Aplicação de análises térmicas na identificação constituintes químicos em blendas de diesel/biodiesel e bio-óleo/óleo de soja

Tese (doutorado)—Universidade de Brasília, Instituto de Química, 2014.A utilização de novas técnicas analíticas para estudos de controle de qualidade permite que diversos compostos químicos sejam detectados em amostras distintas. O uso da quimiometria para este fim fornece suporte para averiguar a eficiência da metodologia experimental criada, bem como permite a padronização e validação dos resultados obtidos no experimento. Neste trabalho foram efetuadas analises calorimétricas e termogravimétricas, e com o auxilio de modelos matemáticos por meio da técnica de termogravimétrica pode-se detectar mudanças na composição química em varias amostras de diesel, biodiesel e bio-oleo. Resultados calorimétricos mostraram que os valores de calor de combustão foram 41,36 } 0,17; 38,70 } 0,16; e36,71 } 0,17 mJ kg-1 para o diesel, bio-oleo e biodiesel,respectivamente, os quais estão de acordo com a literatura. Nas analises termogravimétricas, por meio dos métodos de calibração porregressao por mínimos quadrados parciais, pode-se determinar os valores de RMSEC, RMSECV e RMSEP que descrevem qual modelo conseguiria explicar a mudança de composição química das amostras por meio do perfil térmico das analises de TG. Os resultados para o primeiro conjunto constituído por blendas de bio-oleo com óleo de soja, as analises termogravimétricas associadas ao PLS (PLS/TG) apresentam o melhor desempenho para a detecção do teor de óleo de soja em biooleo com valores de 0,23 de erro de calibração (RMSEC, % w/w), com3,6 %, de erro de predição (RMSEP, %w/w). Para as amostras de diesel com biodiesel, os resultados obtidos foram: RMSEC = 0,32; RMSECV =0,92; RMSEP = 2,85 com duas variáveis latentes e RMSEC = 0,41;RMSECV = 0,67; RMSEP = 1,39 com oito variáveis latentes analisadas numa faixa de temperatura ate 350 oC. Para o segundo conjunto de amostras, o modelo matemático que mostrou mais robusto para determinação da composição química das blendas foi o siPLS e para o terceiro conjunto o iPLS com valores de RMSEC, RMSECV e RMSEP para o segundo conjunto de 0,46; 0,90 e 1,19 e para o terceiro conjunto de 0,43; 1,05 e 0,55 respectivamente. Assim, devido ao sucesso de detecção da mudança de compostos químicos nas amostras, a técnica de termogravimétrica mostra-se promissora para identificação decomposição química das blendas de bio-oleo com óleo de soja e nas blendas de diesel com biodiesel em diferentes proporções. _______________________________________________________________________________________ ABSTRACTThe use of new analytical techniques for studies of quality control al lows various chemical compounds are detected in different samples. The use of chemometrics for this purpose provides support forascertaining the efficiency of the experimental methodology created, andallows for standardization and validation of the results obtained in the experiment. In this work calorimetry and thermogravimetric analysiswere performed and with the aid of mathematical models by thermogravimetric technique it was possible to detect changes in the chemical composition of several samples of diesel, biodiesel and bio-oil. Calorimetric results showed that the heat of combustion values were41.36 } 0.17; 38.70 } 0.16; and 36.71 } 0.17 mJ kg-1 for diesel, bio-oiland biodiesel, respectively, which are in agreement with the literature.In the thermogravimetric analysis, by methods of calibration partialleast squares regression, one can determine the values of RMSEC,RMSECV and RMSEP, model describing which could explain the change of chemical composition of samples through thermal profile analyzes ofTG. The results for the first set of blends comprising bio-oil and soybean oil, associated with the thermogravimetric analysis PLS (PLS/TG) showthe best performance for the detection of soybean oil content in bio-oilwith values 0 23 calibration error (RMSEC,% w/w), with 3.6% error of prediction (RMSEP% w/w). For samples of diesel with biodiesel, the results were: RMSEC = 0.32; RMSECV = 0.92; RMSEP = 2.85 with two latent variables and RMSEC = 0.41; RMSECV = 0.67; RMSEP = 1.39with eight latent variables in a temperature range up to 350 ° C. For the second set of samples showed that the mathematical model more robust to determine the chemical composition of the blends was siPLS and the third set of values with the iPLS RMSEC, RMSECV and RMSEP for the second set of 0.46; 0.90 and 1.19 and 0.43 of the third set; 1.05 and0.55 respectively. Thus, due to successful detection of the change of chemical compounds in the sample, the thermogravimetric technique is shown promise for identification of the chemical composition of the blends of bio-oil and soybean oil blends in diesel and biodiesel indifferent proportions

Efficacy of chitosan supported organic acaricide extract from Melia azedarach leaves on Rhipicephalus (Boophilus) microplus ticks

The Rhipicephalus (Boophilus) microplustick control is mainly performed by chemicals products, but organic acaricides use has higher advantages compared to conventional products. Brazilian cerrado native plants are known for their bioactive potential. Due to this fact, the objective of this study is to evaluate the acaricide action of native cerrado specie, Meliaazedarach, known as Santa Barbara in the tick control. Also, the chitosan nanosphere was evaluated on the extract adsorption and release, as a proposal to raise the acaricide phytotherapic profile. The ethanol extract was obtained by cool extraction from dried leaves of the plant. Chitosan nanospheres were obtained by the phase inversion method. Conductometric titration, ultraviolet-visible ("UV-Vis") and Fourier transform infrared spectroscopy (FTIR) analysis were conducted with materials to evaluate the chitosan anchoring ability. In vitro test was used in engorged females for each treatment, which consisted of control, raw extract and three treatments with increasing concentrations of 0.2; 0.4 and 1%. The organic product effectiveness of 0.2% concentration was found by observing reduction in the eggs mass compared to control group. The nanomaterial proved capable to anchor and release the acaricide gradually in pH between 6 and 7, which makes it feasible for use in cattle, prolonging the exposure time between the tick and acaricide.Keywords: Cerrado specie, Rhipicephalus (Boophilus) microplustick, ectoparasites, tick control, acaricide, chitosan nanoparticl

Calor de combustão de Blendas do tipo diesel/biodiesel e diesel/bio-óleo

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, 2009.O programa brasileiro de biocombustíveis prevê a adição de 2% de biocombustíveis em diesel até 2008 e 5% até 2013. Assim, o estudo do calor de combustão das blendas biocombustível/diesel é um gargalo tecnológico que necessita ser solucionado. O biodiesel foi obtido a partir da reação de transesterificação de óleo de soja, com um rendimento de 87% o bio-óleo foi obtido pelo craqueamento térmico do óleo de soja e tiveram a maioria os parâmetros de acordo com as normas da ANP. Os resultados calorimétricos mostraram que os valores de calor de combustão foram 41,36 ± 0,17; 38,70 ± 0,16; e 36,71 ± 0,17 MJ/kg para o diesel, bio-óleo e biodiesel, respectivamente. Os resultados mostraram que o calor de combustão dos biocombustíveis são aproximadamente 17 % inferiores aos valores do calor de combustão do diesel de petróleo. Mais ainda, os dados mostraram que os valores de calor de combustão dos biocombustíveis dependem do método de produção do biocombustível. Os valores de calor de combustão das blendas biocombustível/diesel fóssil diminui linearmente com a adição do biocombustível nas blendas. Os valores do calor de combustão encontrados na amostra B5 mostraram resultados muito semelhantes com os valores do calor de combustão do diesel de petróleo, justificando seu uso de acordo com a lei n° 11.097/2005 que determina a adição de 5% de biodiesel no diesel de petróleo. __________________________________________________________________________________________ ABSTRACTThe Brazilian government has also present biofuel program, which it has the main to add 2 % of biofuel in fossil diesel in 2008 and 5 % up to 2013. Thus, the knowledge of heat of combustion of biofuel/diesel blends is necessary. The biodiesel was produced by transesterification of soybean oil with yield of 87%. The diesel-like was obtained by pyrolysis of soybean oil; this biofuel presented all parameters in according to ANP. The obtained heats of combustion were 41.36 ± 0.17; 38.70 ± 0.16; e 36.71 ± 0.17 MJ/kg for diesel, diesel-like and biodiesel, respectively. The results show the heats of combustion of biofuels are approximately 17 % smaller than fossil diesel. The data also show the heats of combustion depend on the methodology used for the biofuel production. Addition of biofuels to traditional diesel fuel results in a linear decreasing of the heat of combustion with the amount of the alternative fuel added to the diesel

Polymer nanoparticles: adsorption and desorption of the weedkiller Tebuthiuron turned to green chemistry

The herbicide Tebuthiuron is a major responsible for controlling and combating weeds in sugarcane crops, but its use poses serious environmental risks. In order to reduce the amount of product used, a study of herbicide anchoring in nanospheres and controlled release was performed, observing factors such as conductivity and pH variation. The results of conductimetric titrations and UV analysis in the visible region showed the efficiency of the chitosan nanospheres in the controlled release process of the anchored herbicide.</p

Application of polymeric nanoparticles for controlled release of ethanolic extract of guapeva leaves (Pouteria gardneriana Radlk) against Riphicephalus (Boophilus) microplus through in vitro studies

The study was designed to evaluate the ethanolic extract acaricide action from Pouteria gardneriana Radlk specie adsorbed in chitosan nanoparticles for controlled release against Riphicephalus (Boophilus) microplus. Leaves of P. gardneriana Radlk were collected, air-dried, ground and extracted with ethanol. Chitosan nanospheres were obtained by the phase inversion method. Conductometric titration, UV-Vis and FTIR analysis were conducted with the materials to evaluate the chitosan anchoring ability. In vitro test was performed using engorged females for each treatment, which consisted of the control, raw extract and three treatments diluted, with increasing concentrations of 0.2, 0.4 and 1%. The most effectiveness extract was for 0.4% concentration by observing reduction in the eggs mass compared to control group. The nanomaterial proved to be able to anchor and release the insecticide gradually in pH between 5 and 6 regions, which makes it feasible for use in cattle, prolonging the exposure time between the tick and acaricide.Key words: Extracts, nanoparticle, controlled release, tick

DEGRADAÇÃO FOTOCATALÍTICA DE ATRAZINA NA PRESENÇA DE CATALISADORES NANOPARTICULADOS

Atrazine is a persistent herbicide and several studies have detected their presence in drinking water sources. In this work the atrazine photocatalytic degradation was investigated in aqueous solution using TiO2, ZnO and TiO2/ZnO catalysts. The catalysts were synthesized by Pechini's method and characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The process was monitored using absorption spectroscopy in ultraviolet and visible (UV-vis) region and high performance liquid chromatography (HPLC). The prepared catalysts were used in ultrafine powder form and its characterization showed nanometer order particle sizes. The atrazine absorbance decrease was observed after samples irradiation in catalysts presence and HPLC analysis showed a significant herbicide reduction and other compounds formation as degradation products. The ZnO catalyst use was more effective in atrazine molecule degradation compared to the other nanoparticles

NEOTROPICAL CARNIVORES: a data set on carnivore distribution in the Neotropics

Mammalian carnivores are considered a key group in maintaining ecological health and can indicate potential ecological integrity in landscapes where they occur. Carnivores also hold high conservation value and their habitat requirements can guide management and conservation plans. The order Carnivora has 84 species from 8 families in the Neotropical region: Canidae; Felidae; Mephitidae; Mustelidae; Otariidae; Phocidae; Procyonidae; and Ursidae. Herein, we include published and unpublished data on native terrestrial Neotropical carnivores (Canidae; Felidae; Mephitidae; Mustelidae; Procyonidae; and Ursidae). NEOTROPICAL CARNIVORES is a publicly available data set that includes 99,605 data entries from 35,511 unique georeferenced coordinates. Detection/non-detection and quantitative data were obtained from 1818 to 2018 by researchers, governmental agencies, non-governmental organizations, and private consultants. Data were collected using several methods including camera trapping, museum collections, roadkill, line transect, and opportunistic records. Literature (peer-reviewed and grey literature) from Portuguese, Spanish and English were incorporated in this compilation. Most of the data set consists of detection data entries (n = 79,343; 79.7%) but also includes non-detection data (n = 20,262; 20.3%). Of those, 43.3% also include count data (n = 43,151). The information available in NEOTROPICAL CARNIVORES will contribute to macroecological, ecological, and conservation questions in multiple spatio-temporal perspectives. As carnivores play key roles in trophic interactions, a better understanding of their distribution and habitat requirements are essential to establish conservation management plans and safeguard the future ecological health of Neotropical ecosystems. Our data paper, combined with other large-scale data sets, has great potential to clarify species distribution and related ecological processes within the Neotropics. There are no copyright restrictions and no restriction for using data from this data paper, as long as the data paper is cited as the source of the information used. We also request that users inform us of how they intend to use the data

NEOTROPICAL ALIEN MAMMALS: a data set of occurrence and abundance of alien mammals in the Neotropics

Biological invasion is one of the main threats to native biodiversity. For a species to become invasive, it must be voluntarily or involuntarily introduced by humans into a nonnative habitat. Mammals were among first taxa to be introduced worldwide for game, meat, and labor, yet the number of species introduced in the Neotropics remains unknown. In this data set, we make available occurrence and abundance data on mammal species that (1) transposed a geographical barrier and (2) were voluntarily or involuntarily introduced by humans into the Neotropics. Our data set is composed of 73,738 historical and current georeferenced records on alien mammal species of which around 96% correspond to occurrence data on 77 species belonging to eight orders and 26 families. Data cover 26 continental countries in the Neotropics, ranging from Mexico and its frontier regions (southern Florida and coastal-central Florida in the southeast United States) to Argentina, Paraguay, Chile, and Uruguay, and the 13 countries of Caribbean islands. Our data set also includes neotropical species (e.g., Callithrix sp., Myocastor coypus, Nasua nasua) considered alien in particular areas of Neotropics. The most numerous species in terms of records are from Bos sp. (n = 37,782), Sus scrofa (n = 6,730), and Canis familiaris (n = 10,084); 17 species were represented by only one record (e.g., Syncerus caffer, Cervus timorensis, Cervus unicolor, Canis latrans). Primates have the highest number of species in the data set (n = 20 species), partly because of uncertainties regarding taxonomic identification of the genera Callithrix, which includes the species Callithrix aurita, Callithrix flaviceps, Callithrix geoffroyi, Callithrix jacchus, Callithrix kuhlii, Callithrix penicillata, and their hybrids. This unique data set will be a valuable source of information on invasion risk assessments, biodiversity redistribution and conservation-related research. There are no copyright restrictions. Please cite this data paper when using the data in publications. We also request that researchers and teachers inform us on how they are using the data