Compaction and Destruction Cross-Sections for α-Glycine from Radiolysis Process via 1.0 keV Electron Beam as a Function of Temperature.

Glycine is an amino acid that has already been detected in space. It is relevant to estimate its resistance under cosmic radiation. In this way, a sublimate of glycine in α-form on KBr substrate was exposed in the laboratory to a 1.0 keV electron beam. The radiolysis study was performed at 40 K, 80 K, and 300 K sample temperatures. These temperatures were chosen to cover characteristics of the outer space environment. The evolution of glycine compaction and degradation was monitored in real time by infrared spectroscopy (Fourier-transform infrared) by investigation in the spectral ranges of 3500-2100, 1650-1200, and 950-750 cm-1. The compaction cross-section increases as the glycine temperature decreases. The glycine film thickness layer of ∼160 nm was depleted completely after ∼15 min at 300 K under irradiation with ∼1.4 µA beam current on the target, whereas the glycine depletion at 40 K and 80 K occurred after about 4 h under similar conditions. The destruction cross-section at room temperature is found to be (13.8 ± 0.2) × 10-17 cm2, that is, about 20 times higher than the values for glycine depletion at lower temperatures (<80 K). Emerging and vanishing peak absorbance related to OCN- and CO bands was observed in 2230-2100 cm-1 during the radiolysis at 40 K and 80 K. The same new IR bands appear in the range of 1600-1500, 1480-1370, and 1350-1200 cm-1 after total glycine depletion for all temperature configurations. A strong N-H deformation band growing at 1510 cm-1 was observed only at 300 K. Finally, the destruction cross-section associated to tholin decay at room temperature is estimated to be (1.30 ± 0.05) × 10-17 cm2. In addition, a correlation between the formation cross-sections for daughter and granddaughter molecules at 300 K is also obtained from the experimental data.

Dissociation of biomolecules in liquid environments during fast heavy-ion irradiation.

The effect of aqueous environment on fast heavy-ion radiation damage of biomolecules was studied by comparative experiments using liquid- and gas-phase amino acid targets. Three types of amino acids with different chemical structures were used: glycine, proline, and hydroxyproline. Ion-induced reaction products were analyzed by time-of-flight secondary-ion mass spectrometry. The results showed that fragments from the amino acids resulting from the C-Cα bond cleavage were the major products for both types of targets. For liquid-phase targets, specific products originating from chemical reactions in solutions were observed. Interestingly, multiple dissociated atomic fragments were negligible for the liquid-phase targets. We found that the ratio of multifragment to total fragment ion yields was approximately half of that for gas-phase targets. This finding agreed with the results of other studies on biomolecular cluster targets. It is concluded that the suppression of molecular multifragmentation is caused by the energy dispersion to numerous water molecules surrounding the biomolecular solutes.

The contribution of mycosporine-like amino acids, chromophoric dissolved organic matter and particles to the UV protection of sea-ice organisms in the Baltic Sea.

The effects of ultraviolet radiation (UVR) on the synthesis of mycosporine-like amino acids (MAAs) in sea-ice communities and on the other UV-absorption properties of sea ice were studied in a three-week long in situ experiment in the Gulf of Finland, Baltic Sea in March 2011. The untreated snow-covered ice and two snow-free ice treatments, one exposed to wavelengths > 400 nm (PAR) and the other to full solar spectrum (PAR + UVR), were analysed for MAAs and absorption coefficients of dissolved (aCDOM) and particulate (ap) fractions, the latter being further divided into non-algal (anap) and algal (aph) components. Our results showed that the diatom and dinoflagellate dominated sea-ice algal community responded to UVR down to 25-30 cm depth by increasing their MAA : chlorophyll-a ratio and by extending the composition of MAA pool from shinorine and palythine to porphyra-334 and an unknown compound with absorption peaks at ca. 335 and 360 nm. MAAs were the dominant absorbing components in algae in the top 10 cm of ice, and their contribution to total absorption became even more pronounced under UVR exposure. In addition to MAAs, the high absorption by chromophoric dissolved organic matter (CDOM) and by deposited atmospheric particles provided UV-protection for sea-ice organisms in the exposed ice. Efficient UV-protection will especially be of importance under the predicted future climate conditions with more frequent snow-free conditions.

Synthesis of ZnO nanoparticles using the cell extract of the cyanobacterium, Anabaena strain L31 and its conjugation with UV-B absorbing compound shinorine.

In the present work, we describe a cheap, unexplored and simple procedure for the synthesis of zinc oxide nanoparticles (ZnONPs) using the cell extract of the cyanobacterium, Anabaena strain L31. An attempt was also made to conjugate synthesized ZnONPs with a UV-absorbing water soluble compound shinorine. UV-vis spectroscopy, X-ray diffraction (XRD), Fourier transform infra-red (FTIR) spectroscopy, transmission electron microscopy (TEM) and TEM-selected area electron diffraction (SAED) analyses were made to elucidate the formation and characterization of ZnONPs and ZnONPs-shinorine conjugate. The synthesized ZnONPs were characterized by a sharp peak at 370 nm in UV-vis spectrum. TEM images showed the formation of spherical shaped nanoparticles with an average size of 80 nm. Results of selective area electron diffraction (SAED) pattern showed a set of rings which suggested uniform shape with hexagonal structure of ZnONPs. XRD spectra confirmed the crystalline structure of particles. Conjugation of ZnONPs with shinorine was successfully achieved at pH 7.0 and 10mM concentration of shinorine. The conjugate showed a zeta potential value of -3.75 mV as compared to +30.25 mV of ZnONPs. The change in zeta potential value of ZnONPs-shinorine conjugate was attributed to the changes in the surface functionalities after conjugation. The generation of in vivo reactive oxygen species (ROS) by Anabaena strain L31 with treatment of ZnONPs-shinorine conjugate showed approximately 75% less ROS generation as compared to ZnONPs. Properties exhibited by the ZnONPs-shinorine conjugate suggest that it may be used as a potential agent in developing environmental-friendly sunscreen filters of biological origin.

Effects of pH value of the electrolyte and glycine additive on formation and properties of electrodeposited Zn-Fe coatings.

Environmentally friendly and cyanide-free sulfate bath under continuous current and the corrosion behavior of electrodeposits of zinc-iron alloys were studied by means of electrochemical tests in a solution of 3.5% NaCl in presence and absence of glycine. The effects of pH on the quality of Zn-Fe coatings were investigated in order to improve uniformity and corrosion protection performance of the coating films. The deposit morphology was analyzed using scanning electron microscopy (SEM), and X-ray diffraction (XRD) was used to determine the preferred crystallographic orientations of the deposits. It was found that the uniformity and corrosion resistance of Zn-Fe coating films were strongly associated with pH of the coating electrolyte. To obtain the effect of pH on the film quality and corrosion performances of the films, the corrosion test was performed with potentiodynamic anodic polarization method. It was also observed that uniformity and corrosion resistivity of the coating films were decreased towards pH = 5 and then improved with increasing pH value of the electrolyte. The presence of glycine in the plating bath decreases the corrosion resistance of Zn-Fe coatings.

Adsorption and desorption behavior of selected pesticides as influenced by decomposition of maize mulch.

Assessing pesticide fate in conservation agricultural systems requires a detailed understanding of their interaction with decomposing surface crop residues (mulch). Adsorption and desorption behavior of glyphosate, s-metolachlor and epoxiconazole was investigated on maize mulch residues decomposed under laboratory and field conditions. Our conceptual approach included characterization of chemical composition and hydrophobicity of mulch residues in order to generate parameters to predict sorption behavior. Adsorption of s-metolachlor and epoxiconazole greatly increased with mulch decomposition, whereas glyphosate adsorption was less affected but its desorption was increased. Mulch characteristics including aromaticity, hydrophobicity and polarity indices were strongly correlated to Koc of the non-ionic pesticides. A predictive model based on compositional data (CoDa) analysis revealed that the sorption capacity of decomposing mulch can be predicted from descriptors such as aromatic and alkyl C corresponding respectively to lignin and NDF biochemical fractions. The decomposition degree of mulch residues should be taken into account while predicting the fate of pesticides.

The influence of crystallinity degree on the glycine decomposition induced by 1 MeV proton bombardment in space analog conditions.

Glycine is the simplest proteinaceous amino acid and is present in all life-forms on Earth. In aqueous solutions, it appears mainly as zwitterion glycine (+NH3CH2COO-); however, in solid phase, it may be found in amorphous or crystalline (α, ß, and γ) forms. The crystalline forms differ from each other by the packing of zwitterions in the unitary cells and by the number of intermolecular hydrogen bonds. This molecular species has been extensively detected in carbonaceous meteorites and was recently observed in the cometary samples returned to Earth by NASA's Stardust spacecraft. In space, glycine is exposed to several radiation fields at different temperatures. We present an experimental study on the destruction of zwitterionic glycine crystals at room temperature by 1 MeV protons, in which the dependence of the destruction rates of the α-glycine and ß-glycine crystals on bombardment fluence is investigated. The samples were analyzed in situ by Fourier transform infrared spectrometry at different proton fluences. The experiments occurred under ultrahigh vacuum conditions at the Van de Graaff accelerator lab at the Pontifical Catholic University at Rio de Janeiro (PUC-Rio), Brazil. For low fluences, the dissociation cross section of α-glycine was observed to be 2.5×10(-14) cm2, a value roughly 5 times higher than the dissociation cross section found for ß-glycine. The estimated half-lives of α-glycine and ß-glycine zwitterionic forms extrapolated to the Earth orbit environment are 9×10(5) and 4×10(6) years, respectively. In the diffuse interstellar medium the estimated values are 1 order of magnitude lower. These results suggest that pristine interstellar ß-glycine is the one most likely to survive the hostile environments of space radiation. A small feature around 1650-1700 cm(-1), tentatively attributed to an amide functional group, was observed in the IR spectra of irradiated samples, suggesting that cosmic rays may induce peptide bond synthesis in glycine crystals. Combining this finding with the fact that this form has the highest solubility among the other glycine polymorphs, we suggest that ß-glycine is the one most likely to have produced the first peptides on primitive Earth.

Life cycle assessment of solar photo-Fenton and solar photoelectro-Fenton processes used for the degradation of aqueous α-methylphenylglycine.

A comparative Life Cycle Assessment (LCA) of solar photo-Fenton and solar photoelectro-Fenton, two solar-driven advanced oxidation processes (AOPs) devoted to the removal of non-biodegradable pollutants in water, is performed. The study is based on the removal, at laboratory scale, of the amino acid α-methylphenylglycine, a good example of soluble and non-biodegradable target pollutant. The system under study includes chemicals, electricity, transport of all raw materials to the plant site, and the generation of emissions, but it does not take into account the impact of the infrastructure needed to build a hypothetical solar plant. Nine environmental impact categories are included in the LCA: global warming potential, ozone depletion potential, aquatic eutrophication potential, acidification potential, human toxicity potential, photochemical ozone formation potential, fresh water aquatic ecotoxicity potential, marine aquatic ecotoxicity potential, and terrestrial ecotoxicity potential and abiotic resource depletion potential. Although previous experimental results show that both AOPs are able to efficiently degrade the pollutant, the LCA indicates that solar-driven photo-Fenton is the most environmentally friendly alternative, mainly because the use of electricity in solar photoelectro-Fenton experiments involves high environmental impacts.

Influencia de la radiación gamma como método de esterilización sobre el polímero poli VPAVG (Valina-Prolina-Alanina-Valina- Glicina) / Influence of gamma radiation as a sterilization method on polymer poli VPAVG (Valine- Proline- Alanine-Valine-Glicine)

El polímero poli (VPAVG) pertenece a la familia de materiales bioelásticos derivados de la elastina y ha demostrado poseer cualidades óptimas para la formación de sistemas de cesión controlada, así como una biocompatibilidad aceptable en determinados tejidos. Las formulaciones preparadas a partir del biomaterial deben ser estériles, si se pretende administrar por una vía que implique ruptura de barreras biológicas. Por lo anterior, resulta esencial conocer el comportamiento del polímero y sus formulaciones frente al proceso de esterilización empleado. El objetivo de este trabajo fue, por tanto, evaluar la influencia de la radiación gamma como método de esterilización sobre las ca - racterísticas físicas del poli (VPAVG) y de las partículas for - madas con éste. En cuanto al polímero, no se apreciaron diferencias en su apariencia física antes y después de la esterilización. Sin embargo, las partículas obtenidas a partir del poli (VPAVG) y posteriormente esterilizadas experimentaban cambios en su morfología. En cuanto al tamaño de las partículas, se determinó que las obtenidas con polímero esterilizado presentaban cierta tendencia a formar agregados de menor tamaño que los encontrados con el polímero sin esterilizar. Se concluyó que el biomaterial ensayado y las formulaciones eran susceptibles a las radiaciones gamma como método de esterilización final, proponiéndose recurrir a otro tratamiento que garantice su esterilidad final.

The poli polymer (VPAVG) belongs to the family of bioelastic materials derived from elastin, and it has showed the best qualities for the creation of systems of controlled cession, as well as an acceptable biocompatibility in certain tissues. If any preparation made from this biomaterial has to be administered in any way that implies the rupture of biological barriers, the preparation must be sterile. By this means, it is essential to know the behaviour of this polymer and its formulations, facing the sterilization process being used. The objective of this research was learn the influence of gamma radiation as a sterilization method over the physical characteristics of poli (VPAVG) and the particles formed by it. As the polymer, we did not observe any differences in physical appearance before and after sterilization. Particles formed by the polymer (VPAVG) and sterilized after, experimented changes in their morphology. As the size of the particles, we observed that those obtained with the sterilized polymer showed a tendency to form smaller aggregates than those found with the non-sterilized polymer. We concluded that the essayed biomaterial and its formulations were susceptible to gamma radiations as final sterilization method, proposing to use another treatment to guarantee the final sterile condition.

Experimental study of the excited-state properties and photostability of the mycosporine-like amino acid palythine in aqueous solution.

Characterization of the excited states of the mycosporine-like amino acid palythine (lambda(max) = 320 nm) in aqueous solutions was achieved experimentally. The low value for the photodegradation quantum yield, (1.2 +/- 0.2) x 10(-5), confirms that palythine is highly photostable in air saturated-aqueous solutions. Laser flash photolysis of acetone in the presence of palythine allowed for the observation of a transient spectrum which is consistent with the triplet-triplet absorption of palythine. Kinetic treatment of the transient signals yields a lifetime of the triplet state of ca. 9 micros and a triplet energy around 330 kJ mol(-1). The photoacoustic calorimetry results are consistent with non-radiative decay as the major fate of excited palythine. A comparison of the photodegradation quantum yields and photophysical properties of palythine with those previously determined for the other mycosporine-like amino acids, shinorine and porphyra-334, suggests that geometrical isomerization around the C=N bond may contribute to the rapid deactivation of this group of molecules.

Coupling solar photo-Fenton and biotreatment at industrial scale: main results of a demonstration plant.

This paper reports on the combined solar photo-Fenton/biological treatment of an industrial effluent (initial total organic carbon, TOC, around 500mgL(-1)) containing a non-biodegradable organic substance (alpha-methylphenylglycine at 500mgL(-1)), focusing on pilot plant tests performed for design of an industrial plant, the design itself and the plant layout. Pilot plant tests have demonstrated that biodegradability enhancement is closely related to disappearance of the parent compound, for which a certain illumination time and hydrogen peroxide consumption are required, working at pH 2.8 and adding Fe(2+)=20mgL(-1). Based on pilot plant results, an industrial plant with 100m(2) of CPC collectors for a 250L/h treatment capacity has been designed. The solar system discharges the wastewater (WW) pre-treated by photo-Fenton into a biotreatment based on an immobilized biomass reactor. First, results of the industrial plant are also presented, demonstrating that it is able to treat up to 500Lh(-1) at an average solar ultraviolet radiation of 22.9Wm(-2), under the same conditions (pH, hydrogen peroxide consumption) tested in the pilot plant.

Photodegradation of glyphosate in the ferrioxalate system.

The photoinduced degradation of glyphosate (GLP) in the ferrioxalate system was investigated under irradiation with a 250W metal halide lamp (lambda>/=365nm). The efficiency of orthophosphates release, representing the photodegradation efficiency of GLP, increased with decreasing the initial concentrations of GLP and Fe(III)/oxalate ratios. At acidic pH value in the range of 3.5-5.0, higher efficiency of orthophosphates release up to 60.6% was achieved, while the efficiency dropped to 42.1% at pH 6.0. The photochemical process mainly involved the predominant species of iron(III), namely Fe(C(2)O(4))(2)(-) and Fe(C(2)O(4))(3)(3-), which lead to the formation of hydroxyl radicals in the presence of dissolved oxygen under UV-vis irradiation. Also, the complexation of GLP with Fe(III) obviously increased the light absorption of GLP and facilitated its degradation by direct photolysis. The ninhydrin test for primary amines showed that the GLP was attacked by hydroxyl radicals with CN cleavage to yield aminomethylphosphonic acid (AMPA) and CP cleavage to yield sarcosine. The photodegradation may be enhanced by the decomposition of reactive radicals produced through ligand-to-metal charge transfer (LMCT) of ferric-GLP complexes.

Study on the photocatalytic degradation of glyphosate by TiO(2) photocatalyst.

In this paper, the photocatalytic degradation of glyphosate selected as the deputy of organic pollutant in aqueous solution with TiO(2) powder as a photocatalyst has been studied. The effects of various parameters, such as the amount of the photocatalyst, illumination time, initial pH value, electron acceptors, metal ions, and anions on the photocatalytic degradation of glyphosate were investigated. From the studies, the best condition for the effect of the parameters on the photocatalytic degradation of glyphosate was obtained. The results show that the optimum amount of the photocatalyst used is 6.0 g l(-1) for the photocatalytic reactions. The photodegradation efficiency of glyphosate increases with the increase of the illumination time. With the addition of Fe(3+), Cu(2+), H(2)O(2), K(2)S(2)O(8) or KBrO(3), the photocatalytic degradation of glyphosate is accelerated. However, with the addition of Na(+), K(+), Mg(2+), Ca(2+), Zn(2+), Co(2+) and Ni(2+), or with the addition of trace amounts of Cl(-), Br(-), SO(4)(2-), there are no obvious effects on the reactions. Acidic or alkaline mediums are favorable for the photocatalytic degradation of glyphosate. The possible roles of the additives on the reactions and the possible mechanisms of effect were discussed.

The deactivation pathways of the excited-states of the mycosporine-like amino acids shinorine and porphyra-334 in aqueous solution.

In vitro studies on the structurally related mycosporine-like amino acids (MAAs) porphyra-334 and shinorine in aqueous solutions were carried out aiming at their full photochemical and photophysical characterization and expanding the evidence on the assigned UV-photoprotective role of the molecules in vivo. The experiments on shinorine confirmed a high photostability and a poor fluorescence quantum yield, in concordance with previous results on porphyra-334. The estimation of triplet production quantum yields for both MAAs was achieved by laser-flash photolysis measurements. In particular, photosensitization experiments on porphyra-334 support the participation of the triplet state in the photodecomposition mechanism yielding a more precise value of [capital Phi](T). As well, photoacoustic calorimetry experiments allowed the first direct quantification of the nonradiative relaxation pathways of the excited MAAs in solution, corroborating that the vast majority (ca. 97%) of the absorbed energy is promptly delivered to the surroundings as heat, consistently with the low photodecomposition and emission yields observed.

Daily variation in cellular content of UV-absorbing compounds mycosporine-like amino acids in the marine dinoflagellate Scrippsiella sweeneyae.

Sudden exposure experiments to high PAR (photosynthetically available radiation) or high PAR+UVR (ultraviolet radiation) were conducted for the marine dinoflagellate Scrippsiella sweeneyae acclimated to either low PAR or high PAR to determine the induction of cellular mycosporine-like amino acid (MAA) in relation to photosynthesis status. When the exposure to high PAR (30.8 Wm(-2)) was provided at different time in the light period for S. sweeneyae acclimated to low PAR (7.7 Wm(-2)) which suppressed photosynthesis, S. sweeneyae could enhance the induction of MAA but it only occurred in the first half of the light period. When UVR exposure was provided for the culture acclimated to high PAR which enhanced photosynthesis, cellular MAA content did not increase during the entire light period, but displayed daily variation similar to the control for two and half days. Daily variation of cellular MAA content did not synchronized with that of cell volume and cellular chlorophyll a content. The individual MAAs also revealed similar daily variations with different phase, which increased for a few hours in the beginning of the light period, except for cellular palythine content. Thus the total cellular MAA content revealed daily variation with changing the relative composition within a few hours. As one of the biological protective strategies against harmful UVR in sunlight, the daily vertical migration in the bloom forming dinoflagellates might be accompanied by the daily variation of cellular MAA content for a photosynthesis at daytime.

EPR study of gamma induced radicals in amino acid powders.

To better understand the composite character of amino acids EPR spectra, the radiolysis and reactions which occurred after irradiation of amino acids, a comparative EPR study of a few simple amino acids has been made in order to identify qualitatively and quantitatively the different radiation-induced radicals in amino acid powders. A spin-trapping methodology has been developed and carried out on irradiated glycine, alanine and valine.

Study of the peptide prebiotic synthesis in context of exobiological investigations on earth orbit.

Dry films of amino acids mixtures glycine+ tryptophan and tryptophan were exposed on the surface of "Mir" station. Similar films were irradiated by vacuum ultra violet (145 nm) and ultra violet (254 nm) in the laboratory experiments. Gly-Gly, Trp-Gly, Gly-Trp, Tpr-Trp and Trp-Trp-Trp were the main reaction products for the experimental mixture glycine + tryptophan and Tpr-Trp and Trp-Trp-Trp for tryptophan. The presence of Lunar soil both in flight and in laboratory experiments increases the reaction yield by 1.5-2.0 times. Therefore, the hypothesis concerning the possibility of safe delivery of peptides and amino acids required for the emergence of life and associated with mineral have got yet another approval.

ESR and UV-Vis studies of semiquinone radical anion and hydroquinone generated by irradiation of 15-deacetyl-13-glycine substituted hypocrellin B.

15-Deacetyl-13-glycine substituted hypocrellin B (GDHB) is a new type of hypocrellin derivative with enhanced red absorption longer than 600 nm and water solubility. When an anaerobic DMSO or DMSO-buffer (pH 7.4) solution of GDHB was illuminated with >470 nm light, a strong electron spin resonance (ESR) signal was formed. The ESR signal was assigned to the semiquinone anion radical of GDHB (GDHB*-) based on a series of experiments. GDHB*- was predominantly photoproducted via the self-electron transfer between the excited- and ground-state species. Decay of this species, both in the presence and absence of electron donor, was consistent with second-order kinetics. In aqueous solution, the TEMPO counter-spin experiment indicated the formation of GDHB*- that could not be detected by ESR method directly. The formation of GDHB*- and hydroquinone of GDHB (GDHBH*-) was also confirmed by spectrometric method. These findings suggested that GDHB was at least a favorable type I phototherapeutic agent.

Rapid analysis of low levels of indolyl-3-acryloylglycine in human urine by high-performance liquid chromatography.

There have been several reports of increased levels of excretion of indolyl-3-acryloylglycine (IAcrGly) in human urine in a number of disease states. However, the metabolic source of this compound is still not clear and there is the possibility of more than one mechanism for IAcrGly production. There was therefore a need for a rapid, low limit of quantitation assay for IAcrGly to enable further study in this area. In the assay described here, these analytical requirements were addressed by utilising a solid-phase extraction method for sample clean-up, reversed-phase LC with an on-column focusing method of sample introduction and UV absorbance detection at 326 nm. The limit of quantitation of this method was 26.2 ng ml(-1). It was also noted that IAcrGly undergoes isomerisation when exposed to light and that this process is reversible.

Formation of oligopeptides on the surface of small bodies in solar system by cosmic radiation.

The present experiment indicates that oligopeptides are easily produced in solid state from mixtures of simple amino acids by irradiating with high energy charged particles. We investigated such amino acids and their mixtures as tryptophan, tyrosine and glycine. The thin films was irradiated with protons (6.6 MeV). Such dipeptides as Trp-Trp, Gly-Tyr, Tyr-Gly, and Tyr-Tyr have been detected as products of irradiation. Cosmic rays might be an effective energy source for abiotic formation of bioorganic compounds on the surface of small bodies in the solar system on early stage of formation of planets as well as at present day.