Circular chemistry (CC) is an approach for establishing chemical processes to become truly circular and sustainable. It adopts the principles of circular economy (CE), employing life cycle approaches and systems thinking, which help to understand and address the sustainability issues of chemical processes and products. Within this whole context, it is possible to identify some problems of the current lifestyle, such as plastic waste disposal, CO2 emission, e-waste, among others, which need to be addressed accordingly. The reuse provided, well-structured within the context of circular chemistry, can bring benefits in all spheres: social, environmental and economic. Thus, the purpose of this revision is to present CE and CC as the pillars for a sustainable development, bringing discussions about: CE and CC systems; sustainable chemistry; and chemistry 4.0, which embeds digitization, sustainability, and circular economy in industrial chemical processes. Through the knowledge of chemistry, both CC and CE can contribute with innovative methods and processes which maximize benefits, eliminating, or, at least, reducing adverse impacts, thus contributing to construct a mutually beneficial relationship between science and society, its surroundings, and the environment. Therefore, implementing this new model is an opportunity that challenges the human imagination in building a better world.

In this work, the combined use of p-sulfonic acid-calix[n]arene and microwave energy to hydrolyze the 1,3-dioxolane ketal of isatin was evaluated with excellent results. This is the first time that p-sulfonic acid-calix[n]arene has been used as the catalyst in a ketal hydrolysis reaction and the deprotection of the ketone carbonyl of isatin is reported. The presence of 2.5 mol% of p-sulfonic acid-calix[4,6]arene at 160 ºC resulted in over 96% conversion of this ketal in 10 min, with the additional advantage of using water as a solvent. This catalytic system (aqueous phase containing p-sulfonic acid-calix[4]arene) was reused for five consecutive cycles, with a conversion above 96% maintained. This reusable system is not practicable using p-toluenesulfonic acid and p-hydroxybenzenesulfonic acid as catalysts since both are extracted to the organic phase with the reaction product. The hydrolysis of 1,3-dioxolane ketal of isatins with different substituents (CH3, I, Br, Cl, F, NO2) in the aromatic ring was also evaluated. The protecting group of 5-methyl-isatin was removed with 73% conversion using 2.5 mol% of p-sulfonic acid-calix[4]arene at 160 ºC for 5 min. In contrast, the ketal of 5-nitro-isatin reached 80% conversion using the same conditions after 40 min.

The crescent number of scientific articles published per year shows that research on biodiesel continues to play an important role to support the growing demand for this biofuel. The second edition of Biodiesel: An Overview presents the worldwide research in the last 15 years. Microalgae biomass is the most studied raw material alternative in this period and several studies have been carried out to develop basic heterogeneous catalysts for biodiesel production. Concerning to production technologies, supercritical conditions and intensification process have been extensively investigated. The development of new antioxidants additives has focused mainly on biomass-derived formulations and there are few studies on biocide candidates. In terms of pollutant emissions, in general, the studies showed that the addition of biodiesel generates lower concentrations of polycyclic aromatic hydrocarbons (PAH), CO and n-alkanes pollutants, but carbonyl compounds, major ions and NOx are emitted in a higher concentration compared to pure diesel.

The corrosion inhibition of mild steel by aqueous extract of cumaru (Dipteryx odorata) seeds and its high molecular weight fraction (HMWF) was investigated in 1 mol L-1 HCl solution. The study was carried out through gravimetric essays, open circuit potential measurements, anodic and cathodic polarization curves and electrochemical impedance analyses, as well as morphological analysis of the mild steel by scanning electron microscopy. Gravimetric tests showed that the inhibition efficiency (IE) increased with immersion time and inhibitor concentration, reaching 98% of IE using 100 mg L-1 of the HMWF, after 6 h immersion time. The activation energy (Ea) increased with the addition of both inhibitors which characterizes a physical adsorption of the constituents of the aqueous extract of cumaru on the metal surface. Polarization curves indicated that both aqueous cumaru seeds extract and its HMWF act as mixed-type inhibitor. Impedance results showed a decrease in double layer capacitance (Cdl) and an increase in charge transfer resistance (Rct) evidencing a typically screening effect. The adsorption of molecules present in the aqueous extract of cumaru followed the Langmuir isotherm. The aqueous cumaru seeds extract was characterized by Fourier transform infrared spectroscopy (FTIR), 1H, 13C and 2D nuclear magnetic resonance (NMR).

Biodiesel demand is increasing all over the world and the inhibition of microbial growth during the storage of this biofuel is extremely important. There are few studies involving the evaluation of biocides specifically for biodiesel. In the present work, we synthesized and evaluated a set of biocide candidates from chemical transformations in triacylglycerides. Samples of pure biodiesel with the products were evaluated against microorganisms which have been isolated from biodiesel/diesel blends (fungi A. niger, A. fumigatus, C. albicans and S. cerevisiae; and bacteria B. subtilis and Acinetobacter sp.). None of the products inhibited the growth of bacteria. Four nitrated derivatives presented fungicidal activity. The nitrated derivatives were also evaluated as cetane number improvers for B7 biodiesel/diesel blend. The nitrates of soybean methoxylated ethylene glycol esters increased the cetane number by more than three points. Despite showing modest biocide activity, the results can guide the planning of new products from triacylglycerides.

In the last decade, the research works on microbial as a potential source of lipid for biodiesel production have been growing. In this work, the potential of a sludge from high-rate lagoons in urban sewage treatment, composed mainly by Chlorella sp., as oil source for biodiesel production, was studied. The potential of Chlorella sp. growth in photobioreactor under controlled conditions was also investigated. Low lipid content (up to 3%) was observed in both cases. The composition of both oils showed high amount of fatty acids and fatty acid based compounds, however there are also other non-fatty acid based lipids. Density and viscosity of biodiesel from biosolid oil were determined and the results showed that these physico-chemical properties do not match the specification required for biodiesel. The results showed that sewage sludge from Samambaia treatment station (DF, Brazil) and Chlorella sp. cultivated under the conditions described in this work are not potential sources of fatty material for biodiesel production.

Biodiesel is obtained from a renewable source and has been used as an alternative to fossil fuels. It has unsaturated fatty acid methyl esters that can degrade due to oxidation of the double bonds. The instability of biodiesel during storage may cause problems regarding the maintenance and operation of motors. This work evaluated the effect of several variables on the storage conditions of biodiesel:diesel blends. The study was performed using an experimental design, and the variables were water content in biodiesel (0.01, 0.05 and 0.09%), biodiesel content in diesel (5.0, 7.5 and 10.0%), time (15, 30 and 45 days) and temperature (30, 40 and 50 °C). The levels simulated actual Brazilian storage conditions. The degradation was evaluated based on direct measurement of methyl linoleate and methyl oleate in the blends by gas chromatography-mass spectrometry. These unsaturated fatty acid methyl esters are target compounds in the oxidation process. All experiments were carried out in sealed flasks. The results suggest that the restriction of oxygen limited the degradation of biodiesel in blends with higher percentage of the biofuel. The variables temperature, time and water content in biodiesel individually did not affect the degradation process within the range investigated at 95% confidence interval.

Catalisadores a base de argilas naturais brasileiras foram preparados, caracterizados, e sua atividade catalítica foi avaliada em reações de esterificação. As argilas naturais foram ativadas por tratamento ácido como recebidas, sem qualquer tratamento prévio. As argilas naturais e as argilas ácidas foram caracterizadas por DRX, TPD-NH3, termodessorção de n-butilamina, análise de adsorção de N2, FT-IR, TGA e DTA. O desempenho catalítico foi investigado em reações de esterificação de diversos ácidos carboxílicos com diferentes álcoois. As reações foram realizadas com razão molar ácido carboxílico/álcool 1:3, a 100 ºC e pressão atmosférica, por 3 h. As argilas ácidas forneceram boas conversões e apresentaram desempenho melhor que a argila comercial K10.

Natural Brazilian clay-based catalysts were prepared, characterised, and their catalytic activity was assessed in esterification reactions. The natural clays were acid activated as received, without any previous treatment. Both natural and acid-activated clays were characterised by XRD, NH3-TPD, thermodesorption of n-butylamine, N2 adsorption analysis, FT-IR, TGA and DTA. The catalytic performance was investigated in the esterification of several carboxylic acids with different alcohols. The reactions were carried out in a 1:3 carboxylic acid/alcohol molar ratio at 100 ºC and atmospheric pressure for 3 h. The acid-activated clays provided good yields and better performance than commercial clay K10.

Óleos essenciais cítricos brasileiros (mandarina, laranja, limão, bergamota e tangerina) foram analisados a fim de determinar resíduos de pesticidas organoclorados (aldrin, clordano, dieldrin e dicofol) e organofosforados (clorpirifós metílico, dimetoato, metidationa e paration metílico). Um estudo comparativo entre cromatografia gasosa acoplada a espectrometria de massas em modo de monitoramento seletivo de íons (CG-EM-MSI) e cromatografia gasosa com detector por captura de elétrons (CG-DCE) foi realizado usando extração em fase sólida (EFS) com fase Florisil® para pré-concentração dos pesticidas. A recuperação média dos pesticidas foi de 71 a 83% por CG-EM-MSI e de 99 a 104% por CG-DCE. O limite de quantificação foi de 0,93 a 3,93 mg L-1 por CG-EM-MSI e de 0,09 a 0,12 mg L-1 por CG-DCE. Quinze amostras comerciais de óleos essenciais cítricos brasileiros foram analisadas e seis amostras apresentaram contaminação com valores acima do limite máximo de resíduos (LMR) permitido pelo Codex Alimentarius.

Brazilian citrus essential oils (mandarin, orange, lemon, bergamot and tangerine) were analyzed for the determination of pesticides residues of organochlorine (aldrin, chlordane, dieldrin and dicofol) and organophosphorus (methyl chlorpyrifos, dimethoate, methidathion and methyl parathion) . A comparative study between gas chromatography-mass spectrometry in selective ion monitoring mode (GC-MS-SIM) and gas chromatography-electron capture detector (GC-ECD) was performed using solid phase extraction (SPE) with Florisil® cartridge for the pre-concentration of pesticides. The average recovery of pesticides was from 71 to 83% as determined by GC-MS-SIM analysis and 99 to 104% by GC-ECD. The limit of quantification was from 0.93 to 3.93 mg L-1 in GC-MS-SIM and 0.09 to 0.12 mg L-1 in GC-ECD. Fifteen samples of commercial Brazilian citrus essential oils were analyzed and six samples showed contamination with values above the maximum residue limit (MRL) allowed by the Codex Alimentarius.

Convolutamydine A is a member of a family of oxindole alkaloids isolated from the Floridian marine bryozan Amathia convoluta in 8.6x10-6 % yield. This compound is interesting as it has been described in the literature to have significant pharmacological activity. When bioactive substances are isolated in low yields, such as in the case of convolutamydine A, the use of synthetic organic chemistry to prepare larger quantities of these substances is necessary. This paper describes the isolation, structural characterization and synthesis of convolutamydine A, using readily available reagents and reaction conditions that may be applied in any organic chemistry undergraduate laboratory course.

The aim of this work was to develop and validate a method of analysis of biodiesel:diesel blends using HRGC-MS in SIM mode. The proposed method is applicable to biodiesel from linoleic oils, such as soybean oil. The following results were obtained: linearity over the methyl linoleate concentration range of 250-2500 mg L-1 (R² > 0.999); limits of detection and quantification of 2 and 5 mg L-1, respectively; recovery from 82 to 96% of biodiesel in diesel and repeatability < 2% (RSD). Comparison between two operators showed that it is not necessary the same operator to do the analysis.

A importância da produção de biodiesel, nos últimos cinco anos, é apresentada a partir de artigos científicos publicados e patentes depositadas. Foi realizada uma análise crítica sobre as fontes oleaginosas mais utilizadas como matéria-prima para produção de biodiesel, os catalisadores e os métodos de acompanhamento da reação de transesterificação. Também foram avaliados estudos comparativos entre emissões de diesel fossil e misturas, em várias proporções, com biodiesel. Finalmente, foram indicados desafios enfocando aspectos tecnológicos, agronômicos e de infra-estrutura para produção de biodiesel.

The importance of biodiesel production was analyzed based on scientific articles and patents. A critical analysis was presented on the most used oil sources, the catalysts and the methods to verify the transesterification yields. Also analyzed were the comparative studies on emissions from pure fossil diesel and mixtures with biodiesel in variable proportions. Finally some challenges and considerations focused on technological, agronomic and infrastructure aspects of biodiesel production were indicated.