Aplicação de métodos quimiométricos na otimização da extração de Ca, Mg, K, Fe, Zn, Cu e Mn em folhas de braquiária

This work applied a 2² factorial design to the optimization of the extraction of seven elements (calcium, magnesium, potassium, iron, zinc, copper and manganese) in brachiaria leaves, determined by flame atomic absorption spectrometry. The factors sample mass and digestion type were evaluated at two levels: 200/500 mg, and dry/wet, respectively. Principal component analysis allowed simultaneous discrimination of all the significant effects in one biplot. Wet digestion and mass of 200 mg were considered the best conditions. The decrease of 60% in sample mass allowed to save costs and reagents. The method was validated through the estimation of figures of merit.

Recuperação de compostos de iodo de reagentes e soluções laboratoriais

This work presents simple routes to recover iodine compounds from oxidized laboratory chemicals and aqueous solutions (HI and KI) used in laboratory chemistry classes. These routes are based on the oxidation of iodide ions (I-) to iodine (I2) by an oxidant (H2O2) or reduction of oxidized iodine by red phosphorus or hydrazine. Both routes presented high yields. The oxidative route is of general use whereas the reductive one is appropriate for restoring original iodine reagents. Final wastes were generated in low amounts. This work is appropriate for teaching many laboratory techniques (e.g., distillation, titration and filtration) in the chemical laboratory.

Síntese da Epoxone a partir de D-frutose: um experimento didático em laboratório de Química Orgânica com foco nos princípios da Química Verde

In recent years, the introduction of the Green Chemistry concepts in undergraduate chemistry classes has been intensively pursued. In this regard, the two-step preparation of Epoxone (an organocatalyst developed by Shi & col.) from commercial D-fructose, through ketalization of vicinal diols followed by oxidation of a sterically congested secondary alcohol, involves important topics in Organic Chemistry and employs inexpensive and nontoxic reagents. The reactions are easy to perform and the products from both steps are readily obtained as crystalline solids after simple procedures, thus facilitating their chemical characterization.

Application of ftir in the determination of acrylate content in poly(sodium acrylate-co-acrylamide) superabsorbent hydrogels

Hydrogels have been prepared by free-radical solution copolymerization of acrylamide and sodium acrylate (NaAc), with molar ratio ranging from 25/75 to 80/20, respectively, using methylene bisacrylamide as the crosslinking agent. A FTIR spectroscopy procedure to determine the acrylate/acrylamide ratio in these hydrogels was proposed based on absorbance at 1410 cm-1 (nCOO-) and 2940 cm-1 (nCH and nCH2). A straight line with a good linear correlation coefficient (0.998) was obtained by plotting the acrylate content (Ac%) versus relative absorbance (Arel = A1410/A2940). Results were confirmed by the amount of sodium cation released in acid medium determined by atomic absorption spectrometry.

Especiação de cobre e zinco em urina: importância dos metais em doenças neurodegenerativas

Metals such as copper and zinc are essential for the development and maintenance of numerous enzymatic activities, mitochondrial functions, neurotransmission, and also for memorization and learning. However, disruption in their homeostasis can cause neurodegenerative disorders such as the Alzheimer and Parkinson diseases. In this work, the speciation of copper and zinc in urine samples was carried out. To this end, free and total metal concentrations were determined by square wave anodic stripping voltammetry using a glassy carbon electrode coated with bismuth film. The digestion of the samples was performed in a microwave with the addition of oxidant reagents.

Síntese e caracterização de hidrogéis compósitos a partir de copolímeros acrilamida-acrilato e caulim: efeito da constituição de diferentes caulins do nordeste brasileiro

Superabsorbent hydrogels based on poly (acrylamide-co-acrylate) and different kaolins, were prepared by free-radical aqueous copolymerization. FTIR and WAXS techniques were employed for characterization of a series of hydrogels, obtained by varying the percentage of clay, crosslinking and constitution of kaolin. The water absorbency at equilibrium (Weq) decreased with increasing clay content and the amount of crosslinking agent. Superabsorbent hydrogel (Weq > 1084 g H2O/g gel) was obtained as 10 wt% of white kaolin and 0.05 mol% of crosslinking agent were used. The hydrogel proved sensitive to pH variation and the presence of salts.

Hydrogels of cellulose acetate crosslinked with pyromellitic dianhydride: part I: synthesis and swelling kinetics

This work describes the synthesis of hydrogels of cellulose acetate (AC) crosslinked with 1,2,4,5-benzenotetracarboxylic dianhydride (PMDA). The crosslinking reaction was monitored by FTIR. Analysis of aromatic fragments from the alkaline hydrolysis of the gels by UV spectroscopy indicated that an increase in the stoichiometric ratio of dianhydride resulted in higher degrees of crosslinking. The non-porous nature of the gels was confirmed by analysis of nitrogen adsorption. Water absorption isotherms showed that as the temperature and degree of crosslinking increased, the percentage of water absorbed at equilibrium (%Seq) also increased. The hydrogels presented second order swelling kinetics.

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.

Hidrogeles microestructurados de acrilamida y determinación de su capacidad de absorber agua y etanol

This paper reports the synthesis of nanostructured hydrogels of acrylamide by a two-step polymerisation process. The first step is performed by inverse microemulsion polymerization (water-in-oil) of N-isopropylacrylamide (NIPA), with these particles then added to aqueous solutions of acrylamide (AM), adding a crosslinking agent. The polymerization reaction is then initiated, thereby producing nanostructured hydrogels. We determined the capacity to absorb water, water and / or ethanol when nanostructured hydrogels were immersed in aqueous solutions with different concentrations of ethanol. It was found that the hydrogels were selective in absorbing water in all cases increasing with the ethanol concentration of the solutions.

Determinação de parâmetros cinéticos em fluxo com câmara de gradiente e deteção espectrofotométrica: aplicação à reação entre o violeta de cristal e o ião hidróxido

A didactic experiment is proposed aimed to extend the Flow Injection Analysis (FIA) based methodology to the area of physical chemistry/chemical reactors for undergraduate labs. Our prime objective was to describe the use of a gradient chamber for determination of the rate constant for the reaction between crystal violet and the hydroxide ion. The study was complemented by determining the effect of temperature on the rate constant. The kinetic parameters, activation energy and reaction rate constant are determined based on an assumption of rate orders. The main didactic advantages of the proposed experimental set-up are the use of less reagents, contributing to a more environmental friendly experiment. The experiment illustrates also the reduction of associated errors and time by using automated analysis owing to decreased operator manipulation.

Oceanografia e Química: unindo conhecimentos em prol dos oceanos e da sociedade

The marine environment is certainly one of the most complex systems to study, not only because of the challenges posed by the nature of the waters, but especially due to the interactions of physical, chemical and biological processes that control the cycles of the elements. Together with analytical chemists, oceanographers have been making a great effort in the advancement of knowledge of the distribution patterns of trace elements and processes that determine their biogeochemical cycles and influences on the climate of the planet. The international academic community is now in prime position to perform the first study on a global scale for observation of trace elements and their isotopes in the marine environment (GEOTRACES) and to evaluate the effects of major global changes associated with the influences of megacities distributed around the globe. This action can only be performed due to the development of highly sensitive detection methods and the use of clean sampling and handling techniques, together with a joint international program working toward the clear objective of expanding the frontiers of the biogeochemistry of the oceans and related topics, including climate change issues and ocean acidification associated with alterations in the carbon cycle. It is expected that the oceanographic data produced this coming decade will allow a better understanding of biogeochemical cycles, and especially the assessment of changes in trace elements and contaminants in the oceans due to anthropogenic influences, as well as its effects on ecosystems and climate. Computational models are to be constructed to simulate the conditions and processes of the modern oceans and to allow predictions. The environmental changes arising from human activity since the 18th century (also called the Anthropocene) have made the Earth System even more complex. Anthropogenic activities have altered both terrestrial and marine ecosystems, and the legacy of these impacts in the oceans include: a) pollution of the marine environment by solid waste, including plastics; b) pollution by chemical and medical (including those for veterinary use) substances such as hormones, antibiotics, legal and illegal drugs, leading to possible endocrine disruption of marine organisms; and c) ocean acidification, the collateral effect of anthropogenic emissions of CO2 into the atmosphere, irreversible in the human life time scale. Unfortunately, the anthropogenic alteration of the hydrosphere due to inputs of plastics, metal, hydrocarbons, contaminants of emerging concern and even with formerly "exotic" trace elements, such us rare earth elements is likely to accelerate in the near future. These emerging contaminants would likely soon present difficulties for studies in pristine environments. All this knowledge brings with it a great responsibility: helping to envisage viable adaptation and mitigation solutions to the problems identified. The greatest challenge faced by Brazil is currently to create a framework project to develop education, science and technology applied to oceanography and related areas. This framework would strengthen the present working groups and enhance capacity building, allowing a broader Brazilian participation in joint international actions and scientific programs. Recently, the establishment of the National Institutes of Science and Technology (INCTs) for marine science, and the creation of the National Institute of Oceanographic and Hydrological Research represent an exemplary start. However, the participation of the Brazilian academic community in the latest assaults on the frontier of chemical oceanography is extremely limited, largely due to: i. absence of physical infrastructure for the preparation and processing of field samples at ultra-trace level; ii. limited access to oceanographic cruises, due to the small number of Brazilian vessels and/or absence of "clean" laboratories on board; iii. restricted international cooperation; iv. limited analytical capacity of Brazilian institutions for the analysis of trace elements in seawater; v. high cost of ultrapure reagents associated with processing a large number of samples, and vi. lack of qualified technical staff. Advances in knowledge, analytic capabilities and the increasing availability of analytical resources available today offer favorable conditions for chemical oceanography to grow. The Brazilian academic community is maturing and willing to play a role in strengthening the marine science research programs by connecting them with educational and technological initiatives in order to preserve the oceans and to promote the development of society.

Ressonância: desenvolvimento, utilização e avaliação de um software educacional

Resonance is a useful concept that shows how electrons are shared between two or more atoms and allows a prediction of the chemical reactivity and relative stability of reagents, intermediates, and products. An educational software that enables interactive exploration of the concepts related to resonance and thereby facilitates its understanding was developed. The software was field-tested, and an evaluation questionnaire concerning the software as an educational tool was answered by the students and professors involved in the test. The results led to the conclusion that the developed computer application can be characterized as an auxiliary tool that assists teachers in their lectures and students in their learning process.

Bateria de métricas para avaliação da verdura material de reações de síntese

The use of a battery of three mass metrics (atomic economy - AE, reaction mass efficiency - RME, and mass intensity - MI) for systemic evaluation of the material greenness of synthesis reactions is presented. Material greenness is discussed in terms of materialization/dematerialization of the reaction system and also according to the first two Principles of Green Chemistry, and is shown to involve two components: atomic greenness (incorporation of the atoms provided by reagents into the product, evaluated by AE and RME); and massic greenness (global mass of reagents and non-stoichiometric materials, evaluated by MI, related to the production of residues).

METODOLOGIAS DE COLETA, PRESERVAÇÃO E ARMAZENAMENTO DE AMOSTRAS DE ÁGUA PARA ANÁLISE DE MERCÚRIO - UMA REVISÃO

Knowing the mercury levels of an environment allows a diverse array of biogeochemical studies into the mercury cycle on a local or global scale. Among matrices commonly evaluated, water remains a challenge for research because its mercury levels can be very low, requiring development of complex analytical protocols. Currently, sample preservation methods, protocols that avoid contamination, and analytical techniques with low detection limits allow analysis of mercury in pristine waters. However, different protocols suggest different methods depending on a range of factors such as the characteristics of water sampled and storage time. In remote areas, such as oceanic and Amazonian regions, sample preservation and transport to a laboratory can be difficult, requiring processing of the water during the sampling expedition and the establishment of a field laboratory. Brazilian research on mercury in water can be limited due to difficulty obtaining reagents, lack of laboratory structure, qualified personnel, and financial support. Considering this complexity for analyzing water, we reviewed methodologies for sampling, preservation, and storage of water samples for analysis of the most commonly evaluated mercury species (dissolved gaseous mercury, reactive mercury, methylmercury and total mercury).

ADAPTAÇÃO DA METODOLOGIA DE ANÁLISE DE METEMOGLOBINA COMO BIOMARCADOR DE EFEITO DA EXPOSIÇÃO AO AGROTÓXICO DIFLUBENZURON

This work aimed to adapt the analysis of methemoglobin recommended by Evelyn - Malloy (visible spectrophotometry), in order to facilitate its application in the field, or to analysis in clinical laboratory, of existing sites of diflubenzuron application. The parameters changed included: centrifuge rotation speed; time between the collection of biological sample and analysis, and storage temperature of the samples; and the volume of reagents. The comparison of the rotation speed (rpm) of the reference methodology with the rpm of a "clinical centrifuge" did not reveal a statistically significant difference in the levels of methemoglobin. The time between the collection of biological sample and analysis was extended for a period of up to 48 hours for both conservation by refrigeration and ambient temperature, producing no statistically significant difference when compared to the standard duration of 2 hours. Regarding the reagents, the reference methodology already uses the volume necessary to ensure complete reaction, whereas a wider range from the recommended volume to a 5-fold reduction in comparison to the reference methodology could be used. It was concluded that the proposed changes to the methodology for adapting the analysis are applicable to studies of field / workplace exposure and ensure the reliability of results. The adapted methodology was inter-laboratory validated and the parameters changed can be selected according to the requirements of the laboratory at which the methemoglobin is to be measured.