Preparação de derivados do lapachol em meio ácido e em meio básico: uma proposta de experimentos para a disciplina de Química Orgânica Experimental

In this educational paper we describe the extraction of lapachol from its natural source according to acid-base concepts in organic chemistry and the use of its derivatives β-lapachone and hydroxy-hydrolapachol to exemplify intramolecular cyclization, carbocation stability, Michael addition reaction and chromatography. The experiments were performed during three different undergraduate organic chemistry laboratory classes using low cost material, while avoiding color reagents for TLC visualization, as well as small-scale column chromatography to isolate the mixture of lapachol and β-lapachone.

Preparative separation and purification of bufadienolides from ChanSu by high-speed counter-current chromatography combined with preparative HPLC

Eight bufadienolides were successfully isolated and purified from ChanSu by high-speed counter-current chromatography (HSCCC) combined with preparative HPLC (prep-HPLC). First, a stepwise elution mode of HSCCC with the solvent system composed of petroleum ether - ethyl acetate - methanol - water (4:6:4:6, 4:6:5:5, v/v) was employed and four bufadienolides, two partially purified fractions were obtained from 200 mg of crude extract. The partially purified fractions III and VI were then further separated by prep-HPLC, respectively, and another four bufadienolides were recovered. Their structures were confirmed by ESI-MS and ¹H-NMR spectra.

Preparative separation of polyphenols from artichoke by polyamide column chromatography and high-speed counter-current chromatography

An efficient method for the rapid separation and purification of polyphenols from artichoke by polyamide column chromatography in combination with high-speed counter-current chromatography (HSCCC) was successfully built. The crude ethanol extracts from dry artichoke were first pre-separated by polyamide column chromatography and divided in two parts as sample 1 and sample 2. Then, the samples were further separated by HSCCC and yielded 7.8 mg of chlorogenic acid (compound I), 24.5 mg of luteolin-7-O-β-D-rutinoside (compound II), 18.4 mg of luteolin-7-O-β-D-glucoside (compound III), and 33.4 mg of cynarin (compound IV) with purity levels of 92.0%, 98.2%, 98.5%, and 98.0%, respectively, as determined by high-performance liquid chromatography (HPLC) method. The chemical structures of these compounds were identified by electrospray ionization-mass spectrometry (ESI-MS) and nuclear magnetic resonance (NMR).

Phytotoxic effects of metabolites from Alternaria euphorbiicola against its host plant Euphorbia heterophylla

A bioassay-guided fractionation of culture filtrates of the fungus Alternaria euphorbiicola, a pathogen of the weed Euphorbia heterophylla, led to the isolation of anhydromevalonolactone (1), tyrosol (2), (R)-( - )-mevalonolactone (3), and cycloglycylproline (4). When tested on the punctured leaves of the host plant, these compounds produced bleached lesions with dark brown margins at concentrations as low as 80 µM. When tested on the leaves of other relevant weeds, only cycloglycylproline showed selective activity against E. heterophylla. This is the first report on the isolation of phytotoxins from A. euphorbiicola and on the phytotoxicity of anhydromevalonolactone, (R)-( - )-mevalonolactone, and cycloglycylproline.

Chemical composition of volatiles from male and female specimens of Baccharis trimera collected in two distant regions of southern brazil: a comparative study using chemometrics

GC/MS/FID analyses of volatile compounds from cladodes and inflorescences from male and female specimens of Baccharis trimera (Less.) DC. collected in the states of Paraná and Santa Catarina, Brazil, showed that carquejyl acetate was the primary volatile component (38% to 73%), while carquejol and ledol were identified in lower concentrations. Data were subjected to hierarchical cluster analysis and principal component analysis, which confirmed that the chemical compositions of all samples were similar. The results presented here highlight the occurrence of the same chemotype of B. trimera in three southern states of Brazil.

Biosorption and removal of chromium from water by using moringa seed cake (Moringa oleifera Lam.)

This study evaluated the adsorption capacity of chromium from contaminated aqueous solutions by using Moringa oleifera Lam. seeds. Parameters such as solution pH, adsorbent mass, contact time between solution and adsorbent, isotherms, thermodynamic, kinetics, and desorption were evaluated. The maximum adsorption capacity (Qm) calculated to be 3.191 mg g-1 for the biosorbent. Activated carbon was used for comparison purposes in addition to the biosorbent. The best fit was obtained by the Langmuir model for both adsorbents. The average desorption value indicated that both the biosorbent and activated carbon have a strong interaction with the metal. The results showed that the biosorbent has advantages owing to its low cost and efficiency in Cr3+ removal from contaminated waters.

Ligandless cloud point extraction of trace amounts of palladium and rhodium in road dust samples using Span 80 prior to their determination by flame atomic absorption spectrometry

In this study, a procedure is developed for cloud point extraction of Pd(II) and Rh(III) ions in aqueous solution using Span 80 (non-ionic surfactant) prior to their determination by flame atomic absorption spectroscopy. This method is based on the extraction of Pd(II) and Rh(III) ions at a pH of 10 using Span 80 with no chelating agent. We investigated the effect of various parameters on the recovery of the analyte ions, including pH, equilibration temperature and time, concentration of Span 80, and ionic strength. Under the best experimental conditions, the limits of detection based on 3Sb for Pd(II) and Rh(III) ions were 1.3 and 1.2 ng mL-1, respectively. Seven replicate determinations of a mixture of 0.5 µg mL-1 palladium and rhodium ions gave a mean absorbance of 0.058 and 0.053 with relative standard deviations of 1.8 and 1.6%, respectively. The developed method was successfully applied to the extraction and determination of the palladium and rhodium ions in road dust and standard samples and satisfactory results were obtained.

TREATMENT OF WASTE FROM ATOMIC EMISSION SPECTROMETRIC TECHNIQUES AND REUSE IN UNDERGRADUATE LAB CLASSES FOR QUALITATIVE ANALYSIS

Flame atomic absorption spectrometry (FAAS) and inductively coupled plasma optical emission spectrometry (ICP OES) are widely used in academic institutions and laboratories for quality control to analyze inorganic elements in samples. However, these techniques have been observed to underperform in sample nebulization processes. Most of the samples processed through nebulization system are discarded, producing large volumes of waste. This study reports the treatment and reuse of the waste produced from ICP OES technique in a laboratory of analytical research at the Universidade Federal do Ceará, Brazil. The treatment of the waste was performed by the precipitation of elements using (NH4)2CO3. Subsequently, the supernatant solution can be discarded in accordance with CONAMA 430/2011. The precipitate produced from the treatment of residues can be reused as a potential sample in undergraduate qualitative analytical chemistry lab classes, providing students the opportunity to test a real sample.

Effect of extracts from citric biomass, rusted coffee leaves and coffee berry husks on Phoma costarricencis of coffee plants

Phoma leaf spot, caused by Phoma costarricensis poses a serious threat to coffee (Coffea arabica) production, especially in the highlands of the state of Minas Gerais, Brazil. Extracts of citric biomass, coffee berry husks and coffee leaves severely affected by rust caused by Hemileia vastatrix, were evaluated against P. costarricensis. In an in vitro assay, aqueous extracts of rusted leaves and berry husks plus the commercial extracts based on citric biomass named Ecolife® and Agromil® were tested at various dilutions on the mycelial growth inhibition of P. costarricensis. In vivo, coffee seedlings maintained in glasshouse, were sprayed with these extracts seven days before inoculation of P. costarricensis. Only extracts from citric biomass had inhibitory effects on the fungus. In vivo, Ecolife® (5 ml/l), Agromil® (5 g/l) and the aqueous extract of rusted coffee leaves (dilution 1:6) reduced Phoma leaf spot. Both, Ecolife® and the extract of rusted coffee leaves were significantly more effective in reducing the area under the lesion progress curve when applied at lower doses, indicating a possible effect on the induction of resistance.

Uses of natural zeolite in the removal of Pb2+ from contaminated water

In this paper, we carry out a study on the process of sorption of lead in polluted waters usingnatural zeolites, with the objective of analyzing their behavior in the purification of water.Experiments are carried out under static and dynamic conditions to determine the influence of other metal ions, such as: Ca (II), Mg (II), K (I) and Na (I), on this process. We demonstrate that the affinity of Pb (II) with regard to zeolite is higher than that of the ions mentioned above. It allows us to use this material in the capture of lead in residual waters. A lineal model of regression was obtained using a computer program called Eureka which relates the capacity of interchange of zeolite with respect to the concentration of the metal ions present in waters. We also studied the selectivity of zeolite in the process of sorption of Pb (II) compared with other heavy metals like Zn (II) and Cd (II).The results achieved in both cases increase the expectancy about the usage of zeolite as a low cost material for purifing waters.

Analysis of metabolites from plants of the Swartzia genus using chemical indexes: evolutionary tendencies

The chemical indexes, suggested by Gottlieb et al., have not been used before regarding evolutionary tendency of species in the Swartzia genus. However, the importance of this work encouraged for an analysis of the Swartzia genus using the metabolites isolated from nine species. The analysis, based on calculated chemical indexes, provided an evolutionary tendency for these plants, which correlates with the classification based on morphological analysis.

Production of biodiesel from babassu oil using methanol-ethanol blends

Maranhão state in Brazil presents a big potential for the cultivation of several oleaginous species, such as babassu, soybean, castor oil plant, etc... These vegetable oils can be transformed into biodiesel by the transesterification reaction in an alkaline medium, using methanol or ethanol. The biodiesel production from a blend of these alcohols is a way of adding the technical and economical advantages of methanol to the environmental advantages of ethanol. The optimized alcohol blend was observed to be a methanol/ethanol volume ratio of 80 % MeOH: 20 % EtOH. The ester content was of 98.70 %, a value higher than the target of the ANP, 96.5 % (m/m), and the biodiesel mass yield was of 95.32 %. This biodiesel fulfills the specifications of moisture, specific gravity, kinematic viscosity and percentages of free alcohols (methanol plus ethanol) and free glycerin.

The transcendence of time in the epistemology of observation from a phenomenological standpoint

In this article I deal with time as a notion of epistemological content associated though with the notion of a subjective consciousness co-constitutive of physical reality. In this phenomenologically grounded approach I attempt to establish a 'metaphysical' aspect of time, within a strictly epistemological context, in the sense of an underlying absolute subjectivity which is non-objectifiable within objective temporality and thus non-susceptible of any ontological designation. My arguments stem, on the one hand, from a version of quantum-mechanical theory (History Projection Operator theory, HPO theory) in view of its formal treatment of two different aspects of time within a quantum context. The discrete, partial-ordering properties (the notions of before and after) and the dynamical-parameter properties reflected in the wave equations of motion. On the other hand, to strengthen my arguments for a transcendental factor of temporality, I attempt an interpretation of some relevant conclusions in the work of J. Eccles ([5]) and of certain results of experimental research of S. Deahaene et al. ([2]) and others.

Application of response surface methodology to study the biological removal of nitrogen from effluent of cattle slaughterhouse in a sequencing batch reactor

The aim of this study was to evaluate the efficiency of a sequencing batch reactor (SBR) on biological removal of nitrogen from cattle slaughterhouse wastewater by nitrification/denitrification processes. The effects of initial concentration of ammoniacal nitrogen were investigated at 100; 150 and 200 mg L-1 and air flow rate at 0.125; 0.375 and 0.625 L min¹ Lreactor-1 on the nitrogen compounds removal, by a Central Composite Rotational Design (CCRD) configuration. There were variations from 9.2 to 94.9%, 4.0 to 19.6% and 20.8 to 92.0% in the conversion of ammoniacal nitrogen to nitrate and nitrite concentration and removal of total nitrogen, respectively. The increase of air flow rate and decrease of the initial concentration of ammoniacal nitrogen resulted in higher efficiencies of total nitrogen removal, as well as the conversion of ammoniacal nitrogen to nitrate. During the pre-established intervals of this study, the removal and conversion efficiencies of nitrogen compounds above 85% were achieved in air flow rate variations from 0.375 to 0.725 L min-1 Lreactor-1 and initial concentration of ammoniacal nitrogen from 80 to 200 mg L-1. On denitrification process, we obtained efficiencies from 91.5 to 96.9% on the removal of nitrite/nitrate and from 78.3 to 87.9% on the removal of organic matter.

CHARACTERIZATION AND EVALUATION OF THE POTENTIAL USE OF SLUDGE FROM STP AND WTP IN PAVING

ABSTRACT Water and sewage treatment plants (STP and WTP) generate as byproduct a significant amount of sludge with environment harmful elements. Sending to landfills or depositing on the ground or rivers are respectively expensive and dangerous alternatives. In this scenario, the use of this waste in paving processes is a promising alternative for disposal thereof. In this study, we focused on characterizing sludge and evaluating its use in paving, which showed satisfactory results for use in base and sub-base floors.