Síntese de nanomateriais de carbono a partir do resíduo de milho (DDGS)

The world's largest ethanol producer (USA) uses corn as feedstock. DDGS (distillers dried grains with solubles) is the main waste generated from this process (around 32 million t/year). DDGS samples were pyrolyzed at 1000 ºC in a furnace with controlled atmosphere. The effluent was channeled to a second furnace, in which catalyst substrates were placed. Chromatographic analysis was used to evaluate the gaseous effluents, showing that the catalyst reduced hydrocarbon emissions. The solid products formed were analyzed by SEM and TEM. Graphitic structures and carbon nanofibers, 50 µm in length and with diameters of 80-200 nm, were formed.

Improved method to obtain pfaffic acid as a marker for quality control

Pfaffic acid, a marker of Hebanthe eriantha (Brazilian ginseng), was first isolated in 1983 but is not yet commercially available. This lack of availability compromises the quality control of this plant and its derivatives. This paper proposes a process for pfaffic acid isolation from roots of H. eriantha at a purity suitable for analytical purposes. The steps involved in this process included extraction, hydrolysis, fractionation and purification by preparative HPLC. This process led to isolation of pfaffic acid with a chromatographic purity of 98.5% in a 0.25% yield from dried roots of H. eriantha; this yield is more than forty times higher than that of the current method in the literature.

Interaction of naproxen with calcium carbonate: physicochemical characterization and in vitro drug release studies

Interaction and physicochemical characterization of dispersions of naproxen in calcium carbonate after freeze-drying the wet-state equilibrated mixture have been investigated by analytical methods. The FT-IR study revealed the acid-base reaction between naproxen and calcium carbonate. The DSC study indicated physical interaction and significantly diminished crystallinity of naproxen in the formulation containing higher quantities of calcium carbonate. Furthermore, the SEM study showed the reduced particle size and loss of crystalline morphology in the same sample. Drug release increased with the increase of calcium carbonate in the formulations. Formulation of naproxen with calcium carbonate in 1:2 ratio allowed its dissolution to the greatest extent (94.96%) while other compositions, 1:0.5 and 1:1, showed 80.86% and 78.30% release, respectively.

Imobilização de lipase por encapsulação em sílica aerogel

Lipase from Burkholderia cepacia was immobilized in a silica matrix and dried in high pressure carbon dioxide media (aerogel). The protic ionic liquid (PIL) was used in the immobilization process by encapsulation. The objective of this work was to evaluate the influence of the drying technique using supercritical carbon dioxide in biocatalysts obtained through the sol-gel technique by evaluating temperature and pressure and, after selecting the best drying conditions, to investigate the application of the technique for the biocatalyst using ionic liquid as an additive in the immobilization process. The results for immobilized biocatalysts showed that the best conditions of pressure and temperature were 100 bar and 25 ºC, respectively, giving a total activity recovery yield of 37.27% without PIL (EN) and 44.23% with PIL (ENLI). The operational stability of the biocatalysts showed a half-life of 11.4 h for ENLI and 6 h for EN. Therefore, solvent extraction using supercritical CO2, besides shortening drying time, offers little resistance to the immobilization of lipases, since their macropores provide ample room for their molecules. The use of the ionic liquid as an additive in the process studied for the immobilization of enzymes produced attractive yields for immobilization and therefore has potential for industrial applications in the hydrolysis of vegetable oils.

Determinação simultânea de carbamazepina, fenitoína e fenobarbital em sangue seco em papel por cromatografia líquida de alta eficiência

Carbamazepine, phenobarbital and phenytoin were determined in dried blood spots (DBS) by high performance liquid chromatography, after extraction of 8 mm DBS using a mixture of acetonitrile and methanol. Analytes were separated by reversed-phase chromatography, with a run time of 17 minutes. Intra-assay and inter-assay precisions were in the 5.3 to 8.4% and 3.3 to 5.2% ranges, respectively. Accuracy was in the 98.8 to 104.3% range. The method had sensitivity to detect all analytes at levels below minimum therapeutic concentrations. The analytes were stable at 4 ºC and room temperature for up to 12 days and at 45 ºC for 9 days. The method was applied to 14 paired clinical samples of blood serum and DBS.

Variation of essential oil composition of Tapirira guianensis Aubl. (Anacardiaceae) from two sandbank forests, north of Brazil

Tapirira guianensis (Anacardiaceae) is used in traditional medicine and is important for the recovery of degraded areas and riparian forests because the T. guianensis fruits are highly consumed by wildlife. Volatile components from dried leaves and branches of five individual plants of T. guianensis were collected in two sandbank forests of the State of Pará (Extractive Reserve Maracanã and Area of Environmental Protection Algodoal/Maiandeua), extracted by hydrodistillation using a Clevenger-type apparatus, and analyzed by GC/MS. The ten oils obtained are comprised mostly of sesquiterpene hydrocarbons (58.49 to 100%), with (E)-caryophyllene, β-selinene, α-selinene, β-sesquiphellandrene, and α-zingiberene being the most prominent. The results of the oil compositions were processed by Hierarchical Component Analysis (HCA) allowing the establishment of three groups of essential oils for T. guianensis differentiated by the content of β-selinene/α-selinene (Type I), (E)-caryophyllene (Type II), and β-sesquiphellandrene/α-zingiberene (Type III).

Desenvolvimento de procedimento de extração para análise de sedativos e B-bloqueadores em rim suíno

A procedure was developed for determination of 5 sedatives and 14 β-blockers in swine kidney and subsequent analysis by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). Three different procedures for extraction were tested, evaluated through recovery studies. The procedure using acetonitrile for extraction and cleanup with freezing at low temperature and dispersive solid phase extraction using 500 mg celite® 545 before the concentration step presented the better results. The dried samples were redissolved with methanol and analyzed using a LC-MS/MS system with electrospray ionization (ESI) operating in positive MRM mode. The recovery values for this procedure were in the 75-88% range. The robustness of the method was tested against small variations. The method was used to analyze carazolol, azaperone and azaperol in collaborative assay, obtaining results close to designed value.

Simultaneous determination of four phenolic compounds in extracts of aerial parts of Ipomoea pes-caprae (L.) R. Br. (Convolvulaceae) by HPLC-UV

Among other applications, Ipomoea pes-caprae is popularly used to treat jellyfish stings, supporting the development of a product for dermatological use. Hydroethanolic spray-dried extract was chosen for the further development of phytomedicines, and a stability-indicative HPLC-UV method was developed and validated for the determination of isoquercitrin and isochlorogenic acids A, B and C. The method was developed using a C18 column (250 x 4.6 mm, 5 µm) with an acetonitrile:water mobile phase at pH 3.0 in a gradient run. The four constituents and other unidentified components of the extract were appropriately resolved without interference of degradation products after stress tests (acid, alkali, neutral, oxidant, photolysis). The method showed linearity in the isoquercitrin concentration range from 5.0-50.0 µg mL-1, with adequate precision (RSD% < 2.5% for the intra- and inter-day studies), accuracy (recovery of 100.0 ± 2.0%), and robustness. Both the herbal drug and spray-dried extract of I. pes-caprae were subjected to stability studies in accelerated and long-term conditions over four months. The samples maintained their characteristics and marker contents (< 10% of variation).

PARÂMETROS TERMODINÂMICOS DA CASCA DE LARANJA DESIDRATADA

The global energy scenario is currently a widely discussed topic, with growing concern about the future supplies. Thus, much attention has been dedicated to the utilization of biomass as an energy resource. In this respect, orange peel has become a material of great interest, especially to Brazil, which generates around 9.5 million tons of this waste per year. To this end, the authors studied the kinetics of the thermal processing of dried orange peel in inert and oxidizing atmosphere. The thermodynamic parameters were determined by the Ozawa-Flynn-Wall method for the global process observed during heating from the 25°C up to 800°C. The thermal analysis in air and nitrogen showed 3-2 stages of mass loss, respectively, with approximately 20% residual mass under a nitrogen atmosphere. The increase in the values of activation energy for the conversion points between 20% and 60% for thermal effects in air and nitrogen atmosphere was observed. The activation energy obtained in an oxidizing atmosphere was higher than that obtained under a nitrogen atmosphere. The fourier-transform infrared spectroscopy and X-ray diffraction analysis showed that the material has a high level of complexity with the presence of alkali and alkaline earth groups as well as phosphate, plus substances such as pectin, cellulose and lignin.

CURCUMINA, O PÓ DOURADO DO AÇAFRÃO-DA-TERRA: INTROSPECÇÕES SOBRE QUÍMICA E ATIVIDADES BIOLÓGICAS

Turmeric, obtained from the dried rhizomes of Curcuma longa (Zingiberaceae), is a golden colored material, commonly used around the world for seasoning and coloring food dishes. Since antiquity, turmeric has been widely used in the treatment of several diseases in traditional Chinese and Indian medicine (Ayurveda), where it is also known by other names such as Kanchani (goddess gold) or also Gauri (having a bright and luminous face), a designation stemming from the gilded appearance of the plant material. Curcumin, the main chemical component of turmeric, is responsible both for its properties as dyes as well as its biological activities. This diarylheptanoid was first isolated almost two centuries ago and had its chemical structure determined in 1910 as being diferuloylmethane. Subsequently, more detailed and relevant data were obtained furthering the understanding of structural features of curcumin. The classical methodology for the synthesis of curcumin and other curcuminoids was described in 1960 by Pabon. Subsequently, different variations on this methodology have been developed, culminating with the synthesis of different curcuminoids. Several studies have been published in recent years on the biological activities exhibited by curcumin including its antioxidant, antitumor, anti-inflammatory, antiviral, antibacterial, antifungal, antimalarial and leishmanicidal activities.

INFLUÊNCIA DO CATALISADOR EM SOLUÇÕES POLIMÉRICAS PARA O PREPARO DE GÉIS ORGÂNICOS DE RESORCINOL-FORMALDEÍDO

Resorcinol-formaldehyde (RF) organic gels have been extensively used to produce carbon aerogels. The organic gel synthesis parameters greatly affect the structure of the resulting aerogel. In this study, the influence of the catalyst quantity on the polymeric solution sol-gel process was investigated. Sodium carbonate was used as a basic catalyst. RF gels were synthesized with a resorcinol to formaldehyde molar ratio of 0.5, a resorcinol to catalyst (R/C) molar ratio equal to 50 or 300, and a resorcinol to solvent ratio of 0.1 g mL-1. The sol-gel process was evaluated in situ by Fourier transform infrared spectroscopy using a universal attenuated total reflectance sensor and measurements of the kinematic viscosity. The techniques showed the evolution of the sol-gel process, and the results showed that the lower catalyst quantity induced a higher gel point, with a lower viscosity at the gel point. Differential scanning calorimetry was used to investigate the thermal behavior of the RF dried gel, and results showed that the exothermic event related to the curing process was shifted to higher temperatures for solutions containing higher R/C ratios.

Effect of organic amendments on sclerotial germination, mycelial growth, and Sclerotium rolfsii-induced diseases

The addition of organic residues to soil is an option to control some soil-borne diseases. Benzaldehyde and powders of kudzu (Pueraria lobata), velvetbean (Mucuna deeringiana), and pine-bark (Pinus elliottii and P. taeda) added to soil could reduce certain soil-borne diseases. This study evaluated the effects of benzaldehyde and the dried powders of kudzu, velvetbean, and pine-bark as soil amendments on germination and formation of sclerotia, on mycelial growth of Sclerotium rolfsii, on plant survival, and disease incidence. The data showed that high amounts of benzaldehyde (0.4 ml kg-1 of soil) and velvetbean (100 g kg-1) inhibited S. rolfsii mycelial growth and sclerotium germination. However, low amounts of benzaldehyde (0.1 ml kg-1), kudzu (25 g kg-1), and pine-bark (25 g kg-1) stimulated mycelial growth and sclerotium germination. Kudzu (25-100 g kg-1) and velvetbean (25-100 g kg-1) inhibited the formation of sclerotia. Nevertheless, benzaldehyde at 0.2 and 0.4 ml kg-1 stimulated the formation of sclerotia. Kudzu (50 and 100 g kg-1) and pine-bark (50 g kg-1) favored the colonization of sclerotia by Trichoderma sp. The numbers of soybean (Glycine max) plants were higher and diseased plants were lower than the non-amend soil in the following treatments: kudzu (50 and 100 g kg-1), velvetbean (50 and 100 g kg-1), and pine-bark (50 g kg-1). Disease severity on tomato (Lycopersicon esculentum) plants was low in soil treated with kudzu or velvetbean (30 and 35 g kg-1) and pine-bark (35 g kg-1). Dried powders of kudzu, velvetbean, or pine-bark added to soil can reduce disease by reducing pathogen inoculum.

Powders of kudzu, velvetbean, and pine bark added to soil increase microbial population and reduce Southern blight of soybean

Southern blight (Sclerotium rolfsii) of soybean (Glycine max) is an important disease throughout the world. Some soil amendments can reduce disease levels by improving soil microbial activity. The main goals of this study were to investigate the effects of soil amendments such as dried powders of kudzu (Pueraria lobata), velvetbean (Mucuna deeringiana), and pine bark (Pinus taeda), on soil microbial population and disease caused by S. rolfsii on soybean. Pine bark, velvetbean (mucuna) and kudzu (25 g kg-1) added to soil were effective in reducing disease incidence [non-amended (NA) ~ 39%; amended (A) ~ 2 to 11%)]. Bacillus megaterium was the bacteria most frequently isolated in soils with velvetbean or kudzu (NA ~ log 5.7 CFU g-1 of dried soil; A ~ log 6.2). Soils with velvetbean and kudzu stimulated increase in population of Enterobacter aerogenes (NA ~ log 3; A ~ log 5.1-5.8). Pseudomonas putida population was higher in A than in NA (NA ~ log 4; A ~ log 5.5), and was negatively correlated (r = -0.83, P = 1%) to disease incidence. Soil amended with kudzu and pine bark stimulated increases in populations of Trichoderma koningii (NA ~ log 1.6; A ~ log 2.9) and Penicillium citreonigrum (NA ~ log 1.3; A ~ log 2.6), respectively. Penicillium herquei soil population increased with addition of kudzu (NA ~ log 1.2; A, ~ log 2.5). These microorganisms are antagonists of soil-borne pathogens. Powders of velvetbean, kudzu, and pine bark can increase antagonistic population in soil and reduce disease.

Determination of herbicides residues in soil by small scale extraction

Herbicides such as trifluralin, simazine, atrazine, metribuzin and metolachlor are used in Brazilian agriculture. The efficiency of a small scale method for determination of these herbicides and two degradation products (deisopropylatrazine and deethylatrazine) in soil samples was evaluated. The compounds were extracted from soil samples (5 g) with 20 ml of ethyl acetate in a mechanical shaker for 50 min. Following the extraction, the supernatant was dried through anhydrous sodium sulphate, concentrated and analysed by high resolution gas chromatography (HRGC) with thermionic specific detection (TSD). Mean recoveries obtained from soil samples fortified at three different levels ranged from 81 to 115% with relative standard deviation (RSD) values varying from 1.2 to 12.7%. The method detection limits ranged from 0.01 to 0.06 mg kg-1. The methodology was applied using soil samples from farms located near the town of Araraquara, in the State of São Paulo, Brazil.

Flavonoid extraction from Alpinia zerumbet (Pers.) Burtt et Smith leaves using different techniques and solvents

The current study aims to verify the best method for a rapid and efficient extraction of flavonoids from Alpinia zerumbet. Dried leaves were extracted using distillated water and ethanol 70% by extraction methods of shaking maceration, ultrasonic, microwave and stirring. By the application of TLC and reversed-phase HPLC techniques the rutin and kaempferol-3-O-glucuronide were detected. Ethanol 70% was more efficient for flavonoids extraction than water. No significant yielding variation was verified for ultrasonic, microwave and stirring methods using ethanol 70% (11 to 14%). The relative concentration of rutin and kaempferol-3-O-glucuronide, respectively, was higher by ultrasonic (1.5 and 5.62 mg g-1 dried leaves, respectively) and by microwave (1.0 and 6.64 mg g-1 dried leaves) methods using ethanol. Rapid and simplified extraction proceeding optimize phytochemical work and acquisition of secondary metabolites.