Adsorption energy and spin state of first-row transition metals adsorbed on MgO(100)

Slab and cluster model spin-polarized calculations have been carried out to study various properties of isolated first-row transition metal atoms adsorbed on the anionic sites of the regular MgO(100) surface. The calculated adsorption energies follow the trend of the metal cohesive energies, indicating that the changes in the metal-support and metal-metal interactions along the series are dominated by atomic properties. In all cases, except for Ni at the generalized gradient approximation level, the number of unpaired electron is maintained as in the isolated metal atom. The energy required to change the atomic state from high to low spin has been computed using the PW91 and B3LYP density-functional-theory-based methods. PW91 fails to predict the proper ground state of V and Ni, but the results for the isolated and adsorbed atom are consistent within the method. B3LYP properly predicts the ground state of all first-row transition atom the high- to low-spin transition considered is comparable to experiment. In all cases, the interaction with the surface results in a reduced high- to low-spin transition energy.

Mutations in the heat-shock protein A9 (HSPA9) gene cause the EVEN-PLUS syndrome of congenital malformations and skeletal dysplasia.

We and others have reported mutations in LONP1, a gene coding for a mitochondrial chaperone and protease, as the cause of the human CODAS (cerebral, ocular, dental, auricular and skeletal) syndrome (MIM 600373). Here, we delineate a similar but distinct condition that shares the epiphyseal, vertebral and ocular changes of CODAS but also included severe microtia, nasal hypoplasia, and other malformations, and for which we propose the name of EVEN-PLUS syndrome for epiphyseal, vertebral, ear, nose, plus associated findings. In three individuals from two families, no mutation in LONP1 was found; instead, we found biallelic mutations in HSPA9, the gene that codes for mHSP70/mortalin, another highly conserved mitochondrial chaperone protein essential in mitochondrial protein import, folding, and degradation. The functional relationship between LONP1 and HSPA9 in mitochondrial protein chaperoning and the overlapping phenotypes of CODAS and EVEN-PLUS delineate a family of "mitochondrial chaperonopathies" and point to an unexplored role of mitochondrial chaperones in human embryonic morphogenesis.

Statistical Optimum Design of Heat Exchangers

The optimal design of a heat exchanger system is based on given model parameters together with given standard ranges for machine design variables. The goals set for minimizing the Life Cycle Cost (LCC) function which represents the price of the saved energy, for maximizing the momentary heat recovery output with given constraints satisfied and taking into account the uncertainty in the models were successfully done. Nondominated Sorting Genetic Algorithm II (NSGA-II) for the design optimization of a system is presented and implemented inMatlab environment. Markov ChainMonte Carlo (MCMC) methods are also used to take into account the uncertainty in themodels. Results show that the price of saved energy can be optimized. A wet heat exchanger is found to be more efficient and beneficial than a dry heat exchanger even though its construction is expensive (160 EUR/m2) compared to the construction of a dry heat exchanger (50 EUR/m2). It has been found that the longer lifetime weights higher CAPEX and lower OPEX and vice versa, and the effect of the uncertainty in the models has been identified in a simplified case of minimizing the area of a dry heat exchanger.

Heat transfer in superheaters of the bubbling fluidized bed boiler conversions

It is often reasonable to convert old boiler to bubbling fluidized bed boiler instead of building a new one. Converted boiler consists of old and new heat surfaces which must be fitted to operate together. Prediction of heat transfer in not so ideal conditions sets challenges for designers. Two converted boilers situated in Poland were studied on the grounds of acceptance tests and further studies. Calculation of boiler process was performed with boiler design program. Main interest was heat transfer in superheaters and factors affecting it. Theory for heat transfer is presented according to information found from literature. Results obtained from experimental studies and calculations have been compared. With correct definitions calculated parameters corresponded well to measured data at boiler maximum design load. However overload situations revealed to be difficult to model at least without considering changes in the combustion process which requires readjustments to the design program input values.

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.

Statistical Analysis and Numerics of Heat Exchanger Models

The identifiability of the parameters of a heat exchanger model without phase change was studied in this Master’s thesis using synthetically made data. A fast, two-step Markov chain Monte Carlo method (MCMC) was tested with a couple of case studies and a heat exchanger model. The two-step MCMC-method worked well and decreased the computation time compared to the traditional MCMC-method. The effect of measurement accuracy of certain control variables to the identifiability of parameters was also studied. The accuracy used did not seem to have a remarkable effect to the identifiability of parameters. The use of the posterior distribution of parameters in different heat exchanger geometries was studied. It would be computationally most efficient to use the same posterior distribution among different geometries in the optimisation of heat exchanger networks. According to the results, this was possible in the case when the frontal surface areas were the same among different geometries. In the other cases the same posterior distribution can be used for optimisation too, but that will give a wider predictive distribution as a result. For condensing surface heat exchangers the numerical stability of the simulation model was studied. As a result, a stable algorithm was developed.

Moisture sorption isotherms and isosteric heat determination in Chilean papaya (Vasconcellea pubescens)

The moisture sorption isotherms of Chilean papaya were determined at 5, 20, and 45 ºC, over a relative humidity range of 10-95%. The GAB, BET, Oswin, Halsey, Henderson, Smith, Caurie and Iglesias-Chirife models were applied to the sorption experimental data. The goodness of fit of the mathematical models was statistically evaluated by means of the determination coefficient, mean relative percentage deviation, sum square error, root-mean-square error, and chi-square values. The GAB, Oswin and Halsey models were found to be the most suitable for the description of the sorption data. The sorption heats calculated using the Clausius-Clapeyron equation were 57.35 and 59.98 kJ·mol-1, for adsorption and desorption isotherms, respectively.

Adsorption of glyphosate in a forest soil: a study using Mössbauer and FT-IR spectroscopy

We studied the adsorption of glyphosate (GPS) onto soil mineral particles, using FT-IR and Mössbauer spectroscopy. From IR measurements for samples collected under native vegetation of a forest reserve, bands at 1632 and 1407 cm-1 could be attributed to the interaction between the carboxylic group of GPS and structural Al3+ and Fe3+ on the surface of mineral particles; bands at 1075 and 1000 cm-1 were observed only for cultivated soil. Mössbauer spectra for these soils were definitely fitted using a broad central doublet in addition to the magnetic component. This multiple quadrupolar component may be attributed to all non-magnetic Fe3+ contributions, including that of the GPS/Fe3+ complex.

Validation of a spectrophotometric method to estimate the adsorption on nanoemulsions of an antimalarial oligonucleotide

This study describes the validation of a spectrophotometric method to estimate oligonucleotides association with cationic nanoemulsions. Phosphodiester and phosphorothioate oligonucleotides targeting Plasmodium falciparum topoisomerase II were analyzed at 262 nm. Linear response (r > 0.998) was observed from 0.4 to 1.0 nmol/mL, the relative standard deviation values for the intra- and inter-days precision were lower than 2.6% and the recovery ranged from 98.8 to 103.6% for both oligonucleotides. The association efficiency was estimated based on an ultrafiltration/centrifugation method. Oligonucleotides recovery through 30 kDa-membranes was higher than 92%. The extent of oligonucleotides association (42 to 98%) varied with the composition of nanoemulsions

Evaluation of pesticide adsorption in gas chromatographic injector and column

Components in complex matrices can cause variations in chromatographic response during analysis of pesticides by gas chromatography. These variations are related to the competition between analytes and matrix components for adsorption sites in the chromatographic system. The capacity of the pesticides chlorpyrifos and deltamethrin to be adsorbed in the injector and chromatographic column was evaluated by constructing three isotherms and changing the column heating rate to 10 and 30 ºC min-1. By using ANCOVA to compare the slope of calibration graphs, results showed that the higher the injector temperature (310 ºC) the lower the pesticide adsorption. Also, deltamethrin influenced the adsorption of chlorpyrifos on the column chromatographic.

Concentration of Pb (II) by adsorption and its atomic absorption spectrometric determination

A sorption concentration method using impregnated silica has been developed to determine small concentration of lead in water by Atomic Absorption Spectrometry.