Resumo em Inglês:

Humankind has experienced a remarkable development since it began to design and optimize chemical reactions to achieve valuable compounds. The key to accomplish these tasks is the proper understanding of how chemical transformations occur at a molecular level, that is, their reaction mechanisms. Based on a suitable mechanistic proposal, experimentalists choose a given chemical protocol to optimize experimental conditions, design new synthetic routes, and circumvent competing reactions. In this context, computational chemistry has become a valuable ally for mechanistic elucidation. We present herein a review of complementary collaborations between experimentalists and theoretical chemists to rationalize processes at the molecular level, focusing mainly on the fields of organic synthesis, natural product chemistry, and systems with environmental interest. Throughout this review, we highlight the ability of computational evaluations to provide answers to questions raised from experiments in a clear and direct way, indicating to experimentalists alternative paths to help them solve their problems.

Resumo em Inglês:

The plasmonic properties of Au nanoparticles (AuNP), which allow the observation of enhanced spectroscopic effects, are strongly affected by the aggregation and precipitation caused by the strong interactions between nanoparticles. To avoid AuNP aggregation and precipitation, the present study proposes coating with MnO2, forming AuNP@MnO2 core-shell structures. The MnO2 layers presented 1-10 nm thickness so that highly surface-enhanced fluorescence was obtained with maximum intensity given by 5 nm thick MnO2. The decrease in Raman intensity could be controlled, despite the inherent reduction in surface-enhanced Raman scattering (SERS) intensity with increasing adsorbate-surface distance. The decrease in Raman intensity was compensated by increasing AuNP stability caused by the MnO2 shell.

Resumo em Inglês:

Cagaiteira, the fruit popularly known as cagaite, belongs to the Myrtaceae family. Seed oil cagaite (Eugenia dysenterica DC) was obtained by three methods of extraction, extraction using an ultrasound (OCU), extraction by mechanical pressing (OCP) and extraction with Soxhlet extractor (OCS) in 3 different times (3, 6 and 9 h) and the content of fatty acids and physicalchemical properties were compared. The rate of saturated fatty acids ranged from 19.46% (OCP03) to 31.18% (OCS09), while the amount of unsaturated fatty acids ranged from 54.72% (OCP03) to 67.64% (OCS09). Linoleic and linolenic acids, important in nutrition food, varied between 32.22-38.11 and 5.55-8.78%, respectively. For oxidative stability, OCUAq (heated ultrasound extraction) samples showed the highest induction periods, showing a positive correlation with antioxidant activity and phenol content, demonstrating the efficiency of the use of ultrasonic extraction to obtain quality oils from cagaite seeds.

Resumo em Inglês:

Hybrid organic-inorganic perovskites have attracted interest in photovoltaic applications due to their excellent optoelectronic properties and low-temperature processability. From 2009 to 2021, lab-scale perovskite solar cells (PSC) reached a power conversion efficiency (PCE) of 25.7%, and a PCE of 17.9% for perovskite solar modules with an area of 800 cm2. Here, we present an investigation using three deposition techniques, spin-coating, blade-coating, and spray-coating, to process the charge transport layers and the active layer of perovskite solar cells onto 5 cm × 5 cm sized substrates, with device structure glass/fluorine-doped tin oxide (FTO)/c-TiO2/meso-TiO2+Perovskite/2,2’,7,7’-tetrakis(N,N-di-p-methoxyphenyl-amine)9,9’-spirobifluorene (spiro-OMeTAD) or poly(3-hexylthiophene) (P3HT)/Au. Large-area PSC achieved an open-circuit voltage of around 1.1 V and PCE of 6%. The power generated was sufficient to start a fan. Furthermore, the connection in series of two large-area PSCs generated a voltage of 1.9 V. Then, we developed a simple method for manufacturing a monolithic perovskite mini-module containing two series-connected PSCs without using laser-scribing processes (usually named P1, P2, and P3 processes). This mini-module delivered a voltage of 1.52 V. Both voltages (1.9 and 1.52 V) were enough to turn on a red (or yellow) light-emitting diode (LED). To our knowledge, this is the first scientific report describing the assembly of a large-area n-i-p perovskite single cell and mini-module in Brazil.

Resumo em Inglês:

In this work, iron ore tailing (IOT) was used for the production of two different materials: sodium silicate and geopolymers. Initially, reactions of IOT with NaOH were carried out by hydrothermal reaction in autoclave at 200 °C (1:1.5 and 1:2.5 SiO2:NaOH molar ratio) and reaction times of 4 and 8 h. X-ray fluorescence by dispersive energy (XRF), X-ray diffraction (XRD), Mössbauer spectroscopy, scanning electron microscopy (SEM-EDS) and titrations showed that IOT:NaOH ratios of 1:2.5 and reaction time 8 h completely dissolved the quartz from the IOT, obtaining a solid fraction consisting mainly of hematite and an aqueous phase of sodium silicate, which showed contents of ca. 23% SiO2 and 19% Na2O. This sodium silicate obtained was then combined with IOT (25 and 50 wt.%) to produce geopolimeric material with excellent physico-chemical properties, fast curing time and very good compressive strength results, which ranged from 41 to 58 MPa and many potential applications.

Resumo em Inglês:

Latent fingerprint is an important crime scene evidence, but it is not always recoverable or technically suitable for analysis with fingerprint patterns. Forensic science has shown that other information can be explored from traces using chemical compounds. Infrared spectroscopy is a nondestructive technique that is widely applied to a variety of forensic evidence. In this work, infrared spectroscopy and partial least square discriminant analysis were used to determine the human sex based on latent fingermark analysis. Fingerprint samples were taken from 42 male and female donors, then kept in either dark or light storage conditions, and the Fourier transform infrared (FTIR) spectra were measured considering a period of up to 30 days from collection. The regions from 3000 to 2800 cm-1 and 1790 to 1150 cm-1 presented the greatest differences in the peak intensities among the two sex groups. The results showed a correct discrimination rate higher than 80%.

Resumo em Inglês:

The chemical-mineralogical characterization of rupestrian paintings in red, white, black and yellow colors, which decorate the rocky walls from the archaeological sites of Ema and Furna dos Índios (Inhuma, Piauí, Brazil) was performed. The chemical analyses were performed in situ by the non-invasive analytical technique X-ray fluorescence spectrometry (XRF) as well as in laboratory using a non-destructive approach, without previous sample preparation, and Raman microscopy, and scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS) techniques. The results, when together, allowed unequivocal identification of the main substances responsible for the color pigments, namely, hematite (red pigment), gypsum (white pigment), amorphous carbon from charcoal (black pigment) and goethite (yellow pigment).

Resumo em Inglês:

Infusions of Mikania glomerata Sprengel (guaco) leaves are used in Brazil for the treatment of respiratory diseases. Coumarin is the chemical marker of guaco for quality control purposes. This work proposes a voltammetric methodology to determine coumarin by using a boron-doped diamond electrode. At pH 10 (0.1 mol L-1 Britton-Robinson buffer solution), coumarin is irreversibly oxidized around +1.77 V in a process predominantly controlled by diffusion. The methodology described here presented a linear range from 1.54 to 15.3 µg mL-1 with limits of detection and quantification of 0.20 and 0.62 µg mL-1, respectively. Analysis of variance confirmed the significance of the regression and the absence of lack-of-fit at the confidence level of 95%. Infusion of commercial guaco leaves was directly analyzed, and results were in agreement with high-performance liquid chromatography after applying the paired t-test at a confidence level of 95%.

Resumo em Inglês:

Sulfonamides (SAs) are low-cost synthetic antimicrobials widely used in veterinary and human medicine to treat diseases and prevent infections. However, long periods of exposure to sulfonamides can cause adverse effects such as allergic reactions. This work aims to study dispersive solid-liquid microextraction as an alternative method for extracting total SAs in meat samples. The procedure uses a colorimetric reaction based on the formation of a pink compound (imine salt) to determine total sulfonamides (sulfamethazine, sulfadimethoxine, sulfathiazole) with digital measurements. A linear response was observed between 33-233 µg kg-1 for total sulfonamides, and the coefficient of variation (n = 11; 67 µg kg-1 of total SAs) and the limit of detection were estimated to be 0.63% and 10 µg kg-1, respectively. For a 750 mg meat sample, 0.11 mg of 4-dimethylaminocinnamaldehyde, 2.60 mg of sodium dodecyl sulfate, and 275 µL of 1-butanol were consumed per sample, and consequently, generating only 335 µL of residue. Besides this, addition-recovery tests were performed, resulting in a 71-100% recovery range, indicating the trueness of the proposed method.

Resumo em Inglês:

The mutations of breast cancer susceptibility gene 1 (BRCA1) play an important role in inherited breast cancers. Thus, the sensitive assay of the BRCA1 gene is extremely important for disease diagnosis and human health. Herein, a fast, sensitive and selective assay technique has been constructed based on fluorescent copper nanoclusters (CuNCs). The CuNCs were successfully formed with poly(AT-TA) double stranded DNA (dsDNA) as template. In the absence of the target, a strong red emission was observed under 365 nm ultraviolet (UV) lamp and a big fluorescence response was obtained. However, in the presence of BRCA1 gene, there was only weak red emission and a low response signal was produced because of the target-proximity induced quenching of the fluorescence of CuNCs. The linear range for the BRCA1 gene assay was 2-600 nM, and the limit of detection was 2 nM. The assay technique showed good selectivity, good stability and satisfactory recoveries for the detection of BRCA1 gene in diluted serum samples. Moreover, by integrating a UV lamp and a smartphone, the fluorescence sensor would be transferred to a microfluidic chip, providing a prospective application in point-of-care for monitoring breast cancer risk.

Resumo em Inglês:

Cardanol acts to stabilize asphaltene particles in crude oil, but its derivative polycardanol, synthesized with BF3.O(C2H5)2 as initiator, exhibits divergent behavior, acting as both asphaltenes stabilizer and flocculant. This behavior could be related to structural differences in polycardanol samples. Therefore, in this work, we study the influence of some polymerization conditions (monomer purity, initiator concentration, and reaction time) on the structures and molar masses of the reaction products, and the reaction conversion. The materials were characterized by size exclusion chromatography and hydrogen and carbon nuclear magnetic resonance. When reacting with distilled cardanol, the conversion, the molar mass, and the homogeneity of structures increased as increasing initiator concentration in the range tested (1-3% m/m). For both monomers (different purity degrees), when using a lower initiator concentration (1% m/m), the product contained a larger amount of unreacted monomer and different structures were obtained due to the occurrence of rearrangements. The presence of triolefinic molecules in the monomer provoked crosslinked structures for higher initiator concentration (2-3% m/m). This study elucidated the differences among the reaction products of polycardanol.

Resumo em Inglês:

Biochars from peanut shell wastes were produced and further modified with KOH and HNO3 to efficiently remove two industrial dyes, Mordant Orange 1 and Green Malachite oxalate, in aqueous systems. The materials were characterized through elemental analysis, N2 adsorption isotherms, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and the determination of the point of zero charge, pHPZC. The basic and, particularly, the acid treatments increased the specific surface area by 15 and 43%, respectively, and the pHPZC shifted from 6.2 to 9.1 or 3.3 upon treatments with KOH or HNO3. These modifications impacted the adsorption behavior of the dyes; in the case of Mordant Orange 1, the adsorption capacity increased 2 and 4 times, respectively, when compared with the parent biochar. These results show that the performance of biochars can improve substantially through simple modifications using acid or basic treatments that not only increase the specific surface area but also modify adsorbent/adsorbate interactions.