Advanced chemometric methods: Applicability on industrial data

Recent years have produced great advances in the instrumentation technology. The amount of available data has been increasing due to the simplicity, speed and accuracy of current spectroscopic instruments. Most of these data are, however, meaningless without a proper analysis. This has been one of the reasons for the overgrowing success of multivariate handling of such data. Industrial data is commonly not designed data; in other words, there is no exact experimental design, but rather the data have been collected as a routine procedure during an industrial process. This makes certain demands on the multivariate modeling, as the selection of samples and variables can have an enormous effect. Common approaches in the modeling of industrial data are PCA (principal component analysis) and PLS (projection to latent structures or partial least squares) but there are also other methods that should be considered. The more advanced methods include multi block modeling and nonlinear modeling. In this thesis it is shown that the results of data analysis vary according to the modeling approach used, thus making the selection of the modeling approach dependent on the purpose of the model. If the model is intended to provide accurate predictions, the approach should be different than in the case where the purpose of modeling is mostly to obtain information about the variables and the process. For industrial applicability it is essential that the methods are robust and sufficiently simple to apply. In this way the methods and the results can be compared and an approach selected that is suitable for the intended purpose. Differences in data analysis methods are compared with data from different fields of industry in this thesis. In the first two papers, the multi block method is considered for data originating from the oil and fertilizer industries. The results are compared to those from PLS and priority PLS. The third paper considers applicability of multivariate models to process control for a reactive crystallization process. In the fourth paper, nonlinear modeling is examined with a data set from the oil industry. The response has a nonlinear relation to the descriptor matrix, and the results are compared between linear modeling, polynomial PLS and nonlinear modeling using nonlinear score vectors.

Color ad spectral image assessment using novel quality and fidelity techniques

The ongoing development of the digital media has brought a new set of challenges with it. As images containing more than three wavelength bands, often called spectral images, are becoming a more integral part of everyday life, problems in the quality of the RGB reproduction from the spectral images have turned into an important area of research. The notion of image quality is often thought to comprise two distinctive areas – image quality itself and image fidelity, both dealing with similar questions, image quality being the degree of excellence of the image, and image fidelity the measure of the match of the image under study to the original. In this thesis, both image fidelity and image quality are considered, with an emphasis on the influence of color and spectral image features on both. There are very few works dedicated to the quality and fidelity of spectral images. Several novel image fidelity measures were developed in this study, which include kernel similarity measures and 3D-SSIM (structural similarity index). The kernel measures incorporate the polynomial, Gaussian radial basis function (RBF) and sigmoid kernels. The 3D-SSIM is an extension of a traditional gray-scale SSIM measure developed to incorporate spectral data. The novel image quality model presented in this study is based on the assumption that the statistical parameters of the spectra of an image influence the overall appearance. The spectral image quality model comprises three parameters of quality: colorfulness, vividness and naturalness. The quality prediction is done by modeling the preference function expressed in JNDs (just noticeable difference). Both image fidelity measures and the image quality model have proven to be effective in the respective experiments.

Multi-Eruption Solar Energetic Particle Events Observed by SOHO/ERNE

In the last two decades of studying the Solar Energetic Particle (SEP) phenomenon, intensive emphasis has been put on how and when and where these SEPs are injected into interplanetary space. It is well known that SEPs are related to solar flares and CMEs. However, the role of each in the acceleration of SEPs has been under debate since the major role was taken from flares ascribed to CMEs step by step after the skylab mission, which started the era of CME spaceborn observations. Since then, the shock wave generated by powerful CMEs in between 2-5 solar radii is considered the major accelerator. The current paradigm interprets the prolonged proton intensity-time profile in gradual SEP events as a direct effect of accelerated SEPs by shock wave propagating in the interplanetary medium. Thus the powerful CME is thought of as a starter for the acceleration and its shock wave as a continuing accelerator to result in such an intensity-time profile. Generally it is believed that a single powerful CME which might or might not be associated with a flare is always the reason behind such gradual events.

In this work we use the Energetic and Relativistic Nucleus and Electrons ERNE instrument on board Solar and Heliospheric Observatory SOHO to present an empirical study to show the possibility of multiple accelerations in SEP events. In the beginning we found 18 double-peaked SEP events by examining 88 SEP events. The peaks in the intensity-time profile were separated by 3-24 hours. We divided the SEP events according to possible multiple acceleration into four groups and in one of these groups we find evidence for multiple acceleration in velocity dispersion and change in the abundance ratio associated at transition to the second peak. Then we explored the intensity-time profiles of all SEP events during solar cycle 23 and found that most of the SEP events are associated with multiple eruptions at the Sun and we call those events as Multi-Eruption Solar Energetic Particles (MESEP) events. We use the data available by Large Angle and Spectrometric Coronograph LASCO on board SOHO to determine the CME associated with such events and YOHKOH and GOES satellites data to determine the flare associated with such events. We found four types of MESEP according to the appearance of the peaks in the intensity-time profile in large variation of energy levels. We found that it is not possible to determine whether the peaks are related to an eruption at the Sun or not, only by examining the anisotropy flux, He/p ratio and velocity dispersion. Then we chose a rare event in which there is evidence of SEP acceleration from behind previous CME. This work resulted in a conclusion which is inconsistent with the current SEP paradigm. Then we discovered through examining another MESEP event, that energetic particles accelerated by a second CME can penetrate a previous CME-driven decelerating shock. Finally, we report the previous two MESEP events with new two events and find a common basis for second CME SEPs penetrating previous decelerating shocks. This phenomenon is reported for the first time and expected to have significant impact on modification of the current paradigm of the solar energetic particle events.

A multi-screening approach for marine-derived fungal metabolites and the isolation of cyclodepsipeptides from Beauveria felina

Extracts obtained from 57 marine-derived fungal strains were analyzed by HPLC-PDA, TLC and ¹H NMR. The analyses showed that the growth conditions affected the chemical profile of crude extracts. Furthermore, the majority of fungal strains which produced either bioactive of chemically distinctive crude extracts have been isolated from sediments or marine algae. The chemical investigation of the antimycobacterial and cytotoxic crude extract obtained from two strains of the fungus Beauveria felina have yielded cyclodepsipeptides related to destruxins. The present approach constitutes a valuable tool for the selection of fungal strains that produce chemically interesting or biologically active secondary metabolites.

Espectrometria de absorção atômica: o caminho para determinações multi-elementares

This paper present an overview of way covered for the spectrometry of atomic absorption (AAS), tracing a line of the historical events in its development and its establishment as a multielement technique. Additionally, the efforts carried by through several researchers in the search for the instrumental evolution, the advances, advantages, limitations, and trends of this approach are related. Several works focusing its analytical applications are cited employing simultaneous multielement determination by flame (FAAS) and/or graphite furnace (GF AAS), and fast sequential multielement determination using FAAS are reported in the present review.

Social Presence Approach Within the Question and Answering eLearning Model: An Experiment with a Multi-Agent System

The model of Questions Answering (Q&A) for eLearning is based on collaborative learning through questions that are posed by students and their answers to that questions which are given by peers, in contrast with the classical model in which students ask questions to the teacher only. In this proposal we extend the Q&A model including the social presence concept and a quantitative measure of it is proposed; besides it is considered the evolution of the resulting Q&A social network after the inclusion of the social presence and taking into account the feedback on questions posed by students and answered by peers. The social network behaviorwas simulated using a Multi-Agent System to compare the proposed social presence model with the classical and the Q&A models

Self-condensation of n-(N-propyl)butanimine: NMR and mass spectral analyses and investigation by theoretical calculation

The stability of N-propylbutanimine (1) was investigated under different experimental conditions. The acid-catalyzed self-condensation that produced the E-enimine (4) and Z-inimine (5) was studied by experimental analyses and theoretical calculations. Since the calculations for the energy of 5 indicated that it had a lower energy than 4, yet 4 was the principal product, the self-condensation of 1 must be kinetically controlled.

Electron paramagnetic resonance (EPR) spectral components of spin-labeled lipids in saturated phospholipid bilayers: effect of cholesterol

Electron paramagnetic resonance (EPR) spectroscopy was used to study the main structural accommodations of spin labels in bilayers of saturated phosphatidylcholines with acyl chain lengths ranging from 16 to 22 carbon atoms. EPR spectra allowed the identification of two distinct spectral components in thermodynamic equilibrium at temperatures below and above the main phase transition. An accurate analysis of EPR spectra, using two fitting programs, enabled determination of the thermodynamic profile for these major probe accommodations. Focusing the analysis on two-component EPR spectra of a spin-labeled lipid, the influence of 40 mol % cholesterol in DPPC was studied.

Síntese de cristais líquidos derivados do nitroazobenzeno: uma proposta de síntese multi-etapas aplicada às aulas de química orgânica experimental

We describe a synthetic route consisting of five steps from aniline to obtain liquid crystal compounds derived from nitroazobenzene. Syntheses were performed during the second half of the semester in organic chemistry laboratory classes. Students characterized the liquid crystal phase by the standard melting point techniques, differential scanning calorimetry and polarized optical microscopy. These experiments allow undergraduate students to explore fundamentally important reactions in Organic Chemistry, as well as modern concepts in Chemistry such as self-assembly and self-organization, nanostructured materials and molecular electronics.

Magnetic, thermal and spectral characterization of 2,6-dimethoxybenzoates of Co(II), Ni(II) and Cu(II)

The complexes of 2,6-dimethoxybenzoic acid anion with ions of Co(II), Ni(II), and Cu(II) have been synthesized as polycrystalline solids, and characterized by elemental analysis, spectroscopy, magnetic studies, and also by X-ray diffraction and thermogravimetric measurements. The analysed complexes have following colours: pink for Co(II), green for Ni(II), and blue for Cu(II) compounds. The carboxylate group binds as monodentate, and bidentate bridging and chelating ligands. On heating in air to 1173 K the complexes decompose in four, three or two steps. At first, they dehydrate in one or two steps to anhydrous salts, that next decompose to oxides of the respective metals. The solubility of the investigated dimethoxybenzoates in water at 293 K is of the order of 10-2 mol/dm3. Their magnetic moments were determined in the temperature range of 76-303 K. The results reveal the compounds of Co(II) and Ni(II) to be high-spin complexes and that of Cu(II) to form dimer.

Magnetic, thermal and spectral properties of Ni(II) 2,3- , 3,5- and 2,6-dimethoxybenzoates

Complexes of Ni(II) 2,3-, 3,5- and 2,6-dimethoxybenzoates have been synthesized, their physico-chemical properties have been compared and the influence of the position of -OCH3 substituent on their properties investigated. The analysed compounds are crystalline, hydrated salts with green colour. The carboxylate ions show a bidentate chelating or bridging coordination modes. The thermal stabilities of Ni(II) dimethoxybenzoates were investigated in air in the range of 293-1173 K. The complexes decompose in three steps, yelding the NiO as the final product of decomposition. Their solubilities in water at 293 K are in the order of 10-2-10-4 mol×dm-3. The magnetic susceptibilities for the analysed dimethoxybenzoates of Ni(II) were measured over the range of 76-303 K and the magnetic moments were calculated. The results reveal that the complexes are the high-spin ones and the ligands form the weak electrostatic field in the octahedral coordination sphere of the central Ni(II) ion. The various position -OCH3 groups in benzene ring cause the different steric, mesomeric and inductive effects on the electron density in benzene ring.

Magnetic, thermal and spectral behaviour of 3-chloro-2-nitrobenzoates of Co(II), Ni(II), and Cu(II)

Physico-chemical properties of 3-chloro-2-nitrobenzoates of Co(II), Ni(II) and Cu(II) were synthesized and studied. The complexes were obtained as mono- and dihydrates with a metal ion to ligand ratio of 1 : 2. All analysed 3-chloro-2-nitrobenzoates are polycrystalline compounds with colours depending on the central ions: pink for Co(II), green for Ni(II) and blue for Cu(II) complexes. Their thermal decomposition was studied in the range of 293 ­ 523 K, because it was found that on heating in air above 523 K 3-chloro-2-nitrobenzoates decompose explosively. Hydrated complexes lose crystallization water molecules in one step and anhydrous compounds are formed. The final products of their decomposition are the oxides of the respective transition metals. From the results it appears that during dehydration process no transformation of nitro group to nitrite takes place. The solubilities of analysed complexes in water at 293 K are of the order of 10-4 ­ 10-2 mol / dm³. The magnetic moment values of Co2+, Ni2+ and Cu2+ ions in 3-chloro-2-nitrobenzoates experimentally determined at 76 ­ 303 K change from 3.67µB to 4.61µB for Co(II) complex, from 2.15µB to 2.87µB for Ni(II) 3-chloro-2-nitrobenzoate and from 0.26µB to 1.39µB for Cu(II) complex. 3-Chloro-2-nitrobenzoates of Co(II) and Ni(II) follow the Curie-Weiss law. Complex of Cu(II) forms dimer.