884 resultados para Espectroscopia. Ultravioleta. Infravermelho. Diclofenaco. Quimiometria
Resumo:
Metal Organic Frameworks (MOFs) are hybrids materials, often crystalline, consisting of metal or metal clusters, connected by polytopic organic ligands repetitively, leading to structures, usually porous. In this work, MOFs based on lanthanide ions (La3+ and Gd3+) and dicarboxylate type of ligands (isophthalic and terephthalic acids), were synthesized by hydrothermal, solvothermal and hydro(solvo)thermal methods. The effects of the synthetic route as well as the type of heating, conventional or by microwave, on the structure and properties of MOFs were studied. The powder samples obtained were characterized by X-ray diffraction, infrared spectroscopy, thermal analysis and scanning electron microscopy. The results suggest that the addition of an organic or inorganic base is needed to promote the deprotonation of the ligand, since in the samples prepared by the hydrothermal method, without the use of a base, no formation of the metalorganic framework was observed. On the other hand, the presence of DMF as solvent or cosolvent, afforded the deprotonation of the ligand with the consequent formation of MOFs. At least two different crystalline structures were identified for the samples prepared with terephthalic acid. These samples are isostructural with those reported for phases Eu(1,3-BDC)DMF, Eu2(1,4-BDC)3 (DMF)2 and Tb(1,4-BDC)H2O. The presence of water in the reaction medium in the hydro(solvo)thermal method, provoked the growth of the structure different from that observed in the absence of water. This can be explained by the difference in the coordination mode of water and DMF to lanthanide ions. Although not identified by XRD, the samples prepared with isophthalic acid, also present metalorganic structures, which was confirmed by the presence of the characteristic displacement of the carbonyl group band in their infrared spectra, compared to the spectrum of the pure ligand. This shift was also observed in the samples prepared with terephthalic acid. Thermal analisys shows that the metal organic frameworks do not collapse occurs at a temperature below 430°C.The analysis of scanning electron microscopy suggests that the morphology of powders is highly dependent on the type of heating used, conventional or by microwave.
Resumo:
Glucans are polysaccharides with different pharmacological and biological activities described. However, there are some reports about the activities of the glucan type α (alpha). In this context, a group of α-D-glucans called dextrans extracted from Leuconostoc mesenteroides bacteria, with molecular weights of 10 (D10), 40 (D40) and 147 (D147) kDa and their phosphorylated derivatives P10, P40 and P147, were evaluated as for their antioxidant, anticoagulant and immunomodulatory potential for the first time, in order to elucidate compounds with potent activities and low toxicity. Infrared spectroscopy analysis, monosaccharide composition and chemical dosages showed that these dextrans are the same polysaccharide, but with different molecular weights, besides confirming the success of phosphorylation. None presented with anticoagulant features. The reducing power test showed that D147 was twice as potent as other dextrans. On the other hand, all six samples showed similar activity (50%) when it came to scavenging the OH radical. To the superoxide ion scavenging, only D10 had a pronounced activity (50%). D40 was the single native dextran that presented with immunomodulatory features since it double stimulated the proliferation of murine macrophages (RAW 264.7) and double the release of nitric oxide by the cells, both in the absence and presence of lipopolysaccharides (LPS). In addition, D40 showed a greater scavenging activity (50%) for the hydrogen peroxide, which caused it to also be the more potent dextran when it came to inhibiting lipid peroxidation (70%). On other hand, P147 showed the highest iron and copper ion chelation activity (~85%). P10 proved be the most effective compound to macrophage proliferation. The results point toward dextrans with a 40 kDa weight as being ideal for antioxidant and immunomodulatory use, could be supplemented with phosphorylated derivatives. However, future studies with the D40 and other similarly dextrans are to confirm this hypothesis.
Resumo:
Lubricants and cutting middle distillates typically have large amounts of n-paraffins to increase its freezing point and fluidity. Accordingly, the removal of n-paraffins of long chain lubricants oils and diesel is essential to get a product with good cold flow properties. The development of new catalysts, which exhibit thermal stability and catalytic activity for the hydroisomerization reaction is still a challenge. Thus, silicoaluminophosphates (SAPO) were synthesized by different routes. Have been used also post-synthesis treatment for obtaining hybrid structures and others synthesis have been carried out with mesoporous template (soft and hard-template). Therefore, SAPO have been impregnated with H2PtCl6 solution by the incipient wetness method. Then assessments of catalytic activities in hydroisomerization and hydrocracking reactions of hexadecane have been held. Besides SAPO, niobium phosphate - NbP - were also impregnated with platinum and evaluated in the same reaction. After impregnation, these catalysts have been characterized by X-ray diffraction (XRD), nitrogen adsorption, infrared spectroscopy with adsorbed pyridine (IV-PY), scanning electron microscopy (SEM) and resonance nuclear magnetic 29Si (29Si-NMR). The characterization results by XRD have shown that it has been possible to obtain mesoporous SAPOs. However, for the syntheses with soft template there was collapse of the structure after removal of the organic template. Even so, these catalysts have been actives. It was possible to obtain hybrid materials through the synthesis of SAPO-11 made with hard templates and by means of post-synthesis treatments samples of SAPO-11. Moreover, NbP has shown characteristic XRD of amorphous materials, with high acidity and were active in the conversion of hexadecane.
Resumo:
Lubricants and cutting middle distillates typically have large amounts of n-paraffins to increase its freezing point and fluidity. Accordingly, the removal of n-paraffins of long chain lubricants oils and diesel is essential to get a product with good cold flow properties. The development of new catalysts, which exhibit thermal stability and catalytic activity for the hydroisomerization reaction is still a challenge. Thus, silicoaluminophosphates (SAPO) were synthesized by different routes. Have been used also post-synthesis treatment for obtaining hybrid structures and others synthesis have been carried out with mesoporous template (soft and hard-template). Therefore, SAPO have been impregnated with H2PtCl6 solution by the incipient wetness method. Then assessments of catalytic activities in hydroisomerization and hydrocracking reactions of hexadecane have been held. Besides SAPO, niobium phosphate - NbP - were also impregnated with platinum and evaluated in the same reaction. After impregnation, these catalysts have been characterized by X-ray diffraction (XRD), nitrogen adsorption, infrared spectroscopy with adsorbed pyridine (IV-PY), scanning electron microscopy (SEM) and resonance nuclear magnetic 29Si (29Si-NMR). The characterization results by XRD have shown that it has been possible to obtain mesoporous SAPOs. However, for the syntheses with soft template there was collapse of the structure after removal of the organic template. Even so, these catalysts have been actives. It was possible to obtain hybrid materials through the synthesis of SAPO-11 made with hard templates and by means of post-synthesis treatments samples of SAPO-11. Moreover, NbP has shown characteristic XRD of amorphous materials, with high acidity and were active in the conversion of hexadecane.
Resumo:
MELO, D. M. A. et al. Synthesis and charactezarion of lanthanum and yttrium doped Fe2O3 pigments. Cerâmica, São Paulo, v. 53, p. 79-82, 2007.
Resumo:
The red deer (Cervus elaphus) is currently one of the most widespread and abundant wild ungulates in the Iberian Peninsula and is extremely important both ecologically, as a key species for the functioning of the ecosystems, and economically, as a major game species. In Iberia, red deer populations are subjected to different management systems that may affect the physical condition of the individuals, with further consequences for population dynamics. Studies investigating the effects of management practices and environmental conditions on the performance of red deer are still rare regarding Mediterranean ecosystems. Much of the knowledge concerning the ecology of red deer and the impact of management on its physical condition is based on studies conducted in northern and central regions of Europe, where climatological features and management practices differ from those observed in the Mediterranean areas of Iberia. Studies on a biogeographical scale can provide important insights into the relationships between species and a particular environment and contribute to the development of more targeted and appropriate management practices. The optimisation of sampling procedures and the fine-tuning of pre-existing analytical techniques are also fundamental to a more cost-effective monitoring and, therefore, are of enormous value to wildlife managers. In this context, the main aims of this thesis were: 1) to optimise the procedures used to assess the physical condition of red deer; and 2) to identify relevant management and environmental factors affecting the nutritional condition and stress physiology of red deer in the Mediterranean ecosystems of Iberia, as well as any potential interactions between those factors. Two studies with a methodological focus, presented in the first part of the thesis, demonstrated that the physical condition of red deer can be evaluated more simply, using more cost- and time-effective procedures than those traditionally used: i) it was shown that only one kidney and its associated fat is enough to assess nutritional condition in red deer; and ii) the feasibility of using near infrared spectroscopy to predict the concentrations of stress hormone metabolites was demonstrated using faeces of red deer for the first time. Subsequently, two large-scale observational studies, conducted in representative red deer populations found in Mediterranean Iberia, highlighted the importance of considering seasonal environmental variations and variables related to hunting management practices to better understand the nutritional and physiological ecology of red deer. High population densities had adverse effects on the nutritional condition of the deer and were associated with increased stress levels in natural populations without supplementary feeding. Massive hunting events involving the use of hounds were also identified as a potential source of chronic stress in red deer. The research presented in this thesis has clear implications regarding the management and monitoring of red deer populations in Mediterranean environments and is intended to help wildlife managers to implement more effective monitoring programmes and sustainable management practices.
Resumo:
MELO, D. M. A. et al. Synthesis and charactezarion of lanthanum and yttrium doped Fe2O3 pigments. Cerâmica, São Paulo, v. 53, p. 79-82, 2007.
Resumo:
The sponges are simple multicellularorganisms; they inhabit in marine environments from the polar seas to the tropical waterswhere they are more abundant. These species are exposed to large populations of microbes, reason that explains their complex morphological and cellular defense mechanism, which are used by these organisms to fight against pathogens. The purpose of this study was to evaluate the antibacterial activity of the marine sponge Ircinia campana, whichinhabits in the south of the Caribbean coast of Costa Rica against Sthapylococcus aureus gram-positive bacteria. Sampleswere collected in Punta Uva in Limónduring July of 2007. The active compounds were obtainedby extraction with acetone (crude extract); and subsequently, chromatographic extracts were obtained using fractions 1:4 hexane: ethyl acetate. The antibacterial activities of the different fractions, including the crude extract were tested.Our results suggest a zone of inhibition of 14.60 ±0.25 mm for the crude extract and18.70±0.25mm for the most active fraction separated by chromatography. The metabolite responsible for the antibacterial activity was isolated by High Performance Liquid Chromatography (HPLC)and preliminarily characterized through ultraviolet (UV) and infrared (IR) spectroscopy.
Resumo:
The increased longevity of humans and the demand for a better quality of life have led to a continuous search for new implant materials. Scientific development coupled with a growing multidisciplinarity between materials science and life sciences has given rise to new approaches such as regenerative medicine and tissue engineering. The search for a material with mechanical properties close to those of human bone produced a new family of hybrid materials that take advantage of the synergy between inorganic silica (SiO4) domains, based on sol-gel bioactive glass compositions, and organic polydimethylsiloxane, PDMS ((CH3)2.SiO2)n, domains. Several studies have shown that hybrid materials based on the system PDMS-SiO2 constitute a promising group of biomaterials with several potential applications from bone tissue regeneration to brain tissue recovery, passing by bioactive coatings and drug delivery systems. The objective of the present work was to prepare hybrid materials for biomedical applications based on the PDMS-SiO2 system and to achieve a better understanding of the relationship among the sol-gel processing conditions, the chemical structures, the microstructure and the macroscopic properties. For that, different characterization techniques were used: Fourier transform infrared spectrometry, liquid and solid state nuclear magnetic resonance techniques, X-ray diffraction, small-angle X-ray scattering, smallangle neutron scattering, surface area analysis by Brunauer–Emmett–Teller method, scanning electron microscopy and transmission electron microscopy. Surface roughness and wettability were analyzed by 3D optical profilometry and by contact angle measurements respectively. Bioactivity was evaluated in vitro by immersion of the materials in Kokubos’s simulated body fluid and posterior surface analysis by different techniques as well as supernatant liquid analysis by inductively coupled plasma spectroscopy. Biocompatibility was assessed using MG63 osteoblastic cells. PDMS-SiO2-CaO materials were first prepared using nitrate as a calcium source. To avoid the presence of nitrate residues in the final product due to its potential toxicity, a heat-treatment step (above 400 °C) is required. In order to enhance the thermal stability of the materials subjected to high temperatures titanium was added to the hybrid system, and a material containing calcium, with no traces of nitrate and the preservation of a significant amount of methyl groups was successfully obtained. The difficulty in eliminating all nitrates from bulk PDMS-SiO2-CaO samples obtained by sol-gel synthesis and subsequent heat-treatment created a new goal which was the search for alternative sources of calcium. New calcium sources were evaluated in order to substitute the nitrate and calcium acetate was chosen due to its good solubility in water. Preparation solgel protocols were tested and homogeneous monolithic samples were obtained. Besides their ability to improve the bioactivity, titanium and zirconium influence the structural and microstructural features of the SiO2-TiO2 and SiO2-ZrO2 binary systems, and also of the PDMS-TiO2 and PDMS-ZrO2 systems. Detailed studies with different sol-gel conditions allowed the understanding of the roles of titanium and zirconium as additives in the PDMS-SiO2 system. It was concluded that titanium and zirconium influence the kinetics of the sol-gel process due to their different alkoxide reactivity leading to hybrid xerogels with dissimilar characteristics and morphologies. Titanium isopropoxide, less reactive than zirconium propoxide, was chosen as source of titanium, used as an additive to the system PDMS-SiO2-CaO. Two different sol-gel preparation routes were followed, using the same base composition and calcium acetate as calcium source. Different microstructures with high hydrophobicit were obtained and both proved to be biocompatible after tested with MG63 osteoblastic cells. Finally, the role of strontium (typically known in bioglasses to promote bone formation and reduce bone resorption) was studied in the PDMS-SiO2-CaOTiO2 hybrid system. A biocompatible material, tested with MG63 osteoblastic cells, was obtained with the ability to release strontium within the values reported as suitable for bone tissue regeneration.
Resumo:
O trabalho apresentado nesta tese focou-se no estudo do amido, nomeadamente na avaliação das características físico-químicas, morfológicas, térmicas e reológicas do amido de seis variedades de milho crioulo, preservadas no estado de Santa Catarina (Brasil), com o intuito de contribuir para a valorização e preservação de variedades locais que são cultivadas em sistemas de produção orgânica, também conhecidas como variedades crioulas. Estas sementes são importantes quer para a preservação da biodiversidade quer para os pequenos produtores que as conservam e as produzem fazendo uso de uma agricultura sustentável e independente comercialmente. Para além da caracterização dos amidos crioulos foram também analisadas as alterações que ocorrem nos processos de gelatinização e retrogradação do amido quando realizados na presença de outros biopolímeros, nomeadamente a quitosana e galactomananas. No Capítulo I é apresentada uma breve revisão do conhecimento científico sobre o amido e sobre a quitosana e galactomananas, os outros biopolímeros utilizados. Igualmente é feita uma sucinta abordagem sobre as principais técnicas analíticas que foram utilizadas: reologia fundamental, calorimetria diferencial de varrimento, microscopia eletrónica de varrimento e espectroscopia de infravermelho médio. No capítulo II apresenta-se o isolamento dos amidos das seis variedades de milho crioulo e a sua caracterização junto com um amido comercial usado como modelo de comparação. Os amidos apresentaram genericamente características físicoquímicas semelhantes e o amido extraído das variedades crioulas MT e MPA 01 apresentaram menor temperatura de gelatinização e maior percentagem de retrogradação, respetivamente. Os efeitos da adição da quitosana e de três galactomananas (goma guar, goma de alfarroba e goma cassia) em sistemas mistos com o amido são analisados nos Capítulos III e IV respetivamente. A adição dos biopolímeros aos amidos resultou no aumento das temperaturas de gelatinização, na alteração da retrogradação do amido pelas galactomananas e na alteração das propriedades viscoeláticas dos géis formados. Os dados de infravermelho esclareceram que nos sistemas com quitosana, o amido formou complexos com o ácido acético usado para dissolver a quitosana e que esta por sua vez formou acetato de quitosana. O comportamento durante a gelatinização do amido comercial quando comparado com o amido do milho crioulo MPA na sua interação com as galactomananas é diferenciado.
Resumo:
The chemical changes in clay minerals has been widely studied in order to improve its properties for use in various applications. However kaolinite has strong hydrogen bonds between their adjacent layers hindering the process changes in its structure. With the objective to facilitate the process of intercalation monobasic potassium phosphate, bibasic potassium phosphate and potassium acetate we was performed on kaolinite heat treatment at 600 °C and activated acidic with phosphoric acid and 5 to 10 mol L-1. The samples they were characterized by energy dispersive spectroscopy (EDS), X-Ray Diffraction (XRD), Infrared Spectroscopy Fourier Transform (FTIR) and Thermogravimetric Analysis (TG) and Differential Thermal Analysis (DTG) and the superficial and textural changes the samples with heat treatment and acid activation they were characterized by scanning electron microscopy (SEM) and Textural Analysis of Adsorption/desorption N2. With the help of the techniques found that, the heat treatment becomes more susceptible to acid activation kaolinite making the samples with two treatments show larger amounts of phosphorus. It was also found that bibasic potassium phosphate binds more strongly the structure of kaolinite by having a structure with two-coordinating oxygens and intercalation with potassium acetate in acid-activated kaolin increases the interlayer distance of the kaolinite and the intercalation occurs with higher response index (RI) for samples with acid activation to 5 mol /L.
Resumo:
Lasiodiplodan is an exocellular β-glucan with biological functionalities such as antioxidant, antiproliferative, hypocholesterolemic, protective activity against DNA damage induced by doxorubicin and hypoglycemic activity. Chemical derivatization of polysaccharide macromolecules has been considered as a potentiating mechanism for bioactivity. In this context, this work proposes the derivatization of lasiodiplodan by acetylation. Acetic anhydride was used as derivatizing agent and pyridine as catalyst and reaction medium. The derivatives obtained were evaluated by its water solubility, degree of substitution (DS), antioxidant potential, and characterized by infrared spectroscopy (FT-IR), thermal analysis, differential scanning calorimetry, X-ray diffraction and scanning electron microscopy. Acetylated derivatives with different degrees of substitution (1.26; 1.03; 0.66 and 0.48) were obtained, and there was correlation between the concentration of derivatizing agent and DS. FT-IR spectroscopy analysis confirmed the insertion of acetyl groups into derivatized macromolecules (LAS-AC) through of specific bands concerning to carbonyl group (C = O) and increase in C-O vibration. SEM analysis indicated that native lasiodiplodan presents morphological structure in the form of thin films with translucent appearance and folds along its length. Derivatization led to morphological changes in the polymer, including aspects thickness, translucency and agglomeration. Thermal analysis indicated the native sample and derivative with DS 0.48 presented three weight loss stages. The first stage occurred until 125 ° C (loss of water) and there were two consecutive events of weight loss (200 ° C - 400 ° C) attributed to molecule degradation. Samples with DS 1.26; 1.03 and 0.66 demonstrated four weight loss stages. The first stage occurred until 130 ° C (loss of water), following by two consecutive events of weight loss (200 ° C - 392 ° C) attributed to degradation of the biopolymer. The fourth stage was between 381 ° C and 532 ° C (final decomposition) with exothermic peaks between 472 ° C and 491 ° C. X-ray diffraction patterns showed that native and acetylated lasiodiplodan have amorphous structure with semicrystalline regions. Derivatization did not contribute to increased solubility of the macromolecule, but potentiated its antioxidant capacity. Acetylation of lasiodiplodan allowed to obtaining a new macromolecule with higher antioxidant potential than the native molecule and with technological properties applicable in various industrial sectors.
Resumo:
Amidas graxas são compostos orgânicos nitrogenados derivados de ácidos carboxílicos, as quais contém em sua estrutura uma longa cadeia carbônica (C16- C24), possuindo ou não insaturações. Estes compostos podem ser encontrados em vegetais terrestres ou aquáticos, microorganismos e animais. Já em meados do século passado, a identificação de duas amidas graxas: a N-araquidonoiletanolamina (AEA, 5) e a cis-oleamida (cOA, 6), membros mais conhecidos e estudados desta família, devido as suas propriedades como indutora do sono fisiológico e canabinomimética respectivamente; levantou o interesse para a investigação das propriedades, identificação, síntese e isolamento de novas amidas graxas. Atualmente as pesquisas acerca das amidas graxas se devem as suas atividades biológicas tais como: aumento da libido sexual, analgesia, inseticida ou agente redutor da fome. Neste contexto, objetivo desse trabalho foi desenvolver metodologias para a síntese de novas amidas graxas. As amidas foram produzidas a partir de ácidos graxos, via cloreto de ácido ou via ésteres metílicos graxos, em rendimentos compreendidos entre 44% e 88%. Todos os compostos sintetizados foram caracterizados por espectroscopia de Infravermelho e RMN de 1H e 13C. Ensaios citotóxicos em células eritroleucêmicas K562 para a série das pirrolidil amidas demonstraram atividade citotóxica e capacidade de inibir proliferação celular em menos de 72 horas na concentração máxima de 1000µg/mL.
Resumo:
Since the first description of sulfated polysaccharides from seaweeds, the biological activities of these compounds have been evaluated under different aspects and experimental procedures. Among the broad biological activities presented by seaweed polysaccharides, anticoagulant action appears as a promising function. In this present study we have obtained sulfated polysaccharides from the green seaweed Codium isthmocladium by proteolytic digestion, followed by separation into five fractions (0.3, 0.5, 0.7, 0.9 and 1.2) by sequential acetone precipitation. The chemical analyses have demonstrated that all fractions are composed mainly by sulfated polysaccharides. The anticoagulant activity of these fractions was determined by activated partial thromboplastin time (aPTT) and prothrombin time test (PT) using citrate normal human plasma. None fraction has shown anticoagulant activity by PT test. Furthermore, all of them have shown anticoagulant activity by aPTT test. These results indicated that the molecular targets of these sulfated polysaccharides are mainly in the intrinsic via of the coagulation cascade. Agarose gel electrophoresis in 1,3-diaminopropane acetate buffer, pH 9.0, stained with 0.1% toluidine blue showed the presence of two or three bands in several fractions while the fraction 0.9 showed a single spot. By anion exchange chromatography, the acid polysaccharides from the 0.9 acetone fraction were separated into two new fractions eluted respectively with 2.0 and 3.0 M NaCl. These compounds showed a molecular weight of 6.4 and 7.4 kDa respectively. Chemical analyses and infrared spectroscopy showed that Gal 1 and Gal 2 are sulfated homogalactans and differ one from the other in degree and localization of sulfate groups. aPPT test demonstrated that fractions 2,0 and 3,0M (Gal1 and Gal 2, respectively) have anticoagulant activity. This is the first time that anticoagulant sulfated homogalatans have been isolated from green algae. To prolong the coagulation time to double the baseline value in the aPTT, the required amount of sulfated galactan 1 (6,3mg) was similar to low molecular heparin Clexane®, whereas only 0,7mg of sulfated galactan 2 was needed to obtain the same effect. Sulfated galactan 2 in high doses (250mg) induces platelet aggregation. These results suggest that these galactans from C. isthmocladum have a potential application as an anticoagulant drug
Resumo:
Sulfated polysaccharides (PS) are biomolecules with a great biotechnological potential. There are few data about PS from high plants. In addition, pharmacological activities of PS from plants have not been carrying out. The aim of this work was extract PS from the angiosperm Halodule wrightii and study their anticoagulant and antioxidant activities. Histological analysis showed the presence of the PS manly in the roots. A polysaccharide-rich extract was obtained from H. wrightii by proteolysis followed by methanol and TCA precipitation. Chemical, infra-red analysis and agarose gel electrophoresis in 1.3 diaminopropane acetate buffer confirmed the presence of sulfated polysaccharides made by glucose, galactose, xylose and sulfate residues in the proportion 1: 0,9: 1: 1. In addition polyacrilamide electrophoresis have shown that extract is mainly compose by 11kDa sulfated polysaccharides. Pharmacological analysis have shown total antioxidant capacity (CAT) that resulted in 15,21 μg for equivalent of ascorbic acid, scavenging activity of the DPPH radical with 41,36 % of scavenging, activity of reducing power with the maximum of 0,290 nm (50 % of vitamin C activity) and scavenging activity superoxide radical (O2-) with a maximum of 32,23 %. Chelating activity of metal less than 4% and scavenging activity of the radical hydroxyl (OH-) less than 2%. Time of activated partial tromboplastin (aPTT) doubling the time of coagulation from 20μg of and protrombin time (PT) was not present. The data indicate that PS from Halodule wrightii could be considered for future applications in medicine, food production or cosmetic industry