Abstract: Flammability analysis of extruded polystyrene (XPS) has become crucial due to its utilization as insulation material for energy efficient buildings. Using the Kissinger-Akahira-Sunose and Flynn-Wall-Ozawa methods, the degradation kinetics of two pure XPS from the local market, red and grey ones, were obtained from the results of thermogravity analysis (TG) and microscale combustion calorimetry (MCC) experiments performed under the same heating rates. From the experiments, it was discovered that red XPS released more heat than grey XPS and both materials showed two mass loss stages. Consequently, the kinetic parameters for red XPS were higher than grey XPS. A comparative evaluation of activation energies from MCC and TG showed an insignificant degree of deviation signifying an equivalent apparent activation energy from both methods. However, different activation energy profiles as a result of the different chemical pathways were presented when the dependencies of the activation energies on extent of conversion for TG and MCC were compared.
Abstract: Propellants based on Hydroxyl Terminated Polybutadiene/Ammonium Perchlorate (HTPB/AP) are the most commonly used in most of the rocket engines used by the Brazilian Armed Forces. This work aimed at the possibility of extending its useful life (currently in 10 years) by performing kinetic-chemical analyzes of its energetic material via Differential Scanning Calorimetry (DSC) and also performing computer simulation of aging process using the software Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS). Thermal analysis via DSC was performed in triplicates and in three heating ratios (5 ºC, 10 ºC, and 15 ºC) of rocket motor with 11 years shelf-life, using the Arrhenius equation to obtain its activation energy, using Ozawa and Kissinger kinetic methods, allowing comparison with manufacturing period data (standard motor). In addition, the kinetic parameters of internal pressure of the combustion chamber in 08 rocket engines with 11 years of shelf-life were also acquired, for comparison purposes with the engine start-up data.
Abstract: Developing complete mechanistic models for polymerization reactors is not easy, because complex reactions occur simultaneously; there is a large number of kinetic parameters involved and sometimes the chemical and physical phenomena for mixtures involving polymers are poorly understood. To overcome these difficulties, empirical models based on sampled data can be used instead, namely regression methods typical of machine learning field. They have the ability to learn the trends of a process without any knowledge about its particular physical and chemical laws. Therefore, they are useful for modeling complex processes, such as the free radical polymerization of methyl methacrylate achieved in a batch bulk process. The goal is to generate accurate predictions of monomer conversion, numerical average molecular weight and gravimetrical average molecular weight. This process is associated with non-linear gel and glass effects. For this purpose, an adaptive sampling technique is presented, which can select more samples around the regions where the values have a higher variation. Several machine learning methods are used for the modeling and their performance is compared: support vector machines, k-nearest neighbor, k-nearest neighbor and random forest, as well as an original algorithm, large margin nearest neighbor regression. The suggested method provides very good results compared to the other well-known regression algorithms.
Abstract: Power law approximation was used in this study to evaluate the reaction orders of calcium oxide, CaO catalyzed transesterification of refined cottonseed oil and methanol. The kinetics study was carried out at temperatures of 45, 55 and 65 oC. The kinetic parameters such as reaction order 2.02 and rate constant 2.8 hr-1g-1cat, obtained at the temperature of 65 oC best fitted the kinetic model. The activation energy, Ea obtained was 127.744 KJ/mol. The results indicate that the transesterification reaction of the refined cottonseed oil using calcium oxide catalyst is approximately second order reaction.
Abstract: This work studied the isomerization of 1-butene over
hydrotalcite catalyst. The experiments were conducted at various gas
hourly space velocity (GHSV), reaction temperature and feed
concentration. No catalyst deactivation was observed over the
reaction time of 16 hours. Two major reaction products were trans-2-
butene and cis-2-butene. The reaction temperature played an
important role on the reaction selectivity. At high operating
temperatures, the selectivity of trans-2-butene was higher than the
selectivity of cis-2-butene while it was opposite at lower reaction
temperature. In the range of operating condition, the maximum
conversion of 1-butene was found at 74% when T = 673 K and GHSV
= 4 m3/h/kg-cat with trans- and cis-2-butene selectivities of 54% and
46%, respectively. Finally, the kinetic parameters of the reaction
were determined.
Abstract: Advanced head and neck cancers are aggressive
tumours, which require aggressive treatment. Treatment efficiency is
often hindered by cancer cell repopulation during radiotherapy,
which is due to various mechanisms triggered by the loss of tumour
cells and involves both stem and differentiated cells. The aim of the
current paper is to present in silico simulations of radiotherapy
schedules on a virtual head and neck tumour grown with biologically
realistic kinetic parameters. Using the linear quadratic formalism of
cell survival after radiotherapy, altered fractionation schedules
employing various treatment breaks for normal tissue recovery are
simulated and repopulation mechanism implemented in order to
evaluate the impact of various cancer cell contribution on tumour
behaviour during irradiation. The model has shown that the timing of
treatment breaks is an important factor influencing tumour control in
rapidly proliferating tissues such as squamous cell carcinomas of the
head and neck. Furthermore, not only stem cells but also
differentiated cells, via the mechanism of abortive division, can
contribute to malignant cell repopulation during treatment.
Abstract: Abundant and cheap agricultural waste of oil palm trunk (OPT) juice was used to produce bioethanol. Two strains of Saccharomyces cerevisiae and a strain of Pichia stipitis were used to produce bioethanol from the OPT juice. Fermentation was conducted at previously optimized condition at 30oC and without shaking. The kinetic parameters were estimated and calculated. Monod equation and Hinshelwood model is used to relate the specific growth to the concentration of the limiting substrate and also to simulate bioethanol production rate. Among the three strains, single S. cerevisiae Kyokai no. 7 produce the highest ethanol yield of 0.477 g/l.h within the shortest time (12 h). This yeast also produces more than 20 g/l ethanol concentration within 10 h of fermentation.
Abstract: Aldehyde oxidase is molybdo-flavoenzyme involved in the oxidation of hundreds of endogenous and exogenous and N-heterocyclic compounds and environmental pollutants. Uncharged N-heterocyclic aromatic compounds such phenanthridine are commonly distributed pollutants in soil, air, sediments, surface water and groundwater, and in animal and plant tissues. Phenanthridine as uncharged N-heterocyclic aromatic compound was incubated with partially purified aldehyde oxidase from rainbow trout fish liver. Reversed-phase HLPC method was used to separate the oxidation products from phenanthridine and the metabolite was identified. The 6(5H)-phenanthridinone was identified the major metabolite by partially purified aldehyde oxidase from fish liver. Kinetic constant for the oxidation reactions were determined spectrophotometrically and showed that this substrate has a good affinity (Km = 78 ± 7.6µM) for hepatic aldehyde oxidase, will be a significant pathway. This study confirms that partially purified aldehyde oxidase from fish liver is indeed the enzyme responsible for the in vitro production 6(5H)-phenanthridinone metabolite as it is a major metabolite by mammalian aldehyde oxidase, coupled with a relatively high oxidation rate (0.77± 0.03 nmol/min/mg protein). In addition, the kinetic parameters of hepatic fish aldehyde oxidase towards the phenanthridine substrate indicate that in vitro biotransformation by hepatic fish aldehyde oxidase will be a significant pathway. This study confirms that partially purified aldehyde oxidase from fish liver is indeed the enzyme responsible for the in vitro production 6(5H)-phenanthridinone metabolite as it is a major metabolite by mammalian aldehyde oxidase.
Abstract: Currently, mathematical and computer modeling are widely used in different biological studies to predict or assess behavior of such a complex systems as a biological are. This study deals with mathematical and computer modeling of bi-substrate enzymatic reactions, which play an important role in different biochemical pathways. The main objective of this study is to represent the results from in silico investigation of bi-substrate enzymatic reactions in the presence of uncompetitive inhibitors, as well as to describe in details the inhibition effects. Four models of uncompetitive inhibition were designed using different software packages. Particularly, uncompetitive inhibitor to the first [ES1] and the second ([ES1S2]; [FS2]) enzyme-substrate complexes have been studied. The simulation, using the same kinetic parameters for all models allowed investigating the behavior of reactions as well as determined some interesting aspects concerning influence of different cases of uncompetitive inhibition. Besides, it has been shown that uncompetitive inhibitors exhibit specific selectivity depending on mechanism of bi-substrate enzymatic reaction.
Abstract: The purpose of the present work was to study the
production and process parameters optimization for the synthesis of
cellulase from Trichoderma viride in solid state fermentation (SSF)
using an agricultural wheat straw as substrates; as fungal conversion
of lignocellulosic biomass for cellulase production is one among the
major increasing demand for various biotechnological applications.
An optimization of process parameters is a necessary step to get
higher yield of product. Several kinetic parameters like pretreatment,
extraction solvent, substrate concentration, initial moisture content,
pH, incubation temperature and inoculum size were optimized for
enhanced production of third most demanded industrially important
cellulase. The maximum cellulase enzyme activity 398.10±2.43
μM/mL/min was achieved when proximally analyzed lignocellulosic
substrate wheat straw inocubated at 2% HCl as pretreatment tool
along with distilled water as extraction solvent, 3% substrate
concentration 40% moisture content with optimum pH 5.5 at 45°C
incubation temperature and 10% inoculum size.
Abstract: In this study, a mathematical model was proposed and
the accuracy of this model was assessed to predict the growth of
Pseudomonas aeruginosa and rhamnolipid production under nitrogen
limiting (sodium nitrate) fed-batch fermentation. All of the
parameters used in this model were achieved individually without
using any data from the literature.
The overall growth kinetic of the strain was evaluated using a
dual-parallel substrate Monod equation which was described by
several batch experimental data. Fed-batch data under different
glycerol (as the sole carbon source, C/N=10) concentrations and feed
flow rates were used to describe the proposed fed-batch model and
other parameters. In order to verify the accuracy of the proposed
model several verification experiments were performed in a vast
range of initial glycerol concentrations. While the results showed an
acceptable prediction for rhamnolipid production (less than 10%
error), in case of biomass prediction the errors were less than 23%. It
was also found that the rhamnolipid production by P. aeruginosa was
more sensitive at low glycerol concentrations.
Based on the findings of this work, it was concluded that the
proposed model could effectively be employed for rhamnolipid
production by this strain under fed-batch fermentation on up to 80 g l-
1 glycerol.
Abstract: This research project aims to investigate difference in
relative rates concerning phosphoryl transfer relevant to biological
catalysis of DNA and RNA in the pH-independent reactions.
Activated Models of DNA and RNA for alkyl-aryl phosphate diesters
(with 4-nitrophenyl as a good leaving group) have successfully been
prepared to gather kinetic parameters. Eyring plots for the pH–
independent hydrolysis of 1 and 2 were established at different
temperatures in the range 100–160 °C. These measurements have
been used to provide a better estimate for the difference in relative
rates between the reactivity of DNA and RNA cleavage. Eyring plot
gave an extrapolated rate of kH2O = 1 × 10-10 s -1 for 1 (RNA model)
and 2 (DNA model) at 25°C. Comparing the reactivity of RNA
model and DNA model shows that the difference in relative rates in
the pH-independent reactions is surprisingly very similar at 25°. This
allows us to obtain chemical insights into how biological catalysts
such as enzymes may have evolved to perform their current
functions.
Abstract: Four phenylurea herbicides (isoproturon, chlortoluron, diuron and linuron) were dissolved in different water matrices in order to study their chemical degradation by using UV radiation, ozone and some advanced oxidation processes (UV/H2O2, O3/H2O2, Fenton reagent and the photo- Fenton system). The waters used were: ultra-pure water, a commercial mineral water, a groundwater and a surface water taken from a reservoir. Elimination levels were established for each herbicide and for several global quality parameters, and a kinetic study was performed in order to determine basic kinetic parameters of each reaction between the target phenylureas and these oxidizing systems.
Abstract: Complex assemblies of interacting proteins carry out
most of the interesting jobs in a cell, such as metabolism, DNA
synthesis, mitosis and cell division. These physiological properties
play out as a subtle molecular dance, choreographed by underlying
regulatory networks that control the activities of cyclin-dependent
kinases (CDK). The network can be modeled by a set of nonlinear
differential equations and its behavior predicted by numerical
simulation. In this paper, an innovative approach has been proposed
that uses genetic algorithms to mine a set of behavior data output by
a biological system in order to determine the kinetic parameters of
the system. In our approach, the machine learning method is
integrated with the framework of existent biological information in a
wiring diagram so that its findings are expressed in a form of system
dynamic behavior. By numerical simulations it has been illustrated
that the model is consistent with experiments and successfully shown
that such application of genetic algorithms will highly improve the
performance of mathematical model of the cell division cycle to
simulate such a complicated bio-system.
Abstract: The purpose of this study is to investigate the capacity
of natural Turkish zeolite for NH4-N removal from landfill leachate.
The effects of modification and initial concentration on the removal
of NH4-N from leachate were also investigated. The kinetics of
adsorption of NH4-N has been discussed using three kinetic models,
i.e., the pseudo-second order model, the Elovich equation, the
intraparticle diffuion model. Kinetic parameters and correlation
coefficients were determined. Equilibrium isotherms for the
adsorption of NH4-N were analyzed by Langmuir, Freundlich and
Tempkin isotherm models. Langmuir isotherm model was found to
best represent the data for NH4-N.
Abstract: The kinetic properties of enzymes are often reported
using the apparent KM and Vmax appropriate to the standard
Michaelis-Menten enzyme. However, this model is inappropriate to
enzymes that have more than one substrate or where the rate
expression does not apply for other reasons. Consequently, it is
desirable to have a means of estimating the appropriate kinetic
parameters from the apparent values of KM and Vmax reported for each
substrate. We provide a means of estimating the range within which
the parameters should lie and apply the method to data for glutamate
dehydrogenase from the nematode parasite of sheep Teladorsagia
circumcincta.
Abstract: In this study, the kinetic of biogas production was studied by performing a series laboratory experiment using rumen fluid of animal ruminant as inoculums. Cattle manure as substrate was inoculated by rumen fluid to the anaerobic biodigester. Laboratory experiments using 400 ml biodigester were performed in batch operation mode. Given 100 grams of fresh cattle manure was fed to each biodigester and mixed with rumen fluid by manure : rumen weight ratio of 1:1 (MR11). The operating temperatures were varied at room temperature and 38.5 oC. The cumulative volume of biogas produced was used to measure the biodigester performance. The research showed that the rumen fluid inoculated to biodigester gave significant effect to biogas production (P
Abstract: The mathematical modeling of different biological
processes is usually used to predict or assess behavior of systems in
which these processes take place. This study deals with mathematical
and computer modeling of bi-substrate enzymatic reactions with
ping-pong mechanism, which play an important role in different
biochemical pathways. Besides that, three models of competitive
inhibition were designed using different software packages. The main
objective of this study is to represent the results from in silico
investigation of bi-substrate enzymatic reactions with ordered pingpong
mechanism in the presence of competitive inhibitors, as well as
to describe in details the inhibition effects. The simulation of the
models with certain kinetic parameters allowed investigating the
behavior of reactions as well as determined some interesting aspects
concerning influence of different cases of competitive inhibition.
Simultaneous presence of two inhibitors, competitive to the S1 and S2
substrates have been studied. Moreover, we have found the pattern of
simultaneous influence of both inhibitors.
Abstract: Gluconic acid is one of interesting chemical products
in industries such as detergents, leather, photographic, textile, and
especially in food and pharmaceutical industries. Fermentation is an
advantageous process to produce gluconic acid. Mathematical
modeling is important in the design and operation of fermentation
process. In fact, kinetic data must be available for modeling. The
kinetic parameters of gluconic acid production by Aspergillus niger
in batch culture was studied in this research at initial substrate
concentration of 150, 200 and 250 g/l. The kinetic models used were
logistic equation for growth, Luedeking-Piret equation for gluconic
acid formation, and Luedeking-Piret-like equation for glucose
consumption. The Kinetic parameters in the model were obtained by
minimizing non linear least squares curve fitting.
Abstract: The electrokinetic flow resistance (electroviscous
effect) is predicted for steady state, pressure-driven liquid flow at
low Reynolds number in a microfluidic contraction of rectangular
cross-section. Calculations of the three dimensional flow are
performed in parallel using a finite volume numerical method. The
channel walls are assumed to carry a uniform charge density and the
liquid is taken to be a symmetric 1:1 electrolyte. Predictions are
presented for a single set of flow and electrokinetic parameters. It is
shown that the magnitude of the streaming potential gradient and the
charge density of counter-ions in the liquid is greater than that in
corresponding two-dimensional slit-like contraction geometry. The
apparent viscosity is found to be very close to the value for a
rectangular channel of uniform cross-section at the chosen Reynolds
number (Re = 0.1). It is speculated that the apparent viscosity for the
contraction geometry will increase as the Reynolds number is
reduced.