Characterization and Control Strategies of an Integrated Chemical-Biological System for the Remediation of Toxic Pollutants in Wastewater: A case of study

In a previous work, a hybrid system consisting of an advanced oxidation process (AOP) named Photo-Fenton (Ph-F) and a fixed bed biological treatment operating as a sequencing batch biofilm reactor (SBBR) was started-up and optimized to treat 200 mg·L-1 of 4-chlorophenol (4-CP) as a model compound. In this work, studies of reactor stability and control as well as microbial population determination by molecular biology techniques were carried out to further characterize and control the biological reactor. Results revealed that the integrated system was flexible and even able to overcome toxic shock loads. Oxygen uptake rate (OUR) in situ was shown to be a valid tool to control the SBBR operation, to detect toxic conditions to the biomass, and to assess the recovery of performance. A microbial characterization by 16S rDNA sequence analysis reveals that the biological population was varied, although about 30% of the bacteria belonged to the Wautersia genus.

Highly improved chromium (III) uptake capacity in modified sugarcane bagasse using different chemical treatments

The present paper focuses on improving chromium (III) uptake capacity of sugarcane bagasse through its chemical modification with citric acid and/or sodium hydroxide. The chemical modifications were confirmed by infrared spectroscopy, with an evident peak observed at 1730 cm-1, attributed to carbonyl groups. Equilibrium was reached after 24 h, and the kinetics followed the pseudo-second-order model. The highest chromium (III) maximum adsorption capacity (MAC) value was found when using sugarcane bagasse modified with sodium hydroxide and citric acid (58.00 mg g-1) giving a MAC value about three times greater (20.34 mg g-1) than for raw sugarcane bagasse.

Modulating the electronic structure of amino acids: interaction of model lewis acids with anthranilic acid

On the basis of theoretical B3LYP calculations, Yáñez and co-workers (J. Chem. Theory Comput. 2012, 8, 2293) illustrated that beryllium ions are capable of significantly modulating (changing) the electronic structures of imidazole. In this computational organic chemistry study, the interaction of this β-amino acid and five model Lewis acids (BeF1+, Be2+, AlF2(1+), AlF2+, and Al3+) were investigated. Several aspects were addressed: natural bond orbitals, including second order perturbation analysis of intra-molecular charge delocalization and the natural population analysis atomic charges; molecular geometries; selected infrared stretching frequencies (C-N, C-O, and N-H), and selected ¹H-NMR chemical shifts. The data illustrate that this interaction can weaken the H-O bond and goes beyond strengthening the intra-molecular hydrogen bond (N...H-O) to cause a spontaneous transfer of the proton to the nitrogen atom in five cases generating zwitterion structures. Many new features are observed. Most importantly, the zwitterion structures include a stabilizing hydrogen bond (N-H...O) that varies in relative strength according to the Lewis acid. These findings explain the experimental observations of α-amino acids (for example: J. Am. Chem. Soc. 2001, 123, 3577) and are the first reported fundamental electronic structure characterization of β-amino acids in zwitterion form.

CHEMICAL COMPOSITION AND ANTI-INFLAMMATORY ACTIVITY OF Roldana platanifolia

The chemical study of Roldana platanifolia led to the isolation of β-caryophyllene, five eremophilanolides, chlorogenic acid, and a mixture of β-sitosterol-stigmasterol, β-sitosteryl glucopyranoside, and sucrose. The anti-inflammatory activities of the extracts and isolated products were tested using the 12-O-tetradecanoylphorbol-13-acetate (TPA) model of induced acute inflammation. The acetone and methanol extracts showed dose dependent activities (ID50 0.21 and 0.32 mg/ear, respectively), while none of the isolated compounds exhibited relevant edema inhibition. The active extracts were also evaluated with the myeloperoxidase assay technique (MPO) to determine their ability to prevent neutrophil infiltration. Results showed that the anti-inflammatory activity was related to the compound’s ability to inhibit pro-inflammatory mediators such as neutrophils.

COMPARISON BETWEEN ASPHALTENES (SUB)FRACTIONS EXTRACTED FROM TWO DIFFERENT ASPHALTIC RESIDUES: CHEMICAL CHARACTERIZATION AND PHASE BEHAVIOR

Asphaltenes are blamed for various problems in the petroleum industry, especially formation of solid deposits and stabilization of water-in-oil emulsions. Many studies have been conducted to characterize chemical structures of asphaltenes and assess their phase behavior in crude oil or in model-systems of asphaltenes extracted from oil or asphaltic residues from refineries. However, due to the diversity and complexity of these structures, there is still much to be investigated. In this study, asphaltene (sub)fractions were extracted from an asphaltic residue (AR02), characterized by NMR, elemental analysis, X-ray fluorescence and MS-TOF, and compared to asphaltene subfractions obtained from another asphaltic residue (AR01) described in a previous article. The (sub)fractions obtained from the two residues were used to prepare model-systems containing 1 wt% of asphaltenes in toluene and their phase behavior was evaluated by measuring asphaltene precipitation onset using optical microscopy. The results obtained indicated minor differences between the asphaltene fractions obtained from the asphaltic residues of distinct origins, with respect to aromaticity, elemental composition (CHN), presence and content of heteroelements and average molar mass. Regarding stability, minor differences in molecule polarity appear to promote major differences in the phase behavior of each of the asphaltene fractions isolated.

A generalized 1D particle transport method for convection diffusion reaction model

This work is devoted to the development of numerical method to deal with convection diffusion dominated problem with reaction term, non - stiff chemical reaction and stiff chemical reaction. The technique is based on the unifying Eulerian - Lagrangian schemes (particle transport method) under the framework of operator splitting method. In the computational domain, the particle set is assigned to solve the convection reaction subproblem along the characteristic curves created by convective velocity. At each time step, convection, diffusion and reaction terms are solved separately by assuming that, each phenomenon occurs separately in a sequential fashion. Moreover, adaptivities and projection techniques are used to add particles in the regions of high gradients (steep fronts) and discontinuities and transfer a solution from particle set onto grid point respectively. The numerical results show that, the particle transport method has improved the solutions of CDR problems. Nevertheless, the method is time consumer when compared with other classical technique e.g., method of lines. Apart from this advantage, the particle transport method can be used to simulate problems that involve movingsteep/smooth fronts such as separation of two or more elements in the system.

Development of chemical looping combustion process

Chemical looping combustion (CLC) provides a promising technology to help cut carbon dioxide emissions. CLC is based on separated oxidation and reduction processes. Oxygen carrier, which is made from metal and supporting material, is in continuous recirculation between the air and fuel reactors. The CLC process does not require separation unit for carbon dioxide. The fuel reactor can produce an almost pure carbon dioxide feed which decrease costs of carbon capture and storage (CCS). The CLC method is one of the most promising ones for energy efficient carbon capture. A large amount of literature was examined for this study and from it the most promising methods and designs were chosen. These methods and designs were combined as reactor system design which was then sized during the making of this thesis. Sizing was done with a mathematical model that was further improved during the study.

Wood as a model material for medical biomaterials. In vivo and in vitro studies with bone and Betula pubescens Ehrh

Novel biomaterials are needed to fill the demand of tailored bone substitutes required by an ever‐expanding array of surgical procedures and techniques. Wood, a natural fiber composite, modified with heat treatment to alter its composition, may provide a novel approach to the further development of hierarchically structured biomaterials. The suitability of wood as a model biomaterial as well as the effects of heat treatment on the osteoconductivity of wood was studied by placing untreated and heat‐treated (at 220 C , 200 degrees and 140 degrees for 2 h) birch implants (size 4 x 7mm) into drill cavities in the distal femur of rabbits. The follow‐up period was 4, 8 and 20 weeks in all in vivo experiments. The flexural properties of wood as well as dimensional changes and hydroxyl apatite formation on the surface of wood (untreated, 140 degrees C and 200 degrees C heat‐treated wood) were tested using 3‐point bending and compression tests and immersion in simulated body fluid. The effect of premeasurement grinding and the effect of heat treatment on the surface roughness and contour of wood were tested with contact stylus and non‐contact profilometry. The effects of heat treatment of wood on its interactions with biological fluids was assessed using two different test media and real human blood in liquid penetration tests. The results of the in vivo experiments showed implanted wood to be well tolerated, with no implants rejected due to foreign body reactions. Heat treatment had significant effects on the biocompatibility of wood, allowing host bone to grow into tight contact with the implant, with occasional bone ingrowth into the channels of the wood implant. The results of the liquid immersion experiments showed hydroxyl apatite formation only in the most extensively heat‐treated wood specimens, which supported the results of the in vivo experiments. Parallel conclusions could be drawn based on the results of the liquid penetration test where human blood had the most favorable interaction with the most extensively heat‐treated wood of the compared materials (untreated, 140 degrees C and 200 degrees C heat‐treated wood). The increasing biocompatibility was inferred to result mainly from changes in the chemical composition of wood induced by the heat treatment, namely the altered arrangement and concentrations of functional chemical groups. However, the influence of microscopic changes in the cell walls, surface roughness and contour cannot be totally excluded. The heat treatment was hypothesized to produce a functional change in the liquid distribution within wood, which could have biological relevance. It was concluded that the highly evolved hierarchical anatomy of wood could yield information for the future development of bulk bone substitutes according to the ideology of bioinspiration. Furthermore, the results of the biomechanical tests established that heat treatment alters various biologically relevant mechanical properties of wood, thus expanding the possibilities of wood as a model material, which could include e.g. scaffold applications, bulk bone applications and serving as a tool for both mechanical testing and for further development of synthetic fiber reinforced composites.

Repair of segmental bone defects with fiber-reinforced composite: a study of material development and an animal model on rabbits

The Repair of segmental defects in load-bearing long bones is a challenging task because of the diversity of the load affecting the area; axial, bending, shearing and torsional forces all come together to test the stability/integrity of the bone. The natural biomechanical requirements for bone restorative materials include strength to withstand heavy loads, and adaptivity to conform into a biological environment without disturbing or damaging it. Fiber-reinforced composite (FRC) materials have shown promise, as metals and ceramics have been too rigid, and polymers alone are lacking in strength which is needed for restoration. The versatility of the fiber-reinforced composites also allows tailoring of the composite to meet the multitude of bone properties in the skeleton. The attachment and incorporation of a bone substitute to bone has been advanced by different surface modification methods. Most often this is achieved by the creation of surface texture, which allows bone growth, onto the substitute, creating a mechanical interlocking. Another method is to alter the chemical properties of the surface to create bonding with the bone – for example with a hydroxyapatite (HA) or a bioactive glass (BG) coating. A novel fiber-reinforced composite implant material with a porous surface was developed for bone substitution purposes in load-bearing applications. The material’s biomechanical properties were tailored with unidirectional fiber reinforcement to match the strength of cortical bone. To advance bone growth onto the material, an optimal surface porosity was created by a dissolution process, and an addition of bioactive glass to the material was explored. The effects of dissolution and orientation of the fiber reinforcement were also evaluated for bone-bonding purposes. The Biological response to the implant material was evaluated in a cell culture study to assure the safety of the materials combined. To test the material’s properties in a clinical setting, an animal model was used. A critical-size bone defect in a rabbit’s tibia was used to test the material in a load-bearing application, with short- and long-term follow-up, and a histological evaluation of the incorporation to the host bone. The biomechanical results of the study showed that the material is durable and the tailoring of the properties can be reproduced reliably. The Biological response - ex vivo - to the created surface structure favours the attachment and growth of bone cells, with the additional benefit of bioactive glass appearing on the surface. No toxic reactions to possible agents leaching from the material could be detected in the cell culture study when compared to a nontoxic control material. The mechanical interlocking was enhanced - as expected - with the porosity, whereas the reinforcing fibers protruding from the surface of the implant gave additional strength when tested in a bone-bonding model. Animal experiments verified that the material is capable of withstanding load-bearing conditions in prolonged use without breaking of the material or creating stress shielding effects to the host bone. A Histological examination verified the enhanced incorporation to host bone with an abundance of bone growth onto and over the material. This was achieved with minimal tissue reactions to a foreign body. An FRC implant with surface porosity displays potential in the field of reconstructive surgery, especially regarding large bone defects with high demands on strength and shape retention in load-bearing areas or flat bones such as facial / cranial bones. The benefits of modifying the strength of the material and adjusting the surface properties with fiber reinforcement and bone-bonding additives to meet the requirements of different bone qualities are still to be fully discovered.

Detection of Horizontal Two-Phase Flow Patterns Through a Neural Network Model

One of the main problems related to the transport and manipulation of multiphase fluids concerns the existence of characteristic flow patterns and its strong influence on important operation parameters. A good example of this occurs in gas-liquid chemical reactors in which maximum efficiencies can be achieved by maintaining a finely dispersed bubbly flow to maximize the total interfacial area. Thus, the ability to automatically detect flow patterns is of crucial importance, especially for the adequate operation of multiphase systems. This work describes the application of a neural model to process the signals delivered by a direct imaging probe to produce a diagnostic of the corresponding flow pattern. The neural model is constituted of six independent neural modules, each of which trained to detect one of the main horizontal flow patterns, and a last winner-take-all layer responsible for resolving when two or more patterns are simultaneously detected. Experimental signals representing different bubbly, intermittent, annular and stratified flow patterns were used to validate the neural model.

Model based analysis of the post-combustion calcium looping process for carbon dioxide capture

This thesis presents a one-dimensional, semi-empirical dynamic model for the simulation and analysis of a calcium looping process for post-combustion CO2 capture. Reduction of greenhouse emissions from fossil fuel power production requires rapid actions including the development of efficient carbon capture and sequestration technologies. The development of new carbon capture technologies can be expedited by using modelling tools. Techno-economical evaluation of new capture processes can be done quickly and cost-effectively with computational models before building expensive pilot plants. Post-combustion calcium looping is a developing carbon capture process which utilizes fluidized bed technology with lime as a sorbent. The main objective of this work was to analyse the technological feasibility of the calcium looping process at different scales with a computational model. A one-dimensional dynamic model was applied to the calcium looping process, simulating the behaviour of the interconnected circulating fluidized bed reactors. The model incorporates fundamental mass and energy balance solvers to semi-empirical models describing solid behaviour in a circulating fluidized bed and chemical reactions occurring in the calcium loop. In addition, fluidized bed combustion, heat transfer and core-wall layer effects were modelled. The calcium looping model framework was successfully applied to a 30 kWth laboratory scale and a pilot scale unit 1.7 MWth and used to design a conceptual 250 MWth industrial scale unit. Valuable information was gathered from the behaviour of a small scale laboratory device. In addition, the interconnected behaviour of pilot plant reactors and the effect of solid fluidization on the thermal and carbon dioxide balances of the system were analysed. The scale-up study provided practical information on the thermal design of an industrial sized unit, selection of particle size and operability in different load scenarios.

Cell Model Systems in Characterizing Alpha2-Adrenoceptors as Drug Targets.

The three alpha2-adrenoceptor (alpha2-AR) subtypes belong to the G protein-coupled receptor superfamily and represent potential drug targets. These receptors have many vital physiological functions, but their actions are complex and often oppose each other. Current research is therefore driven towards discovering drugs that selectively interact with a specific subtype. Cell model systems can be used to evaluate a chemical compound's activity in complex biological systems. The aim of this thesis was to optimize and validate cell-based model systems and assays to investigate alpha2-ARs as drug targets. The use of immortalized cell lines as model systems is firmly established but poses several problems, since the protein of interest is expressed in a foreign environment, and thus essential components of receptor regulation or signaling cascades might be missing. Careful cell model validation is thus required; this was exemplified by three different approaches. In cells heterologously expressing alpha2A-ARs, it was noted that the transfection technique affected the test outcome; false negative adenylyl cyclase test results were produced unless a cell population expressing receptors in a homogenous fashion was used. Recombinant alpha2C-ARs in non-neuronal cells were retained inside the cells, and not expressed in the cell membrane, complicating investigation of this receptor subtype. Receptor expression enhancing proteins (REEPs) were found to be neuronalspecific adapter proteins that regulate the processing of the alpha2C-AR, resulting in an increased level of total receptor expression. Current trends call for the use of primary cells endogenously expressing the receptor of interest; therefore, primary human vascular smooth muscle cells (SMC) expressing alpha2-ARs were tested in a functional assay monitoring contractility with a myosin light chain phosphorylation assay. However, these cells were not compatible with this assay due to the loss of differentiation. A rat aortic SMC cell line transfected to express the human alpha2B-AR was adapted for the assay, and it was found that the alpha2-AR agonist, dexmedetomidine, evoked myosin light chain phosphorylation in this model.

Particle model for simulating limestone reactions in novel fluidised bed energy applications

The development of carbon capture and storage (CCS) has raised interest towards novel fluidised bed (FB) energy applications. In these applications, limestone can be utilized for S02 and/or CO2 capture. The conditions in the new applications differ from the traditional atmospheric and pressurised circulating fluidised bed (CFB) combustion conditions in which the limestone is successfully used for SO2 capture. In this work, a detailed physical single particle model with a description of the mass and energy transfer inside the particle for limestone was developed. The novelty of this model was to take into account the simultaneous reactions, changing conditions, and the effect of advection. Especially, the capability to study the cyclic behaviour of limestone on both sides of the calcination-carbonation equilibrium curve is important in the novel conditions. The significances of including advection or assuming diffusion control were studied in calcination. Especially, the effect of advection in calcination reaction in the novel combustion atmosphere was shown. The model was tested against experimental data; sulphur capture was studied in a laboratory reactor in different fluidised bed conditions. Different Conversion levels and sulphation patterns were examined in different atmospheres for one limestone type. The Conversion curves were well predicted with the model, and the mechanisms leading to the Conversion patterns were explained with the model simulations. In this work, it was also evaluated whether the transient environment has an effect on the limestone behaviour compared to the averaged conditions and in which conditions the effect is the largest. The difference between the averaged and transient conditions was notable only in the conditions which were close to the calcination-carbonation equilibrium curve. The results of this study suggest that the development of a simplified particle model requires a proper understanding of physical and chemical processes taking place in the particle during the reactions. The results of the study will be required when analysing complex limestone reaction phenomena or when developing the description of limestone behaviour in comprehensive 3D process models. In order to transfer the experimental observations to furnace conditions, the relevant mechanisms that take place need to be understood before the important ones can be selected for 3D process model. This study revealed the sulphur capture behaviour under transient oxy-fuel conditions, which is important when the oxy-fuel CFB process and process model are developed.

Connexin domains relevant to the chemical gating of gap junction channels

Most cells exchange ions and small metabolites via gap junction channels. These channels are made of two hemichannels (connexons), each formed by the radial arrangement of six connexin (Cx) proteins. Connexins span the bilayer four times (M1-M4) and have both amino- and carboxy-termini (NT, CT) at the cytoplasmic side of the membrane, forming two extracellular loops (E1, E2) and one inner (IL) loop. The channels are regulated by gates that close with cytosolic acidification (e.g., CO2 treatment) or increased calcium concentration, possibly via calmodulin activation. Although gap junction regulation is still unclear, connexin domains involved in gating are being defined. We have recently focused on the CO2 gating sensitivity of Cx32, Cx38 and various mutants and chimeras expressed in Xenopus oocytes and studied by double voltage clamp. Cx32 is weakly sensitive to CO2, whereas Cx38 is highly sensitive. A Cx32 chimera containing the second half of the inner loop (IL2) of Cx38 was as sensitive to CO2 as Cx38, indicating that this domain plays an important role. Deletion of CT by 84% did not affect CO2 sensitivity, but replacement of 5 arginines (R) with sparagines (N) at the beginning of CT (C1) greatly enhanced the CO2 sensitivity of Cx32. This suggests that whereas most of CT is irrelevant, positive charges of C1 maintain the CO2 sensitivity of Cx32 low. As a hypothesis we have proposed a model that involves charge interaction between negative residues of the beginning of IL1 and positive residues of either C1 or IL2. Open and closed channels would result from IL1-C1 and IL1-IL2 interactions, respectively

Analysis and modelling of chemical looping combustion process with and without oxygen uncoupling

Effective control and limiting of carbon dioxide (CO₂) emissions in energy production are major challenges of science today. Current research activities include the development of new low-cost carbon capture technologies, and among the proposed concepts, chemical combustion (CLC) and chemical looping with oxygen uncoupling (CLOU) have attracted significant attention allowing intrinsic separation of pure CO₂ from a hydrocarbon fuel combustion process with a comparatively small energy penalty. Both CLC and CLOU utilize the well-established fluidized bed technology, but several technical challenges need to be overcome in order to commercialize the processes. Therefore, development of proper modelling and simulation tools is essential for the design, optimization, and scale-up of chemical looping-based combustion systems. The main objective of this work was to analyze the technological feasibility of CLC and CLOU processes at different scales using a computational modelling approach. A onedimensional fluidized bed model frame was constructed and applied for simulations of CLC and CLOU systems consisting of interconnected fluidized bed reactors. The model is based on the conservation of mass and energy, and semi-empirical correlations are used to describe the hydrodynamics, chemical reactions, and transfer of heat in the reactors. Another objective was to evaluate the viability of chemical looping-based energy production, and a flow sheet model representing a CLC-integrated steam power plant was developed. The 1D model frame was succesfully validated based on the operation of a 150 kWth laboratory-sized CLC unit fed by methane. By following certain scale-up criteria, a conceptual design for a CLC reactor system at a pre-commercial scale of 100 MWth was created, after which the validated model was used to predict the performance of the system. As a result, further understanding of the parameters affecting the operation of a large-scale CLC process was acquired, which will be useful for the practical design work in the future. The integration of the reactor system and steam turbine cycle for power production was studied resulting in a suggested plant layout including a CLC boiler system, a simple heat recovery setup, and an integrated steam cycle with a three pressure level steam turbine. Possible operational regions of a CLOU reactor system fed by bituminous coal were determined via mass, energy, and exergy balance analysis. Finally, the 1D fluidized bed model was modified suitable for CLOU, and the performance of a hypothetical 500 MWth CLOU fuel reactor was evaluated by extensive case simulations.