Teses em Química (Doutorado) - PPGQ/ICEN
URI Permanente para esta coleçãohttp://10.7.2.76:4000/handle/2011/4047
O Doutorado Acadêmico pertence ao Programa de Pós-Graduação em Química (PPGQ) do Instituto de Ciências Exatas e Naturais (ICEN) da Universidade Federal do Pará (UFPA).
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Item Acesso aberto (Open Access) Estudo computacional de arilpiperidina e arilpiperazina como inibidores de tirosinase: aplicações cosméticas e terapêuticas(Universidade Federal do Pará, 2025-04-08) BENTES, Beatriz Alves; SILVA, José Rogério de Araújo; SILVA, Jerônimo Lameira; http://lattes.cnpq.br/7711489635465954Tyrosinases (TYR) catalyze the oxidation of phenols and catechols, playing a crucial role in melanogenesis, which regulates melanin production and provides protection against UV radiation. However, pigmentation-related disorders drive the search for effective TYR inhibitors. Compounds such as hydroquinone, arbutin, and kojic acid have limitations, highlighting the need for new inhibitors. In this study, arylpiperidine- and arylpiperazine-based compounds demonstrated potent inhibitory activity against TYR. Computational analysis included molecular docking, molecular dynamics (MD) simulations, and binding free energy calculations using the Linear Interaction Energy (LIE) method, revealing a strong correlation with experimental affinity data. To enhance the understanding of structure-activity relationships (SAR), Free Energy Perturbation (FEP) transformations were performed for selected ligand pairs. Additionally, Density Functional Theory (DFT) calculations were applied to inhibitors L04 and L19, enabling the determination of electronic descriptors and frontier molecular orbitals. The inhibitors interact with TYR mainly through electrostatic interactions with the copper ion and van der Waals forces with critical residues such as Phe197, Pro201, Val218, Asn205, and Arg209. These findings are promising for both cosmetic and therapeutic applications, enabling the development of skin-lightening agents to treat melasma and sunspots, as well as potential treatments for hyperpigmentation-related diseases and melanomas. The development of more selective inhibitors with lower toxicity may expand the clinical and cosmetic use of these compounds, offering safer and more effective alternatives for melanin production modulation.Item Acesso aberto (Open Access) Obtenção e caracterização da raiz pulverizada da espécie entada polyphylla benth visando aplicação tecnológica em produto sapônico bioecológico(Universidade Federal do Pará, 2024-12-09) JESUS, Mário Lucivaldo Barreto de; BRASIL, Davi do Socorro Barros; http://lattes.cnpq.br/0931007460545219; HTTPS://ORCID.ORG/0000-0002-1461-7306; ALVES, Cláudio Nahum; http://lattes.cnpq.br/8315600067791313; https://orcid.org/0000-0001-6576-4229This study focuses on the physicochemical characterization of the pulverized roots of Entada polyphylla Benth, commonly known as gipioca, aiming at its application in the development of a bioecological soap product, the “vegetable soap.” This Amazonian species is rich in saponins, compounds with bioactive properties including antioxidant, surfactant, and emulsifying actions, as well as cytotoxic potential. Samples were collected from three locations in the municipality of Acará, Pará, identified at the Embrapa herbarium (NID 51/2023), and subjected to physicochemical and biological analyses. Results revealed 75.92% antioxidant compounds, 17.26% total saponins, 20.32% moisture, and 12.28% tannins, highlighting the plant's potential as a source of amphiphilic and bioactive compounds. Saponin extraction was performed via sustainable water maceration, avoiding the use of harmful chemical solvents. Laboratory tests demonstrated that the pulverized material generates significant foam upon contact with water, confirming its surfactant properties and suitability for cleaning applications. The developed product was patented (BR 102024016942 5) and presented at scientific events, such as the SBPC, where it was recognized for its innovation and alignment with circular economy principles. The study also assessed the biological activity of saponins through cytotoxicity assays on tumor cell lines (AGP01, A-549, SK-MEL 19) and a non-neoplastic cell line (MRC5). Results indicated selective cytotoxicity against tumor cells, emphasizing the therapeutic potential of the extract. In addition to promoting sustainable technological solutions, the study contributes to the valorization of regional biodiversity and offers socioeconomic benefits to riverside communities, including job creation and income generation through sustainable resource management. This research expands the understanding of Amazonian legumes’ chemistry, particularly the bioactive properties of saponins, and underscores their potential as substitutes for synthetic surfactants in industries such as cosmetics, therapeutic products, and cleaning agents. It is concluded that Entada polyphylla is a promising source of natural bioactives, with technological applications that integrate innovation, socioeconomic development, and environmental preservation.Item Acesso aberto (Open Access) Estudo químico e atividade antibacteriana do fungo endofítico Scedosporium apiospermum de Bauhinia guianensis e de fungos da Serra de Carajás(Universidade Federal do Pará, 2016-06-22) CORDEIRO, Jorgeffson da Silva; MARINHO, Patricia Santana Barbosa; http://lattes.cnpq.br/4826647905254039; MARINHO, Andrey Moacir do Rosario; http://lattes.cnpq.br/2511998363000599Endophytic fungi are microorganisms that lives in association with the host species, and they're a promising source of important natural products. With a equal importance, the soil fungi also are capable of producing so many substances of economic value. Thus, the following work was objective to obtain bioactive composts produced by endophytic fungi M. acutistipula var. ferrea and soil Carajás Saw, besides the endophytic S. apiospermium from liana of Bauhinia guianensis Auble. The species M. acutistipula var. ferrea, were isolated 56 endophytic and 64 soil fungi. They were randomly, selected, 12 fungi to be reactivated in Petri dishes containing PDA medium. After reactivating the micro-extracts of 12 fungi were obtained as the adapted methodology Smedsgaar. The micro-extracts were evaluated by HPLC-DAD to determine the chromatographic profile and, also, submitted antimicrobial testing. The FSF 12 (trichoderma sp.), selected after the screening of chemical and biological profile was grown on a large scale in a solid medium (rice) and led to the isolation of five substances: fatty acid polyunsaturated (E1), 5'-inosil (E2), tyrosol (E3), harzialactone A (E4) and 2-anhydro mevalonic (E5). In relation to the fungus EJCP13 (S. apiospermium) where compounds isolated, triacyl (J1), ergosterol peroxide (J2), ergosterol (JA19), cerivisterol (JA29), methylester (JA24), dulcitol (D), and brefeldin A (JA). The compound Brefeldin A showed significant antimicrobial activity and, also, proved to be the major secondary metabolite in extracts from S. apiospermium. Thus, it decides to quantify a substance in the extract, which corroborate results, which indicate the presence of brefeldin A only in AcOEt and the hexane extracts. The isolation of the substances was performed by chromatographic techniques, such as CCVU and, monitoring, by ADCC. The chemical structures were elucidated with the aid of spectroscopic (1H and 13C NMR, HMQC, HMBC), and spectrometric (ESI-MS).Item Acesso aberto (Open Access) Estudo químico e atividade biológica de Nephrolepis brownii e da biomassa produzida pelo fungo endofítico NB-1 associado à espécie(Universidade Federal do Pará, 2016-09-23) CAVALCANTE, Francisco Otávio da Rocha; GUILHON, Giselle Maria Skelding Pinheiro; http://lattes.cnpq.br/6603694331802001; SANTOS, Lourivaldo da Silva; http://lattes.cnpq.br/3232898465948962The species Nephrolepis brownii, commonly known as fern, can be easily found in the Amazon region. It is a creeping species, which spreads easily and inhibits small around plants. N. brownii like other ferns are also known as "sky ladder", which are widely used as ornamental plants and medicinal purposes. This is the first work which is carried out the chemical study of N. brownii, where the Fernene substances were isolated (S1) and Pinitol (S2) from the aerial parts of it. In the study of the essential oil of N. brownii were identified 80 substances, most belonging to the aldehyde functions (26.62%), alcohol (25.11%) and ketone (17.15%), among those Z-2-(3,3-dimetilciclohexlidene)-ethanol (8.65%), safrole (8.81%) undecan-2-one (8.89%), teaspirano (8.99%), n-tridecane (9.05 %), n-undecanal (9.20%), o-methyl-orcinol (9.32%) and deca-(2E,4E)-dienal (9.41%) were majority. Aerial parts of N. brownii was isolated as endophytic fungus called NB-1, which was grown on solid medium (rice) and liquid medium (Czapek) for the growth of fungal colonies and obtain extracts. From the ethyl acetate extract fungal (rice) were isolated p-Hydroxybenzaldehyde substances (S3), p-hydroxyphenylacetic acid (S4) and 4-hydroxybenzoic acid (S5). From the culture in liquid medium (cazpek) were isolated substances ergosterol peroxide (S6) stoloniferol B (S7) both phases ethyl acetate (1 and 2). The NB-1 fungus has been shown to biotransform substances such as chalcone 3-(2,3,4-trimethoxyphenyl)-1-(4-methoxy)-2-propen-1-one and aromatic ketone 4-nitroacetophenone. Tests were conducted to evaluate the phytotoxicity of extracts and compounds in the face of evil seeds and kills pasture where the best results were for EBM/Hex, EBM/EtOAc and EBM/n-But extracts, highlighting the EBM / AcOEt had 100% inhibition against the germination of seeds of malice. The EFMeOH extract showed significant inhibitory effect on the germination of seeds of malice and kill pasture, with high values, 75% and 100%, respectively. The substances tested showed no satisfactory results in the face of evil seeds and kills pasture. It investigated the biological potential of the substances S1, S2, S3 and S5, which have not been active for L. amazonensis promastigote form a species.Item Acesso aberto (Open Access) Estudo de eletrocatalisadores de PtRu, PtRuRh e PtRuPd obtidos por modificação no Método Borohidreto de Sódio para eletro-oxidação de metanol e etanol(Universidade Federal do Pará, 2016-01-25) ANDRADE, Flávio Vargas; SOUZA, José Pio Iúdice de; http://lattes.cnpq.br/1448978342555218PtRu, PtRuRh and PtRuPd electrocatalysts supported on carbon has been widely studied for electro-oxidation of methanol and ethanol. Among different possibilities of preparing these electrocatalysts is the method of reducing with sodium borohydride. For the catalytic activity is optimized, it is necessary that the electrocatalyst is distributed evenly. One possibility is the use of complex precursor salts, including those with amine linker. In this work, we tried to assess the effect of adding an ammonium hydroxide solution (NH4OH) the solution of precursors. The electrocatalysts were characterized physically by Transmission Electron Microscopy (TEM), Energy Dispersive X-ray (EDX) and X-ray diffraction (XRD). For the electrochemical characterization, the techniques of chronoamperometry and cyclic voltammetry were used. The results of EDX showed that the compositions of the electrocatalysts were very close to the nominal composition. The crystallite size and the lattice parameter obtained by XRD showed changes with the change of the method. The TEM results show a homogeneous distribution more particle on electrocatalysts preparations with the addition of NH4OH solution 4 mol L-1 although this is not be determinant in electrocatalytic activity. Nos electrochemical testicles, as chains were for standard electro-oxidation of CO and load monolayer for the mass activity and compared this way. The cyclic voltammetry and chronoamperometry results showed different activities paragraph an electro-oxidation of methanol and ethanol. The results of DEMS electrocatalysts trimetallic of PtRuRh and PtRuPd showed different amounts of products and volatile. This way possible and establish an activity order these electrocatalysts.Item Acesso aberto (Open Access) Estudo de suportes alternativos de carbono ativado de biomassa para aplicação em células a combustível de álcool direto - DAFC’s(Universidade Federal do Pará, 2016-08-05) SILVA, Marconiel Neto da; SOUZA, José Pio Iúdice de; http://lattes.cnpq.br/1448978342555218This work deals with the synthesis, characterization and catalytic activity of electrocatalysts Pt and PtSn supported on activated carbon biomass with high surface area, obtained by carbonization and chemical activation of carbonaceous material at different temperatures and concentration of the activator chemical. The series under study are BSC (obtained from the shell of Brazil nut, Bertholletia excelsa) and BO (obtained from bur fiber Brazil nut). The electrocatalysts were synthesized by ethylene glycol via reduction method. The physical characterization was performed using the techniques of X-ray Diffraction (XRD), Energy Dispersive Spectroscopy X-ray (EDS), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). The electrochemical behavior of the catalysts for the reactions of electro-oxidation of alcohols was evaluated by cyclic voltammetry and chronoamperometry by using the technique of ultrathin layer electrode. To compare the catalytic activity of electrocatalysts used to normalize currents through the mass of metal contained in each electrode. The activated carbon biomass showed good electrical capacity 52 to 550 g F-1 and high specific area 1030 to 3154 m2 g-1 which gave good dispersion of nanoparticles on the material support. The chronoamperometry measures in acid ethanol solution, show higher catalytic activity for Pt73Sn27/BSC800K5R; Pt72Sn28/BO600K3 and Pt57Sn43/BSC600K1F. Already in acidic methanol solution electrocatalysts Pt86Sn14/BSC800K5; Pt72Sn28/BO800K5 and Pt57Sn43/BSC600K1F showed the best catalytic responses.Item Acesso aberto (Open Access) Perfil cromatográfico e potencial químico e biológico de fungos de solo e fungos endofíticos isolados de Bauhinia guianensis e Mimosa acutistipula var. Ferrea(Universidade Federal do Pará, 2016-03-04) PINHEIRO, Eduardo Antonio Abreu; MARINHO, Andrey Moacir do Rosario; http://lattes.cnpq.br/2511998363000599; MARINHO, Patrícia Santana Barbosa; http://lattes.cnpq.br/4826647905254039The study of natural sources and that exhibit little explored specific ecological interactions their habitat has been emphasized as a strategy for the discovery of new substances with biological activities. In this context, this study aims to carry out the chemical and bioactive study of endophytic fungi and the Amazon soil fungi, to contribute in the search for bioactive compounds. In this study, 15 fungal species were reactivated in Petri dishes containing PDA medium. After reactivation, microfungal extracts 15 were obtained according to a methodology adapted Smedsgaar. The micro extracts were evaluated by UPLC / MS to determine the chromatographic profile and was made to evaluate the clusters separation main components, and are also subjected to antimicrobial assays and test preliminary cytotoxicity on Artemia salina for the assessment of biological potential. chemical studies were conducted with Aspergillus sp. EJC08, Exserohilum rostratum 1:11 Er and Aspergillus sp. FRIZ12. The three fungal species were grown on solid medium (rice) in sufficient quantity for the isolation of secondary metabolites. The compounds were isolated by chromatographic methods and identified by spectroscopic methods. Twelve compounds were obtained, three steroids in common fungal species (ergosterol, ergosterol peroxide and cerivisterol), mixture of two steroids commonly found in plants (β-sitosterol and estigmaterol), five substances polyketide source (2-benzyl- 4H- pyran-4-one, flavasperona, annularinas I and J monocerina), a carbohydrate (5- hydroxymethylfurfural) and a nucleoside (uridine). Of the isolated compounds, there are the annularinas I and J, novel natural products, and 2-benzyl-4H-pyran-4-one, second occurrence as a natural product. The polyketides and uridine showed good antimicrobial activity and moderate cytotoxic activities in general.Item Acesso aberto (Open Access) Produção de biodiesel metílico e etílico de oleaginosas Amazônicas: caracterização físico-química e estudos térmico e cinético(Universidade Federal do Pará, 2016-01-29) LIMA, Rogério Pereira; ROCHA FILHO, Geraldo Narciso da; http://lattes.cnpq.br/7580236895339455This study aimed to synthesize methyl and ethyl biodiesel from six amazonian species of vegetable oils and fat through the transesterification reaction process using alkaline homogeneous catalysis, determine the heat capacity values of oils and methyl and ethyl biodiesel by differential scanning calorimetry (DSC) in the temperature range of 55 to 195°C, and correlate with information estimated by the group contribution method, to investigate the thermal stability of oils and biodiesel produced by thermogravimetric analysis (TG/DTG) and perform kinetic study of the decomposition thermal of biodiesels using the Ozawa method. Classic physicochemical analysis for the characterization the vegetable oils and the biodiesel synthesized samples were used. The results for the physicochemical properties of methyl biodiesel samples were consistent with the values specified by the Resolution No. 45 of 2014 of the National Agency of Petroleum, Natural Gas and Biofuels (RANP 45/14). The results of heat capacity determined by DSC showed that the methyl biodiesel pracaxi showed the highest values, while for ethyl, it was observed for the biodiesel buriti, andiroba and pracaxi. Most heat capacity data obtained for the methyl and ethyl biodiesel determined by DSC and by the group contribution method were satisfactory, as they showed smaller relative deviations or equal to 15% and showed good correlation coefficients ranged from 0, 8617 to 0.9947. The studies on the thermal stability by thermogravimetric analysis indicated that the oils and fat were stable in the temperature range of 110 to 220°C, in inert atmosphere and, in an oxidizing atmosphere, were thermally stable to 130 at 165°C. All the synthesized biodiesel samples is degraded at temperatures up to 150°C, which is highly volatile, a very important feature for the application in diesel engines. The kinetic study of the thermal decomposition of the methyl and ethyl biodiesel met activation energy values ranging from the 46.23 124.93 kJ.mol-1 and showed that the ethyl biodiesel were more stable than the methyl biodiesel.Item Acesso aberto (Open Access) Técnicas voltamétricas com eletrodo de filme de bismuto modificado com edta e ebt para determinação de Ca2+ e Mg2+ em biodiesel(Universidade Federal do Pará, 2016-08-19) MULLER, Renata Medeiros Lobo; MARQUES, Aldalea Lopes Brandes; http://lattes.cnpq.br/0121030502015990; MÜLLER, Regina Celi Sarkis; http://lattes.cnpq.br/654941494386147This study presents the development of alternative electrochemical methods for the determination of Mg2+ and Ca2+ through voltammetry technique of adsorptive stripping voltammetry (VAdR) with anodic scan. Bismuth film electrode modified with eriochrome black-T (EBT) was used for modification of the electrode in the determination of Mg2+ in the pulse differential mode (DPAdSV), while EDTA has been used for determination of Ca2+ in wave mode square (SWAdSV). The determination of Mg2+ was performed using acetate buffer (0.1 mol L-1) at pH = 4.5, EBT as supporting electrolyte and 1.0 x 10-3 mol L-1 as a binder. Successive additions of aliquots of the stock solution were made Mg2+ 1.0 x 10-3 mol L-1 so that the ion was pre-concentrated on the sensor surface under the following conditions optimized voltammetric: deposition potential (EDEP) = - 1.0 V; Pre time - concentration (Tpre) = 120 s; scan speed (v) = 0.050 V s-1; pulse amplitude (Amp) = 0.1 V. The complex formed Mg2+ EBT showed a peak current of about - 0.6 V. The determination of Ca2+ was made using ammonium buffer (0.01 mol L-1) at pH 9.4, as supporting electrolyte and EDTA 1.0 x 10-2 mol L-1 as a binder under the following optimum conditions: deposition potential (EDEP) = -1.0 V; preconcentration time (Tpre) = 90 sec; frequency (freq.) = 15 Hz; width = 0,075V and Step E) = 0.004 V. The complex formed Ca2+ EDTA showed a peak current of approximately - 0.2 V. The result was consistent statistically considering t -test for a 95% confidence level. The levels were lower CV of 11.0% (Mg2+ and Ca2+), recoveries were in the range 95.0 to 108.0% (Mg2+) and from 97.8 to 105.0% (Ca2+) and the values of detection limits were 1.05 x 10-6 mol L-1 (Mg2+) and 2.8 x 10-7 mol L-1 (Ca2+), and quantitation 3.51 x 10-6 mol L-1 (Mg2+) and 9.46 x 10-7 mol L-1 (Ca2+) for the samples analyzed, showing good accuracy and sensitivity of the proposed method. The values obtained for the samples ranged from 1.47 x 10-5 ± 1.28 x 10-6 mol L-1 (Mg2+) and 5.57 x 10-6 ± 3.77 x 10-7 mol L-1 (Ca2+) on samples of biodiesel. The determination of metals such as Ca2+ and Mg2+ by electrochemical techniques with chemically modified electrodes has as main advantages its detectability and the selectivity.Item Acesso aberto (Open Access) Intercalação do ibuprofeno em hidróxidos duplos lamelares: caracterizações físico-químicas e avaliações biológicas(Universidade Federal do Pará, 2016-10-14) SOUSA, Paulo Robson Monteiro de; ALVES, Claudio Nahum; http://lattes.cnpq.br/8315600067791313; SILVA, Jerônimo Lameira; http://lattes.cnpq.br/7711489635465954Ibuprofen-intercalated layered double hydroxides (LDH-IBU) have been successfully synthesized via a co-precipitation method with a nominal [Al3+]/[Mg2+] ratio of 0.5 and a variable molar IBU/([Al3+]+[Mg2+]) ratio of 0, 0.15, 0.18, 0.24, 0.36 and 0.72. After an accurate determination of the composition, the nature of the intercalated species and the effective intercalation yield from NO3 - to IBU, it is shown that the synthesis route used allows a good control of the quantity of intercalated IBU within the LDH framework. This results in different samples with full or partial IBU intercalation in the interlayer space in exchange of nitrate anions. The analysis of the X-ray diffraction basal reflections reveals that the intercalation of IBU in the framework only increases the basal distances with no alteration of the brucite-type layers. Also, a computational study used to model the positions and shapes of the basal reflections showed that the structure of the non-fully intercalated compounds follows a random interstratification scheme. Finally three samples ranging from slightly to fully IBU-intercalated galleries were selected for preliminary in vivo assays. These tests showed a strong tendency that after 24 hours the low yield of IBUintercalated compounds are almost as efficient as the fully intercalated sample.Item Acesso aberto (Open Access) Investigação de metabólitos secundários de folhas de Derris urucu (Killip et Smith) Macbr. com atividades biológicas(Universidade Federal do Pará, 2009-06-30) LÔBO, Lívia Trindade; SILVA, Milton Nascimento da; http://lattes.cnpq.br/6742390457977989; ARRUDA, Mara Silvia Pinheiro; http://lattes.cnpq.br/8047078292358267Derris urucu, belonging to the family Leguminosae / Fabaceae, is popularly known as “timbó”. The roots of this species are commonly used as pesticides and poison to fish. From Derris genus many phytochemical studies have been reported, the roots being of the most studied part from the plants of this genus. The name “timbó” is most general for the species Derris urucu and Derris nicou, which are the species that produce, in their roots, rotenoids such as rotenone and deguelin, from which derives the importance of these plants. The extracts, and the substances isolated from this genus are responsible for a wide range of biological activities, mainly the insecticidal activity. From the ethanolic extract of leaves of D. urucu, twelve compounds were isolated and purified by High Performance Liquid Chromatography: five stilbenes, six dihydroflavonols and one flavanone. The structural identification was based on the mass, 1H and 13C NMR spectrometric analysis and two dimensional NMR, beyond comparison with literature data . The ethanolic extract of leaves of D. urucu was submitted to bioassays to avaluate the allelophatic potential, presenting relevant percentage of inhibition of seed germination and development of weeds in pastures. Aiming to detect the substances responsible for allelophatic activity, three stilbenes and three dihydroflavonols were selected and submitted to bioassays of inhibition of germination and development of the radicle and hypocotyl of weeds. The allelophatic tests were performed with the substances isolated and with the combination of them, aiming to assess the synergism between them, but the magnitude of inhibition observed was very low. By other side, when the substances were tested in mixtures there was a significant increase in the percentage of inhibition, so these substances in mixtures, can be considered promising for future studies involving allelophatic activity. An other test was carried out with the isolated compounds. Three stilbenes and five dihydroflavonols were evaluated for DPPH radical scavenging activity (antioxidant activity). In this bioassay, was not observed a significant antioxidant activity, justified by the analysis in the structures of the substances tested.