Estudo de complexos de ferro e de cobre com a base de Shiff 3-Meosalen e ligantes de relevância biológica

The goal set for this work was to synthesize and to characterize new iron and copper complexes with the Schiff base 3-MeOsalen and ligands of biological relevance, whose formulas are [Fe(3-MeOsalen)NO2], [Fe(3-MeOsalen)(etil2-dtc)], [Fe(3-MeOsalen)NO] and Na[Cu(3-MeOsalen)NO2]. The compounds were characterized by vibrational spectroscopy in the infrared region (IV) and Electronic spectroscopy in the ultraviolet and visible region (Uv-Vis). From the analysis of infrared spectra, they proved to formation of precursor complexes, as evidenced by changes in the vibrationals frequencies ν(C=N) e ν(C-O) and the emergence of vibrationals modes metal-oxygen and metal-nitrogen. For nitro complexes of iron and copper were observed ν(NO2)ass around 1300 cm-1 e ν(NO2)sim in 1271 cm-1 , indicating that the coordination is done via the nitrogen atom. The complex spectrum [Fe(3-MeOsalen)(etil2-dtc)] exhibited two bands, the ν(C-NR2) in 1508 cm-1 e ν(C-S) in 997 cm-1 , the relevant vibrational modes of coordinating ligand in the bidentate form. For the complex [Fe(3-MeOsalen)NO] was observed a new intense band in 1670 cm-1 related to the ν(NO). With the electronic spectra, the formation of complexes was evidenced by shifts of bands intraligands transitions and the emergence of new bands such as LMCT (p Cl-  d* Fe3+) in [Fe(3-MeOsalen)Cl] and the d-d in [Cu(3-MeOsalen)H2O]. As for the [Fe(3-MeOsalen)NO2] has highlighted the absence of LMCT band present in the precursor complex as for the [Cu(3-MeOsalen)NO2] found that the displacement of the band hipsocrômico d-d on 28 nm. The electronic spectrum of [Fe(3-MeOsalen)(etil2-dtc)] presented LMCT band shifts and changes in intraligantes transitions. With regard to [Fe(3-MeOsalen)NO], revealed a more energetic transitions intraligands regions from the strong character π receiver NO and MLCT band of transition dπFe(II)π*(NO).

Aplicação de géis de goma guar no processo de clarificação de salmouras e águas produzidas

Produced water is considered the main effluent of the oil industry, due to their increased volume in mature fields and its varied composition. The oil and grease content (TOG) is the main parameter for the final disposal of produced water. In this context, it is of great significance to develop an alternative method based on guar gum gel for the treatment of synthetic produced water, and using as the differential a polymer having high hydrophilicity for clarifying waters contaminated with oil. Thus, this study aims to evaluate the efficiency of guar gum gels in the remotion of oil from produced water. Guar gum is a natural polymer that, under specific conditions, forms three-dimensional structures, with important physical and chemical properties. By crosslinking the polymer chains by borate ions in the presence of salts, the effect salting out occurs, reducing the solubility of the polymer gel in water. As a result, there is phase separation with the oil trapped in the collapsed gel. The TOG was quantified from the spectroscopy in the ultraviolet and visible region. The system was proven to be highly efficient in the removal of dispersed oil from water produced synthetically, reaching removal percentages above 90%.

Loading effect in copper(II) oxide cluster-surface-modified titanium(IV) oxide on visible- and UV-light activities

Cu(acac)2 is chemisorbed on TiO2 particles [P-25 (anatase/rutile = 4/1 w/w), Degussa] via coordination by surface Ti–OH groups without elimination of the acac ligand. Post-heating of the Cu(acac)2-adsorbed TiO2 at 773 K yields molecular scale copper(II) oxide clusters on the surface (CuO/TiO2). The copper loading amount (Γ/Cu ions nm–2) is controlled in a wide range by the Cu(acac)2 concentration and the chemisorption–calcination cycle number. Valence band (VB) X-ray photoelectron and photoluminescence spectroscopy indicated that the VB maximum of TiO2 rises up with increasing Γ, while vacant midgap levels are generated. The surface modification gives rise to visible-light activity and concomitant significant increase in UV-light activity for the degradation of 2-naphthol and p-cresol. Prolonging irradiation time leads to the decomposition to CO2, which increases in proportion to irradiation time. The photocatalytic activity strongly depends on the loading, Γ, with an optimum value of Γ for the photocatalytic activity. Electrochemical measurements suggest that the surface CuO clusters promote the reduction of adsorbed O2. First principles density functional theory simulations clearly show that, at Γ < 1, unoccupied Cu 3d levels are generated in the midgap region, and at Γ > 1, the VB maximum rises and the unoccupied Cu 3d levels move to the conduction band minimum of TiO2. These results suggest that visible-light excitation of CuO/TiO2 causes the bulk-to-surface interfacial electron transfer at low coverage and the surface-to-bulk interfacial electron transfer at high coverage. We conclude that the surface CuO clusters enhance the separation of photogenerated charge carriers by the interfacial electron transfer and the subsequent reduction of adsorbed O2 to achieve the compatibility of high levels of visible and UV-light activities.

LOTUS: A low cost, ultraviolet spectrograph

We describe the design, construction and commissioning of LOTUS; a simple, low-cost long-slit spectrograph for the Liverpool Telescope. The design is optimized for near-UV and visible wavelengths and uses all transmitting optics. It exploits the instrument focal plane field curvature to partially correct axial chromatic aberration. A stepped slit provides narrow (2.5x95 arcsec) and wide (5x25 arcsec) options that are optimized for spectral resolution and flux calibration respectively. On sky testing shows a wavelength range of 3200-6300 Angstroms with a peak system throughput (including detector quantum efficiency) of 15 per cent and wavelength dependant spectral resolution of R=225-430. By repeated observations of the symbiotic emission line star AG Peg we demonstrate the wavelength stability of the system is less than 2 Angstroms rms and is limited by the positioning of the object in the slit. The spectrograph is now in routine operation monitoring the activity of comet 67P/Churyumov-Gerasimenko during its current post-perihelion apparition.

Remoción de la hemoglobina por adsorción sobre nanopartículas magnéticas de Fe3O4/TiO2

La remoción de la hemoglobina (Hb) por adsorción de la proteína sobre nanopartículas (Nps) magnéticas de Fe3O4/TiO2 (núcleo/coraza) aplicando un campo magnético externo, fue investigada mediante espectroscopia ultravioleta en el rango del ultravioleta y visible (UV-VIS). Durante la etapa de contacto de las Nps con la Hb se varió la concentración de las Nps y la temperatura, complementariamente durante la etapa de remoción del complejo Fe3O4/TiO2-Hb se varió la intensidad del campo magnético externo. Con una concentración inicial de Nps de 8 mg ml-1, el valor de la absorbancia del sobrenadante disminuye en un 11% con respecto a la solución inicial de Hb (0,8 g l-1) y al aumentar en un 50% la concentración de Nps, el valor disminuye hasta un 17%. Al incrementar la temperatura de 25 a 35ºC disminuye la adsorción de la Hb pero no se observa indicios de desnaturalización de la misma. Durante la etapa de remoción del complejo Fe3O4/TiO2-Hb, al incrementar la fuerza magnética se logra una caída en la intensidad de la absorbancia, casi un 30%. Finalmente, se determinó la demanda bioquímica de oxígeno (DBO5) de la solución inicial de Hb y del sobrenandante, el valor para la solución inicial de Hb fue de 100 mg ml-1 y los resultados obtenidos para todas las soluciones tratadas fueron inferiores (62 mg ml-1) verificando el impacto que tuvo el uso de las Nps magnéticas de Fe3O4/TiO2 en la remoción de la Hb.

José de Escovar at the Chapel of the Souls: Technical and Material Study of a 1603 Panel Painting

This article reports the preliminary results of a technical and material study carried out on a 17th century panel painting located at the Chapel of the Souls in the main church of Vila Nova da Baronia (30 km away from Evora city, in southern Portugal). This painting is attributed to Jose the Escovar, a painter that worked for Evora Archiepiscopate between 1583 and 1622. Jose the Escovar is known by his mural paintings all across the Alentejo region. This is the first time that a panel painting made by this artist was studied. Analytical methods used included in situ technical photography (visible (Vis), raking light (RAK), infrared (IR), and ultraviolet (UV)), optical microscopy of cross sections, scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-EDS), micro Raman spectroscopy, and micro Fourier transform infrared spectroscopy (m-FT-IR). The goal was to ascertain the techniques and colored materials used by Escovar on this painting so that the data can be used in future comparisons with others works attributed to this painter based on stylistic aspects.

Yellowing And Bleaching Of Grey Hair Caused By Photo And Thermal Degradation.

Yellowing is an undesirable phenomenon that is common in people with white and grey hair. Because white hair has no melanin, the pigment responsible for hair colour, the effects of photodegradation are more visible in this type of hair. The origin of yellowing and its relation to photodegradation processes are not properly established, and many questions remain open in this field. In this work, the photodegradation of grey hair was investigated as a function of the wavelength of incident radiation, and its ultrastructure was determined, always comparing the results obtained for the white and black fibres present in grey hair with the results of white wool. The results presented herein indicate that the photobehaviour of grey hair irradiated with a mercury lamp or with solar radiation is dependent on the wavelength range of the incident radiation and on the initial shade of yellow in the sample. Two types of grey hair were used: (1) blended grey hair (more yellow) and (2) grey hair from a single-donor (less yellow). After exposure to a full-spectrum mercury lamp for 200 h, the blended white hair turned less yellow (the yellow-blue difference, Db(*) becomes negative, Db(*)=-6), whereas the white hair from the single-donor turned slightly yellower (Db(*)=2). In contrast, VIS+IR irradiation resulted in bleaching in both types of hair, whereas a thermal treatment (at 81 °C) caused yellowing of both types of hair, resulting in a Db(*)=3 for blended white hair and Db(*)=9 for single-donor hair. The identity of the yellow chromophores was investigated by UV-Vis spectroscopy. The results obtained with this technique were contradictory, however, and it was not possible to obtain a simple correlation between the sample shade of yellow and the absorption spectra. In addition, the results are discussed in terms of the morphology differences between the pigmented and non-pigmented parts of grey hair, the yellowing and bleaching effects of grey hair, and the occurrence of dark-follow reactions.

Measuring The Hydrodynamic Radius Of Quantum Dots By Fluorescence Correlation Spectroscopy.

Fluorescence Correlation Spectroscopy (FCS) is an optical technique that allows the measurement of the diffusion coefficient of molecules in a diluted sample. From the diffusion coefficient it is possible to calculate the hydrodynamic radius of the molecules. For colloidal quantum dots (QDs) the hydrodynamic radius is valuable information to study interactions with other molecules or other QDs. In this chapter we describe the main aspects of the technique and how to use it to calculate the hydrodynamic radius of quantum dots (QDs).

Effects Of Sterilization Methods On The Physical, Chemical, And Biological Properties Of Silk Fibroin Membranes.

Silk fibroin has been widely explored for many biomedical applications, due to its biocompatibility and biodegradability. Sterilization is a fundamental step in biomaterials processing and it must not jeopardize the functionality of medical devices. The aim of this study was to analyze the influence of different sterilization methods in the physical, chemical, and biological characteristics of dense and porous silk fibroin membranes. Silk fibroin membranes were treated by several procedures: immersion in 70% ethanol solution, ultraviolet radiation, autoclave, ethylene oxide, and gamma radiation, and were analyzed by scanning electron microscopy, Fourier-transformed infrared spectroscopy (FTIR), X-ray diffraction, tensile strength and in vitro cytotoxicity to Chinese hamster ovary cells. The results indicated that the sterilization methods did not cause perceivable morphological changes in the membranes and the membranes were not toxic to cells. The sterilization methods that used organic solvent or an increased humidity and/or temperature (70% ethanol, autoclave, and ethylene oxide) increased the silk II content in the membranes: the dense membranes became more brittle, while the porous membranes showed increased strength at break. Membranes that underwent sterilization by UV and gamma radiation presented properties similar to the nonsterilized membranes, mainly for tensile strength and FTIR results.

Classification Of Frankfurters By Ft-raman Spectroscopy And Chemometric Methods.

Frankfurters are widely consumed all over the world, and the production requires a wide range of meat and non-meat ingredients. Due to these characteristics, frankfurters are products that can be easily adulterated with lower value meats, and the presence of undeclared species. Adulterations are often still difficult to detect, due the fact that the adulterant components are usually very similar to the authentic product. In this work, FT-Raman spectroscopy was employed as a rapid technique for assessing the quality of frankfurters. Based on information provided by the Raman spectra, a multivariate classification model was developed to identify the frankfurter type. The aim was to study three types of frankfurters (chicken, turkey and mixed meat) according to their Raman spectra, based on the fatty vibrational bands. Classification model was built using partial least square discriminant analysis (PLS-DA) and the performance model was evaluated in terms of sensitivity, specificity, accuracy, efficiency and Matthews's correlation coefficient. The PLS-DA models give sensitivity and specificity values on the test set in the ranges of 88%-100%, showing good performance of the classification models. The work shows the Raman spectroscopy with chemometric tools can be used as an analytical tool in quality control of frankfurters.

Monte Carlo Simulation Of The Response Functions Of Cdte Detectors To Be Applied In X-ray Spectroscopy.

In this work, the energy response functions of a CdTe detector were obtained by Monte Carlo (MC) simulation in the energy range from 5 to 160keV, using the PENELOPE code. In the response calculations the carrier transport features and the detector resolution were included. The computed energy response function was validated through comparison with experimental results obtained with (241)Am and (152)Eu sources. In order to investigate the influence of the correction by the detector response at diagnostic energy range, x-ray spectra were measured using a CdTe detector (model XR-100T, Amptek), and then corrected by the energy response of the detector using the stripping procedure. Results showed that the CdTe exhibits good energy response at low energies (below 40keV), showing only small distortions on the measured spectra. For energies below about 80keV, the contribution of the escape of Cd- and Te-K x-rays produce significant distortions on the measured x-ray spectra. For higher energies, the most important correction is the detector efficiency and the carrier trapping effects. The results showed that, after correction by the energy response, the measured spectra are in good agreement with those provided by a theoretical model of the literature. Finally, our results showed that the detailed knowledge of the response function and a proper correction procedure are fundamental for achieving more accurate spectra from which quality parameters (i.e., half-value layer and homogeneity coefficient) can be determined.

Measurement Of The Hydrodynamic Radius Of Quantum Dots By Fluorescence Correlation Spectroscopy Excluding Blinking.

One of the most important properties of quantum dots (QDs) is their size. Their size will determine optical properties and in a colloidal medium their range of interaction. The most common techniques used to measure QD size are transmission electron microscopy (TEM) and X-ray diffraction. However, these techniques demand the sample to be dried and under a vacuum. This way any hydrodynamic information is excluded and the preparation process may alter even the size of the QDs. Fluorescence correlation spectroscopy (FCS) is an optical technique with single molecule sensitivity capable of extracting the hydrodynamic radius (HR) of the QDs. The main drawback of FCS is the blinking phenomenon that alters the correlation function implicating in a QD apparent size smaller than it really is. In this work, we developed a method to exclude blinking of the FCS and measured the HR of colloidal QDs. We compared our results with TEM images, and the HR obtained by FCS is higher than the radius measured by TEM. We attribute this difference to the cap layer of the QD that cannot be seen in the TEM images.

Comparing Near-infrared Conventional Diffuse Reflectance Spectroscopy And Hyperspectral Imaging For Determination Of The Bulk Properties Of Solid Samples By Multivariate Regression: Determination Of Mooney Viscosity And Plasticity Indices Of Natural Rubber.

Conventional reflectance spectroscopy (NIRS) and hyperspectral imaging (HI) in the near-infrared region (1000-2500 nm) are evaluated and compared, using, as the case study, the determination of relevant properties related to the quality of natural rubber. Mooney viscosity (MV) and plasticity indices (PI) (PI0 - original plasticity, PI30 - plasticity after accelerated aging, and PRI - the plasticity retention index after accelerated aging) of rubber were determined using multivariate regression models. Two hundred and eighty six samples of rubber were measured using conventional and hyperspectral near-infrared imaging reflectance instruments in the range of 1000-2500 nm. The sample set was split into regression (n = 191) and external validation (n = 95) sub-sets. Three instruments were employed for data acquisition: a line scanning hyperspectral camera and two conventional FT-NIR spectrometers. Sample heterogeneity was evaluated using hyperspectral images obtained with a resolution of 150 × 150 μm and principal component analysis. The probed sample area (5 cm(2); 24,000 pixels) to achieve representativeness was found to be equivalent to the average of 6 spectra for a 1 cm diameter probing circular window of one FT-NIR instrument. The other spectrophotometer can probe the whole sample in only one measurement. The results show that the rubber properties can be determined with very similar accuracy and precision by Partial Least Square (PLS) regression models regardless of whether HI-NIR or conventional FT-NIR produce the spectral datasets. The best Root Mean Square Errors of Prediction (RMSEPs) of external validation for MV, PI0, PI30, and PRI were 4.3, 1.8, 3.4, and 5.3%, respectively. Though the quantitative results provided by the three instruments can be considered equivalent, the hyperspectral imaging instrument presents a number of advantages, being about 6 times faster than conventional bulk spectrometers, producing robust spectral data by ensuring sample representativeness, and minimizing the effect of the presence of contaminants.

Synthesis, characterization, DFT and Td-dfT study of the [Fe(mnt)(L)(t-BuNC) 2] octahedral complex (L = phen, bipy)

FeBr2 has reacted with an equivalent of mnt2- (mnt = cis-1,2-dicyanoethylene-1,2-dithiolate) and the α-diimine L (L = 1,10'-phenantroline, 2,2'-bipyridine) in THF solution, and followed by adding of t-butyl-isocyanide to give [Fe(mnt)(L)(t-BuNC)2] neutral compound. The products were characterized by infrared, UV-visible and Mössbauer spectroscopy, besides thermogravimetric and conductivity data. The geometry in the equilibrium was calculated by the density functional theory and the electronic spectrum by the time-dependent. The experimental and theoretical results in good agreement have defined an octahedral geometry with two isocyanide neighbours. The π→π* intraligand electronic transition was not observed for cis-isomers in the near-IR spectral region.