Modeling reaction kinetics and mass transfer in ozonation in water solutions

This dissertation is based on four articles dealing with modeling of ozonation. The literature part of this considers some models for hydrodynamics in bubble column simulation. A literature review of methods for obtaining mass transfer coefficients is presented. The methods presented to obtain mass transfer are general models and can be applied to any gas-liquid system. Ozonation reaction models and methods for obtaining stoichiometric coefficients and reaction rate coefficients for ozonation reactions are discussed in the final section of the literature part. In the first article, ozone gas-liquid mass transfer into water in a bubble column was investigated for different pH values. A more general method for estimation of mass transfer and Henry’s coefficient was developed from the Beltrán method. The ozone volumetric mass transfer coefficient and the Henry’s coefficient were determined simultaneously by parameter estimation using a nonlinear optimization method. A minor dependence of the Henry’s law constant on pH was detected at the pH range 4 - 9. In the second article, a new method using the axial dispersion model for estimation of ozone self-decomposition kinetics in a semi-batch bubble column reactor was developed. The reaction rate coefficients for literature equations of ozone decomposition and the gas phase dispersion coefficient were estimated and compared with the literature data. The reaction order in the pH range 7-10 with respect to ozone 1.12 and 0.51 the hydroxyl ion were obtained, which is in good agreement with literature. The model parameters were determined by parameter estimation using a nonlinear optimization method. Sensitivity analysis was conducted using object function method to obtain information about the reliability and identifiability of the estimated parameters. In the third article, the reaction rate coefficients and the stoichiometric coefficients in the reaction of ozone with the model component p-nitrophenol were estimated at low pH of water using nonlinear optimization. A novel method for estimation of multireaction model parameters in ozonation was developed. In this method the concentration of unknown intermediate compounds is presented as a residual COD (chemical oxygen demand) calculated from the measured COD and the theoretical COD for the known species. The decomposition rate of p-nitrophenol on the pathway producing hydroquinone was found to be about two times faster than the p-nitrophenol decomposition rate on the pathway producing 4- nitrocatechol. In the fourth article, the reaction kinetics of p-nitrophenol ozonation was studied in a bubble column at pH 2. Using the new reaction kinetic model presented in the previous article, the reaction kinetic parameters, rate coefficients, and stoichiometric coefficients as well as the mass transfer coefficient were estimated with nonlinear estimation. The decomposition rate of pnitrophenol was found to be equal both on the pathway producing hydroquinone and on the path way producing 4-nitrocathecol. Comparison of the rate coefficients with the case at initial pH 5 indicates that the p-nitrophenol degradation producing 4- nitrocathecol is more selective towards molecular ozone than the reaction producing hydroquinone. The identifiability and reliability of the estimated parameters were analyzed with the Marcov chain Monte Carlo (MCMC) method. @All rights reserved. No part of the publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior permission of the author.

A Headspace needle-trap method for the analysis of volatile organic compounds in whole blood

Needle trap devices (NTDs) are a relatively new and promising tool for headspace (HS) analysis. In this study, a dynamic HS sampling procedure is evaluated for the determination of volatile organic compounds (VOCs) in whole blood samples. A full factorial design was used to evaluate the influence of the number of cycles and incubation time and it is demonstrated that the controlling factor in the process is the number of cycles. A mathematical model can be used to determine the most appropriate number of cycles required to adsorb a prefixed amount of VOCs present in the HS phase whenever quantitative adsorption is reached in each cycle. Matrix effect is of great importance when complex biological samples, such as blood, are analyzed. The evaluation of the salting out effect showed a significant improvement in the volatilization of VOCs to the HS in this type of matrices. Moreover, a 1:4 (blood:water) dilution is required to obtain quantitative recoveries of the target analytes when external calibration is used. The method developed gives detection limits in the 0.020–0.080 μg L−1 range (0.1–0.4 μg L−1 range for undiluted blood samples) with appropriate repeatability values (RSD < 15% at high level and <23% at LOQ level). Figure of merits of the method can be improved by using a smaller phase ratio (i.e., an increase in the blood volume and a decrease in the HS volume), which lead to lower detection limits, better repeatability values and greater sensibility. Twenty-eight blood samples have been evaluated with the proposed method and the results agree with those indicated in other studies. Benzene was the only target compound that gave significant differences between blood levels detected in volunteer non-smokers and smokers

Enantioselective synthesis of aziridines using asymmetric transfer hydrogenation as a precursor for chiral derivatives used as bonding agent for rocket solid propellants

A rapid, expedient and enantioselective method for the synthesis of beta-hydroxy amines and monosubstituted aziridines in up to 99% e.e., via asymmetric transfer hydrogenation of a-amino ketones and cyclisation through treatment with tosyl chloride and base, is described. (1R,2R)-N-(para-toluenesulfonyl)-1,2-ethylenediamine with formic acid has been utilised as a ligand for the Ruthenium (II) catalysed enantioselective transfer hydrogenation of the ketones.The chiral 2-methyl aziridine, which is a potentially more efficient bonding agent for Rocket Solid Propellant has been successfully achieved.

A three dimensional study of heat transfer in a supercritical circulating fluidized bed combustor

From the boiler design point of view, it is imperative to know and understand the operation of the boiler. Since comprehensive measurement of a large furnace is impossible, the furnace can be modeled in order to study its behavior and phenomena. This requires the used model to be validated to correspond with the physical furnace behavior. In this thesis, a three dimensional furnace model is validated to match a bituminous coal utilizing, supercritical once-through circulating fluidized bed combustor based on measurement data. The validated model is used for analyzing the furnace heat transfer. Other heat transfer analysis methods are energy balance method based on tube surface temperature measurements and a method based on measured temperature difference between the tube crest and the fin. The latter method was developed in the thesis using Fluent-software. In the theory part, literature is reviewed and the fundamental aspects of circulating fluidized bed are discussed. These aspects are solid particle behavior in fluidization known as hydrodynamics, behavior of fuel and combustion and heat transfer. Fundamental aspects of modeling are also presented.

Non-resorbable glass fibre-reinforced composite with porous surface as bone substitute material: Experimental studies in vitro and in vivo focused on bone-implant interface

The development of load-bearing osseous implant with desired mechanical and surface properties in order to promote incorporation with bone and to eliminate risk of bone resorption and implant failure is a very challenging task. Bone formation and resoption processes depend on the mechanical environment. Certain stress/strain conditions are required to promote new bone growth and to prevent bone mass loss. Conventional metallic implants with high stiffness carry most of the load and the surrounding bone becomes virtually unloaded and inactive. Fibre-reinforced composites offer an interesting alternative to metallic implants, because their mechanical properties can be tailored to be equal to those of bone, by the careful selection of matrix polymer, type of fibres, fibre volume fraction, orientation and length. Successful load transfer at bone-implant interface requires proper fixation between the bone and implant. One promising method to promote fixation is to prepare implants with porous surface. Bone ingrowth into porous surface structure stabilises the system and improves clinical success of the implant. The experimental part of this work was focused on polymethyl methacrylate (PMMA) -based composites with dense load-bearing core and porous surface. Three-dimensionally randomly orientated chopped glass fibres were used to reinforce the composite. A method to fabricate those composites was developed by a solvent treatment technique and some characterisations concerning the functionality of the surface structure were made in vitro and in vivo. Scanning electron microscope observations revealed that the pore size and interconnective porous architecture of the surface layer of the fibre-reinforced composite (FRC) could be optimal for bone ingrowth. Microhardness measurements showed that the solvent treatment did not have an effect on the mechanical properties of the load-bearing core. A push-out test, using dental stone as a bone model material, revealed that short glass fibre-reinforced porous surface layer is strong enough to carry load. Unreacted monomers can cause the chemical necrosis of the tissue, but the levels of leachable resisidual monomers were considerably lower than those found in chemically cured fibre-reinforced dentures and in modified acrylic bone cements. Animal experiments proved that surface porous FRC implant can enhance fixation between bone and FRC. New bone ingrowth into the pores was detected and strong interlocking between bone and the implant was achieved.

Development of a flotation method for preconcentration-separation of trace amounts of some metal ions in plant tissues prior to their FAAS determinations

An efficient flotation method based on the combination of flame atomic absorption spectrometry (FAAS) and separation and preconcentration step for determination of Cr3+, Cu 2+, Co2+, Ni2+, Zn2+, Cd 2+, Fe3+ and Pb2+ ions in various real samples by the possibility of applying bis(2-hydroxyacetophenone)-1,4-butanediimine (BHABDI) as a new collector was studied. The influence of pH, amount of BHABDI as collector, sample matrix, type and amount of eluting agent, type and amount of surfactant as floating agent, ionic strength and air flow rates i.e. variables affecting the efficiency of the extraction system was evaluated. It is ascertained that metal ions such as iron can be separated simultaneously from matrix in the presence of 0.012 mM ligand, 0.025% (w/v) of CTAB to a test sample of 750 mL at pH 6.5. These ions can be eluted quantitatively with 6 mL of 1.0 mol L-1 HNO3 in methanol which lead to the enrichment factor of 125. The detection limits for analyte ions were in the range of 1.3-2.4 ng mL-1. The method has been successfully applied for determination of trace amounts of ions in various real samples.

Development and validation of a dissolution test for primaquine/polyethylene oxide matrix tablets

A simple, precise, specific, repeatable and discriminating dissolution test for primaquine (PQ) matrix tablets was developed and validated according to ICH and FDA guidelines. Two UV assaying methods were validated for determination of PQ released in 0.1 M hydrochloric acid and water media. Both methods were linear (R²>0.999), precise (R.S.D.<1.87%) and accurate (97.65-99.97%). Dissolution efficiency (69-88%) and equivalence of formulations (f2) was assessed in different media and apparatuses (basket/100 rpm and paddle/50 rpm) tested. Discriminating condition was 900 mL aqueous medium, basket at 100 rpm and sampling times at 1, 4 and 8 h. Repeatability (R.S.D.<2.71%) and intermediate precision (R.S.D.<2.06%) of dissolution method were satisfactory.

EVALUATION OF A BUFFERED SOLID PHASE DISPERSION PROCEDURE ADAPTED FOR PESTICIDE ANALYSES IN THE SOIL MATRIX

An evaluation of the pesticides extracted from the soil matrix was conducted using a citrate-buffered solid phase dispersion sample preparation method (QuEChERS). The identification and quantitation of pesticide compounds was performed using gas chromatography-mass spectrometry. Because of the occurrence of the matrix effect in 87% of the analyzed pesticides, the quantification was performed using matrix-matched calibration. The method's quantification limits were between 0.01 and 0.5 mg kg-1. Repeatability and intermediate precision, expressed as a relative standard deviation percentage, were less than 20%. The recoveries in general ranged between 62% and 99%, with a relative standard deviation < 20%. All the responses were linear, with a correlation coefficient (r) ≥0.99.

Electron transfer by singlet excited state of porphyn and electron acceptor affinity in rigid medium: photoacoustic phase angle analysis

Photoacoustic spectroscopy provides information about both amplitude and phase of the response of a system to an optical excitation process. This paper presents the studies of the phase in the electron transfer process between octaethylporphyn (OEP) and quinone molecules dispersed in a polymeric matrix. It was observed a tendency in the phase behavior to small values only in the spectral region near to 620 nm, while for shorter wavelength did not show any tendency. These measurements suggested that the electron transfer to acceptor occurred with the participation of octaethylporphyn singlet excited state.

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.

Adsorption of hidrogen peroxide on the surface of silica - titania mixed oxide obtained by the sol-gel processing method

This work describes the sol-gel mixed oxide SiO2/TiO2 property, ST, as prepared, and submitted to heat treatment a 773 K, STC. SEM and EDS images show, within magnification used, a uniform distribution of the TiO2 particles in SiO2/TiO2 matrix. Both, ST and STC adsorb hydrogen peroxide on the surface and through EPR and UV-Vis diffuse reflectance spectra, it was possible to conclude that the species on the surface is the peroxide molecule attached to the Lewis acid site of titanium particle surface, alphaTi(H2O2)+. As the material is very porous, presumably the hydrogen peroxide molecule is confined in the matrix pores on the surface, a reason why the adsorbed species presents an exceptional long lived stability.

Upconverting Phosphor Technology: Exceptional Photoluminescent Properties Light Up Homogeneous Bioanalytical Assays

The aim of the present study was to demonstrate the wide applicability of the novel photoluminescent labels called upconverting phosphors (UCPs) in proximity-based bioanalytical assays. The exceptional features of the lanthanide-doped inorganic UCP compounds stem from their capability for photon upconversion resulting in anti-Stokes photoluminescence at visible wavelengths under near-infrared (NIR) excitation. Major limitations related to conventional photoluminescent labels are avoided, rendering the UCPs a competitive next-generation label technology. First, the background luminescence is minimized due to total elimination of autofluorescence. Consequently, improvements in detectability are expected. Second, at the long wavelengths (>600 nm) used for exciting and detecting the UCPs, the transmittance of sample matrixes is significantly greater in comparison with shorter wavelengths. Colored samples are no longer an obstacle to the luminescence measurement, and more flexibility is allowed even in homogeneous assay concepts, where the sample matrix remains present during the entire analysis procedure, including label detection. To transform a UCP particle into a biocompatible label suitable for bioanalytical assays, it must be colloidal in an aqueous environment and covered with biomolecules capable of recognizing the analyte molecule. At the beginning of this study, only UCP bulk material was available, and it was necessary to process the material to submicrometer-sized particles prior to use. Later, the ground UCPs, with irregular shape, wide size-distribution and heterogeneous luminescence properties, were substituted by a smaller-sized spherical UCP material. The surface functionalization of the UCPs was realized by producing a thin hydrophilic coating. Polymer adsorption on the UCP surface is a simple way to introduce functional groups for bioconjugation purposes, but possible stability issues encouraged us to optimize an optional silica-encapsulation method which produces a coating that is not detached in storage or assay conditions. An extremely thin monolayer around the UCPs was pursued due to their intended use as short-distance energy donors, and much attention was paid to controlling the thickness of the coating. The performance of the UCP technology was evaluated in three different homogeneous resonance energy transfer-based bioanalytical assays: a competitive ligand binding assay, a hybridization assay for nucleic acid detection and an enzyme activity assay. To complete the list, a competitive immunoassay has been published previously. Our systematic investigation showed that a nonradiative energy transfer mechanism is indeed involved, when a UCP and an acceptor fluorophore are brought into close proximity in aqueous suspension. This process is the basis for the above-mentioned homogeneous assays, in which the distance between the fluorescent species depends on a specific biomolecular binding event. According to the studies, the submicrometer-sized UCP labels allow versatile proximity-based bioanalysis with low detection limits (a low-nanomolar concentration for biotin, 0.01 U for benzonase enzyme, 0.35 nM for target DNA sequence).

Effective diffusivity and convective mass transfer coefficient during the drying of bananas

In this article, a methodology is used for the simultaneous determination of the effective diffusivity and the convective mass transfer coefficient in porous solids, which can be considered as an infinite cylinder during drying. Two models are used for optimization and drying simulation: model 1 (constant volume and diffusivity, with equilibrium boundary condition), and model 2 (constant volume and diffusivity with convective boundary condition). Optimization algorithms based on the inverse method were coupled to the analytical solutions, and these solutions can be adjusted to experimental data of the drying kinetics. An application of optimization methodology was made to describe the drying kinetics of whole bananas, using experimental data available in the literature. The statistical indicators enable to affirm that the solution of diffusion equation with convective boundary condition generates results superior than those with the equilibrium boundary condition.

A platform for anti-biofilm assays combining viability, biomass and matrix quantifications in susceptibility assessments of antimicrobials against Staphylococcus aureus biofilms

Bacteria can exist as planktonic, the lifestyle in which single cells exist in suspension, and as biofilms, which are surface-attached bacterial communities embedded in a selfproduced matrix. Most of the antibiotics and the methods for antimicrobial work have been developed for planktonic bacteria. However, the majority of the bacteria in natural habitats live as biofilms. Biofilms develop dauntingly fast high resistance towards conventional antibacterial treatments and thus, there is a great need to meet the demands of effective anti-biofilm therapy. In this thesis project it was attempted to fill the void of anti-biofilm screening methods by developing a platform of assays that evaluate the effect that screened compounds have on the total biomass, viability and the extracellular polysaccharide (EPS) layer of the biofilms. Additionally, a new method for studying biofilms and their interactions with compounds in a continuous flow system was developed using capillary electrochromatography (CEC). The screening platform was utilized with a screening campaign using a small library of cinchona alkaloids. The assays were optimized to be statistically robust enough for screening. The first assay, based on crystal violet staining, measures total biofilm biomass, and it was automated using a liquid handling workstation to decrease the manual workload and signal variation. The second assay, based on resazurin staining, measures viability of the biofilm, and it was thoroughly optimized for the strain used, but was then a very simple and fast method to be used for primary screening. The fluorescent resazurin probe is not toxic to the biofilms. In fact, it was also shown in this project that staining the biofilms with resazurin prior to staining with crystal violet had no effect on the latter and they can be used in sequence on the same screening plate. This sequential addition step was indeed a major improvement on the use of reagents and consumables and also shortened the work time. As a third assay in the platform a wheat germ agglutinin based assay was added to evaluate the effect a compound has on the EPS layer. Using this assay it was found that even if compounds might have clear effect on both biomass and viability, the EPS layer can be left untouched or even be increased. This is a clear implication of the importance of using several assays to be able to find “true hits” in a screening setting. In the pilot study of screening for antimicrobial and anti-biofilm effects using a cinchona alkaloid library, one compound was found to have antimicrobial effect against planktonic bacteria and prevent biofilm formation at low micromolar concentration. To eradicate biofilms, a higher concentration was needed. It was also shown that the chemical space occupied by the active compound was slightly different than the rest of the cinchona alkaloids as well as the rest of the compounds used for validatory screening during the optimization processes of the separate assays.

Transfer of passive immunity and serum proteinogram in the first six months of life of Criollo Lageano and black and white holstein calves

The objective of this study was to evaluate and compare the transfer of passive immunity and the proteinogram in Criollo Lageano (CL) and Black and White Holstein (BWH) calves. Two groups were utilized with 13 Criollo Lageano and 10 BWH calves. Blood samples were collected for the measurement of total serum protein, electrophoresis of serum proteins, activity of the gamma glutamyl transferase, and concentration of IgG by the method of the zinc sulfate turbidity in periods between 24 and 36 hours of life, 15, 30, 60, 90, 120, 150 and 180 days. Statistical analysis was performed by ANOVA and Tukey test at 5% significance level, and correlations between variables were calculated. Variations of serum proteins followed a pattern of physiological behavior over the first six months of life and production of immunoglobulins was active earlier in BWH calves and slower in the Criollo Lageano, without causing any impact on their health. Gamma globulin in the first days of life (24-36h) was correlated with IgG (r=0.87 for CL and r=0.89 for BWH), PTS (r=0.91 for CL and r=0.92 for BWH), Glob (r=0.99 for CL and r=0.98 for BWH) and GGT (r=0.14 for CL and r=0.83 for BWH). It was concluded that there was no failure in the transfer of passive immunity in Criollo Lageano calves but this failure occurred in the BWH calves. IgG values estimated by the zinc sulfate turbidity and serum proteins were considered good indicators of the transfer of passive immunity in calves between 24 and 36 hours of life.