Numerical prediction of diffusion and electric field-induced iron nanoparticle transport

Zero valent iron nanoparticles (nZVI) are considered very promising for the remediation of contaminated soils and groundwaters. However, an important issue related to their limited mobility remains unsolved. Direct current can be used to enhance the nanoparticles transport, based on the same principles of electrokinetic remediation. In this work, a generalized physicochemical model was developed and solved numerically to describe the nZVI transport through porous media under electric field, and with different electrolytes (with different ionic strengths). The model consists of the Nernst–Planck coupled system of equations, which accounts for the mass balance of ionic species in a fluid medium, when both the diffusion and electromigration of the ions are considered. The diffusion and electrophoretic transport of the negatively charged nZVI particles were also considered in the system. The contribution of electroosmotic flow to the overall mass transport was included in the model for all cases. The nZVI effective mobility values in the porous medium are very low (10−7–10−4 cm2 V−1 s−1), due to the counterbalance between the positive electroosmotic flow and the electrophoretic transport of the negatively charged nanoparticles. The higher the nZVI concentration is in the matrix, the higher the aggregation; therefore, low concentration of nZVI suspensions must be used for successful field application.

Design of bio-inspired ionic liquids for protein stabilisation

Ionic Liquids (ILs) consist in organic salts that are liquid at/or near room temperature. Since ILs are entirely composed of ions, the formation of ion pairs is expected to be one essential feature for describing solvation in ILs. In recent years, protein - ionic liquid (P-IL) interactions have been the subject of intensive studies mainly because of their capability to promote folding/unfolding of proteins. However, the ion pairs and their lifetimes in ILs in P-IL thematic is dismissed, since the action of ILs is therefore the result of a subtle equilibrium between anion-cation interaction, ion-solvent and ion-protein interaction. The work developed in this thesis innovates in this thematic, once the design of ILs for protein stabilisation was bio-inspired in the high concentration of organic charged metabolites found in cell milieu. Although this perception is overlooked, those combined concentrations have been estimated to be ~300 mM among the macromolecules at concentrations exceeding 300 g/L (macromolecular crowding) and transient ion-pair can naturally occur with a potential specific biological role. Hence the main objective of this work is to develop new bio-ILs with a detectable ion-pair and understand its effects on protein structure and stability, under crowding environment, using advanced NMR techniques and calorimetric techniques. The choline-glutamate ([Ch][Glu]) IL was synthesized and characterized. The ion-pair was detected in water solutions using mainly the selective NOE NMR technique. Through the same technique, it was possible to detect a similar ion-pair promotion under synthetic and natural crowding environments. Using NMR spectroscopy (protein diffusion, HSQC experiments, and hydrogen-deuterium exchange) and differential scanning calorimetry (DSC), the model protein GB1 (production and purification in isotopic enrichment media) it was studied in the presence of [Ch][Glu] under macromolecular crowding conditions (PEG, BSA, lysozyme). Under dilute condition, it is possible to assert that the [Ch][Glu] induces a preferential hydration by weak and non-specific interactions, which leads to a significant stabilisation. On the other hand, under crowding environment, the [Ch][Glu] ion pair is promoted, destabilising the protein by favourable weak hydrophobic interactions , which disrupt the hydration layer of the protein. However, this capability can mitigates the effect of protein crowders. Overall, this work explored the ion-pair existence and its consequences on proteins in conditions similar to cell milieu. In this way, the charged metabolites found in cell can be understood as key for protein stabilisation.

Carbonation front progress in mortars containing fly ash considering the presence of chloride ions

The incorporation of fly ash (FA) in cementitious matrices have been frequently used in order to make the matrix more resistant to the action of chlorides. On the other hand, it is known that Ca (OH)2 existing in the matrix is partially consumed by the pozzolanic reactions, which facilitates the advancement of carbonation. Given that the combined action between carbonation and chloride penetration is a fact little known, we speculate about the behaviour of the matrix in this context. This study investigates the influence of the presence of chlorides on the carbonation in mortars with FA. Samples with 0% and 40% replacement of cement CEM I 42.5 R for FA were molded with water/binder 0.56 and 0.52 respectively. After 90 days of curing the specimens were subjected to cycles of immersion/drying for 56 days. Half of the samples was subjected to the following cycle: two days in a solution containing NaCl (concentration equal to 3.5 %); 12 days in the carbonation chamber (4% of CO2). The other half was: two days in water; 12 days in the carbonation chamber. Then, the development of carbonation was evaluated. The results indicate that the presence of chlorides influences the carbonation. The specimens submitted to the exclusive action of CO2 showed a greater depth of carbonation compared to that presented by the specimens subjected to combined action. This may be related to changes in properties of the matrix which may lead to further refinement of the pores and related to the presence of the salt that can lead to partial filling of the pores and the increase in moisture content.

(Un)suitability of the use of pH buffers in biological, biochemical and environmental studies and their interaction with metal ions - a review

The use of buffers to maintain the pH within a desired range is a very common practice in chemical, biochemical and biological studies. Among them, zwitterionic N-substituted aminosulfonic acids, usually known as Good's buffers, although widely used, can complex metals and interact with biological systems. The present work reviews, discusses and updates the metal complexation characteristics of thirty one commercially available buffers. In addition, their impact on biological systems is also presented. The influences of these buffers on the results obtained in biological, biochemical and environmental studies, with special focus on their interaction with metal ions, are highlighted and critically reviewed. Using chemical speciation simulations, based on the current knowledge of the metal-buffer stability constants, a proposal of the most adequate buffer to employ for a given metal ion is presented.

Measurement of charged-particle spectra in Pb+Pb collisions at √sNN = 2.76TeV with the ATLAS detector at the LHC

Charged-particle spectra obtained in 0.15nb−1 of Pb+Pb interactions at sNN−−−√=2.76TeV and 4.2pb−1 of pp interactions at s√=2.76TeV with the ATLAS detector at the LHC are presented in a wide transverse momentum (0.5ions, the spectra are presented as a function of collision centrality, which is determined by the response of the forward calorimeter located on both sides of the interaction point. The nuclear modification factors RAA and RCP are presented in detail as function of centrality, pT and η. They show a distinct pT-dependence with a pronounced minimum at about 7GeV. Above 60GeV, RAA is consistent with a plateau at a centrality-dependent value, within the uncertainties. The value is 0.55±0.01(stat.)±0.04(syst.) in the most central collisions. The RAA distribution is consistent with flat |η| dependence over the whole transverse momentum range in all centrality classes.

Search for anomalous production of prompt same-sign lepton pairs and pair-produced doubly charged Higgs bosons with s√ = 8 TeV pp collisions using the ATLAS detector

A low-background inclusive search for new physics in events with same-sign dileptons is presented. The search uses proton--proton collisions corresponding to 20.3 fb−1 of integrated luminosity taken in 2012 at a centre-of-mass energy of 8 TeV with the ATLAS detector at the LHC. Pairs of isolated leptons with the same electric charge and large transverse momenta of the type e±e±,e±μ±, and μ±μ± are selected and their invariant mass distribution is examined. No excess of events above the expected level of Standard Model background is found. The results are used to set upper limits on the cross sections for processes beyond the Standard Model. Limits are placed as a function of the dilepton invariant mass within a fiducial region corresponding to the signal event selection criteria. Exclusion limits are also derived for a specific model of doubly charged Higgs boson production.

Absorption of scalars by nonextremal charged black holes in string theory

We analyze the low frequency absorption cross section of minimally coupled massless scalar fields by different kinds of charged static black holes in string theory, namely the D1–D5 system in d=5 and a four dimensional dyonic four-charged black hole. In each case we show that this cross section always has the form of some parameter of the solution divided by the black hole Hawking temperature. We also verify in each case that, despite its explicit temperature dependence, such quotient is finite in the extremal limit, giving a well defined cross section. We show that this precise explicit temperature dependence also arises in the same cross section for black holes with string \alpha' corrections: it is actually induced by them.

Development of Monoolein-based lipofection vectors for therapeutic siRNA delivery

Tese de Doutoramento em Biologia Molecular e Ambiental - Especialidade em Biologia Celular e Saúde

Influence of ischemic preconditioning in myocardial protection in patients undergoing myocardial revascularization with intermittent crossclamping of the aorta. Analysis of ions and blood gases

OBJECTIVE: To test the hypothesis that short periods of ischemia may increase the myocardial protection obtained with intermittent crossclamping of the aorta. METHODS: In the control group (18 patients), surgery was performed with systemic hypothermia at 32ºC and intermittent crossclamping of the aorta. Extracorporeal circulation was used. In the preconditioning group (17 patients), 2 crossclampings of the aorta lasting 3min each were added prior to the intermittent crossclamping of the conventional technique with an interval of 2min of reperfusion between them. Blood samples for analyses of pH, pCO2, pO2, sodium, potassium, calcium, and magnesium were obtained from the coronary sinus at the beginning of extracorporeal circulation (time 1), at the end of the first anastomosis (time 2), and at the end of extracorporeal circulation (time 3). RESULTS: No difference was observed in the results of the 2 groups, except for a variation in the ionic values in the different times of blood withdrawal; sodium values, however, remained stable. All patients had a good clinical outcome. CONCLUSION: The results of intermittent crossclamping of the aorta with moderate hypothermia were not altered by the use of ischemic preconditioning.

Some results of study of variations of light ions concentration and their connections with the ionizing radiation and sub-micron aerosol content in air under the conditions of Tbilisi city

Results of analysis of variations of sum light ions concentration and their connections with radon, galactic cosmic rays intensity and content of sub-micron aerosols by diameter ≥ 0.1 micron in surface boundary layer of Tbilisi city are given.

The Feedback Effect of Intensity of Ionizing Radiation With the Light Ions Content in Atmosphere. Paradox (the Tbilisi Type of a Smog), or Usual Phenomenon for the Strongly Pollution Cities?.

თბილისში მსუბუქი იონების, რადონის და გალაქტიკური კოსმოსური სხივების ნეიტრონული კომპონენტის ინტენსივობის 2009-2010 წლებში კომპლექსური მონიტორინგის მონაცემების მიხედვით გამოვლენილია მაიონიზებელი გამოსხივების ინტენსივობისა და ატმოსფეროში მსუბუქი იონების შემცველობის უკუკავშირის ეფექტი.

Negative Correlation Between of Light Ions Content and Radon Concentration: Particularity of Tbilisi City Air Pollution, or Norm for the Urbanized Locality?

In Tbilisi according to the data of the complex monitoring of light ions concentration, radon and sub-micron aerosols the effect of feedback of intensity of ionizing radiation with the light ions content in atmosphere is discovered.

Comparative Characteristics of Light Ions Content in the Urban and Ecologically Clean Locality in Georgia

The results of the stationary and expeditionary investigations of the light ions content in surface boundary layer in the urban and ecologically clean locality for different regions of Georgia are represented.

The effects of drugs, ions, and poly-l-lysine on the excretory system of Schistosoma mansoni

We have been able to label the excretory system of cercariae and all forms of schistosomula, immature and adult worms with the highly fluorescent dye resorufin. We have shown that the accumulation of the resorufin into the excretory tubules and collecting ducts of the male adult worm depends on the presence of extracellular calcium and phosphate ions. In the adult male worms, praziquantel (PZQ) prevents this accumulation in RPMI medium and disperses resorufin from tubules which have been prelabelled. Female worms and all other developmental stages are much less affected either by the presence of calcium and phosphate ions, or the disruption caused by PZQ. The male can inhibit the excretory system in paired female. Fluorescent PZQ localises in the posterior gut (intestine) region of the male adult worm, but not in the excretory system, except for the anionic carboxy fluorescein derivative of PZQ, which may be excreted by this route. All stages of the parasite can recover from damage by PZQ treatment in vitro. The excretory system is highly sensitive to damage to the surface membrane and may be involved in vesicle movement and damage repair processes. In vivo the adult parasite does not recover from PZQ treatment, but what is inhibiting recovery is unknown, but likely to be related to immune effector molecules.

Evaluation of HA negatively charged membranes in the recovery of human adenoviruses and hepatitis A virus in different water matrices

Human adenoviruses (HAdV) and hepatitis A virus (HAV) are shed in the faeces and consequently may be present in environmental waters, resulting in an increase in pathogen concentration that can affect water quality and human health. The aim of this study was to evaluate an adsorption-elution method which utilizes negatively charged membrane HA to determine the efficient recovery of HAdV and HAV from different water matrices and to combine this procedure with a qualitative molecular method (nested RT-PCR and nested PCR). The best efficiency recovery was achieved in distilled water and treated wastewater effluent (100%) for both viruses and in recreational lagoon water for HAV (100%). The efficiency recovery was 10% for HAdV and HAV in seawater and 10% for HAdV in lagoon water. The viral detection limit by nested PCR for HAV in water samples ranged between 20-0.2 FFU/mL and 250 and 25 TCID50/mL for HAdV. In conclusion, these results suggest that the HA negatively charged membranes vary their efficiency for recovery of viral concentration depending upon the types of both enteric viruses and water matrices.