In the criminal sphere, it is extremely important to identify perpetrators of crimes based on latent fingerprints (invisible to the naked eye) revealed at crime scenes and their corresponding objects. The present work aimed to evaluate four synthetic analogues of curcumin as possible IDL developers, and to compare their results with those of carbon black developer, as well as to reach the most adequate parameters in the use of the LTQ and FT-ICR mass spectrometers with the paper spray ionization (PS) source to study the chemical composition of the endogenous substances contained in the IDL. For this, a 24-1 factorial design was developed, where it was verified that the distance and voltage factors were the most influential for the increase in the response of signals, in the analysis of latent fingerprints by PS. Among the detected substances we can mention around 20 fatty acids, and squalene. Finally, four potential developers, synthetic analogues of curcumin, were compared with carbon black developer. The revelation of latent fingerprints occurred efficiently, allowing the visualization of minutiae, such as bifurcation and end of line, making it possible to classify them, according to the Vucetich Fingerprint Classification System.

Among stimulant drugs, cocaine deserves attention due to its high rates of seizures worldwide. This work presents the synthesis and characterization of hybrid molecularly imprinted polymers (MIPs) for use in preparing biological samples using a homemade microextraction in a packed sorbent device to extract cocaine. The MIPs synthesized using caffeine and cocaine as templates have been compared. Caffeine was used due to its low value and be easier to obtain than cocaine. Additionally, restricted access molecularly imprinted polymers (RAMIPs) were also produced for comparison purposes. The polymeric materials were characterized using scanning electron microscopy, textural analysis, Fourier transform infrared spectroscopy, and cross polarization/ magic angle spinning 13C nuclear magnetic resonance. The method optimization was performed using linear ion trap mass spectrometer to evaluate the effects of sample pH, type of eluent, washing solvent, adsorption cycles, and eluent volume. In the optimized method, RAMIPs indicated better cocaine extraction compared to MIPs. The quantitative study demonstrated that the developed method was able to accurately quantify cocaine in urine samples with values close to actual concentrations. drugs worldwide (MIPs Additionally (RAMIPs purposes microscopy analysis spectroscopy polarization C resonance pH solvent cycles volume concentrations

Multi-drug-resistant bacteria (MDR) are the cause of different infections and diseases that have affected humanity for a long time, and have been an emerging global health problem that has led to increased morbidity and mortality. The growing emergence of MDR bacteria has underlined the need for development and discovery of new antibacterial compounds. In this context, a series of new paeonol 1,2,3-triazole and ether derivatives were synthesized using copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction and nucleophilic substitution. Paeonol has been a natural product widely studied due to its many biological activities, as well as its derivatives. Three ether derivatives (two unpublished) and ten triazole derivatives (six unpublished) of paeonol were obtained, which were determined by nuclear magnetic resonance (NMR), Fourier transform infrared spectrometry (FTIR), Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and six of them by X-rays, which is the first study of this type presented for these compounds. All the synthesized compounds were evaluated as antibacterial agents against Staphylococcus aureus and Escherichia coli, obtaining a minimum inhibitory concentration (MIC) above 100 µg mL-1. The results showed that CuAAC and nucleophilic substitution were very useful to obtain new paeonol triazole and ether derivatives and the products were obtained in yields from 21.3 to 98.5%. The advantages of these reactions (high yield in most compounds, reaction time, low impurities) show that using the method to produce new derivatives is advisable thus assisting in the discovery of new potential bioactive compounds.

Abstract The control of weeds in agriculture is mainly conducted with the use of synthetic herbicides. However, environmental and human health concerns and increased resistance of weeds to existing herbicides have increased the pressure on researchers to find new active ingredients for weed control which present low toxicity to non-target organisms, are environmentally safe, and can be applied at low concentrations. It is herein described the synthesis of glycerol-fluorinated triazole derivatives and evaluation of their phytotoxic and cytogenotoxic activities. Starting from glycerol, ten fluorinated triazole derivatives were prepared in four steps. The assessment of them on Lactuca sativa revealed that they present effects on phytotoxic and cytogenotoxic parameters with different degrees of efficiency. The compounds 4a, 4b, 4d, 4e, 4i, and 4j have pre-emergent inhibition behavior, while all the investigated compounds showed post emergent effect. Mechanism of action as clastogenic, aneugenic, and epigenetic were observed in the lettuce root meristematic cells, with alterations as stick chromosome, bridge, delay, c-metaphase, and loss. It is believed that glycerol-fluorinated triazole derivatives possess a scaffold that can be explored towards the development of new chemicals for the control of weed species.

Food additives are chemical substances added to improve organoleptic characteristics, in this context, there are several synthetic dyes, such as sunset yellow, tartrazine, erioglaucine, allura red, indigo carmine, and new coccine, that can also be identified through different analytical techniques such as infrared spectroscopy, UV-Vis spectrophotometry, high performance liquid chromatography with diode array detector and mass spectrometry. Therefore, the objective of this work was to compare methods developed for different analytical techniques, in order to identify the one that presents greater efficiency in certain applications. For this, the patterns of the dyes were analyzed, as well as their mixtures and foods that had them. As a result, the CLAE-DAD presents excellent selectivity and linearity of the calibration curves, but it presents higher LD and LQ values when compared to the UV-Vis, in turn the infrared provides information regarding functional groups and bonds. Mass spectrometry showed great capabilities in identifying the molecular formula and better selectivity in the absence of the erioglaucine dye. It is not feasible to indicate the best or worst analytical approach, but it is possible to point out which one is more suitable for each application. Regarding the quantification capacity, chromatography and UV-Vis are good alternatives, but in mixtures containing more than one dye, CLAE-DAD is more suitable due to the better selectivity. Regarding the identification capacity, mass spectrometry, especially FT-ICR MS, is the most appropriate technique to propose molecular formulas due to its high resolution and mass accuracy. The advantage of FTIR was the easier sample preparation, being able to analyze the dyes in the solid state.

Abstract: Despite the long history of comic books, many people believe that they still play an incipient role in the development of scientific literacy. This article sought to analyze the understandings and conceptions of invited readers and specialists about one comic book concerning Forensic Sciences, as well as investigate its potential for science communication and scientific literacy. The investigations were conducted using a digital questionnaire, followed by content and document analysis. The data revealed an understanding of the theme's relevance as well as the significance of a basic understanding of fundamental scientific terms, knowledge, and concepts (the first structuring axis of scientific literacy) related to the topic. It was also possible to identify the main connections among comics, formal content and specific educational objectives using content analysis. These conceptions, together with the other investigated hypotheses, have attested to the studied comic book as a promising tool in promoting science communication and scientific literacy.

Resumo: As histórias em quadrinhos (HQ), apesar do seu longo período histórico, ainda são consideradas incipientes no processo de alfabetização científica. Nesse sentido, este artigo buscou analisar compreensões e concepções de leitores e especialistas convidados, sobre uma HQ com a temática Ciências Forenses, bem como investigar suas potencialidades de divulgação e alfabetização científica. Para isso, foram realizadas investigações por meio de um questionário digital e posteriores análises de conteúdo e documental. Os dados obtidos indicaram a compreensão da relevância do tema e a importância da compreensão básica de termos, conhecimentos e conceitos científicos fundamentais (primeiro eixo estruturante da alfabetização científica) sobre a temática. Além disso, por meio da análise de conteúdo, foi possível identificar as principais associações da HQ aos conteúdos formais e a objetivos educacionais específicos. Essas concepções, reunidas às demais investigadas, certificaram a HQ estudada como uma ferramenta promissora para divulgação e para a alfabetização científica.

In recent years, technological development in analytical instrumentation has progressed vigorously, which has allowed the evolution of analytical techniques that play an indispensable role within society, highlighting mass spectrometry. Parallel to the technological advance of this technique, the development of new ionization methods that are simpler, faster, and allow direct analysis without the need for prior treatment or sample processing is underway. The methods of ambient ionization derived from paper spray have been developing rapidly in current days, mainly in the forensic field, due to the chemical modifications made in the paper substrate and the introduction of new types of organic materials that function as a probe/substrate to collect, store, and ionize the sample, then enabling more efficient and selective analyzes. This review highlights direct analyzes by applying paper spray ionization in the forensic field and some variations of this technique, including Thread Spray Ionization (TSI) when a fabric thread is used; Touch Spray Ionization (TSI), which uses materials such as metallic needles, medical swabs, and wooden sticks; Fiber Spray Ionization (FSI), which applies polymeric fibers as substrates.

Eugenol (C10H12O2, 4-allyl-2-methoxyphenol) is a phenolic natural product that has several biological activities and possibilities of applications. It is herein described the synthesis of eugenol-fluorinated triazole derivatives and evaluation of their fungicidal activity. The reaction of eugenol with epichlorohydrin resulted in the preparation of (±)-2-((4-allyl-2-methoxyphenoxy)methyl)oxirane (1) in 88% yield. The azidolysis of 1 with sodium azide gave the azido-alcohol (±)-1-(4-allyl-2-methoxyphenoxy)-3-azidopropan-2-ol (2) in 94% yield. The CuAAc reaction between compound 2 and different terminal alkynes afforded a series of eleven derivatives (3a 3k) within 48-80% yield. All the synthesized compounds were characterized by infrared (IR) and nuclear magnetic resonance (1H and 13C) spectroscopies and high-resolution mass spectrometry. The in vitro inhibitory activity of the compounds on the mycelial growth of a strain of Colletotrichum sp., that causes anthracnose disease on papaya fruits, was evaluated. The best result was observed for compound 1-(4-allyl-2-methoxyphenoxy)-3-(4-(2-fluorophenyl)-1H-1,2,3-triazol-1-yl)propan-2-ol (3d) that showed a mean growth-inhibition zone of 5.10 mm in a well-diffusion assay, and may serve as a template for additional structural modifications, aiming for more potent fungicidal activity.

The control of fungal species in agriculture is mainly conducted with the use of contact or systemic fungicides. However, environmental and human health concerns and increased resistance of fungal species to existing fungicides have increased the pressure on researchers to find new active ingredients for fungal control which present low toxicity to non-target organisms, are environmentally safe, and can be applied at very low concentrations. It is herein described the synthesis of eleven glycerol triazole containing compounds (ten of them fluorinated derivatives) and evaluation of their fungicidal activity. Eight out of eleven synthesized compounds are novel and all of the glycerol derivatives were characterized using infrared (IR), nuclear magnetic ressonance (NMR), and mass spectrometry (MS) techniques. Theoretical calculations were also carried out and the results are discussed. Starting from glycerol, the triazole derivatives were prepared in four steps. Evaluation of them against Colletrotricum gloesporioides showed that compound 1-((2,2-dimethyl-1,3 dioxolan-4-yl)methyl)-4-(2-fluorophenyl)-1H-1,2,3-triazole (4d) (ED50 = 59.14 µg mL-1) was slightly more active than commercial fungicide tebuconazole (61.35 µg mL-1). Compound 4d presented attractive physicochemical features for agrochemical purposes as revealed by the calculated physicochemical parameters. It is believed that glycerol-fluorinated triazole derivatives can be explored towards the development of new chemicals for the control of fungal species.

This study proposed using a portable microscope combined with a smartphone and application (PhotoMetrix® application) to evaluate the authenticity of Brazilian banknotes (R$50 and R$100) and national driver’s licenses (NDL) through image acquisition (Samsung S7) and chemometric treatment (principal component analysis (PCA)). Six regions of the banknote were analyzed: holographic band; lower and upper tactile regions containing the number referring to the value of the note; microprints above the effigy (obverse); and numbers and the surroundings of the animal formed by microprints (reverse). For NDLs, the regions were the following: the coat of arms of the republic; the state map with microprints; optical ink variation; distorted positive microletters with technical failure; negative guilloche; typographic numbering; micro letter wire; and region with line printing. For the chemometric study with Photometrix®, we selected a region of interest (ROI) of 32 × 32 and 64 × 64 pixels with autoscaled data using the channels red (R), green (G), blue (B), hue (H), saturation (S), value (V), lightness (L) and intensity (I). We obtained excellent results for differentiating banknotes and NDLs, both by visual and chemometric analyses (PCA). This study demonstrates the effectiveness of using a portable microscope and a smartphone as a portable forensic tool that is fast, robust, low-cost and reliable.

The study of the spectrum of light has increased its range of action in the field of chemistry, with the help of several advanced equipment and innovative techniques that have become a strong ally of analytical chemistry. However, the simplicity of obtaining results integrated with mobile devices appears as an interesting path to be taken in the field of chemical analysis. This work addresses the dissemination of an application called REDGIM for smartphones on the Android platform capable of working with multivariate image analysis using chemometric methods through the luminous intensities of photos and R (red), G (green) and B (blue) channels. In order to show the potential of REDGIM, we propose two applications using the partial least squares (PLS) regression method: 1) quantification of free chlorine in tap water; and 2) quantification of cannabinol, (CBN, a type of cannabinoid) in marijuana and hashish samples. The free chlorine concentration obtained for two investigated samples was 0.73 and 0.74 mg L-1 and 0.74 and 0.76 mg L-1 by the spectrophotometer and by the application (container: cuvette), respectively. For the quantification of CBN in marijuana and hashish samples, the mean concentration ranged from 6.137 to 8.823 mg mL-1. The results obtained by the application are compatible with results from traditional techniques, such as UV-Vis spectrophotometry, for example. Therefore, REDGIM was proved to be a simple and accessible technological tool for the scientific community, being viable for chemical tests of a multivariate nature.

Beer is commonly produced with four inputs: water, malt, hops, yeast and, in some cases, brewing adjuncts. Industrial and artisanal processes essentially follow the same steps and may undergo minor changes due to the style of beer. Despite this, many consumers attribute higher quality to craft beer compared to industrial ones. In this study, we applied the analytical techniques of infrared (IR), hydrogen nuclear magnetic resonance (1H NMR) and mass spectrometry (ESI(±)FT-ICR MS) to discriminate craft beers from industrial ones (brands common to the Brazilian market). In addition, Partial Least Squares (PLS) and Support Vector Machine (SVR) regression were used to estimate some beer properties (pH, total acidity (meq·L-1, color (EBC), bitterness (IBU), alcohol content (%v/v) and density (g·mL-1)). The use of the IR allowed the identification of vibrations attributed to chemical compounds common to beverages, such as water (3320 and 1640 cm-1), carbohydrates (1500 cm-1) and ethanol (1050-1040 and 875-865 cm-1). 1H NMR showed good applicability in identifying classes of organic compounds in the beverage, where signs attributed to alcohols, organic acids, carbohydrates and amino acids were observed. The ESI(+)FT-ICR MS allowed the identification of chemical compounds present in beverages, allowing the construction of a fingerprint of the beers. In addition, the application of chemometric tools enabled the prediction of physicochemical properties, presenting promising results in the prediction of alcohol content (RMSEC 0.2430 and RMSEP 0.3929) and bitterness (RMSEC 1.3022 and RMSEP 1.6008), and also in the classification regarding the manufacturing process (craft and industrial beer).

This work describes the synthesis and application of an europium(III) complex, [Eu(TTA)3(2-pyr) (H2O)], containing 2-thenoyltrifuoroacetonate (TTA) and 2-pyrrolidone (2-pyr) as ligands, obtained as white solid and soluble in ethanol. In solution, the complex showed red emission, characteristic of the EuIII emission in the solid state (λexc = 375 nm and λem = 612 nm). The complex was tested with PbII, CdII, and HgII ions in water. The effect of metal ions was monitored and evaluated by hypersensitive transition 5D0 → 7F2 (612 nm). The results show that PbII suppresses the complex luminescence and present high sensitivity, according to the values for the Stern-Volmer constant (K SV = 2300 L mol−1), showing good linearity, i.e., determination coefficient (R 2) of 0.9913, and low limit of detection (LOD = 6.03 µM). Luminescence quenching increased with the increasing concentration of PbII. These results indicate that the synthesized complex is a potential luminescent sensor for detecting PbII in a simple and fast way, being applicable for routine environmental analysis. When applied as an ethanol sensor in gasoline, the complex hypersensitive transition intensity decreased with the increasing volume of ethanol in gasoline, reaching the values of R 2 = 0.9815 and LOD = 4.94% v/v.

RESUMO: O acúmulo de nutrients em plantas/frutos variam de acordo com o estádio de desenvolvimento das culturas, sendo que sua quantificação é importante na determinação da exportação de nutrientes para o planejamento da adubação e para o balanceamento de nutrientes. Esse estudo objetivou determinar o acúmulo de nutrientes em diferentes partes dos cachos de Piper nigrum ‘Bragantina’ colhidos em dois estágios de maturação (coloração da casca verde e coloração da casca vermelha). As avaliações foram feitas separadamente nos cachos de Piper nigrum com coloração verde (fruto e pedúnculo) e vermelha (grão, casca e pedúnculo), em que os cachos foram colhidos, secos e as partes foram separadas para análises químicas. N e Mn foram os macro e micronutrientes mais acumulados nos frutos dos cachos com coloração da casca verde e nos grãos dos cachos com coloração da casca vermelha, enquanto K e B foram mais acumulados em outras partes da planta, independente do estágio de maturação. O processo de removação da casca para produção de pimenta branca levou a uma diferença na concentração e no acúmulo de nutrientes nos frutos de pimenta preta e nos grãos de pimenta branca. Uma contribuição significativa para entrada de nutrientes pode ser obtida se as cascas e pedúnculos forem mantidos na área de cultivo, o que diminui a dependência de fertilização, contribuindo para uma agricultura mais sustentável.

ABSTRACT: Nutrients accumulation in plants/fruits varies according to the crop development stage and its quantification is important to determine nutrients exportation for fertilization planning and nutrient balancing. This study determined the accumulation of nutrients in different parts of Piper nigrum ‘Bragantina’ spikes harvested at two ripening stages (still-green and red-colored spikes). Assessments in separate parts of still-green spikes (fruits and peduncles) as well as in red-colored spikes (grains, flesh and peduncles) were performed. Piper nigrum spikes were harvested, dried, and the parts were thereafter separated for chemical analysis. N and Mn were the macro and micronutrient most accumulated in the fruits of still-green spikes and in the grains of red-colored spikes, while K and B were most accumulated in the other parts of black pepper assessed, regardless of the ripening stage. The process of removing the flesh from the fruits for white pepper production led to a difference in nutrient concentration and accumulation between the fruits of still-green spikes and the grains of red-colored spikes. A significant contribution of nutrient input can be achieved by maintained flesh and peduncles in the crop area, decreasing the dependence of external fertilizers and thus contributing to a more sustainable agriculture.

Mass spectrometry (MS) is a high-performance analytical technique that allows a measurement of the mass/charge (m/z) ratio of compounds present in a sample. MS is able to separate two m/z ions with determined values (mass resolution), being an important characteristic, especially in the analysis of biochemical components and complex mixtures. Mass analyzers define the resolving power and accuracy of different types of mass spectrometers. Herein, the performance of two mass analyzers (Fourier Transform Ion Cyclotronic Resonance (FT-ICR) and quadrupole ion trap (LTQ)) was tested on low (Mw = 165-679 Da) and high (Mw = 783-8.58 kDa) molecular weight molecules (Phenacetin, Procaine, Benzocaine, Caffeine anhydrous, Lidocaine, two metal porphyrin standards, the first cobalt and the second vanadium, and two protein standards, Ubiquitin and Beauvericin), and finally, for an oil sample. LTQ-MS and FT-ICR-MS had similar performance and high reproducibility. However, the mass accuracy and resolution power of the FT-ICR (error lower than 5 ppm and RP higher than 400,000) was higher, being therefore, it was more suitable for the analysis of proteins and oil, for instance. On the other hand, the CID analysis via LTQ demonstrated its applicability in fragmentation experiments, being able to determinate the chemical connectivity of organic compounds in non-complex mixtures.