Application of catalytic ozonation using Y zeolite in the elimination of pharmaceuticals in effluents from municipal wastewater treatment plants.

Catalytic ozonation using faujasite-type Y zeolite with two different SiO2/Al2O3 molar ratios (60 and 12) was evaluated for the first time in the removal of 25 pharmaceutical compounds (PhCs) present in real effluents from two municipal wastewater treatment plants both located in the Mediterranean coast of Spain. Additionally, control experiments including adsorption and direct ozonation, were conducted to better understand the fundamental aspects of the different individual systems in wastewater samples. Commercial zeolites were used in sodium form (NaY). The results showed that the simultaneous use of ozone and NaY zeolites significantly improved the micropollutants degradation rate, able to degrade 95 % of the total mixture of PhCs within the early 9 min using the zeolite NaY-12 (24.4 mg O3 L-1 consumed), while 12 min of reaction with the zeolite NaY-60 (31 mg O3 L-1 consumed). In the case of individual experiments, ozonation removed 95 % of the total mixture of PhCs after 25 min (46.2 mg O3 L-1 consumed), while the direct adsorption, after 60 min of contact time, eliminated 30 % and 44 % using the NaY-12 and NaY-60 zeolites, respectively. Results showed that the Brønsted acid sites seemed to play an important role in the effectiveness of the treatment with ozone. Finally, the environmental assessment showed that the total risk quotients of pharmaceuticals were reduced between 87 %-99 % after ozonation in the presence of NaY-60 and NaY-12 zeolites. The results of this study demonstrate that catalytic ozonation using NaY zeolites as catalysts is a promising alternative for micropollutant elimination in real-world wastewater matrices.

Sustainable Production of Hydrogen by Steam Reforming of Ethanol Using Cobalt Supported on Nanoporous Zeolitic Material.

Cobalt catalysts supported on Y zeolite and mesoporized Y zeolite (Y-mod) have been studied in steam reforming of ethanol (SRE). Specifically, the effect of the mesoporosity and the acidity of the y zeolite as a support has been explored. Mesoporous were generated on Y zeolite by treatment with NH4F and the acidity was neutralized by Na incorporation. Four cobalt catalysts supported on Y zeolite have been prepared, two using Y zeolite without mesoporous (Co/Y, Co/Y-Na), and two using Y zeolite with mesoporous (Co/Y-mod and Co/Y-mod-Na). All catalysts showed a high activity, with ethanol conversion values close to 100%. The main differences were found in the distribution of the reaction products. Co/Y and Co/Y-mod catalysts showed high selectivity to ethylene and low hydrogen production, which was explained by their high acidity. On the contrary, neutralization of the acid sites could explain the higher hydrogen selectivity and the lower ethylene yields exhibited by the Co/Y-Na and Co/Y-mod-Na. In addition, the physicochemical characterization of these catalysts by XRD, BET surface area, temperature-programmed reduction (TPR), and TEM allowed to connect the presence of mesoporous with the formation of metallic cobalt particles with small size, high dispersion, and with high interaction with the zeolitic support, explaining the high reforming activity exhibited by the co/y-mod-Na sample as well as its higher hydrogen selectivity. It has been also observed that the formation of coke is affected by the presence of mesoporous and acidity. Both properties seem to have an opposite effect on the reforming catalyst, decreasing and increasing the coke deposition, respectively.

Effect of spermine conjugation on the interaction of acridine with alternating purine-pyrimidine oligodeoxyribonucleotides studied by CD, fluorescence and absorption spectroscopies.

We studied by electronic spectroscopies the interaction between double-stranded oligonucleotides containing either adenine-thymine or guanine-cytosine alternating sequences and N(1)-(acridin-9-yl)-1,16-diamino-4,8,13-triazahexadecane, which is a conjugated molecule formed by the covalent binding of spermine and 9-aminoacridine moieties via a trimethylene chain. Solutions containing the oligonucleotides and the conjugate, at different molar ratios, were studied by using electronic absorption, fluorescence emission and circular dichroism. Calculated association constants and fluorescence emission spectra showed that spermine conjugation induces sequence selectivity. The orientation of the intercalated acridine rings with respect to the oligonucleotide base planes was deduced from the electronic circular dichroism spectra. Evidence of the formation of spermine-induced aggregated structures, with potential applications to DNA packaging, gene therapy and anti-tumor therapy, was also achieved. Our data demonstrates that this spermine-acridine conjugate adds several specific characteristics provided by the polyamine moiety, as sequence selectivity, to the interesting properties of acridine derivatives.

Psychological responses of terminally ill patients who are experiencing suffering: A qualitative study.

BACKGROUND: Suffering is not only characterized by the feeling of being threatened, but also by the feeling of impotence to deal with such a threat. Literature identifies a terminal illness as a period during which several experiences implying an intense suffering are endured, but little attention has been paid to the psychological responses when reacting to threats. OBJECTIVE: Identify the psychological responses that terminally ill patients put in place to face up to the demands of the end of life, as a foundation for future nursing interventions. DESIGN: Qualitative methodology with an interpretative phenomenological approach. SETTINGS: Different hospitals health centers around the region of Granada (Spain). PARTICIPANTS: Twenty-four participants were finally chosen to take part in the research. The sampling procedure was intentional, and it was made taking into account exclusion and inclusion criteria. Patients with a cognitive impairment, who had been diagnosed with psychiatric alterations, who at that time suffered from uncontrollable symptoms such as intense pain were excluded from the sample. METHODS: The patients were interviewed following a script (semistructured interview) carried out using the suggested theoretical framework. The interviews were analyzed using the sequence suggested by Strauss and Corbin: Open, axial and selective codification. RESULTS: The analysis of the participants' answers to the different questions of the semi-structured interview has allowed us to identify a main category "To realize that life is short". There are three categories where the different ways of facing up to the end of life concentrate: "Re-Evaluation of life", "Opportunity for growth", "Resignation/Acceptance". CONCLUSIONS: Nurses, have to try to alleviate the impact the terminal illness has on the subject, not only by controlling the symptoms but also encouraging the patients responses, by promoting the feeling of satisfaction in life, providing honest and sensitive information, establishing with the patient realistic goals, and facilitating a quality communication between patients and their family.

Selective catalytic oxidation of organosulfur compounds with tert-butyl hydroperoxide.

Rates and selectivities for the oxidation of various organosulfur compounds with tert-butyl hydroperoxide were measured on CoAPO-5 (APO = aluminophosphate; Co/P = 0.05), Co/H-Y (Co/Al = 0.15), and MoO(x)/Al2O3 (15 % wt MoO3). Rates increased with increasing electron density at the sulfur atom (methyl phenyl sulfide>diphenyl sulfide>4-methyldibenzothiophene>2,5-dimethyl thiophene). Rates (per metal atom) were significantly higher on CoAPO-5 than on Co/H-Y, MoO(x)/Al2O3, or homogeneous Co acetate catalysts. Small amounts of sulfoxides (1-oxide) were detected on all catalysts at low reactant conversions, together with their corresponding sulfones; at higher conversions, only sulfones (1,1-dioxide) were detected, indicating that the oxidation of sulfoxides is much faster than for organosulfur reactants in the sequential oxidation pathways prevalent on these catalysts. Framework Co cations were not leached from CoAPO-5 during the oxidation of 4-methyldibenzothiophene, but most exchanged Co cations in H-Y and >20 % of Mo cations in MoO(x)/Al2O3 were extracted during these reactions. The fraction of redox-active Co cations in CoAPO-5 and Co/H-Y was measured by reduction-oxidation cycles using H2 and O2 and by UV-visible spectroscopy. This fraction was much larger in CoAPO-5 (0.35) than in Co/H-Y (0.01), consistent with the higher oxidation rates measured on CoAPO-5 and with the involvement of redox-active species in kinetically-relevant steps in catalytic oxidation sequences. Redox-active Co cations at framework positions within accessible channels are required for catalytic activity and structural stability during oxidative desulfurization, whether hydroperoxides are used as reactants or as intermediates (when O2 is used as the oxidant).

Adsorption, desorption, and conversion of thiophene on H-ZSM5.

The dynamics and stoichiometry of thiophene adsorption and of rearrangements of thiophene-derived adsorbed species in O(2), He, H(2), and C(3)H(8) carriers were measured using chromatographic methods and mass spectrometry on H-ZSM5 and H-Y zeolites. Thiophene adsorption obeyed Langmuir isotherms on both zeolites. Adsorption uptakes were 1.7 and 2.8 thiophene/Al at 363 K on H-ZSM5 and H-Y zeolites, respectively, after removal of physisorbed thiophene. These stoichiometries differed for these two zeolite structures but did not depend on their Al content (Si/Al = 13-85). Adsorption from a thiophene-toluene mixture showed thiophene selectivities ( approximately 10) greater than expected from van der Waals interactions. These adsorption stoichiometries, without contributions from physisorption, and the color changes detected indicate that thiophene adsorption occurs concurrently with oligomerization on acidic OH groups and that oligomer size depends on spatial constraints within channels. Thiophene oligomers decompose at approximately 534 K during subsequent thermal treatment to form molecular thiophene with all carriers, leaving behind unsaturated thiophene-derived species with a 0.9-1.1 thiophene/Al stoichiometry, confirming the specificity of OH groups and the oligomeric nature of bound thiophene during adsorption at 363 K. With He, H(2), and C(3)H(8), residual thiophene-derived species desorb as stable fragments, such as H(2)S, ethene, propene, arenes, and heavier organosulfur compounds (methylthiophene and benzothiophene) during thermal treatment; they also form unsaturated organic deposits that cannot desorb without hydrogenation events. H(2) and C(3)H(8) remove larger amounts of adsorbed species as unreacted thiophene than He, suggesting that dehydrogenation reactions are inhibited or reversed by a hydrogen source. C(3)H(8) removes a larger fraction of thiophene-derived intermediates as hydrocarbons and organosulfur compounds than H(2) or He; thus, hydrogen atoms formed during C(3)H(8) dehydrogenation are more effective in the removal of unsaturated deposits than those formed from H(2). Thiophene-derived adsorbed species are completely removed only with O(2)-containing streams at 873 K, a process that fully recovers initial adsorption capacities. This study provides a rigorous assessment of the nature and specificity of thiophene adsorption processes on acidic OH groups and of the identity and removal pathways of adsorbed species in various reactive environments.