Infrared complex refractive index of N-containing astrophysical ices free of water processed by cosmic-ray simulated in laboratory.

Several nitrogen-containing molecules have been unambiguously identified in the Solar System and in the Interstellar Medium. It is believed that such a rich inventory of species is a result of the energetic processing of astrophysical ices during the interaction with ionizing radiation. An intrinsic parameter of matter, the complex refractive index, stores all the "chemical memory" triggered by energetic processing, and therefore might be used to probe ice observations in the infrared. In this study, four N-containing ices have been condensed in an ultra-high vacuum chamber and processed by heavy ions (O and Ni) with energies between 0.2 and 15.7 MeV at the Grand Accélérateur National d'Ions Lourds (GANIL), in Caen, France. All chemical changes were monitored in situ by Infrared Absorption Spectroscopy. The complex refractive index was calculated directly from the absorbance spectrum, by using the Lambert-Beer and Kramers-Kroning relations, and the values are available in an online database: https://www1.univap.br/gaa/nkabs-database/data.htm. As a result, other than the database, it was observed that non-polar ices are more destroyed by sputtering than polar ones. Such destruction and chemical evolution lead to variation in the IR albedo of samples addressed in this paper.

Sequestrating anionic and cationic dyes from wastewater using spray dried biopolymeric magnetic composite: Experimental and theoretical studies.

Spray dried cross-linked chitosan/cobalt ferrite composite was synthesized and applied as an adsorbent for the removal of acid orange II and methylene blue. The composite was structurally, thermally, morphologically and magnetically characterized. The result obtained shows that the magnetic composite was in form of microspheres, while cobalt ferrite was encapsulated in the cross-linked chitosan with saturation magnetization of 10.79 emu g-1. Adsorption studies revealed that acid orange II adsorbed more favorably on the composite than methylene blue. The adsorption process is spontaneous and exothermic. Liu isotherm model was found to be applicable for the adsorption process. Computational studies showed that the formation of hydrogen bond between acid orange II and the magnetic composite (at both acidic and alkaline pH) contributed to its better adsorption than methylene blue. Adsorption capacity of acid orange II at pH 3 and methylene blue at pH 12 are 542 and 173 mg g-1 respectively at 303 K base on Liu isotherm model.

Screening and optimizing fermentation production of l-asparaginase by Aspergillus terreus strain S-18 isolated from the Brazilian Caatinga Biome.

AIMS: The aim of this study was to find new eukaryotic sources of the l-asparaginase (l-ASNase), since the prokaryotic sources of the enzyme are well-reported as causing allergic hypersensitivity reactions in a significant number of patients. This report describes screening for l-ASNase production by filamentous fungi isolated from the Brazilian Caatinga, and the optimization of fermentation parameters to increase fungal growth and improve yield in the production of l-ASNase. METHODS AND RESULTS: Thirty-two filamentous fungi were investigated in this study. When Aspergillus terreus strain S-18 was cultured in a proline-enriched medium, intracellular l-ASNase was expressed in concurrence with reduced l-glutaminase (l-GLUase) and protease activities. Fermentation conditions were then optimized in a 5-l bioreactor system to produce a maximum volumetric yield of 108 U total of l-ASNase activity. CONCLUSIONS: The work reported here represents the first attempt to produce l-ASNase by filamentous fungi isolated from Brazil and offers a promising alternative eukaryotic source for l-ASNase production. SIGNIFICANCE AND IMPACT OF THE STUDY: In order to minimize the side effects caused by bacterial l-ASNase, the search of eukaryotic micro-organism for l-ASNase was carried out in fungi. This study demonstrates the diversity of filamentous fungi isolated from the Brazilian Caatinga Biome and the importance of knowledge of the microbial metabolism to obtain high concentrations of biotechnological products.

Photochemistry and desorption induced by X-rays in water rich astrophysical ice analogs: implications for the moon Enceladus and other frozen space environments.

Soft X-rays are an important agent for chemical processing in the Solar System and in the interstellar medium. The photolysis and photodesorption processes of H2O-rich ices triggered by soft X-rays was, experimentally, addressed in this paper. The experiments were performed at the Brazilian synchrotron facility LNLS/CNPEN employing broadband radiation (from 6 to 2000 eV; mainly soft X-rays and a small fraction of VUV) in solid samples at temperatures of 20 and 80 K. The icy samples were monitored by infrared spectroscopy. We determined the effective destruction cross section (in the order 10-18 cm2) as well as the formation cross section for the new species produced after the irradiation. Among them, we list OCN-, CO, CO3, CH3OH, H2O2, HCOO-, NH4 +, HCONH2 and CH3HCO, mostly formed in the experiment at 80 K. The chemical equilibrium stage was characterized and molecular abundances were quantified. In addition, we discuss a methodology to estimate the amount of unknown species in the ice produced by photolysis. The samples reach chemical equilibrium at fluences around 2-3 × 1018 cm-2. Timescales for reaching chemical equilibrium in space environments illuminated by X-rays were given, as well as the desorption yields induced by X-rays. The astrophysical implication on the surface chemistry and desorption processes at the moon Enceladus are provided.

Radiolysis of N2-rich astrophysical ice by swift oxygen ions: implication for space weathering of outer solar system bodies.

In order to investigate the role of medium mass cosmic rays and energetic solar particles in the processing of N2-rich ice on frozen moons and cold objects in the outer solar system, the bombardment of an N2 : H2O : NH3 : CO2 (98.2 : 1.5 : 0.2 : 0.1) ice mixture at 16 K employing 15.7 MeV 16O5+ was performed. The changes in the ice chemistry were monitored and quantified by Fourier transformed infrared spectroscopy (FTIR). The results indicate the formation of azide radicals (N3), and nitrogen oxides, such as NO, NO2, and N2O, as well as the production of CO, HNCO, and OCN-. The effective formation and destruction cross-sections are roughly on the order of 10-12 cm2 and 10-13 cm2, respectively. From laboratory molecular analyses, we estimated the destruction yields for the parent species and the formation yields for the daughter species. For N2, this value was 9.8 × 105 molecules per impact of ions, and for the most abundant new species (N3), it was 1.1 × 105 molecules per impact of ions. From these yields, an estimation of how many species are destroyed or formed in a given timescale (108 years) in icy bodies in the outer solar system was calculated. This work reinforces the idea that such physicochemical processes triggered by cosmic rays, solar wind, and magnetospheric particles (medium-mass ions) in nitrogen-rich ices may play an important role in the formation of molecules (including pre-biotic species precursors such as amino acids and other "CHON" molecules) in very cold astrophysical environments, such as those in the outer region of the solar system (e.g. Titan, Triton, Pluto, and other KBOs).

Ion irradiation of pure and amorphous CH4 ice relevant for astrophysical environments.

This work presents a physicochemical study of frozen amorphous methane (at 16 K) under bombardment by medium-mass ions (15.7 MeV 16O5+) with implications for icy bodies in the outer Solar System exposed to the action of cosmic rays and energetic particles. The experiment was performed at the Grand Accélérateur National d'Ions Lourds (GANIL) located in Caen, France. The results demonstrate that irradiation of CH4-containing ices by swift medium mass ions with delivered energy covering both stopping power regimes until its implantation on ice (i.e. electronic and nuclear) leads to the production of many hydrocarbons, such as C2H2, C2H4, C2H6, and C3H8 (the most abundant daughter species produced). Values for the effective dissociation cross section of CH4 and the average value for the effective formation cross-sections of its daughter species were about 10-14 cm2 and 10-15 cm2, respectively. The half-life of methane ice in the presence of swift medium mass ions extrapolated to some outer Solar System environments is estimated to be around 106 years. The measured sputtering yield of methane due to incoming swift ions was about 7.30 × 105 molecules per impact. Such parameters can be used as models to estimate the amount of CH4 and other molecular species desorbed from the icy surfaces that are constantly being incorporated to the gaseous atmosphere in the vicinity of these outer Solar System bodies due to the presence of energetic particles and cosmic rays.

Determination of optical constants n and k of thin films from absorbance data using Kramers-Kronig relationship.

We present a code, called NKABS, to determine optical constants (complex refractive index) of thin films directly from the absorbance data in the infrared. The code is written in the Python language, which is more accurate and faster than previous methods in the literature. For solving the Kramers-Kronig relationship, we used the Maclaurin's methodology. Unlike other codes, which found convergence in 30-40 iterations, the NKABS reach the convergence in just 4 or 5 iterations. Additionally, to evaluate the error, this code calculates the MAPE (Mean Absolute Percentage Error) and the chi-square χ(2). The typical MAPE error obtained using NKABS is less than 1×10(-3)%. To illustrate the functionality of this code, we calculate the optical constants in the infrared spectral region of 28 different samples of astrophysical interest at different temperatures (10-300K), which simulates molecules in space environments, mostly the ones called astrophysical ices. The samples were obtained from the condensation of pure gases (e.g. CO, CO2, NH3, SO2), from the sublimation in vacuum of pure liquids (e.g. water, acetone, acetonitrile, acetic acid, formic acid, ethanol and methanol) and from mixtures of different species (e.g. H2O:CO2, H2O:CO:NH3, H2O:CO2:NH3:CH4). Additionally films of solid biomolecules samples of astrochemistry/astrobiology interest (e.g. glycine, adenine) were probed. The code and the data-base obtained here are available on-line. The NKABS can also be employed to calculate refractive index of processed samples (by heating or radiation). Such data and the refractive index of virgin samples are required as input in several astrophysical models that calculate the radiative transfer in dusty astrophysical environments such as protoplanetary disks and circumstellar environments as well as dense molecular clouds.