O Estado da arte da cromatografia líquida bidimensional: conceitos fundamentais, instrumentação e aplicações

The constant evolution of science and the growing demand for new technologies have led to new techniques in instrumentation that can improve detection, separation, resolution, and peak capacity. Comprehensive two-dimensional liquid chromatography (LC×LC) is presented as a powerful tool in complex sample analyses. During an analysis, a sample is subjected to two independent separation mechanisms that are combined, resulting in increased resolving power. For appropriate application of LC×LC, understanding the influence of parameters that require optimization is necessary. The main purpose of optimization is to predict the combination of stationary phases, separation conditions, and instrumental requirements to obtain the best separation performance. This review discusses theoretical, intrumental, and chemometric aspects of LC×LC and focuses on its applications in foods. It aims to provide a clear understanding of the aspects that can be used as strategies in the optimization of this analytical method.

Application of fuzzy logic for the evaluation of livestock slaughtering

The fuzzy logic admits infinite intermediate logical values between false and true. With this principle, it developed in this study a system based on fuzzy rules, which indicates the body mass index of ruminant animals in order to obtain the best time to slaughter. The controller developed has as input the variables weight and height, and as output a new body mass index, called Fuzzy Body Mass Index (Fuzzy BMI), which may serve as a detection system at the time of livestock slaughtering, comparing one another by the linguistic variables "Very Low", "Low", "Average ", "High" and "Very High". For demonstrating the use application of this fuzzy system, an analysis was made with 147 Nellore beeves to determine Fuzzy BMI values for each animal and indicate the location of body mass of any herd. The performance validation of the system was based on a statistical analysis using the Pearson correlation coefficient of 0.923, representing a high positive correlation, indicating that the proposed method is appropriate. Thus, this method allows the evaluation of the herd comparing each animal within the group, thus providing a quantitative method of farmer decision. It was concluded that this study established a computational method based on fuzzy logic that mimics part of human reasoning and interprets the body mass index of any bovine species and in any region of the country.

Water storage in wetted strips under irrigated coffee trees with different criteria of irrigation management

The increasing demand for water resources accentuates the need to reduce water waste through a more appropriate irrigation management. In the particular case of irrigated coffee planting, which in recent years presented growth with the predominance of drip irrigation, the improvement of drip irrigation management techniques is a necessity. The proper management of drip irrigation depends on the knowledge of the spatial pattern of soil moisture distribution inside the wetted strip formed under the irrigation lines. In this study, grids of 24 tensiometers were used to determine the water storage within the wetted strip formed under drippers, with a 3.78 L h-1 discharge, evenly spaced by 0.4 m, subjected to two different management criteria (fixed irrigation interval and 60 kPa tension). Estimates of storage based on a one-dimensional analysis, that only considers depth variations, were compared with two-dimensional estimates. The results indicate that for high-frequency irrigation the one-dimensional analysis is not appropriate. However, under less frequent irrigation, the two-dimensional analysis is dispensable, being the one-dimensional sufficient for calculating the water volume stored in the wetted strip.

FAT-luokkien määritys hitsatuille levyliitoksille käyttämällä lineaarisen murtumismekaniikan särönkasvun simulointia

Työssä tutkittiin hitsattujen levyliitosten väsymiskestävyyden mitoitusarvoja. Hitsien väsymiskestävyyden mitoitusarvot määritettiin lineaarista murtumismekaniikkaa soveltavalla 2D FEM-laskentaohjelmalla. Murtumismekaanisen laskennan tuloksista määriteltiin, eri liitosgeometrioiden ja kuormitustyyppien mukaisia, nimellisen jännityksen väsymismitoitusmenetelmää vastaavia FAT-luokkia, joissa on huomioitu rakenteellinen jännitys hitsiä vastaan kohtisuorassa suunnassa. Tutkittujen liitosten geometriat olivat pääsääntöisesti poikkeavia mitoitusstandardien ja ohjeiden sisältämistä taulukkotapauksista. Laskennassa otettiin huomioon hitsien liittymiskulma perusaineeseen, rajaviivan pyöristykset ja vajaa hitsautumissyvyys. Kuormitustyyppien vaihtelua tutkittiin rakenteellisen jännityksen taivutusosuuden muutoksilla ja kuormaa kantavien X-liitosten risteävien kuormituksien suhteellisilla suuruuksilla. Väsymiskestävyydet määritettiin kuormituskohtaisille kalvo- ja taivutusjännityksille sekä näiden jännitysjakaumien keskiarvoille. Työssä saatuja FAT-luokkia voidaan hyödyntää vastaavien geometrioiden ja kuormitusten yhteydessä, sekä interpoloimalla myös tuloksien väliarvoissa. Työssä käytetyillä menetelmillä voidaan parantaa nimellisen jännityksen mitoitusmenetelmän tarkkuutta ja laajentaa sitä koskemaan myös taulukkotapausten ulkopuolisia liitoksia. Työn tuloksissa on esitetty FAT-luokkia T-, X- ja päittäisliitoksille ja näiden eri kuormitusyhdistelmille.

The duality of tactical thought : a study of how Swedish land forces' commanders view tactics in irregular warfare

This is a sociological study of the views of officers in the Swedish Army and its Amphibious Forces on tactics in Irregular Warfare (IW), in particular, Counterinsurgency (COIN). IW comprises struggles, where the military weaker part uses an indirect approach with smaller units and integrates the civilian and military dimensions in a violence spectrum including subversion, terrorism, Guerrilla Warfare and infantry actions. IW is the main armed warfare style in insurgencies. COIN is the combined political, military, economic, social and legal actions in counter insurgencies. Data has been collected by means of interviews with almost all (n =43) officers, who were either commanding battalions or rifle and manoeuvre companies while undergoing training for general warfare and international operations. The main theoretical and methodological inspiration is the traditional one for research on social fields, inaugurated by the French sociologist Pierre Bourdieu. The statistical technique used is Multiple Correspondence Analysis. As a background and context base, an inquiry inspired by the Begriffsgechichte (Conceptual History) tradition explores the genesis and development of understandings of the term Irregular Warfare. The research question is outlined as; “how can contemporary Swedish military thought on tactics in Irregular Warfare be characterized using descriptive patterns, mapped in relation to background factors and normative standards? The most significant findings are that there are two main opposing notions separating the officers’ views on tactics in Irregular Warfare: (1) a focus on larger, combat oriented and collectively operating military units versus smaller and larger, more intelligence oriented and dispersed operating units, and (2) a focus on military tasks and kinetic effects versus military and civilian tasks as well as “soft” effects. The distribution of these views can be presented as a two-dimensional space structured by the two axes. This space represents four categories of tactics, partly diverging from normative military standards for Counterinsurgency. This social space of standpoints shows different structural tendencies for background factors of social and cultural character, particularly dominant concerning military backgrounds, international mission experiences and civilian education. Compared to military standards for Counterinsurgency, the two tactical types characterized by a Regular Warfare mind-set stands out as counter-normative. Signs of creative thought on military practice and theory, as well as a still persistent Regular Warfare doxa are apparent. Power struggles might thus develop, effecting the transformation to a broadened warfare culture with an enhanced focus also on Irregular Warfare. The result does not support research results arguing for a convergence of military thought in the European transformation of Armed Forces. The main argument goes beyond tactics and suggests sociological analysis on reciprocal effects regarding strategy, operational art, tactics as well as leadership, concerning the mind-set and preferences for Regular, Irregular and Hybrid Warfare.

Heterogeneous mass transfer in fluidized beds by computational fluid dynamics

The main objective of this research is to estimate and characterize heterogeneous mass transfer coefficients in bench- and pilot-scale fluidized bed processes by the means of computational fluid dynamics (CFD). A further objective is to benchmark the heterogeneous mass transfer coefficients predicted by fine-grid Eulerian CFD simulations against empirical data presented in the scientific literature. First, a fine-grid two-dimensional Eulerian CFD model with a solid and gas phase has been designed. The model is applied for transient two-dimensional simulations of char combustion in small-scale bubbling and turbulent fluidized beds. The same approach is used to simulate a novel fluidized bed energy conversion process developed for the carbon capture, chemical looping combustion operated with a gaseous fuel. In order to analyze the results of the CFD simulations, two one-dimensional fluidized bed models have been formulated. The single-phase and bubble-emulsion models were applied to derive the average gas-bed and interphase mass transfer coefficients, respectively. In the analysis, the effects of various fluidized bed operation parameters, such as fluidization, velocity, particle and bubble diameter, reactor size, and chemical kinetics, on the heterogeneous mass transfer coefficients in the lower fluidized bed are evaluated extensively. The analysis shows that the fine-grid Eulerian CFD model can predict the heterogeneous mass transfer coefficients quantitatively with acceptable accuracy. Qualitatively, the CFD-based research of fluidized bed process revealed several new scientific results, such as parametrical relationships. The huge variance of seven orders of magnitude within the bed Sherwood numbers presented in the literature could be explained by the change of controlling mechanisms in the overall heterogeneous mass transfer process with the varied process conditions. The research opens new process-specific insights into the reactive fluidized bed processes, such as a strong mass transfer control over heterogeneous reaction rate, a dominance of interphase mass transfer in the fine-particle fluidized beds and a strong chemical kinetic dependence of the average gas-bed mass transfer. The obtained mass transfer coefficients can be applied in fluidized bed models used for various engineering design, reactor scale-up and process research tasks, and they consequently provide an enhanced prediction accuracy of the performance of fluidized bed processes.

Fuzzy expert system in the prediction of neonatal resuscitation

In view of the importance of anticipating the occurrence of critical situations in medicine, we propose the use of a fuzzy expert system to predict the need for advanced neonatal resuscitation efforts in the delivery room. This system relates the maternal medical, obstetric and neonatal characteristics to the clinical conditions of the newborn, providing a risk measurement of need of advanced neonatal resuscitation measures. It is structured as a fuzzy composition developed on the basis of the subjective perception of danger of nine neonatologists facing 61 antenatal and intrapartum clinical situations which provide a degree of association with the risk of occurrence of perinatal asphyxia. The resulting relational matrix describes the association between clinical factors and risk of perinatal asphyxia. Analyzing the inputs of the presence or absence of all 61 clinical factors, the system returns the rate of risk of perinatal asphyxia as output. A prospectively collected series of 304 cases of perinatal care was analyzed to ascertain system performance. The fuzzy expert system presented a sensitivity of 76.5% and specificity of 94.8% in the identification of the need for advanced neonatal resuscitation measures, considering a cut-off value of 5 on a scale ranging from 0 to 10. The area under the receiver operating characteristic curve was 0.93. The identification of risk situations plays an important role in the planning of health care. These preliminary results encourage us to develop further studies and to refine this model, which is intended to implement an auxiliary system able to help health care staff to make decisions in perinatal care.

The role of secondary hyperparathyroidism in left ventricular hypertrophy of patients under chronic hemodialysis

End-stage renal disease (ESRD) patients frequently develop structural cardiac abnormalities, particularly left ventricular hypertrophy (LVH). The mechanisms involved in these processes are not completely understood. In the present study, we evaluated a possible association between parathyroid hormone (PTH) levels and left ventricular mass (LVM) in patients with ESRD. Stable uremic patients on intermittent hemodialysis treatment were evaluated by standard two-dimensional echocardiography and their sera were analyzed for intact PTH. Forty-one patients (mean age 45 years, range 18 to 61 years), 61% males, who had been on hemodialysis for 3 to 186 months, were evaluated. Patients were stratified into 3 groups according to serum PTH: low levels (<100 pg/ml; group I = 10 patients), intermediate levels (100 to 280 pg/ml; group II = 10 patients) and high levels (>280 pg/ml; group III = 21 patients). A positive statistically significant association between LVM index and PTH was identified (r = 0.34; P = 0.03, Pearson's correlation coefficient) in the sample as a whole. In subgroup analyses, we did not observe significant associations in the low and intermediate PTH groups; nevertheless, PTH and LVM index were correlated in patients with high PTH levels (r = 0.62; P = 0.003). LVM index was also inversely associated with hemoglobin (r = -0.34; P = 0.03). In multivariate analysis, after adjustment for age, hemoglobin, body mass index, and blood pressure, the only independent predictor of LVM index was PTH level. Therefore, PTH is an independent predictor of LVH in patients undergoing chronic hemodialysis. Secondary hyperparathyroidism may contribute to the elevated cardiovascular morbidity associated with LVH in ESRD.

Multicellular spheroids of bone marrow stromal cells: a three-dimensional in vitro culture system for the study of hematopoietic cell migration

Cell fate decisions are governed by a complex interplay between cell-autonomous signals and stimuli from the surrounding tissue. In vivo cells are connected to their neighbors and to the extracellular matrix forming a complex three-dimensional (3-D) microenvironment that is not reproduced in conventional in vitro systems. A large body of evidence indicates that mechanical tension applied to the cytoskeleton controls cell proliferation, differentiation and migration, suggesting that 3-D in vitro culture systems that mimic the in vivo situation would reveal biological subtleties. In hematopoietic tissues, the microenvironment plays a crucial role in stem and progenitor cell survival, differentiation, proliferation, and migration. In adults, hematopoiesis takes place inside the bone marrow cavity where hematopoietic cells are intimately associated with a specialized three 3-D scaffold of stromal cell surfaces and extracellular matrix that comprise specific niches. The relationship between hematopoietic cells and their niches is highly dynamic. Under steady-state conditions, hematopoietic cells migrate within the marrow cavity and circulate in the bloodstream. The mechanisms underlying hematopoietic stem/progenitor cell homing and mobilization have been studied in animal models, since conventional two-dimensional (2-D) bone marrow cell cultures do not reproduce the complex 3-D environment. In this review, we will highlight some of the mechanisms controlling hematopoietic cell migration and 3-D culture systems.

Automated grading of left ventricular segmental wall motion by an artificial neural network using color kinesis images

The present study describes an auxiliary tool in the diagnosis of left ventricular (LV) segmental wall motion (WM) abnormalities based on color-coded echocardiographic WM images. An artificial neural network (ANN) was developed and validated for grading LV segmental WM using data from color kinesis (CK) images, a technique developed to display the timing and magnitude of global and regional WM in real time. We evaluated 21 normal subjects and 20 patients with LVWM abnormalities revealed by two-dimensional echocardiography. CK images were obtained in two sets of viewing planes. A method was developed to analyze CK images, providing quantitation of fractional area change in each of the 16 LV segments. Two experienced observers analyzed LVWM from two-dimensional images and scored them as: 1) normal, 2) mild hypokinesia, 3) moderate hypokinesia, 4) severe hypokinesia, 5) akinesia, and 6) dyskinesia. Based on expert analysis of 10 normal subjects and 10 patients, we trained a multilayer perceptron ANN using a back-propagation algorithm to provide automated grading of LVWM, and this ANN was then tested in the remaining subjects. Excellent concordance between expert and ANN analysis was shown by ROC curve analysis, with measured area under the curve of 0.975. An excellent correlation was also obtained for global LV segmental WM index by expert and ANN analysis (R² = 0.99). In conclusion, ANN showed high accuracy for automated semi-quantitative grading of WM based on CK images. This technique can be an important aid, improving diagnostic accuracy and reducing inter-observer variability in scoring segmental LVWM.

Proteomic inventory of myocardial proteins from patients with chronic Chagas' cardiomyopathy

Chronic Chagas' disease cardiomyopathy (CCC) is an often fatal outcome of Trypanosoma cruzi infection, with a poorer prognosis than other cardiomyopathies. CCC is refractory to heart failure treatments, and is the major indication of heart transplantation in Latin America. A diffuse myocarditis, plus intense myocardial hypertrophy, damage and fibrosis, in the presence of very few T. cruzi forms, are the histopathological hallmarks of CCC. To gain a better understanding of the pathophysiology of CCC, we analyzed the protein profile in the affected CCC myocardium. Homogenates from left ventricular myocardial samples of end-stage CCC hearts explanted during heart transplantation were subjected to two-dimensional electrophoresis with Coomassie blue staining; protein identification was performed by MALDI-ToF mass spectrometry and peptide mass fingerprinting. The identification of selected proteins was confirmed by immunoblotting. We demonstrated that 246 proteins matched in gels from two CCC patients. They corresponded to 112 distinct proteins. Along with structural/contractile and metabolism proteins, we also identified proteins involved in apoptosis (caspase 8, caspase 2), immune system (T cell receptor ß chain, granzyme A, HLA class I) and stress processes (heat shock proteins, superoxide dismutases, and other oxidative stress proteins). Proteins involved in cell signaling and transcriptional factors were also identified. The identification of caspases and oxidative stress proteins suggests the occurrence of active apoptosis and significant oxidative stress in CCC myocardium. These results generated an inventory of myocardial proteins in CCC that should contribute to the generation of hypothesis-driven experiments designed on the basis of the classes of proteins identified here.

Multibody models for examination of touchdown bearing systems

Increased rotational speed brings many advantages to an electric motor. One of the benefits is that when the desired power is generated at increased rotational speed, the torque demanded from the rotor decreases linearly, and as a consequence, a motor of smaller size can be used. Using a rotor with high rotational speed in a system with mechanical bearings can, however, create undesirable vibrations, and therefore active magnetic bearings (AMBs) are often considered a good option for the main bearings, as the rotor then has no mechanical contact with other parts of the system but levitates on the magnetic forces. On the other hand, such systems can experience overloading or a sudden shutdown of the electrical system, whereupon the magnetic field becomes extinct, and as a result of rotor delevitation, mechanical contact occurs. To manage such nonstandard operations, AMB-systems require mechanical touchdown bearings with an oversized bore diameter. The need for touchdown bearings seems to be one of the barriers preventing greater adoption of AMB technology, because in the event of an uncontrolled touchdown, failure may occur, for example, in the bearing’s cage or balls, or in the rotor. This dissertation consists of two parts: First, touchdown bearing misalignment in the contact event is studied. It is found that misalignment increases the likelihood of a potentially damaging whirling motion of the rotor. A model for analysis of the stresses occurring in the rotor is proposed. In the studies of misalignment and stresses, a flexible rotor using a finite element approach is applied. Simplified models of cageless and caged bearings are used for the description of touchdown bearings. The results indicate that an increase in misalignment can have a direct influence on the bending and shear stresses occurring in the rotor during the contact event. Thus, it was concluded that analysis of stresses arising in the contact event is essential to guarantee appropriate system dimensioning for possible contact events with misaligned touchdown bearings. One of the conclusions drawn from the first part of the study is that knowledge of the forces affecting the balls and cage of the touchdown bearings can enable a more reliable estimation of the service life of the bearing. Therefore, the second part of the dissertation investigates the forces occurring in the cage and balls of touchdown bearings and introduces two detailed models of touchdown bearings in which all bearing parts are modelled as independent bodies. Two multibody-based two-dimensional models of touchdown bearings are introduced for dynamic analysis of the contact event. All parts of the bearings are modelled with geometrical surfaces, and the bodies interact with each other through elastic contact forces. To assist in identification of the forces affecting the balls and cage in the contact event, the first model describes a touchdown bearing without a cage, and the second model describes a touchdown bearing with a cage. The introduced models are compared with the simplified models used in the first part of the dissertation through parametric study. Damages to the rotor, cage and balls are some of the main reasons for failures of AMB-systems. The stresses in the rotor in the contact event are defined in this work. Furthermore, the forces affecting key bodies of the bearings, cage and balls can be studied using the models of touchdown bearings introduced in this dissertation. Knowledge obtained from the introduced models is valuable since it can enable an optimum structure for a rotor and touchdown bearings to be designed.

Host-parasite relations in a mycoparasitic system : alterations in membrane permeability and lipid composition in Choanephora cucurbitarum infected by Piptocephalis virginiana /

examined in Choanephora cucurbita rum during the early stages of infection by Piptocephalis virginiana » There was a small but consistent increase in the leakage of electrolytes, amino acids and sugars as a result of infection. These low levels of differential leakage in infected tissues are explained on the basis of the nature of this obligate, biotrophic, mycoparasitic system. Quantitative analysis of the twenty six amino acids and amino compounds detected in the leacheates — showed similar profiles in infected and control host and no new species of amino acids or amino compounds were detected in either infected or control host leacheates. Comparatively high amounts of aspartic acid, glutamic acid and alanine were found in the leacheates of host and infected host . Analyses of the sugars comprising the leacheates of infected and control host showed the presence of eight sugars, among which glucose was found in significant amounts (50-53%) ' The nutritional implication of this preferential leakage is discussed. No significant difference was observed in the leacheates of infected host sugar profiles compared with that of the control host. Profiles of the internal pool sugars of infected and control host did not reflect that obtained from the leacheate data, perhaps owing to leakage of sugars in a selective manner . Membrane lipid analyses yielded higher levels of lipid in infected host compared with the control, both at the 24 h and 36 h analyses. In addition, preliminary investigations of phosphorous-32 incorporation and turnover in phospholipids showed higher levels of 32p incorporation and turnover in infected host compared with the control. No apparent difference was noted in the profiles of the neutral lipid classes and the polar lipid classes of the membrane lipids as determined by one and two dimensional thin-layer chromatography respectively. However, a small but consistently higher degree of unsaturation was detected in the fatty acids of infected tissue compared with the control. Also, '^''-^^''^^'-'-^'^^c acid, a polyunsaturated fatty acid previously reported to show a direct correlation during the early stages of infection and the degree of parasitism of P. virginiana on C. cucurbitarum , was found in higher amounts in infected host membrane lipids compared with that of the control host. The implications of these membrane lipid alterations are discussed with particular reference to the small but consistently higher leakage of electrolytes, amino acids and sugars observed during infection in this study.

Interaction between vortices and impurities in a d-wave superconductor /

High temperature superconductors were discovered in 1986, but despite considerable research efforts, both experimental and theoretical, these materials remain poorly understood. Because their electronic structure is both inhomogeneous and highly correlated, a full understanding will require knowledge of quasiparticle properties both in real space and momentum space. In this thesis, we will present a theoretical analysis of the scanning tunneling microscopy (STM) data in BSCCO. We introduce the Bogoliubov-De Gennes Hamiltonian and solve it numerically on a two-dimensional 20 x 20 lattice under a magnetic field perpendicular to the surface. We consider a vortex at the center of our model. We introduce a Zn impurity in our lattice as a microscopic probe of the physical properties of BSCCO. By direct numerical diagonalization of the lattice BogoliubovDe Gennes Hamiltonian for different positions of the impurity, we can calculate the interaction between the vortex and the impurity in a d-wave superconductor.

The micromorphology of Paleoseismic soft sediment deformation structures in glacial deposits from three sample sites in Scotland /

The nature of this research is to investigate paleoseismic deformation of glacial soft sediments from three sampling sites throughout the Scottish Highlands; Arrat's Mills, Meikleour and Glen Roy. The paleoseismic evidence investigated in this research will provide a basis for applying criteria to soft sediment deformation structures, and the trigger mechanisms that create these structures. Micromorphology is the tool used in this to investigate paleoseismic deformation structures in thin section. Thin section analysis, (micromorphology) of glacial sediments from the three sampling sites is used to determine microscale evidence of past earthquakes that can be correlated to modem-day events and possibly lead to a better understanding of the impact of earthquakes throughout a range of sediment types. The significance of the three sampling locations is their proximity to two major active fault zones that cross Scotland. The fault zones are the Highland Boundary Fault and the Great Glen Fault, these two major faults that parallel each other and divide the country in half Sims (1975) used a set of seven criteria that identified soft sediment deformation structures created by a magnitude six earthquake in Cahfomia. Using criteria set forth by Sims (1975), the paleoseismic evidence can be correlated to the magnitude of the deformation structures found in the glacial sediments. This research determined that the microstructures at Arrat's Mill, Meikleour and Glen Roy are consistent with a seismically induced origin. It has also been demonstrated that, even without the presence of macrostructures, the use of micromorphology techniques in detecting such activity within sediments is of immense value.