Determinação do teor de cálcio em comprimido à base de lactato de cálcio utilizado no tratamento da osteoporose

The present study utilized thermogravimetry (TG) and optical emission spectrometry with inductively coupled plasma (ICP/OES) to determine the amount of calcium in calcium lactate tablets used in the treatment of osteoporosis. Thermogravimetry results indicated that the decomposition temperature of CaCO3 occurred at 603.9 and 609.4 ºC in the samples of calcium lactate and tablets, respectively. The calcium content obtained by TG for the tablets sample showed a similar result to that disclosed by ICP-OES, indicating a value of 8.93% for both techniques.

Conversão química de no e co sobre catalisadores à base de óxidos de cobalto ou de ferro

Cobalt or iron oxides supported or not on zeolite Hbeta were prepared and evaluated in the reduction reaction of NO by CO in presence of O2, SO2 or H2O. XRD results evidenced the Hbeta structure and the formation of Co3O4 and Fe2O3. TPR-H2 analysis showed complete reduction of cobalt oxide at lower temperatures than for iron oxide. The catalysts are quite active and the activity depends on the reaction temperature. The highest conversions rates were observed for pure iron oxide, which can be a relatively low cost catalyst for reduction of NO by CO, with high selectivity towards the N2 formation.

Ni(II), Cu(II), AND Zn(II) COMPLEXES DERIVED FROM A NEW SCHIFF BASE 2-((Z)-(3-METHYLPYRIDIN-2- YLEIMINO)METHYL)PHENOL AND SYNTHESIS OF NANO SIZED METAL OXIDE PARTICLES FROM THESE COMPOUNDS

Synthesis, spectral identification, and magnetic properties of three complexes of Ni(II), Cu(II), and Zn(II) are described. All three compounds have the general formula [M(L)2(H2O)2], where L = deprotonated phenol in the Schiff base 2-((z)-(3-methylpyridin-2-yleimino)methyl)phenol. The three complexes were synthesized in a one-step synthesis and characterized by elemental analysis, Fourier transform infrared spectroscopy, electronic spectra, X-ray diffraction (XRD), and room temperature magnetic moments. The Cu(II) and Ni(II) complexes exhibited room temperature magnetic moments of 1.85 B.M. per copper atom and 2.96 B.M. per nickel atom. The X-band electron spin resonance spectra of a Cu(II) sample in dimethylformamide frozen at 77 K (liquid nitrogen temperature) showed a typical ΔMS = ± 1 transition. The complexes ([M(L)2(H2O)2]) were investigated by the cyclic voltammetry technique, which provided information regarding the electrochemical mechanism of redox behavior of the compounds. Thermal decomposition of the complexes at 750 ºC resulted in the formation of metal oxide nanoparticles. XRD analyses indicated that the nanoparticles had a high degree of crystallinity. The average sizes of the nanoparticles were found to be approximately 54.3, 30.1, and 44.4 nm for NiO, CuO, and ZnO, respectively.

Spectrophotometric determination of metronidazole through Schiff's base system using vanillin and PDAB reagents in pharmaceutical preparations

Two simple sensitive and reproducible spectrophotometric methods have been developed for the determination of metronidazole either in pure form or in their tablets. The proposed methods are based on the reduction of the nitro group to amino group of the drug. The reduction of metronidazole was carried out with zinc powder and 5 N hydrochloric acid at room temperature in methanol. The resulting amine was then subjected to a condensation reaction with aromatic aldehyde namely, vanillin and p-dimethyl amino benzaldehyde (PDAB) to yield yellow colored Schiff's bases. The formed Schiff's bases are quantified spectrophotometrically at their absorption maxima at 422 nm for vanillin and 494 nm for PDAB. Beer's law was obeyed in the concentration ranges 10 to 65 µg mL-1 and 5 to 40 µg mL-1 with a limit of detection (LOD) of 0.080 µg mL-1 and 0.090 µg mL-1 for vanillin and PDAB, respectively. The mean percentage recoveries were found to be 100.05 ± 0.37 and 99.01 ± 0.76 for the two methods respectively. The proposed methods were successfully applied to determine the metronidazole in their tablet formulations and the results compared favorably to that of reference methods. The proposed methods are recommended for quality control and routine analysis.

Cardiovascular, respiratory and metabolic responses to temperature and hypoxia of the winter frog Rana catesbeiana

The objective of the present study was to determine the effects of hypoxia and temperature on the cardiovascular and respiratory systems and plasma glucose levels of the winter bullfrog Rana catesbeiana. Body temperature was maintained at 10, 15, 25 and 35oC for measurements of breathing frequency, heart rate, arterial blood pressure, metabolic rate, plasma glucose levels, blood gases and acid-base status. Reducing body temperature from 35 to 10oC decreased (P<0.001) heart rate (bpm) from 64.0 ± 3.1 (N = 5) to 12.5 ± 2.5 (N = 6) and blood pressure (mmHg) (P<0.05) from 41.9 ± 2.1 (N = 5) to 33.1 ± 2.1 (N = 6), whereas no significant changes were observed under hypoxia. Hypoxia-induced changes in breathing frequency and acid-base status were proportional to body temperature, being pronounced at 25oC, less so at 15oC, and absent at 10oC. Hypoxia at 35oC was lethal. Under normoxia, plasma glucose concentration (mg/dl) decreased (P<0.01) from 53.0 ± 3.4 (N = 6) to 35.9 ± 1.7 (N = 6) at body temperatures of 35 and 10oC, respectively. Hypoxia had no significant effect on plasma glucose concentration at 10 and 15oC, but at 25oC there was a significant increase under conditions of 3% inspired O2. The arterial PO2 and pH values were similar to those reported in previous studies on non-estivating Rana catesbeiana, but PaCO2 (37.5 ± 1.9 mmHg, N = 5) was 3-fold higher, indicating increased plasma bicarbonate levels. The estivating bullfrog may be exposed not only to low temperatures but also to hypoxia. These animals show temperature-dependent responses that may be beneficial since during low body temperatures the sensitivity of most physiological systems to hypoxia is reduced

Triarylamminium radical-cation complexes: design and magnetic properties and Base-catalyzed hydrosilylation: mechanism and substrate scope

1. Triarylamminium radical-cation complexes. The detailed study of manganese, copper and nickel metal-radical complexes with triarylamminium ligands was conducted. Stable, neutral and pseudo-octahedral coordination monometallic complexes with simple monodentate 2,2`-bipyridine ligand containing a redox-active N,N`-(4,4`-dimethoxydiphenyl-amino) substituent were synthesized and fully characterized. The one-electron oxidation process and formation of persistent radical-cation complexes was observed by cyclic voltammetry and spectroelectrochemical measurements. Evans method measurements were performed with radical-cation complexes generated by chemical one-electron oxidation with NOPF6 in acetonitrile. The experimental results indicate ferromagnetic coupling between metal and triarylamminium cation in manganese (II) complex and antiferromagnetic coupling in nickel (II) complex. This data is supported by DFT calculations which also lend weight to the  spin polarization mechanism as an operative model for magnetic exchange coupling. Neutral bimetallic complexes with a new ditopic ligand were synthesized and fully characterized, including magnetic and electrochemical studies. Chemical oxidation of these precursor complexes did not generate radical-cations, but dicationic complexes, which was confirmed by UV-vis and EPR-experiments, as well as varied temperature magnetic measurements. DFT calculations for radical-cation complexes are included. A synthetic pathway for polytopic ligand with multiple redox-active triarylamine sites was developed. The structure of the ligand is presumably suitable for -spin polarization exchange model and allows for production of polymetallic complexes having high spin ground states. 2. Base-catalyzed hydrosilylation. A simple reductive base-catalyzed hydrosilation of aldehydes and ketones was adapted to the use of the cheap, safe, and non-toxic polymethylhydrosiloxane (PMHS) instead of the common PhSiH3 and (EtO)3SiH, which present significant cost and safety concerns, respectively. The conversion of silane into pentacoordinate silicate species upon addition of a base was studied in details for the cases of phenyl silane and PMHS and is believed to be essential for the hydrosilylation process. We discovered that nucleophiles (a base or fluoride-anion) induced the rearrangement of PMHS and TMDS into light silanes: MeSiH3 and Me2SiH2, respectively. The reductive properties of PMHS under basic conditions can be attributed to the formation of methyl silane and its conversion into a silicate species. A procedure for the generation of methyl silane and its use in further efficient reductions of aldehydes and ketones has been developed. The protocol was extended to the selective reduction of esters and tertiary amides into alcohols and aldimines into amines with good isolated yields and reduction of heterocyclic compounds was attempted.

Étude des propriétés de liquides ioniques protiques en tant qu'électrolytes pour des supercapacités à base de dioxyde de ruthénium

Ce mémoire portant sur le développement de liquides ioniques protiques à l'état liquide à température ambiante en tant qu'électrolytes pour des supercapacités faradiques à base de dioxyde de ruthénium est divisé en trois études distinctes. La première permet d'évaluer quelles propriétés de ces sels fondus doivent être optimisées pour cette application en utilisant les données recueillies avec une série de nouveaux liquides ioniques protiques constitués de l'acide trifluoroacétique et différentes bases hétérocycliques azotées. La seconde discute de l'effet d'impuretés colorées sur les propriétés des liquides ioniques ainsi que sur des aspects pratiques devant être pris en considération lors des synthèses. La troisième traite d'importantes relations structure–propriétés pour une série de liquides ioniques protiques ayant des cations du type pyridinium et différents anions. Dans leur ensemble, les travaux présentés devraient permettre une recherche plus efficace de liquides ioniques avec des propriétés désirables en vue d'application comme électrolyte dans le futur.

Développement de tensioactifs à base d’acides biliaires pegylés pour des applications pharmaceutiques

Les acides biliaires sont reconnus comme des tensioactifs d’origine biologique potentiellement applicables dans le domaine pharmaceutique. Leurs structures en font une plateforme idéale pour l’obtention de nouvelles architectures polymères. Des composés synthétisés par polymérisation anionique de dérivés d’oxirane comme l’oxyde d’éthylène, offre des dérivés amphiphiles pegylés démontrant des propriétés d’agrégation intéressantes en vue d’une amélioration de la biocompatibilité et de la capacité d’encapsulation médicamenteuse. Une large gamme d’acides biliaires pegylés (BA(EGn)x) a été préparée avec comme objectif premier leurs applications dans la formulation de principes actifs problématiques. Pour cela, une caractérisation rigoureuse du comportement de ces dérivés (modulation de la longueur (2 < n < 19) et du nombre de bras (2 < x < 4) de PEG) en solution a été réalisée. Dans le but d’améliorer la biodisponibilité de principes actifs lipophiles (cas de l’itraconazole), des nanoémulsions spontanées, composées de BA(EGn)x et d’acide oléique, ont été développées. L’évaluation in vitro, de la toxicité (cellulaire), et de la capacité de solubilisation des systèmes BA(EGn)x, ainsi que les paramètres pharmacocinétiques in vivo (chez le rat), suggèrent une livraison contrôlée par nos systèmes auto-assemblés lors de l’administration orale et intraveineuse. Aussi, la synthèse de copolymères en blocs en étoile à base d’acide cholique pegylés a été effectuée par polymérisation anionique par addition d’un second bloc au caractère hydrophobe de poly(éther d’allyle et de glycidyle) (CA(EGn-b-AGEm)4). Selon le ratio de blocs hydrophiles-hydrophobes CA(EGn-b-AGEm)4, des réponses thermiques en solution (LCST) ont été observées par un point de trouble (Cp) entre 8 oC et 37 oC. Un mécanisme de formation d’agrégats en plusieurs étapes est suggéré. La thiolation des allyles des PAGE permet une fonctionnalisation terminale à haute densité, comparable aux dendrimères. Les caractérisations physico-chimiques des CA(EGn-b-AGEm-NH2)4 et CA(EGn-b-AGEm-COOH)4 indiquent la formation de structures auto-assemblées en solution, sensibles à la température ou au pH. Cette fonctionnalisation élargie le domaine d’application des dérivés d’acides biliaires pegylés en étoile vers la transfection d’ADN, la livraison de siRNA thérapeutiques ou encore à une sélectivité de livraison médicamenteux (ex. sensibilité au pH, greffage ligands).

Étude de l’orientation par déformation de mélanges de polymères à base de polystyrène

La spectroscopie infrarouge à matrice à plan focal (PAIRS) est utilisée pour étudier la déformation et la relaxation des polymères à très haute vitesse, soit de 46 cm/s, grâce à sa résolution temporelle de quelques millisecondes. Des mesures complémentaires de spectroscopie infrarouge d’absorbance structurale par modulation de la polarisation (PM-IRSAS) ont été réalisées pour suivre des déformations plus lentes de 0,16 à 1,6 cm/s avec une résolution temporelle de quelques centaines de millisecondes. Notre étude a permis d’observer, à haute vitesse de déformation, un nouveau temps de relaxation (τ0) de l’ordre d’une dizaine de millisecondes qui n’est pas prédit dans la littérature. Le but de cette étude est de quantifier ce nouveau temps de relaxation ainsi que de déterminer les effets de la température, de la masse molaire et de la composition du mélange sur ce dernier. Des mesures effectuées sur du polystyrène (PS) de deux masses molaires différentes, soit 210 et 900 kg/mol, à diverses températures ont révélé que ce temps est indépendant de la masse molaire mais qu’il varie avec la température. Des mesures effectuées sur des films composés de PS900 et de PS deutéré de 21 kg/mol, ont révélé que ce temps ne dépend pas de la composition du mélange et que la longueur des chaînes de PS n’a aucun impact sur celui-ci. D’autres mesures effectuées sur des films de PS900 mélangé avec le poly(vinyl méthyl éther) (PVME) ont révélé que ce temps est identique pour le PS900 pur et le PS900 dans le mélange, mais qu’il est plus court pour le PVME, de l’ordre de quelques millisecondes.

Modification des propriétés optiques de nanofils à base de GaN par plasma N2/O2

Une sonde électrostatique de Langmuir cylindrique a été utilisée pour caractériser une post-décharge d’un plasma d’ondes de surface de N2-O2 par la mesure de la densité des ions et électrons ainsi que la température des électrons dérivée de la fonction de distribution en énergie des électrons (EEDF). Une densité maximale des électrons au centre de la early afterglow de l’ordre de 1013 m-3 a été déterminée, alors que celle-ci a chuté à 1011 m-3 au début de la late afterglow. Tout au long du profil de la post-décharge, une densité des ions supérieure à celle des électrons indique la présence d’un milieu non macroscopiquement neutre. La post-décharge est caractérisée par une EEDF quasi maxwellienne avec une température des électrons de 0.5±0.1 eV, alors qu’elle grimpe à 1.1 ±0.2 eV dans la early afterglow due à la contribution des collisions vibrationnelles-électroniques (V-E) particulièrement importantes. L’ajout d’O2 dans la décharge principale entraîne un rehaussement des espèces chargées et de la température des électrons suivi d’une chute avec l’augmentation de la concentration d’O2. Le changement de la composition électrique de la post-décharge par la création de NO+ au détriment des ions N2+ est à l’origine du phénomène. Le recours à cette post-décharge de N2 pour la modification des propriétés d’émission optique de nanofils purs de GaN et avec des inclusions d’InGaN a été étudié par photoluminescence (PL). Bien que l’émission provenant des nanofils de GaN et de la matrice de GaN recouvrant les inclusions diminue suite à la création de sites de recombinaison non radiatifs, celle provenant des inclusions d’InGaN augmente fortement. Des mesures de PL par excitation indiquent que cet effet n’est pas attribuable à un changement de l’absorption de la surface de GaN. Ceci suggère un recuit dynamique induit par la désexcitation des métastables de N2 suite à leur collision à la surface des nanofils et la possibilité de passiver les défauts de surface tels que des lacunes d’azote par l’action d’atomes de N2 réactifs provenant de la post-décharge. L’incorporation d’O2 induit les mêmes effets en plus d’un décalage vers le rouge de la bande d’émission des inclusions, suggérant l’action des espèces d’O2 au sein même des nanostructures.

Ni(II) and Ru(II) Schiff base complexes as catalysts for the reduction of benzene

Two new complexes, [MII(L)(Cl)(H2O)2]·H2O (where M=Ni or Ru and L = heterocyclic Schiff base, 3- hydroxyquinoxaline-2-carboxalidene-4-aminoantipyrine), have been synthesized and characterized by elemental analysis, FT-IR, UV–vis diffuse reflectance spectroscopy, FAB-MASS, TG–DTA, AAS, cyclic voltammetry, conductance and magnetic susceptibility measurements. The complexes have a distorted octahedral structure andwere found to be effective catalysts for the hydrogenation of benzene. The influence of several reaction parameters such as reaction time, temperature, hydrogen pressure, concentration of the catalyst and concentration of benzenewas tested. A turnover frequency of 5372 h−1 has been found in the case of ruthenium complex for the reduction of benzene at 80 ◦C with 3.64×10−6 mol catalyst, 0.34 mol benzene and at a hydrogen pressure of 50 bar. In the case of the nickel complex, a turnover frequency of 1718 h−1 has been found for the same reaction with 3.95×10−6 mol catalyst under similar experimental conditions. The nickel complex shows more selectivity for the formation of cyclohexene while the ruthenium complex is more selective for the formation of cyclohexane

Characterisation of the acid-base properties of pillared montmorillonites

Iron and mixed iron aluminium pillared montrnorillonites prepared by partial hydrolysis method were subjected to room temperature exchange with transition metals of the first series. The resulting materials were characterised by different spectroscopic techniques and surface area measurements. About 1-3% transition metals were incorporated into the porous network. The structural stability of the porous network was not affected by exchange. XRD and AI NMR spectroscopy evidenced the presence of iron substituted Al13 like polymers in FeAl pillared systems. Acidity and basicity benefited much as a result of metal exchange. Acidity and basicity were quantified by model reactions, viz., cumene cracking and cyclohexanol decomposition respectively. The presence of basic sites in otherwise acidic pillared clays, though diminutive in amount can be of much importance in acid base catalysed reactions.

Temperature- and Pressure-induced Proton Transfer in the 1:1 Adduct Formed between Squaric Acid and 4,4 '-Bipyridine

We have applied a combination of spectroscopic and diffraction methods to study the adduct formed between squaric acid and bypridine, which has been postulated to exhibit proton transfer associated with a single-crystal to single-crystal phase transition at ca. 450 K. A combination of X-ray single-crystal and very-high flux powder neutron diffraction data confirmed that a proton does transfer from the acid to the base in the high-temperature form. Powder X-ray diffraction measurements demonstrated that the transition was reversible but that a significant kinetic energy barrier must be overcome to revert to the original structure. Computational modeling is consistent with these results. Modeling also revealed that, while the proton transfer event would be strongly discouraged in the gas phase, it occurs in the solid state due to the increase in charge state of the molecular ions and their arrangement inside the lattice. The color change is attributed to a narrowing of the squaric acid to bipyridine charge-transfer energy gap. Finally, evidence for the possible existence of two further phases at high pressure is also presented.

Differential effects of temperature on fruit development and bean quality of contrasting genotypes of cacao (Theobroma cacao)

The effects of temperature and light integral on fruit growth and development of five cacao genotypes (Amelonado, AMAZ 15/15, SCA 6, SPEC 54/1 and UF 676) were studied in semi-controlled environment glasshouses in which the thermal regimes of cacao-growing regions of Brazil, Ghana and Malaysia were simulated. Fruit losses because of physiological will (cherelle will) were greater at higher temperatures and also differed significantly between genotypes, reflecting genetic differences in competition for assimilates between vegetative and reproductive components. Short-term measurements of fruit growth indicated faster growth rates at higher temperatures. In addition, a significant negative linear relationship between temperature and development time was observed. There was an effect of genotype on this relationship, such that time to fruit maturation at a given temperature was greatest for the clone UF 676 and least for AMAZ 15/15. Analysis of base temperatures, derived from these relationships indicated genetic variability in sensitivity of cacao fruit growth to temperature (base temperatures ranged from 7.5 degrees C for Amelonado and AMAZ 15/15 to 12.9 for SPEC 54/1). Final fruit size was a positive function of beam number for all genotypes and a positive function of light integral for Amelonado in the Malaysia simulated environment (where the temperature was almost constant). In simulated environments where temperature was the main variable (Brazil and Ghana) increases in temperature resulted in a significant decrease in final pod size for one genotype (Amelonado) in Brazil and for two genotypes (SPEC 54/1 and UF 676) in Ghana. It was hypothesised that pod growth duration (mediated by temperature), assimilation and beam number are all determinants of final pod size but that under specific conditions one of these factors may override the others. There was variability between genotypes in the response of beam size and beam lipid content to temperature. Negative relationships between temperature and bean size were found for Amelonado and UF 676. Lipid concentration was a curvilinear function of temperature for Amelonado and UF 676, with optimal temperatures of 23 degrees C and 24 degrees C, respectively. The variability observed here of different cacao genotypes to temperature highlights the need and opportunities for appropriate matching of planting material with local environments.

The effects of temperature and light integral on early vegetative growth and chlorophyll fluorescence of four contrasting genotypes of cacao (Theobroma cacao)

The effect of temperature on early vegetative growth, leaf chlorophyll fluorescence and chlorophyll content was examined on four genotypes of cacao (Amelonado, AMAZ 15–15, SCA 6 and SPEC 54/1). A controlled environment glasshouse was used to simulate the temperature conditions of three cacao-growing regions (Bahia, Brazil; Tafo, Ghana and Lower Perak, Malaysia) over the course of a year. Base temperatures calculated from increments in main stem growth varied from 18.6°C for AMAZ 15/15 to 20.8°C for SPEC 54/1. Temporal variation in Fv/Fm observed for two of the clones (SCA 6 and SPEC 54/1) in two of the compartments were correlated with temperature differences over time. Significant differences were also recorded between genotypes in leaf chlorophyll content. It was shown that variation over time in leaf chlorophyll content could be quantified accurately as a function of temperature and light integral. The results imply that genetic variability exists in cacao in response to temperature stress.