Effect of the vanadium(V) concentration on the spectroscopic properties of nanosized europium-doped yttrium phosphates

Nanosized rare earth phosphovanadate phosphors (Y(P,V)O-4:Eu3+) have been prepared by applying the organic-inorganic polymeric precursors methodology. Luminescent powders with tetragonal structure and different vanadate concentrations (0%, 1%, 5%, 10%, 20%, 50%, and 100%, with regard to the phosphate content) were then obtained for evaluation of their structural and spectroscopic properties. The solids were characterized by scanning electron microscopy, X-ray diffractometry, vibrational spectroscopy (Raman and infrared), and electronic spectroscopy (emission, excitation, luminescence lifetimes, chromaticity, quantum efficiencies, and Judd-Ofelt intensity parameters). The solids exhibited very intense D-5(0) -> F-7(J) Eu3+ transitions, and it was possible to control the luminescent characteristics, such as excitation maximum, lifetime and emission colour, through the vanadium(V) concentration. The observed luminescent properties correlated to the characteristics of the chemical environments around the Eu3+ ions with respect to the composition of the phosphovanadates. The Eu3+ luminescence spectroscopy results indicated that the presence of larger vanadium(V) amounts in the phosphate host lattice led to more covalent and polarizable chemical environments. So, besides allowing for control of the luminescent properties of the solids, the variation in the vanadate concentration in the obtained YPO4:Eu3+ phosphors enabled the establishment of a strict correlation between the observable spectroscopic features and the chemical characteristics of the powders.

Thiosaccharine disulfide: synthesis, crystal structure, spectroscopic characterization and theoretical study

The title compound, (thiosaccharine disulfide), bis[1,10dioxide-2,3-dihidro-1,2-benzoisothiazol]disulfide, (tsac)2 has been synthesized and fully characterized by UV–Visible, IR, Raman, 1H and 13C NMR spectroscopy elemental analysis and structural X-ray crystallography. A DFT theoretical study has been performed and good agreement between experimental and theoretical values of structural parameters and vibration frequencies have been achieved.

Application of chromatographic and spectroscopic techniques in the evaluation of the lipid fraction of animal products

Lipolysis and oxidation of lipids in foods are the major biochemical and chemical processes that cause food quality deterioration, leading to the characteristic, unpalatable odour and flavour called rancidity. In addition to unpalatability, rancidity may give rise to toxic levels of certain compounds like aldehydes, hydroperoxides, epoxides and cholesterol oxidation products. In this PhD study chromatographic and spectroscopic techniques were employed to determine the degree of rancidity in different animal products and its relationship with technological parameters like feeding fat sources, packaging, processing and storage conditions. To achieve this goal capillary gas chromatography (CGC) was employed not only to determine the fatty acids profile but also, after solid phase extraction, the amount of free fatty acids (FFA), diglycerides (DG), sterols (cholesterol and phytosterols) and cholesterol oxidation products (COPs). To determine hydroperoxides, primary products of oxidation and quantify secondary products UV/VIS absorbance spectroscopy was applied. Most of the foods analysed in this study were meat products. In actual fact, lipid oxidation is a major deterioration reaction in meat and meat products and results in adverse changes in the colour, flavour and texture of meat. The development of rancidity has long recognized as a serious problem during meat handling, storage and processing. On a dairy product, a vegetal cream, a study of lipid fraction and development of rancidity during storage was carried out to evaluate its shelf-life and some nutritional features life saturated/unsaturated fatty acids ratio and phytosterols content. Then, according to the interest that has been growing around functional food in the last years, a new electrophoretic method was optimized and compared with HPLC to check the quality of a beehive product like royal jelly. This manuscript reports the main results obtained in the five activities briefly summarized as follows: 1) comparison between HPLC and a new electrophoretic method in the evaluation of authenticity of royal jelly; 2) study of the lipid fraction of a vegetal cream under different storage conditions; 3) study of lipid oxidation in minced beef during storage under a modified atmosphere packaging, before and after cooking; 4) evaluation of the influence of dietary fat and processing on the lipid fraction of chicken patties; 5) study of the lipid fraction of typical Italian and Spanish pork dry sausages and cured hams.

Quantum effects and dynamics in hydrogen-bonded systems: a first-principles approach to spectroscopic experiments

Computer simulations have become an important tool in physics. Especially systems in the solid state have been investigated extensively with the help of modern computational methods. This thesis focuses on the simulation of hydrogen-bonded systems, using quantum chemical methods combined with molecular dynamics (MD) simulations. MD simulations are carried out for investigating the energetics and structure of a system under conditions that include physical parameters such as temperature and pressure. Ab initio quantum chemical methods have proven to be capable of predicting spectroscopic quantities. The combination of these two features still represents a methodological challenge. Furthermore, conventional MD simulations consider the nuclei as classical particles. Not only motional effects, but also the quantum nature of the nuclei are expected to influence the properties of a molecular system. This work aims at a more realistic description of properties that are accessible via NMR experiments. With the help of the path integral formalism the quantum nature of the nuclei has been incorporated and its influence on the NMR parameters explored. The effect on both the NMR chemical shift and the Nuclear Quadrupole Coupling Constants (NQCC) is presented for intra- and intermolecular hydrogen bonds. The second part of this thesis presents the computation of electric field gradients within the Gaussian and Augmented Plane Waves (GAPW) framework, that allows for all-electron calculations in periodic systems. This recent development improves the accuracy of many calculations compared to the pseudopotential approximation, which treats the core electrons as part of an effective potential. In combination with MD simulations of water, the NMR longitudinal relaxation times for 17O and 2H have been obtained. The results show a considerable agreement with the experiment. Finally, an implementation of the calculation of the stress tensor into the quantum chemical program suite CP2K is presented. This enables MD simulations under constant pressure conditions, which is demonstrated with a series of liquid water simulations, that sheds light on the influence of the exchange-correlation functional used on the density of the simulated liquid.

From supramolecular sheets to fibers and back: establishing the critical parameters that govern the morphology of pyrene-based self-assembled materials

The precise arraying of functional entities in morphologically well-defined shapes remains one of the key challenges in the processing of organic molecules1. Among various π-conjugated species, pyrene exhibits a set of unique properties, which make it an attractive compound for the utilization in materials science2. In this contribution we report on properties of self-assembled structures prepared from amphiphilic pyrene trimers (Py3) consisting of phosphodiester-linked pyrenes. Depending on the geometry of a pyrene core substitution (1.6-, 1.8-, or 2.7- type, see Scheme), the thermally-controlled self-assembly allows the preparation of supramolecular architectures of different morphologies in a bottom-up approach: two-dimensional (2D) nanosheets3 are formed in case of 1.6- and 2.7-substitution4 whereas one-dimensional (1D) fibers are built from 1.8- substituted isomers. The morphologies of the assemblies are established by AFM and TEM, and the results are further correlated with spectroscopic and scattering data. Two-dimensional assemblies consist of an inner layer of hydrophobic pyrenes, sandwiched between a net of phosphates. Due to the repulsion of the negative charges, the 2D assemblies exist mostly as free-standing sheets. An internal alignment of pyrenes leads to strong exciton coupling with an unprecedented observation (simultaneous development of J- and H-bands from two different electronic transitions). Despite the similarity in spectroscopic properties, the structural parameters of the 2D aggregates drastically depend on the preparation procedure. Under certain conditions extra-large sheets (thickness of 2 nm, aspect ratio area/thickness ~107) in aqueous solution are formed4B. Finally, one-dimensional assemblies are formed as micrometer-long and nanometer-thick fibers. Both, planar and linear structures are intriguing objects for the creation of conductive nanowires that may find interest for applications in supramolecular electronics.

From supramolecular sheets to fibers and back: establishing the critical parameters that govern the morphology of pyrene-based self-assembled materials

The precise arraying of functional entities in morphologically well-defined shapes remains one of the key challenges in the processing of organic molecules1. Among various π-conjugated species, pyrene exhibits a set of unique properties, which make it an attractive compound for the utilization in materials science2. In this contribution we report on properties of self-assembled structures prepared from amphiphilic pyrene trimers (Py3) consisting of phosphodiester-linked pyrenes. Depending on the geometry of a pyrene core substitution (1.6-, 1.8-, or 2.7- type, see Scheme), the thermally-controlled self-assembly allows the preparation of supramolecular architectures of different morphologies in a bottom-up approach: two-dimensional (2D) nanosheets3 are formed in case of 1.6- and 2.7-substitution4 whereas one-dimensional (1D) fibers are built from 1.8- substituted isomers. The morphologies of the assemblies are established by AFM and TEM, and the results are further correlated with spectroscopic and scattering data. Two-dimensional assemblies consist of an inner layer of hydrophobic pyrenes, sandwiched between a net of phosphates. Due to the repulsion of the negative charges, the 2D assemblies exist mostly as free-standing sheets. An internal alignment of pyrenes leads to strong exciton coupling with an unprecedented observation (simultaneous development of J- and H-bands from two different electronic transitions). Despite the similarity in spectroscopic properties, the structural parameters of the 2D aggregates drastically depend on the preparation procedure. Under certain conditions extra-large sheets (thickness of 2 nm, aspect ratio area/thickness ~107) in aqueous solution are formed4B. Finally, one-dimensional assemblies are formed as micrometer-long and nanometer-thick fibers. Both, planar and linear structures are intriguing objects for the creation of conductive nanowires that may find interest for applications in supramolecular electronics.

High resolution spectroscopic characterization of the FGK stars in the Solar neighborhood

We present the most recent results of our ongoing long-term high resolution spectroscopic study of nearby (d ≤ 25 pc) FGK stars which aim is to characterize the local properties of the Galaxy, in particular the star-formation history. A through analysis has been carried out for 253 cool stars in the solar neighborhood. This includes radial and rotational velocities determinations, chromospheric activity levels inference, kinematic analysis, and age estimates. This study does not only shed new light on the issue of stellar formation history but also contributes to any present or future mission aiming to detect extra-solar planets. Exo-planets are likely to be found orbiting around nearby cool stars and their detection and characterization is highly dependent on the precise determination of fundamental stellar parameters such as age, activity levels. Therefore, our study is of paramount importance to ensure the success of any such mission.

Astrophysical parameters and orbital solution of the peculiar X-ray transient IGR J00370+6122

Context. BD + 60° 73 is the optical counterpart of the X-ray source IGR J00370+6122, a probable accretion-powered X-ray pulsar. The X-ray light curve of this binary system shows clear periodicity at 15.7 d, which has been interpreted as repeated outbursts around the periastron of an eccentric orbit. Aims. We aim to characterise the binary system IGR J00370+6122 by deriving its orbital and physical parameters. Methods. We obtained high-resolution spectra of BD + 60° 73 at different epochs. We used the fastwind code to generate a stellar atmosphere model to fit the observed spectrum and obtain physical magnitudes. The synthetic spectrum was used as a template for cross-correlation with the observed spectra to measure radial velocities. The radial velocity curve provided an orbital solution for the system. We also analysed the RXTE/ASM and Swift/BAT light curves to confirm the stability of the periodicity. Results. BD + 60° 73 is a BN0.7 Ib low-luminosity supergiant located at a distance ~3.1 kpc, in the Cas OB4 association. We derive Teff = 24 000 K and log gc = 3.0, and chemical abundances consistent with a moderately high level of evolution. The spectroscopic and evolutionary masses are consistent at the 1-σ level with a mass M∗ ≈ 15 M⊙. The recurrence time of the X-ray flares is the orbital period of the system. The neutron star is in a high-eccentricity (e = 0.56 ± 0.07) orbit, and the X-ray emission is strongly peaked around orbital phase φ = 0.2, though the observations are consistent with some level of X-ray activity happening at all orbital phases. Conclusions. The X-ray behaviour of IGR J00370+6122 is reminiscent of “intermediate” supergiant X-ray transients, though its peak luminosity is rather low. The orbit is somewhat wider than those of classical persistent supergiant X-ray binaries, which when combined with the low luminosity of the mass donor, explains the low X-ray luminosity. IGR J00370+6122 will very likely evolve towards a persistent supergiant system, highlighting the evolutionary connection between different classes of wind-accreting X-ray sources.

Measuring the stellar wind parameters in IGR J17544-2619 and Vela X-1 constrains the accretion physics in supergiant fast X-ray transient and classical supergiant X-ray binaries

Context. Classical supergiant X-ray binaries (SGXBs) and supergiant fast X-ray transients (SFXTs) are two types of high-mass X-ray binaries (HMXBs) that present similar donors but, at the same time, show very different behavior in the X-rays. The reason for this dichotomy of wind-fed HMXBs is still a matter of debate. Among the several explanations that have been proposed, some of them invoke specific stellar wind properties of the donor stars. Only dedicated empiric analysis of the donors’ stellar wind can provide the required information to accomplish an adequate test of these theories. However, such analyses are scarce. Aims. To close this gap, we perform a comparative analysis of the optical companion in two important systems: IGR J17544-2619 (SFXT) and Vela X-1 (SGXB). We analyze the spectra of each star in detail and derive their stellar and wind properties. As a next step, we compare the wind parameters, giving us an excellent chance of recognizing key differences between donor winds in SFXTs and SGXBs. Methods. We use archival infrared, optical and ultraviolet observations, and analyze them with the non-local thermodynamic equilibrium (NLTE) Potsdam Wolf-Rayet model atmosphere code. We derive the physical properties of the stars and their stellar winds, accounting for the influence of X-rays on the stellar winds. Results. We find that the stellar parameters derived from the analysis generally agree well with the spectral types of the two donors: O9I (IGR J17544-2619) and B0.5Iae (Vela X-1). The distance to the sources have been revised and also agree well with the estimations already available in the literature. In IGR J17544-2619 we are able to narrow the uncertainty to d = 3.0 ± 0.2 kpc. From the stellar radius of the donor and its X-ray behavior, the eccentricity of IGR J17544-2619 is constrained to e< 0.25. The derived chemical abundances point to certain mixing during the lifetime of the donors. An important difference between the stellar winds of the two stars is their terminal velocities (ν∞ = 1500 km s-1 in IGR J17544-2619 and ν∞ = 700 km s-1 in Vela X-1), which have important consequences on the X-ray luminosity of these sources. Conclusions. The donors of IGR J17544-2619 and Vela X-1 have similar spectral types as well as similar parameters that physically characterize them and their spectra. In addition, the orbital parameters of the systems are similar too, with a nearly circular orbit and short orbital period. However, they show moderate differences in their stellar wind velocity and the spin period of their neutron star which has a strong impact on the X-ray luminosity of the sources. This specific combination of wind speed and pulsar spin favors an accretion regime with a persistently high luminosity in Vela X-1, while it favors an inhibiting accretion mechanism in IGR J17544-2619. Our study demonstrates that the relative wind velocity is critical in class determination for the HMXBs hosting a supergiant donor, given that it may shift the accretion mechanism from direct accretion to propeller regimes when combined with other parameters.

Spectroscopic analysis of terrestrial analogues for the interpretation of surface composition of rocky bodies in the solar system. Effects of mineral mixing and particle size. Applications to moon, mars and implications for mercury.

Among the Solar System’s bodies, Moon, Mercury and Mars are at present, or have been in the recent years, object of space missions aimed, among other topics, also at improving our knowledge about surface composition. Between the techniques to detect planet’s mineralogical composition, both from remote and close range platforms, visible and near-infrared reflectance (VNIR) spectroscopy is a powerful tool, because crystal field absorption bands are related to particular transitional metals in well-defined crystal structures, e.g., Fe2+ in M1 and M2 sites of olivine or pyroxene (Burns, 1993). Thanks to the improvements in the spectrometers onboard the recent missions, a more detailed interpretation of the planetary surfaces can now be delineated. However, quantitative interpretation of planetary surface mineralogy could not always be a simple task. In fact, several factors such as the mineral chemistry, the presence of different minerals that absorb in a narrow spectral range, the regolith with a variable particle size range, the space weathering, the atmosphere composition etc., act in unpredictable ways on the reflectance spectra on a planetary surface (Serventi et al., 2014). One method for the interpretation of reflectance spectra of unknown materials involves the study of a number of spectra acquired in the laboratory under different conditions, such as different mineral abundances or different particle sizes, in order to derive empirical trends. This is the methodology that has been followed in this PhD thesis: the single factors previously listed have been analyzed, creating, in the laboratory, a set of terrestrial analogues with well-defined composition and size. The aim of this work is to provide new tools and criteria to improve the knowledge of the composition of planetary surfaces. In particular, mixtures composed with different content and chemistry of plagioclase and mafic minerals have been spectroscopically analyzed at different particle sizes and with different mineral relative percentages. The reflectance spectra of each mixture have been analyzed both qualitatively (using the software ORIGIN®) and quantitatively applying the Modified Gaussian Model (MGM, Sunshine et al., 1990) algorithm. In particular, the spectral parameter variations of each absorption band have been evaluated versus the volumetric FeO% content in the PL phase and versus the PL modal abundance. This delineated calibration curves of composition vs. spectral parameters and allow implementation of spectral libraries. Furthermore, the trends derived from terrestrial analogues here analyzed and from analogues in the literature have been applied for the interpretation of hyperspectral images of both plagioclase-rich (Moon) and plagioclase-poor (Mars) bodies.

Influence of parameters of drying on laser induced diffuse reflectance of banana discs

Banana discs of 1 cm thickness were immersed into different antioxidant solutions to slow down potentially disturbing discoloration during drying. Samples were randomly split into 8 groups according to the 2^p experimental design. Two antioxidant solutions with 1.66% and 4.59% ascorbic acid, two levels of drying temperature with 50°C and 80°C, two levels of drying time with 6h and 8h were used or adjusted. Laser diodes of seven wavelengths (532, 635, 650, 780, 808, 850 and 1064 nm) were selected to illuminate the surface and light penetration pattern was evaluated on the basis of radial profiles. Profiles acquired at three wavelengths (532, 635 and 650 nm) were found to respond sensitively to adjusted parameters. As a result of drying, intensity decay was observed to move closer to incident point. Significant effect (p<0.01) of temperature, drying time and their interaction was found on extracted descriptive attributes of intensity profiles: full width at half maximum (FWHM), distance of inflection point (DIP) and slope of logarithmic decay (SLD). Beyond their presence, antioxidant concentration was neutral factor without significant contribution to the model. Results were in agreement with reference spectroscopic measurements, especially with NDVI index. Promising results suggest that evaluated method might be suitable for monitoring purposes during drying of fruits.

Discrimination of honey of different floral origins by a combination of various chemical parameters

Abstract Honey is a high value food commodity with recognized nutraceutical properties. A primary driver of the value of honey is its floral origin. The feasibility of applying multivariate data analysis to various chemical parameters for the discrimination of honeys was explored. This approach was applied to four authentic honeys with different floral origins (rata, kamahi, clover and manuka) obtained from producers in New Zealand. Results from elemental profiling, stable isotope analysis, metabolomics (UPLC-QToF MS), and NIR, FT-IR, and Raman spectroscopic fingerprinting were analyzed. Orthogonal partial least square discriminant analysis (OPLS-DA) was used to determine which technique or combination of techniques provided the best classification and prediction abilities. Good prediction values were achieved using metabolite data (for all four honeys, Q² = 0.52; for manuka and clover, Q² = 0.76) and the trace element/isotopic data (for manuka and clover, Q² = 0.65), while the other chemical parameters showed promise when combined (for manuka and clover, Q² = 0.43).

Effects Of High Pressure Homogenization On The Activity, Stability, Kinetics And Three-dimensional Conformation Of A Glucose Oxidase Produced By Aspergillus Niger.

High pressure homogenization (HPH) is a non-thermal method, which has been employed to change the activity and stability of biotechnologically relevant enzymes. This work investigated how HPH affects the structural and functional characteristics of a glucose oxidase (GO) from Aspergillus niger. The enzyme was homogenized at 75 and 150 MPa and the effects were evaluated with respect to the enzyme activity, stability, kinetic parameters and molecular structure. The enzyme showed a pH-dependent response to the HPH treatment, with reduction or maintenance of activity at pH 4.5-6.0 and a remarkable activity increase (30-300%) at pH 6.5 in all tested temperatures (15, 50 and 75°C). The enzyme thermal tolerance was reduced due to HPH treatment and the storage for 24 h at high temperatures (50 and 75°C) also caused a reduction of activity. Interestingly, at lower temperatures (15°C) the activity levels were slightly higher than that observed for native enzyme or at least maintained. These effects of HPH treatment on function and stability of GO were further investigated by spectroscopic methods. Both fluorescence and circular dichroism revealed conformational changes in the molecular structure of the enzyme that might be associated with the distinct functional and stability behavior of GO.

Understanding Red Blood Cell Parameters In The Context Of The Frailty Phenotype: Interpretations Of The Fibra (frailty In Brazilian Seniors) Study.

Frailty and anemia in the elderly appear to share a common pathophysiology associated with chronic inflammatory processes. This study uses an analytical, cross-sectional, population-based methodology to investigate the probable relationships between frailty, red blood cell parameters and inflammatory markers in 255 community-dwelling elders aged 65 years or older. The frailty phenotype was assessed by non-intentional weight loss, fatigue, low grip strength, low energy expenditure and reduced gait speed. Blood sample analyses were performed to determine hemoglobin level, hematocrit and reticulocyte count, as well as the inflammatory variables IL-6, IL-1ra and hsCRP. In the first multivariate analysis (model I), considering only the erythroid parameters, Hb concentration was a significant variable for both general frailty status and weight loss: a 1.0g/dL drop in serum Hb concentration represented a 2.02-fold increase (CI 1.12-3.63) in an individual's chance of being frail. In the second analysis (model II), which also included inflammatory cytokine levels, hsCRP was independently selected as a significant variable. Each additional year of age represented a 1.21-fold increase in the chance of being frail, and each 1-unit increase in serum hsCRP represented a 3.64-fold increase in the chance of having the frailty phenotype. In model II reticulocyte counts were associated with weight loss and reduced metabolic expenditure criteria. Our findings suggest that reduced Hb concentration, reduced RetAbs count and elevated serum hsCRP levels should be considered components of frailty, which in turn is correlated with sarcopenia, as evidenced by weight loss.

Micronutrient And Physiologic Parameters Before And 6 Months After Rygb.

Bariatric surgery is considered an effective method for sustained weight loss, but may cause various nutritional complications. The aim of this study was to evaluate the nutritional status of minerals and vitamins, food consumption, and to monitor physiologic parameters in patients with obesity before and 6 months after Roux-en-Y gastric bypass surgery (RYGB). Thirty-six patients who had undergone RYGB were prospectively evaluated before and 6 months after surgery. At each phase their weight, height, body mass index (BMI), Electro Sensor Complex (ES Complex) data, food consumption, and total protein serum levels, albumin, prealbumin, parathyroid hormone (PTH), zinc (Zn), B12 vitamin (VitB12), iron (Fe), ferritin, copper (Cu), ionic calcium (CaI), magnesium (Mg), and folic acid were assessed. The mean weight loss from baseline to 6 months after surgery was 35.34±4.82%. Markers of autonomic nervous system balance (P<.01), stiffness index (P<.01), standard deviation of normal-to-normal R-R intervals (SDNN) (P<.01), and insulin resistance (P<.001) were also improved. With regard to the micronutrients measured, 34 patients demonstrated some kind of deficiency. There was a high percentage of Zn deficiency in both pre- (55.55%) and postoperative (61.11%) patients, and 33.33% of the patients were deficient in prealbumin postoperatively. The protein intake after 6 months of surgery was below the recommended intake (<70 g/d) for 88.88% of the patients. Laboratory analyses demonstrated an average decrease in total protein (P<.05), prealbumin (P = .002), and PTH (P = .008) between pre- and postsurgery, and a decrease in the percentage of deficiencies for Mg (P<.05), CaI (P<.05), and Fe (P = .021). Despite improvements in the autonomic nervous system balance, stiffness index markers and insulin resistance, we found a high prevalence of hypozincemia at 6 months post-RYGB. Furthermore, protein supplements were needed to maintain an adequate protein intake up to 6 months postsurgery.