Synthesis of liquid menthol by hydrogenation of dementholized peppermint oil over Ni catalysts

Hydrogenation of (-)-menthone and (+)-isomenthone was studied at 2.7 MPa and 100 ºC. The objective was to produce a liquid menthol mixture rich in (-)-menthol from dementholized peppermint oil. Ni-based catalysts were tested and compared for this reaction: a) 6 and 12% Ni dispersed into a nonstoichiometric magnesium aluminate (Ni-Mg-Al) with spinel structure; b) Ni-Raney catalyst. Both types of catalysts were active for (-)-menthone and (+)-isomenthone hydrogenation. Lower conversion but higher selectivity to (-)-menthol was obtained with Ni-Mg-Al catalysts. However, they rapidly lost their activity. Instead Ni-Raney catalysts kept its original activity even after several hydrogenation runs.

Effect of the structure of commercial poly(ethylene oxide-b-propylene oxide) demulsifier bases on the demulsification of water-in-crude oil emulsions: elucidation of the demulsification mechanism

Water-in-crude oil emulsions are formed during petroleum production and asphaltenes play an important role in their stabilization. Demulsifiers are added to destabilize such emulsions,however the demulsification mechanism is not completely known. In this paper, the performances of commercial poly(ethylene oxide-b-propylene oxide) demulsifiers were studied using synthetic water-in-oil emulsions and model-systems (asphaltenes in organic solvent). No change in the asphaltene aggregate size induced by the demulsifier was observed. The demulsification performance decreased as the asphaltene aggregate size increased, so it can be suggested that the demulsification mechanism is correlated to the voids between the aggregates adsorbed on the water droplets surface.

A green synthesis of α,β-unsaturated carbonyl compounds from glyceraldehyde acetonide

The catalytic behavior of Cs-exchanged and Cs-impregnated zeolites (X and Y) was studied using the Knoevenagel condensation between glyceraldehyde acetonide and ethyl acetoacetate in order to produce the corresponding α,β-unsaturated carbonyl compound that is an important intermediate for fine chemicals. The influence of reaction temperature, type of zeolite, and basicity of the sites on the catalytic behavior of the samples was evaluated. All zeolites were active for the studied reaction. The formation of the main condensation product was favored at lower reaction temperatures. Products of further condensations were also observed especially for samples that were only dried before catalytic test.

Nanostructured systems containing an essential oil: protection against volatilization

The goal of this study was to evaluate the feasibility of preparing nanocapsules and nanoemulsions using tea tree oil as oily phase aiming to protect its volatilization. The nanostructures presented nanometric mean size (160-220 nm) with a polydispersity index below 0.25 and negative zeta potential. The pH values were 6.43 ± 0.37 and 5.98 ± 0.00 for nanoemulsions and nanocapsules, respectively. The oil content after preparation was 96%. The inclusion of tea tree oil in nanocapsules showed higher protection against volatilization. The analysis of mean size and polydispersity index of formulations presented no significant alteration during the storage time.

Development and validation of a method for the analysis of Ochratoxin A in roasted coffee by liquid chromatography/electrospray-mass spectrometry in Tandem (LC/ESI-MS/MS)

A method using LC/ESI-MS/MS for the quantitative analysis of Ochratoxin A in roasted coffee was described. Linearity was demonstrated (r = 0.9175). The limits of detection and quantification were 1.0 and 3.0 ng g-1, respectively. Trueness, repeatability and intermediate precision values were 89.0-108.8%; 2.4-13.7%; 12.5-17.8%, respectively. To the best of our knowledge, this is the first report in which Ochratoxin A in roasted coffee is analysed by LC/ESI-MS/MS, contributing to the field of mycotoxin analysis, and it will be used for future production of Certified Reference Material.

Evaluation of the performance of a castor-oil based formulation in limiting pesticide residues in strawberry crops

A study was made to evaluate the effect of a castor oil-based detergent on strawberry crops treated with different classes of pesticides, namely deltamethrin, folpet, tebuconazole, abamectin and mancozeb, in a controlled environment. Experimental crops of greenhouse strawberries were cultivated in five different ways with control groups using pesticides and castor oil-based detergent. The results showed that the group 2, which was treated with castor oil-based detergent, presented the lowest amount of pesticide residues and the highest quality of fruit produced.

Biomassa em aula prática de Química Orgânica Verde: cravo-da-índia como fonte simultânea de óleo essencial e de furfural

This work presents an optimized integrated experiment for isolation of clove bud essential oil, rich in eugenol, and subsequent utilization of the solid residue for furfural synthesis. The operationally simple laboratory protocols and utilization of water as a solvent in both operations, plus the use of biomass as the starting material for preparation of versatile intermediates in organic synthesis, make the experiments attractive for undergraduate experimental organic chemistry courses in the context of green chemistry. In addition, this is the first description of the use of biomass (clove bud) in the simultaneous preparation of two chemical feedstocks, eugenol and furfural, on experimental organic chemistry courses.

Kinetics of oxidation of biodiesel from soybean oil mixed with TBHQ: determination of storage time

Synthetic antioxidants are an alternative to prevent or retard the degradation of biofuels made from vegetable oils. In this study, it was evaluated the oxidative stability of B100 soybean oil biodiesel, in the presence of tercbutylhydroquinone (TBHQ). The results showed that the induction period, that precedes the seeding process, was delayed in the presence of the antioxidant. Moreover, the obtained results suggest that the B100 biodiesel containing TBHQ can present a storage time at 25 ºC, three times longer than the estimated time for the pure B100.

Towards new botanical pesticides: the toxic effect of Eremanthus goyazensis (Asteraceae) leaves essential oil against Brevipalpus phoenicis (Acari: Tenuipalpidae)

This work reports the chemical characterization of Eremanthusgoyzensis essential oil and its toxic effect over Brevipalpus phoenicis. The essential oil displayed a major composition of sesquiterpenes (61.87%) including trans-caryophillene (26.81%) and germacrene-D (13.31%). The fumigation test indicated a promising bioactivity over adult B. phoenicis individuals at 24 h (2.03 µL/L of air) and 48 h (1.08 µL/L of air) of exposition. A brief discussion of essential oils composition and their singular role on the toxic effect over B. phoenicis is provided here. Our results may contribute to a new and profitable use of a species of Brazilian flora on agribusiness.

Characterization and catalytic performance of potassium loaded on rice husk silica and zeolite nay for transesterification of jatropha seed oil

Rice husk silica (RHS) and NaY were used as supports for potassium (K) prepared from acetate buffer (B) and acetate (A) solutions. K loading did not destroy the NaY structure, but it caused a decrease in the surface area; the K species resided in micropores and on the external surface. In contrast, K loading resulted in the collapse and a decrease in the surface area of RHS. It was found that 12K/NaY-B was the most active catalyst for the transesterification of Jatropha seed oil. The minimum K content in K/NaY-B that provided complete conversion of the Jatropha seed oil was 11 wt%, and the biodiesel yield was 77.9%.

Química Sem Fronteiras: o desafio da energia

Coal, natural gas and petroleum-based liquid fuels are still the most widely used energy sources in modern society. The current scenario contrasts with the foreseen shortage of petroleum that was spread out in the beginning of the XXI century, when the concept of "energy security" emerged as an urgent agenda to ensure a good balance between energy supply and demand. Much beyond protecting refineries and oil ducts from terrorist attacks, these issues soon developed to a portfolio of measures related to process sustainability, involving at least three fundamental dimensions: (a) the need for technological breakthroughs to improve energy production worldwide; (b) the improvement of energy efficiency in all sectors of modern society; and (c) the increase of the social perception that education is a key-word towards a better use of our energy resources. Together with these technological, economic or social issues, "energy security" is also strongly influenced by environmental issues involving greenhouse gas emissions, loss of biodiversity in environmentally sensitive areas, pollution and poor solid waste management. For these and other reasons, the implementation of more sustainable practices in our currently available industrial facilities and the search for alternative energy sources that could partly replace the fossil fuels became a major priority throughout the world. Regarding fossil fuels, the main technological bottlenecks are related to the exploitation of less accessible petroleum resources such as those in the pre-salt layer, ranging from the proper characterization of these deep-water oil reservoirs, the development of lighter and more efficient equipment for both exploration and exploitation, the optimization of the drilling techniques, the achievement of further improvements in production yields and the establishment of specialized training programs for the technical staff. The production of natural gas from shale is also emerging in several countries but its production in large scale has several problems ranging from the unavoidable environmental impact of shale mining as well as to the bad consequences of its large scale exploitation in the past. The large scale use of coal has similar environmental problems, which are aggravated by difficulties in its proper characterization. Also, the mitigation of harmful gases and particulate matter that are released as a result of combustion is still depending on the development of new gas cleaning technologies including more efficient catalysts to improve its emission profile. On the other hand, biofuels are still struggling to fulfill their role in reducing our high dependence on fossil fuels. Fatty acid alkyl esters (biodiesel) from vegetable oils and ethanol from cane sucrose and corn starch are mature technologies whose market share is partially limited by the availability of their raw materials. For this reason, there has been a great effort to develop "second-generation" technologies to produce methanol, ethanol, butanol, biodiesel, biogas (methane), bio-oils, syngas and synthetic fuels from lower grade renewable feedstocks such as lignocellulosic materials whose consumption would not interfere with the rather sensitive issues of food security. Advanced fermentation processes are envisaged as "third generation" technologies and these are primarily linked to the use of algae feedstocks as well as other organisms that could produce biofuels or simply provide microbial biomass for the processes listed above. Due to the complexity and cost of their production chain, "third generation" technologies usually aim at high value added biofuels such as biojet fuel, biohydrogen and hydrocarbons with a fuel performance similar to diesel or gasoline, situations in which the use of genetically modified organisms is usually required. In general, the main challenges in this field could be summarized as follows: (a) the need for prospecting alternative sources of biomass that are not linked to the food chain; (b) the intensive use of green chemistry principles in our current industrial activities; (c) the development of mature technologies for the production of second and third generation biofuels; (d) the development of safe bioprocesses that are based on environmentally benign microorganisms; (e) the scale-up of potential technologies to a suitable demonstration scale; and (f) the full understanding of the technological and environmental implications of the food vs. fuel debate. On the basis of these, the main objective of this article is to stimulate the discussion and help the decision making regarding "energy security" issues and their challenges for modern society, in such a way to encourage the participation of the Brazilian Chemistry community in the design of a road map for a safer, sustainable and prosper future for our nation.

Green tea in transdermal formulation: HPLC method for quality control and in vitro drug release assays

RP-HPLC based analytical method for use in both quality control of green tea in a semisolid formulation and for in vitro drug release assays was developed and validated. The method was precise (CV < 5%), accurate (recovery between 98% and 102%), linear (R² > 0.99), robust, and specific for the determination of epigallocatechin 3-gallate (EGCG), caffeine (CAF), and gallic acid (GA). In a diffusion cell chamber, the release rate of EGCG was 8896.01 µg cm-2. This data showed that EGCG will be able to exert its systemic activity when delivered though the transdermal formulation, due to its good flux rates with the synthetic membrane.

Removal of Pb(II) ions and malachite green dye from wastewater by activated carbon produced from lemon peel

In the present study, a high-surface area activated carbon was prepared by chemical activation of lemon peel with H3PO4 as the active agent. Then, the adsorption behavior of Malachite green dye and Pb(II) ions on the produced activated carbon was studied. Batch process was employed for sorption kinetics and equilibrium studies. Experimental data were fitted to various isotherm models. According to the Langmuir model, the maximum adsorption capacities of Malachite green dye and Pb(II) ions were found to be 66.67 and 90.91 mg g-1, respectively, at room temperature. Kinetic studies showed the adsorption process followed a pseudo second-order rate model. The sorption kinetics were controlled by intra-particle diffusion. The results indicated that the produced activated carbon can be economically and effectively used as an adsorbent for the removal of Malachite green dye and Pb(II) ions from wastewaters.

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).

CONSTITUENTS OF ESSENTIAL OIL AND HYDROLATE OF LEAVES OF Campomanesia viatoris LANDRUM

The chemical composition of the essential oil and hydrolates of Campomanesia viatoris Landrum were investigated by gas chromatography/mass spectrometry (GC/MS) and a GC flame ionization detector (GC-FID). The major constituents were tasmanone (70.50, essential oil; 74.73%, hydrolate), flavesone (12.77, essential oil; 12.24%, hydrolate) and agglomerone (6.79, essential oil; 10.84%, hydrolate). Tasmonone was isolated and its structure was characterized by spectrometric analysis, specifically 1D and 2D nuclear magnetic resonance (NMR) and mass spectrometry (MS). These findings supports the quimiotaxonomic relationship with Campomanesia and Eucalyptus genera.