Chemistry and Chemical Education Through Text and Image: Analysis of Twentieth Century Textbooks Used in Brazilian Context

Assuming that textbooks give literary expression to cultural and ideological values of a nation or group, we propose the analysis of chemistry textbooks used in Brazilian universities throughout the twentieth century. We analyzed iconographic and textual aspects of 31 textbooks which had significant diffusion in the context of Brazilian universities at that period. As a result of the iconographic analysis, nine categories of images were proposed: (1) laboratory and experimentation, (2) industry and production, (3) graphs and diagrams, (4) illustrations related to daily life, (5) models, (6) illustrations related to the history of science, (7) pictures or diagrams of animal, vegetable or mineral samples, (8) analogies and (9) concepts of physics. The distribution of images among the categories showed a different emphasis in the presentation of chemical content due to a commitment to different conceptions of chemistry over the period. So, we started with chemistry as an experimental science in the early twentieth century, with an emphasis change to the principles of chemistry from the 1950s, culminating in a chemistry of undeniable technological influence. Results showed that reflections not only on the history of science, but on the history of science education, may be useful for the improvement of science education.

Influence of land use changes on water chemistry in streams in the State of Sao Paulo, southeast Brazil

Streamwater is affected by several processes in the watershed including anthropogenic activities that result in changes in water quality as well as in the functioning of these stream ecosystems. Therefore, this work aims to evaluate the concentration of major ions (Ca2+, Mg2+, Na+, K+, NH4+, NO3-, NO2-, Cl-, SO42-, PO43-, HCO3-) in streams in the state of Sao Paulo (southeast Brazil). The sampling sites are located at undisturbed (ombrophilus dense forest, semideciduous forest and savanna - cerrado) and disturbed areas (pasture, urbanization and sugar cane crops). Streamwater chemistry varied according to land use change and, in general, was higher in disturbed sites. Streams located in undisturbed sites at Ribeira de Iguape/Alto Paranapanema watershed (streams 1, 2 and 3) seem to be regulated by soil characteristics, as the disturbed streams located at the same watershed covered by pasture (stream 7) showed high concentration for the most of the variables. Exception to streams located at Pontal do Paranapanema watershed where both disturbed (stream 8) and undisturbed streams (stream 4 and 5) presented similar patterns for almost all variables measured.

Hematology and Serum Chemistry of Free-ranging Jaguars (Panthera onca)

We collected and analyzed blood samples from 12 free-ranging jaguars (Panthera onca). Clinical examinations, hematolog, and serum chemistry indicate the jaguars were in good overall health. Results may help as values for free-ranging jaguars under the same handling conditions.

Exploring the coordination chemistry of isomerizable terpyridine derivatives for successful analyses of cis and trans isomers by travelling wave ion mobility mass spectrometry

The photochemical cis-trans isomerization of the 4-{4-[2-(pyridin-4-yl)ethenyl]phenyl}-2,2': 6',2''-terpyridine ligand (vpytpy) was investigated by UV-vis, NMR and TWIM-MS. Ion mobility mass spectrometry was performed pursuing the quantification of the isomeric composition during photolysis, however an in-source trans-to-cis isomerization process was observed. In order to overcome this inherent phenomenon, the isomerization of the vpytpy species was suppressed by complexation, reacting with iron(II) ions, and forming the [Fe(vpytpy)(2)](2+) complex. The strategy of "freezing" the cis-trans isomerizable ligand at a given geometric conformation was effective, preventing further isomerization, thus allowing the distinction of each one of the isomers in the photolysed mixture. In addition, the experimental drift times were related to the calculated surface areas of the three possible cis-cis, cis-trans and trans-trans iron(II) complex isomers. The stabilization of the ligand in a given conformation also allows us to obtain the cis-cis and cis-trans complexes exhibiting the ligand in the metastable cis-conformation, as well as in the thermodynamically stable trans-conformation.

Cyclic Voltammetry and Computational Chemistry Studies on the Evaluation of the Redox Behavior of Parabens and other Analogues

Parabens are antimicrobial preservatives widely used in pharmaceutical, cosmetic and food industries. The alkyl chain connected to the ester group defines some important physicochemical characteristics of these compounds, including the partition coefficient and redox properties. The voltammetric and computational analyses were carried out in order to evaluate the redox behavior of these compounds and other phenolic analogues. A strong correlation between chemical substituents inductive effects of parabens with redox potentials was observed. Using cyclic voltammetry and glassy carbon working electrode, only one irreversible anodic peak was observed around 0.8 V for methylparaben (MP), ethylparaben (EP), propylparaben (PP), butylparaben (BP), benzylparaben (BzP) and p-substituted phenolic analogues. The electrodonating inductive effect of alkyl groups was demonstrated by the anodic oxidation potential shift to lower values as the carbon number increases and, therefore the parabens (and other phenolic analogues) oxidation processes to the quinonoidic forms showed great dependence on the substituent pattern.

Influence of land use changes on water chemistry in streams in the State of São Paulo, southeast Brazil

Streamwater is affected by several processes in the watershed including anthropogenic activities that result in changes in water quality as well as in the functioning of these stream ecosystems. Therefore, this work aims to evaluate the concentration of major ions (Ca2+, Mg2+, Na+, K+, NH4+, NO3-, NO2-, Cl-, SO4(2-), PO4(3-), HCO3-) in streams in the state of São Paulo (southeast Brazil). The sampling sites are located at undisturbed (ombrophilus dense forest, semideciduous forest and savanna - cerrado) and disturbed areas (pasture, urbanization and sugar cane crops). Streamwater chemistry varied according to land use change and, in general, was higher in disturbed sites. Streams located in undisturbed sites at Ribeira de Iguape/Alto Paranapanema watershed (streams 1, 2 and 3) seem to be regulated by soil characteristics, as the disturbed streams located at the same watershed covered by pasture (stream 7) showed high concentration for the most of the variables. Exception to streams located at Pontal do Paranapanema watershed where both disturbed (stream 8) and undisturbed streams (stream 4 and 5) presented similar patterns for almost all variables measured.

Cyclic voltammetry and computational chemistry studies on the evaluation of the redox behavior of parabens and other analogues

Parabens are antimicrobial preservatives widely used in pharmaceutical, cosmetic and food industries. The alkyl chain connected to the ester group defines some important physicochemical characteristics of these compounds, including the partition coefficient and redox properties. The voltammetric and computational analyses were carried out in order to evaluate the redox behavior of these compounds and other phenolic analogues. A strong correlation between chemical substituents inductive effects of parabens with redox potentials was observed. Using cyclic voltammetry and glassy carbon working electrode, only one irreversible anodic peak was observed around 0.8 V for methylparaben (MP), ethylparaben (EP), propylparaben (PP), butylparaben (BP), benzylparaben (BzP) and p-substituted phenolic analogues. The electrodonating inductive effect of alkyl groups was demonstrated by the anodic oxidation potential shift to lower values as the carbon number increases and, therefore the parabens (and other phenolic analogues) oxidation processes to the quinonoidic forms showed great dependence on the substituent pattern.

Studies on Oxidative Couplings in H-Phosphonate Chemistry

In this thesis oxidative coupling of H-phosphonate and H phosphonothioate diesters with different alcohols and amines are presented. Since the reactions with alcohols previously have been particularly unfavourable due to competing side reactions, a modified protocol leading to high coupling yields of structurally diverse hydroxylic components was developed. The phosphorylation reaction was studied using 31P NMR spectroscopy and for the first time the previously only postulated reactive intermediate involved in these reactions was observed. The use of iodine in combination with a bulky chlorosilane in pyridine was found to have a profound effect on both the suppression of side reactions and the rate of the oxidative couplings, and led to a clean formation of phosphorylated products in high yields. This synthetic protocol was then extended to include coupling reactions with bis-functional reagents containing hexamethylene linkers to provide handles for derivatisations of oligonucleotides. A synthetic protocol consisting of the stereospecific oxidative coupling of amines with H-phosphonate diesters to produce phosphoroamidates was designed in such a way that it permitted control of the stereochemical outcome of the reactions. Based on a silylation-mediated reaction utilising phenyl H phosphonothioate monoester as a thiophosphonyl transferring agent, a method was developed and used for the preparation of H-phosphonothioate building blocks for the synthesis of DNA analogues.

Computational chemistry studies of UV induced processes in human skin

This thesis presents and uses the techniques of computational chemistry to explore two different processes induced in human skin by ultraviolet light. The first is the transformation of urocanic acid into a immunosuppressing agent, and the other is the enzymatic action of the 8-oxoguanine glycosylase enzyme. The photochemistry of urocanic acid is investigated by time-dependent density functional theory. Vertical absorption spectra of the molecule in different forms and environments is assigned and candidate states for the photochemistry at different wavelengths are identified. Molecular dynamics simulations of urocanic acid in gas phase and aqueous solution reveals considerable flexibility under experimental conditions, particularly for for the cis isomer where competition between intra- and inter-molecular interactions increases flexibility. A model to explain the observed gas phase photochemistry of urocanic acid is developed and it is shown that a reinterpretation in terms of a mixture between isomers significantly enhances the agreement between theory and experiment , and resolves several peculiarities in the spectrum. A model for the photochemistry in the aqueous phase of urocanic acid is then developed, in which two excited states governs the efficiency of photoisomerization. The point of entrance into a conical intersection seam is shown to explain the wavelength dependence of photoisomerization quantum yield. Finally some mechanistic aspects of the DNA repair enzyme 8-oxoguanine glycosylase is investigated with density functional theory. It is found that the critical amino acid of the active site can provide catalytic power in several different manners, and that a recent proposal involving a SN1 type of mechanism seems the most efficient one.

Variance Reduction in Analytical Chemistry : New Numerical Methods in Chemometrics and Molecular Simulation

This thesis is based on five papers addressing variance reduction in different ways. The papers have in common that they all present new numerical methods. Paper I investigates quantitative structure-retention relationships from an image processing perspective, using an artificial neural network to preprocess three-dimensional structural descriptions of the studied steroid molecules. Paper II presents a new method for computing free energies. Free energy is the quantity that determines chemical equilibria and partition coefficients. The proposed method may be used for estimating, e.g., chromatographic retention without performing experiments. Two papers (III and IV) deal with correcting deviations from bilinearity by so-called peak alignment. Bilinearity is a theoretical assumption about the distribution of instrumental data that is often violated by measured data. Deviations from bilinearity lead to increased variance, both in the data and in inferences from the data, unless invariance to the deviations is built into the model, e.g., by the use of the method proposed in paper III and extended in paper IV. Paper V addresses a generic problem in classification; namely, how to measure the goodness of different data representations, so that the best classifier may be constructed. Variance reduction is one of the pillars on which analytical chemistry rests. This thesis considers two aspects on variance reduction: before and after experiments are performed. Before experimenting, theoretical predictions of experimental outcomes may be used to direct which experiments to perform, and how to perform them (papers I and II). After experiments are performed, the variance of inferences from the measured data are affected by the method of data analysis (papers III-V).

Thermodynamic behavior of the binaries 1-butilpryridinium tetrafluoroborate with water and alkanols: their interpretation using 1H-NMR spectroscopy and quantum-chemistry calculations

[EN]Here we present experimental data of different properties for a set of binary mixtures composed of water or alkanols (methanol to butanol) with an ionic liquid (IL), butylpyridinium tetrafluoroborate [bpy][BF4]. Solubility data (xIL,T) are presented for each of the mixtures, including water, which is found to have a small interval of compositions in IL, xIL, with immiscibility. In each case, the upper critical solubility temperature (UCST) is determined and a correlation was observed between the UCST and the nature of the compounds in the mixtures. Miscibility curves establish the composition and temperature intervals where thermodynamic properties of the mixtures, such as enthalpies Hm E and volumes Vm E, can be determined.

Chemistry of Fe(II) in the presence of organic exudates from phytoplankton and of copper in seawater

Programa de doctorado de Oceanografía ; 2006-2008

Modeling the gas and aqueous phase chemistry of the marine boundary layer

Ein eindimensionales numerisches Modell der maritimenGrenzschicht (MBL) wurde erweitert, um chemische Reaktionenin der Gasphase, von Aerosolpartikeln und Wolkentropfen zu beschreiben. Ein Schwerpunkt war dabei die Betrachtung derReaktionszyklen von Halogenen. Soweit Ergebnisse vonMesskampagnen zur Verfuegung standen, wurden diese zurValidierung des Modells benutzt. Die Ergebnisse von frueheren Boxmodellstudien konntenbestaetigt werden. Diese zeigten die saeurekatalysierteAktivierung von Brom aus Seesalzaerosolen, die Bedeutung vonHalogenradikalen fuer die Zerstoerung von O3, diepotentielle Rolle von BrO bei der Oxidation von DMS und dievon HOBr und HOCl in der Oxidation von S(IV). Es wurde gezeigt, dass die Beruecksichtigung derVertikalprofile von meteorologischen und chemischen Groessenvon grosser Bedeutung ist. Dies spiegelt sich darin wider,dass Maxima des Saeuregehaltes von Seesalzaerosolen und vonreaktiven Halogenen am Oberrand der MBL gefunden wurden.Darueber hinaus wurde die Bedeutung von Sulfataerosolen beidem aktiven Recyceln von weniger aktiven zu photolysierbarenBromspezies gezeigt. Wolken haben grosse Auswirkungen auf die Evolution und denTagesgang der Halogene. Dies ist nicht auf Wolkenschichtenbeschraenkt. Der Tagesgang der meisten Halogene ist aufgrundeiner erhoehten Aufnahme der chemischen Substanzen in die Fluessigphase veraendert. Diese Ergebnisse betonen dieWichtigkeit der genauen Dokumentation der meteorologischenBedingungen bei Messkampagnen (besonders Wolkenbedeckungsgrad und Fluessigwassergehalt), um dieErgebnisse richtig interpretieren und mit Modellresultatenvergleichen zu koennen. Dieses eindimensionale Modell wurde zusammen mit einemBoxmodell der MBL verwendet, um die Auswirkungen vonSchiffemissionen auf die MBL abzuschaetzen, wobei dieVerduennung der Abgasfahne parameterisiert wurde. DieAuswirkungen der Emissionen sind am staerksten, wenn sie insauberen Gebieten stattfinden, die Hoehe der MBL gering istund das Einmischen von Hintergrundluft schwach ist.Chemische Reaktionen auf Hintergrundaerosolen spielen nureine geringe Rolle. In Ozeangebieten mit schwachemSchiffsverkehr sind die Auswirkungen auf die Chemie der MBL beschraenkt. In staerker befahrenen Gebieten ueberlappensich die Abgasfahnen mehrerer Schiffe und sorgen fuerdeutliche Auswirkungen. Diese Abschaetzung wurde mitSimulationen verglichen, bei denen die Emissionen alskontinuierliche Quellen behandelt wurden, wie das inglobalen Chemiemodellen der Fall ist. Wenn die Entwicklungder Abgasfahne beruecksichtigt wird, sind die Auswirkungendeutlich geringer da die Lebenszeit der Abgase in der erstenPhase nach Emission deutlich reduziert ist.