Halogen-bonded tris (2,4-Bis(trichloromethyl)-1,3,5,triazapentadienato)-M(III) [M = Mn, Fe, Co] complexes and their catalytic activity in the peroxidative oxidation of 1-phenylethanol to acetophenone

One-pot template condensation of CCl3C=N with ammonia on a metal source [MnCl2 center dot 4H(2)O, FeCl3 center dot 6H(2)O or Co(CH3COO)(2)center dot 4H(2)O] in DMSO led to the formation of tris(2,4-bis(trichloromethyl)-1,3,5-triazapentadienato)-M(III) complexes, [M(NH=C(CCl3)NC(CCl3)=-NH}(3)]center dot n(CH3)(2)SO [M = Mn, n = 1 (1); M = Fe, n = 2 (2); M = Co, n = 2 (3)1, which were characterized using elemental analysis, and IR, ESI-MS and single-crystal X-ray analysis. The role of inter- and intramolecular non-covalent halogen and hydrogen bonds in the synthesis of 1-3 is discussed. It is shown that the crystal ionic radii of the metal ions [68.5 (Co) < 69 (Fe) < 72 (Mn), pm] are related to the corresponding Cl center dot center dot center dot Cl distances [3.178 (3) > 3.155 (2) > 3.133 (1) Al. Compounds 1-3 and the related di(triazapentadienato)-Cu(v) complex [Cu(NH=C(CCl3)NC(CCl3)=NH}2]center dot 2(CH3)(2)SO (4) act as catalyst precursors for the additive-free microwave (MW) assisted homogeneous oxidation of 1-phenylethanol with tert-butylhydroperoxide (TBHP), leading to the formation of acetophenone with yields up to 99% and TONs up to 5.0 x 10(3) after 1 h of low power (10 W) MW irradiation.

The 1998 Faial earthquake, Azores: Evidence for a transform fault associated with the Nubia-Eurasia plate boundary?

With very few exceptions, M > 4 tectonic earthquakes in the Azores show normal fault solution and occur away from the islands. Exceptionally, the 1998 shock was pure strike-slip and occurred within the northern edge of the Pico-Faial Ridge. Fault plane solutions show two possible planes of rupture striking ENE-WSW (dextral) and NNW-SSE (sinistral). The former has not been recognised in the Azores, but is parallel to the transform direction related to the relative motion between the Eurasia and Nubia plates. Therefore, the main question we address in the present study is: do transform faults related to the Eurasia/Nubia plate boundary exist in the Azores? Knowing that the main source of strain is related to plate kinematics, we conclude that the sinistral strike-slip NNW-SSE fault plane solution is not consistent with either the fault dip (ca. 65, which is typical of a normal fault) or the ca. ENE-WSW direction of maximum extension; both are consistent with a normal fault, as observed in most major earthquakes on faults striking around NNW-SSE in the Azores. In contrast, the dextral strike-slip ENE-WSW fault plane solution is consistent with the transform direction related to the anticlockwise rotation of Nubia relative to Eurasia. Altogether, tectonic data, measured ground motion, observed destruction, and modelling are consistent with a dextral strike-slip source fault striking ENE-WSW. Furthermore, the bulk clockwise rotation measured by GPS is typical of bookshelf block rotations observed at the termination of such master strike-slip faults. Therefore, we suggest that the 1998 earthquake can be related to the WSW termination of a transform (ENE-WSW fault plane solution) associated with the Nubia-Eurasia diffuse plate boundary. (C) 2014 Elsevier B.V. All rights reserved.

Is it possible to remove polymeric nanoparticles from aqueous paints during the activated sludge treatment?

The market for emulsion polymers (latexes) is large and growing at the expense of other manufacturing processes that emit higher amounts of volatile organic solvents. The paint industry is not an exception and solvent-borne paints have been gradually substituted by aqueous paints. In their life-cycle, much of the aqueous paint used for architectural or decorative purposes will eventually be discharged into wastewater treatment facilities, where its polymeric nanoparticles (mainly acrylic and styrene-acrylic) can work as xenobiotics to the microbial communities present in activated sludge. It is well established that these materials are biocompatible at macroscopic scale. But is their behaviour the same at nanoscale? What happens to the polymeric nanoparticles during the activated sludge process? Do nanoparticles agregate and are discharged together with the sludge or remain in emulsion? How do microorganisms interact with these nanoparticles? Are nanoparticles degradated by them? Are they adsorbed? Are these nanoparticles toxic to the microbial community? To study the influence of these xenobiotics in the activated sludge process, an emulsion of cross-linked poly(butyl methacrylate) nanoparticles of ca. 50 nm diameter was produced and used as model compound. Activated sludge from a wastewater treatment plant was tested by the OCDE’s respiration inhibition test using several concentrations of PBMA nanoparticles. Particle aggregation was followed by Dynamic Light Scattering and microorganism surfaces were observed by Atomic Force Microscopy. Using sequential batch reactors (SBRs) and continuous reactors, both inoculated with activated sludge, the consumption of carbon, ammonia, nitrite and nitrate was monitored and compared, in the presence and absence of nanoparticles. No particles were detected in all treated waters by Dynamic Light Scattering. This can either mean that microorganisms can efficiently remove all polymer nanoparticles or that nanoparticles tend to aggregate and be naturally removed by precipitation. Nevertheless respiration inhibition tests demonstrated that microorganisms consume more oxygen in the presence of nanoparticles, which suggests a stress situation. It was also observed a slight decrease in the efficiency of nitrification in the presence of nanoparticles. AFM images showed that while the morphology of some organisms remained the same both in the presence and absence of nanoparticles, others assumed a rough surface with hilly like shapes of ca. 50 nm when exposed to nanoparticles. Nanoparticles are thus likely to be either incorporated or adsorbed at the surface of some organisms, increasing the overall respiration rate and decreasing nitrification efficiency. Thus, despite its biocompatibility at macroscopic scale, PBMA is likely to be no longer innocuous at nanoscale.

Pt/Carbon materials as Bi-Functional catalysts for N-decane hydroisomerization

The activity and selectivity of bi-functional carbon-supported platinum catalysts for the hydroisomerization of n-alkanes have been studied. The influence of the properties of the carbon support on the performance of the catalysts were investigated by incorporating the metallic function on a series of carbons with varied porosity (microporous: GL-50 from Norit, and mesoporous: CMK-3) and surface chemistry (modified by wet oxidation). The characterization results achieved with H-2 chemisorption and TEM showed differences in surface metal concentrations and metal-support interactions depending on the support composition. The highest metal dispersion was achieved after oxidation of the carbon matrix in concentrated nitric acid, suggesting that the presence of surface functional sites distributed in inner and outer surface favors a homogeneous metal distribution. On the other hand, the higher hydrogenating activity of the catalysts prepared with the mesoporous carbon pointed out that a fast molecular traffic inside the pores plays an important role in the catalysts performance. For n-decane hydroisomerization of long chain n-alkanes, higher activities were obtained for the catalysts with an optimized acidity and metal dispersion along with adequate porosity, pointing out the importance of the support properties in the performance of the catalysts.

Production of recombinant protein hLIF in static and dynamic systems of animal cell culture

Thesis for the Degree of Master of Science in Biotechnology Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Estágio curricular na empresa Consulfrio

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Mecânica

Monitoring the ex-vivo expansion of human mesenchymal stem/stromal cells in xeno-free microcarrier-based reactor systems by MIR spectroscopy

Human mesenchymal stem/stromal cells (MSCs) have received considerable attention in the field of cell-based therapies due to their high differentiation potential and ability to modulate immune responses. However, since these cells can only be isolated in very low quantities, successful realization of these therapies requires MSCs ex-vivo expansion to achieve relevant cell doses. The metabolic activity is one of the parameters often monitored during MSCs cultivation by using expensive multi-analytical methods, some of them time-consuming. The present work evaluates the use of mid-infrared (MIR) spectroscopy, through rapid and economic high-throughput analyses associated to multivariate data analysis, to monitor three different MSCs cultivation runs conducted in spinner flasks, under xeno-free culture conditions, which differ in the type of microcarriers used and the culture feeding strategy applied. After evaluating diverse spectral preprocessing techniques, the optimized partial least square (PLS) regression models based on the MIR spectra to estimate the glucose, lactate and ammonia concentrations yielded high coefficients of determination (R2 ≥ 0.98, ≥0.98, and ≥0.94, respectively) and low prediction errors (RMSECV ≤ 4.7%, ≤4.4% and ≤5.7%, respectively). Besides PLS models valid for specific expansion protocols, a robust model simultaneously valid for the three processes was also built for predicting glucose, lactate and ammonia, yielding a R2 of 0.95, 0.97 and 0.86, and a RMSECV of 0.33, 0.57, and 0.09 mM, respectively. Therefore, MIR spectroscopy combined with multivariate data analysis represents a promising tool for both optimization and control of MSCs expansion processes.

Tectónica da região de Sintra

Photo-interpretation of aerial stereopairs of the Sintra region on the approx. 1/32 000 scale together with field work allowed the production of the present Tectonic Map of the Sintra region. It is now possible to separate structures which resulted from two different tectonic events: one, corresponding to the intrusion of the Late Cretaceous Sintra igneous diapir, and the other the Miocene compressive event, the most important tectonic inversion phase of the Lusitanian Basin. The former are present to the south, southeast and east of the intrusion and within the intrusion itself, affecting the peripheral granites and their contacts with the gabbro-syenite core. These structures comprehend: i) faults and conical fractures striking parallel to the massif boundary, which were intruded by dykes, ii) vertical faults and fractures of two conjugate sets, dextral NNW-SSE and sinistral NNE-SSW. These faults are certainly associated with the E-W striking massif's northwards directed thrust and indicate a N-S oriented horizontal maximum compressive stress. The Miocene compressive event reactivated most of the inherited structures as follows. The NNWSSE faults located on the Sintra southern platform were reactivated as dextral strike slip faults and the E-W thrust along the northern boundary of the massif was also reactivated. This thrust propagated to the east. It also enhanced the asymmetry of the rim-syncline, uplifted the massif and reactivated the NNE-SSW faults as sinistral lateral ramps, which also accommodated vertical throw. The present Tectonic Map of Sintra together with the available geophysical data (MOREIRA, 1984, KULLBERG et al., 1991, SILVA & MIRANDA, 1994) allowed reassessment of the models proposed for the emplacement of the Sintra, Sines and Monchique igneous massifs, which intruded during Late Cretaceous times along the deep dextral NNW-SSE oriented strike slip fault (RIBEIRO et al., 1979; TERRINHA, 1998; TERRINHA & KULLBERG, 1998).

The transport of carboxylic acids and important role of the Jen1p transporter during the development of yeast colonies

On solid substrates, yeast colonies pass through distinct developmental phases characterized by the changes in pH of their surroundings from acidic to nearly alkaline and vice versa. At the beginning of the alkali phase colonies start to produce ammonia, which functions as a quorum-sensing molecule inducing the reprogramming of cell metabolism. Such reprogramming includes, among others, the activation of several plasma membrane transporters and is connected with colony differentiation. In the present study, we show that colony cells can use two transport mechanisms to import lactic acid: a ‘saturable’ component of the transport, which requires the presence of a functional Jen1p transporter, and a ‘non-saturable’ component (diffusion) that is independent of Jen1p. During colony development, the efficiency of both transport components changes similarly in central and outer colonial cells. Although the lactate uptake capacity of central cells gradually decreases during colony development, the lactate uptake capacity of outer cells peaks during the alkali phase and is also kept relatively high in the second acidic phase. This lactate uptake profile correlates with the localization of the Jen1p transporter to the plasma membrane of colony cells. Both lactic acid uptake mechanisms are diminished in sok2 colonies where JEN1 expression is decreased. The Sok2p transcription factor may therefore be involved in the regulation of non-saturable lactic acid uptake in yeast colonies.

Measuring the cytochrome c nitrite reductase activity—practical considerations on the enzyme assays

Hindawi Publishing Corporation Bioinorganic Chemistry and Applications Volume 2010, Article ID 634597, 8 pages

Focus on: II – physiological principles of acid-base balance: an integrative perspective

Normal human metabolism leads to the daily production of large amounts of volatile and non-volatile acids. The maintenance of the pH within physiological limits is a demanding task in which several mechanisms are involved. The most immediate answer comes from several physiological buffers that quickly neutralize pH deviations caused by the addition of strong acids or bases to the body. Bicarbonate/carbonic acid is the most important buffer pair of the extracellular milieu, but is chemically inefficient and depends on the continuous activity of the lung and kidney. Other physiological buffers have higher efficacy and are very important in the intracellular environment and renal tubules. The capacity of the various chemical buffers is kept by operating in an open system and by several controlling mechanisms. The lung is responsible for the elimination of the carbon dioxide (CO2) produced in the body. In metabolic disorders, respiratory adjustment of the elimination of CO2 prolongs the effect of the bicarbonate/carbonic acid buffer, but this process consumes bicarbonate. The kidney contributes to acid-base balance through several mechanisms: 1) controls the reabsorption of filtered bicarbonate; 2) regenerates bicarbonate consumed in buffer reactions; 3) eliminates non-volatile acids. Renal elimination of acid and bicarbonate regeneration is only possible due to the existence of several urinary buffers and to the ability of the kidneys to produce ammonia

Liver Depurative Techniques: A Single Liver Transplantation Center Experience

In a liver transplant (LT) center, treatments with Prometheus were evaluated. The main outcome considered was 1 and 6 months survival. Methods. During the study period, 74 patients underwent treatment with Prometheus; 64 were enrolled,with a mean age of 51 13 years; 47men underwent 212 treatments (mean, 3.02 per patient). The parameters evaluated were age, sex, laboratorial (liver enzymes, ammonia) and clinical (model for end-stage liver disease and Child-Turcotte-Pugh score) data. Results. Death was verified in 23 patients (35.9%) during the hospitalization period, 20 patients (31.3%) were submitted to liver transplantation, and 21 were discharged. LT was performed in 4 patients with acute liver failure (ALF, 23.7%), in 7 patients with acute on chronic liver failure (AoCLF, 43.7%), and in 6 patients with liver disease after LT (30%). Seven patients who underwent LT died (35%). In the multivariate analysis, older age (P ¼ .015), higher international normalized ratio (INR) (P ¼ .019), and acute liver failure (P ¼ .039) were independently associated with an adverse 1-month clinical outcome. On the other hand, older age (P ¼ .011) and acute kidney injury (P ¼ .031) at presentation were both related to worse 6-month outcome. For patients with ALF and AoCLF we did not observe the same differences. Conclusions. In this cohort, older age was the most important parameter defining 1- and 6-month survival, although higher INR and presence of ALF were important for 1-month survival and AKI for 6-month survival. No difference was observed between patients who underwent LT or did not have LT.

Fate of nitrogen in bioreactor landfills: lab-scale in situ aeration in well decomposed MSW

Dissertação para obtenção do Grau de Mestre em Engenharia do ambiente, perfil de engenharia sanitária

Determination of microalgae cellular composition after phycoremediation of swine wastewaters.

Phycoremediation of swine wastewaters has been widely reported as an attractive tertiary treatment system, that effectively removes the excessive nutrient loadswhilst offering a valuable source of feedstock biomass. Digestate from an upflow anaerobic sludge blanket (UASB, 6%v/v) and a nitrification reactor (NR; 50% v/v) were used as culturing media to microalgae. Experiments were carried out in lab scale photobioreactors (PBRs) using a consortia of Chlorella and Scenedesmus. Ammonia (44 to 90%) and phosphorus (77%) were efficiently removed from both effluents tested after 4 days. Microalgae biomass harvested from the UASB effluent showed 57, 34 and 1% of proteins, carbohydrates and lipids, respectively. Comparatively, the cellular composition of microalgae grown on NR effluent had lower protein (43%) but higher carbohydrate (42%) contents. Negligible difference in lipid fraction was observed independently of the effluents tested. The results suggest that the biomass harvested from phycoremediation of swine wastewaters can offer a valuable protein and carbohydrate feedstock for nutritional and biotechnological applications.

Biodiversity and quantification of functional bacteria in deammonification process.

2015