secretion, and may impair LT4 absorption. The aim of this study was to evaluate the LT4 absorption in morbidly obese patients before and after RYGB. Thirty morbidly obese patients were divided in two groups: The NS group included 15 patients before RYGB surgery (BMI = 43.1 +/- 4 kg/m(2)), and the S group included 15 patients after surgery (BMI = 37.3 +/- 4 kg/m(2)). Two baseline samples were collected, and 600 mu g of oral LT4 tablets were administered. Blood samples were collected at 30, 60, 120, 180, 240, 300, and 1440 min. Serum-free T4 (FT4), total T4 (TT4), and TSH were measured at each time point. The increase in TT4, FT4, and TSH (Delta TT4, Delta FT4, and Delta TSH) was calculated, subtracting from the baseline mean value. The pharmacokinetics parameters regarding LT4 absorption, maximum Delta TT4, and area under the curve(AUC) of both Delta TT4 and Delta FT4 were significantly higher in the S group compared with the NS group (p < 0.05). It was observed, however, that there was a significant delay in the absorption of LT4 in the S group. Basal serum TSH and leptin levels were higher in the NS group (p = 0.016 and 0.026, respectively), whereas basal serum TT4, FT4, Delta TSH, and the AUC of Delta TSH were similar between groups. In this study, we have demonstrated that Roux-en-Y bypass surgery does not diminish LT4 absorption. A small but significant delayed absorption of LT4, however, was observed in patients after surgery.

Thermal design of a tray-type distillation column of an ammonia/water absorption refrigeration cycle

The goal of this paper is to present an analysis of a segmented weir sieve-tray distillation column for a 17.58 kW (5 TR) ammonia/water absorption refrigeration cycle. Balances of mass and energy were performed based on the method of Ponchon-Savarit, from which it was possible to determine the ideal number of trays. The analysis showed that four ideal trays were adequate for that small absorption refrigeration system having the feeding system to the column right above the second tray. It was carried out a sensitivity analysis of the main parameters. Vapor and liquid pressure drop constraint along with ammonia and water mass flow ratios defined the internal geometrical sizes of the column, such as the column diameter and height, as well as other designing parameters. Due to the lack of specific correlations, the present work was based on practical correlations used in the petrochemical and beverage production industries. The analysis also permitted to obtain the recommended values of tray spacing in order to have a compact column. The geometry of the tray turns out to be sensitive to the charge of vapor and, to a lesser extent, to the load of the liquid, being insensible to the diameter of tray holes. It was found a column efficiency of 50%. Finally, the paper presents some recommendations in order to have an optimal geometry for a compact size distillation column. (c) 2011 Elsevier Ltd. All rights reserved.

Synthesis, characterization, optical absorption, luminescence and defect centres in Er3+ and Yb3+ co-doped MgAl2O4 phosphors

The Er3+-Yb3+ co-doped MgAl2O4 phosphor powders have been prepared by the combustion method. The phosphor powders are well characterized by X-ray diffraction (XRD) and energy dispersive (EDX) techniques. The absorption spectrum of Er3+/Er3+-Yb3+ doped/co-doped phosphor powder has been recorded in the UV-Vis-NIR region of the electro-magnetic spectrum. The evidence for indirect pumping under 980 nm excitation of Er3+ from Yb3+ was observed in the MgAl2O4 matrix material. Electron spin resonance (ESR) studies were carried out to identify the defect centres responsible for the thermally stimulated luminescence (TSL) process in MgAl2O4:Er3+ phosphor. Three defect centres were identified in irradiated phosphor by ESR measurements which were carried out at room temperature and these were assigned to an O- ion and F+ centres. O- ion (hole centre) appears to correlate with the low temperature TSL peak at 210 A degrees C and one of the F+ centres (electron centre) is related to the high temperature peak at 460 A degrees C.

Theoretical study of the absorption and nonradiative deactivation of 1-nitronaphthalene in the low-lying singlet and triplet excited states including methanol and ethanol solvent effects

The photophysics of the 1-nitronaphthalene molecular system, after the absorption transition to the first singlet excited state, is theoretically studied for investigating the ultrafast multiplicity change to the triplet manifold. The consecutive transient absorption spectra experimentally observed in this molecular system are also studied. To identify the electronic states involved in the nonradiative decay, the minimum energy path of the first singlet excited state is obtained using the complete active space self-consistent field//configurational second-order perturbation approach. A near degeneracy region was found between the first singlet and the second triplet excited states with large spin-orbit coupling between them. The intersystem crossing rate was also evaluated. To support the proposed deactivation model the transient absorption spectra observed in the experiments were also considered. For this, computer simulations using sequential quantum mechanic-molecular mechanic methodology was used to consider the solvent effect in the ground and excited states for proper comparison with the experimental results. The absorption transitions from the second triplet excited state in the relaxed geometry permit to describe the transient absorption band experimentally observed around 200 fs after the absorption transition. This indicates that the T-2 electronic state is populated through the intersystem crossing presented here. The two transient absorption bands experimentally observed between 2 and 45 ps after the absorption transition are described here as the T-1 -> T-3 and T-1 -> T-5 transitions, supporting that the intermediate triplet state (T-2) decays by internal conversion to T-1. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4738757]

The Role of Molecular Conformation and Polarizable Embedding for One- and Two-Photon Absorption of Disperse Orange 3 in Solution

Solvent effects on the one- and two-photon absorption (IPA and 2PA) of disperse orange 3 (DO3) in dimethyl sulfoxide (DMSO) are studied using a discrete polarizable embedding (PE) response theory. The scheme comprises a quantum region containing the chromophore and an atomically granulated classical region for the solvent accounting for full interactions within and between the two regions. Either classical molecular dynamics (MD) or hybrid Car-Parrinello (CP) quantum/classical (QM/MM) molecular dynamics simulations are employed to describe the solvation of DO3 in DMSO, allowing for an analysis of the effect of the intermolecular short-range repulsion, long-range attraction, and electrostatic interactions on the conformational changes of the chromophore and also the effect of the solute-solvent polarization. PE linear response calculations are performed to verify the character, solvatochromic shift, and overlap of the two lowest energy transitions responsible for the linear absorption spectrum of DO3 in DMSO in the visible spectral region. Results of the PE linear and quadratic response calculations, performed using uncorrelated solute-solvent configurations sampled from either the classical or hybrid CP QM/MM MD simulations, are used to estimate the width of the line shape function of the two electronic lowest energy excited states, which allow a prediction of the 2PA cross-sections without the use of empirical parameters. Appropriate exchange-correlation functionals have been employed in order to describe the charge-transfer process following the electronic transitions of the chromophore in solution.

Enhancement of optical absorption by modulation of the oxygen flow of TiO2 films deposited by reactive sputtering

Oxygen-deficient TiO2 films with enhanced visible and near-infrared optical absorption have been deposited by reactive sputtering using a planar diode radio frequency magnetron configuration. It is observed that the increase in the absorption coefficient is more effective when the O-2 gas supply is periodically interrupted rather than by a decrease of the partial O-2 gas pressure in the deposition plasma. The optical absorption coefficient at 1.5 eV increases from about 1 x 10(2) cm(-1) to more than 4 x 10(3) cm(-1) as a result of the gas flow discontinuity. A red-shift of similar to 0.24 eV in the optical absorption edge is also observed. High resolution transmission electron microscopy with composition analysis shows that the films present a dense columnar morphology, with estimated mean column width of 40nm. Moreover, the interruptions of the O-2 gas flow do not produce detectable variations in the film composition along its growing direction. X-ray diffraction and micro-Raman experiments indicate the presence of the TiO2 anatase, rutile, and brookite phases. The anatase phase is dominant, with a slight increment of the rutile and brookite phases in films deposited under discontinued O-2 gas flow. The increase of optical absorption in the visible and near-infrared regions has been attributed to a high density of defects in the TiO2 films, which is consistent with density functional theory calculations that place oxygen-related vacancy states in the upper third of the optical bandgap. The electronic structure calculation results, along with the adopted deposition method and experimental data, have been used to propose a mechanism to explain the formation of the observed oxygen-related defects in TiO2 thin films. The observed increase in sub-bandgap absorption and the modeling of the corresponding changes in the electronic structure are potentially useful concerning the optimization of efficiency of the photocatalytic activity and the magnetic doping of TiO2 films. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4724334]

Multivariate analyses of UV-Vis absorption spectral data from cachaca wood extracts: a model to classify aged Brazilian cachacas according to the wood species used

Multivariate analyses of UV-Vis spectral data from cachaca wood extracts provide a simple and robust model to classify aged Brazilian cachacas according to the wood species used in the maturation barrels. The model is based on inspection of 93 extracts of oak and different Brazilian wood species by a non-aged cachaca used as an extraction solvent. Application of PCA (Principal Components Analysis) and HCA (Hierarchical Cluster Analysis) leads to identification of 6 clusters of cachaca wood extracts (amburana, amendoim, balsamo, castanheira, jatoba, and oak). LDA (Linear Discriminant Analysis) affords classification of 10 different wood species used in the cachaca extracts (amburana, amendoim, balsamo, cabreuva-parda, canela-sassafras, castanheira, jatoba, jequitiba-rosa, louro-canela, and oak) with an accuracy ranging from 80% (amendoim and castanheira) to 100% (balsamo and jequitiba-rosa). The methodology provides a low-cost alternative to methods based on liquid chromatography and mass spectrometry to classify cachacas aged in barrels that are composed of different wood species.

Application of the Z-scan technique to determine the optical Kerr coefficient and two-photon absorption coefficient of magnetite nanoparticles colloidal suspension

We investigate the occurrence of the optical Kerr effect and two-photon absorption when an oil-based magnetic Fe3O4 nanoparticles colloidal suspension is illuminated with high intensity femtosecond laser pulses. The frequency of the pulses is controlled and the Z-scan technique is employed in our measurements of the nonlinear optical Kerr coefficient (n(2)) and two-photon absorption coefficient (beta). From these values it was possible to calculate the real and imaginary parts of the third-order susceptibility. We observed that increasing the pulse frequency, additional physical processes take place, increasing artificially the absolute values of n(2) and beta. The experimental conditions are discussed to assure the obtention of reliable values of these nonlinear optical parameters, which may be useful in all-optical switching and optical power limiting applications. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4723829]

Spatial-temporal variations in phytoplankton size and colored detrital matter absorption at global and regional scales, as derived from twelve years of SeaWiFS data (1998-2009)

A procedure has been proposed by Ciotti and Bricaud (2006) to retrieve spectral absorption coefficients of phytoplankton and colored detrital matter (CDM) from satellite radiance measurements. This was also the first procedure to estimate a size factor for phytoplankton, based on the shape of the retrieved algal absorption spectrum, and the spectral slope of CDM absorption. Applying this method to the global ocean color data set acquired by SeaWiFS over twelve years (1998-2009), allowed for a comparison of the spatial variations of chlorophyll concentration ([Chl]), algal size factor (S-f), CDM absorption coefficient (a(cdm)) at 443 nm, and spectral slope of CDM absorption (S-cdm). As expected, correlations between the derived parameters were characterized by a large scatter at the global scale. We compared temporal variability of the spatially averaged parameters over the twelve-year period for three oceanic areas of biogeochemical importance: the Eastern Equatorial Pacific, the North Atlantic and the Mediterranean Sea. In all areas, both S-f and a(cdm)(443) showed large seasonal and interannual variations, generally correlated to those of algal biomass. The CDM maxima appeared in some occasions to last longer than those of [Chl]. The spectral slope of CDM absorption showed very large seasonal cycles consistent with photobleaching, challenging the assumption of a constant slope commonly used in bio-optical models. In the Equatorial Pacific, the seasonal cycles of [Chl], S-f, a(cdm)(443) and S-cdm, as well as the relationships between these parameters, were strongly affected by the 1997-98 El Ni o/La Ni a event.

Two-Photon Cooperative Absorption in Colliding Cold Na Atoms

Two-photon cooperative absorption is common in solid-state physics. In a sample of trapped cold atoms, this effect may open up new possibilities for the study of nonlinear effects. The experiment described herein starts with two colliding Na atoms in the S hyperfine ground state. The pair absorb two photons, resulting in both a P-1/2 and a P-3/2 atom. This excitation is observed by ionization using an external light source. A simple model that considers only dipole-dipole interactions between the atoms allows us to understand the basic features observed in the experimental results. Both the pair of generated atoms and the photons originating from their decay are correlated and may have interesting applications that remain to be explored.

Two-photon absorption in oxazole derivatives: An experimental and quantum chemical study

Experimental and theoretical studies on the two-photon absorption properties of two oxazole derivatives: 2,5-diphenyloxazole (PPO) and 2-(4-biphenylyI)-5-phenyl-1,3,4-oxadiazole (PBD) are presented. The two-photon absorption cross-section spectra were determined by means of the Z-scan technique, from 460 up to 650 nm, and reached peak values of 84 GM for PBD and 27 GM for PPO. Density Functional Theory and response function formalism are used to determine the molecular structures and the one- and two-photon absorption properties and to assist in the interpretation of the experimental results. The Polarizable Continuum Model in one-photon absorption calculations is used to estimate solvent effects. (C) 2011 Elsevier B.V. All rights reserved.

Determination of chlorine in food samples via the AlCl molecule using high-resolution continuum source molecular absorption spectrometry in a graphite furnace

Determination of chlorine using the molecular absorption of aluminum mono-chloride (AlCl) at the 261.418 nm wavelength was accomplished by high-resolution continuum source molecular absorption spectrometry using a transversely heated graphite tube furnace with an integrated platform. For the analysis. 10 mu L of the sample followed by 10 mu L of a solution containing Al-Ag-Sr modifier, (1 g L-1 each), were directly injected onto the platform. A spectral interference due to the use of Al-Ag-Sr as mixed modifier was easily corrected by the least-squares algorithm present in the spectrometer software. The pyrolysis and vaporization temperatures were 500 degrees C and 2200 degrees C, respectively. To evaluate the feasibility of a simple procedure for the determination of chlorine in food samples present in our daily lives, two different digestion methods were applied, namely (A) an acid digestion method using HNO3 only at room temperature, and (B) a digestion method with Ag, HNO3 and H2O2, where chlorine is precipitated as a low-solubility salt (AgCl), which is then dissolved with ammonia solution. The experimental results obtained with method B were in good agreement with the certified values and demonstrated that the proposed method is more accurate than method A. This is because the formation of silver chloride prevented analyte losses by volatilization. The limit of detection (LOD, 3 sigma/s) for Cl in methods A and B was 18 mu g g(-1) and 9 mu g g(-1), respectively, 1.7 and 3.3 times lower compared to published work using inductively coupled plasma optical emission spectrometry, and absolute LODs were 2.4 and 1.2 ng, respectively. (C) 2012 Elsevier B.V. All rights reserved.

Study of singlet excited state absorption spectrum of lutetium bisphthalocyanine using the femtosecond Z-scan technique

In this study we investigate the singlet excited state absorption of lutetium bisphthalocyanine (LuPc2) over a wide spectral range. It was observed distinct nonlinear absorption behaviors; saturable (SA) and reverse saturable absorption (RSA). The RSA effect was observed below 640 and above 680 nm, while SA occurs around the Q-band region, located around 660 nm. To describe the main singlet-singlet transitions, we employed the rate equation model considering the simplified three-energy level diagram. Our results reveal a ratio between excited and ground state absorption smaller than 0.05 at the Q-band region, and of approximately 4 for the other regions. (C) 2012 Elsevier B.V. All rights reserved.