Hair can provide chemical information about drug use. This study employed matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) to detect drugs in hair samples. The technique was used to detect cocaine (COC, molecular weight (Mw) = 303.14 Da) and its main metabolites, benzoylecgonine (BZE, Mw = 289.13 Da), cocaethylene (COCE, Mw = 317.16 Da) and ecgonine methyl ester (EME, Mw = 199.12 Da) in hair strands using 2,5-dihydroxybenzoic acid (DHB, 7.0 mg mL-1) and α-cyano-4-hydroxycinnamic acid (CHCA, at concentrations of 1.5, 3.0, 7.0, and 10 mg mL-1) as the evaluated matrices. Among these, CHCA was selected. Subsequently, the qualitative results obtained by MALDI(+) MS were correlated with the quantitative analyses of gas chromatography-mass spectrometry (GC-MS), demonstrating a significant correlation in responses (70%), with the detection of analytes by MALDI(+) MS even at low concentrations, determined by GC-MS. The concentration ranges obtained by GC MS analysis were from 0.6 to 4.1 ng mg-1 of COC, and from 0.05 to 0.4 ng mg-1 of COCE. The effect of pre-washing on the detection of COC and its metabolites was also evaluated, and the results indicated less influence from the pre-washing stage and confirmed the reduction in COC detection in hair exposed to bleaching. use matrixassisted matrix assisted MALDIMS MALDI (MALDI-MS samples (COC (Mw 30314 303 14 303.1 Da BZE, BZE (BZE 28913 289 13 289.1 Da, , COCE, COCE (COCE 31716 317 16 317.1 EME, EME (EME 19912 199 12 199.1 2,5dihydroxybenzoic 25dihydroxybenzoic dihydroxybenzoic 2,5 2 5 DHB, DHB (DHB 70 7 0 7. mL1 mL 1 mL-1 αcyano4hydroxycinnamic αcyanohydroxycinnamic α cyano 4 hydroxycinnamic CHCA, (CHCA 15 1.5 30 3 3.0 matrices these selected Subsequently MALDI+ + MALDI(+ chromatographymass chromatography GCMS, GCMS (GC-MS) 70%, 70% (70%) GCMS. MS. GC-MS 06 6 0. 41 4. mg1 mg- 005 05 0.0 04 prewashing pre washing bleaching 3031 303. 2891 28 289. 3171 31 317. 1991 19 199. 5dihydroxybenzoic 25 2, mL- αcyano 1. 3. MALDI( (GC-MS (70% 00 (70 (7 (

This study details the preparation, antileishmanial assay, and in silico analysis of twenty 2-hydroxy-3-(1,2,3-triazolyl)propyl vanillin derivatives. These compounds were synthesized in three steps and evaluated against Leishmania infantum, Leishmania amazonensis, and Leishmania braziliensis promastigotes. Compounds 3s and 3t were the most effective, showing good activity against all Leishmania species tested. Molecular docking indicated that all compounds bind favorably to the sterol 14α-demethylase (CYP51) enzyme from L. infantum. ADMET (absorption, distribution, metabolism, excretion and toxicity) analysis indicated good oral bioavailability, non blood-brain barrier penetration, and high gastrointestinal absorption. Posaconazole and compounds 3e, 3s, and 3t remained stable in the CYP51 binding region during 100 ns molecular dynamics (MD) simulations. Root mean square deviation (RMSD) and root mean square fluctuations (RMSF) analyses from the MD trajectory revealed significant conformational fluctuations of the CYP51 N-terminal, suggesting occasional expulsion of 3e, potentially explaining its higher IC50 (half-maximal inhibitory concentration) values. Pairwise decomposition analyses from molecular mechanics Poisson-Boltzmann surface area (MM/PBSA) calculations highlighted the importance of hydrophobic residues in interacting with the synthesized derivatives. preparation assay 2hydroxy31,2,3triazolylpropyl 2hydroxy3123triazolylpropyl hydroxytriazolylpropyl 2 hydroxy 3 1,2,3 triazolyl propyl 1 derivatives infantum amazonensis promastigotes s t effective tested 14αdemethylase αdemethylase 14α demethylase α CYP (CYP51 L absorption, absorption (absorption distribution metabolism toxicity bioavailability bloodbrain blood brain penetration 3e e CYP5 10 (MD simulations RMSD (RMSD RMSF (RMSF Nterminal, Nterminal N terminal, terminal N-terminal IC IC5 halfmaximal half maximal concentration values PoissonBoltzmann Poisson Boltzmann MM/PBSA MMPBSA MM PBSA (MM/PBSA 2hydroxy31 3triazolylpropyl triazolylpropyl 123 1,2, (CYP5 2hydroxy3 12 1,2 (CYP 2hydroxy 1,

Pineapple, important in Brazilian fruit growing and highly consumed worldwide, can be affected by fusariosis, a disease caused by Fusarium guttiforme, which compromises the quality of the fruit and produces a mycotoxin called beauvericin (BEA), which is harmful to the health of consumers. The importance of detecting BEA and establishing maximum permitted limits is urgent, as there are few studies on this mycotoxin and there is still no regulation in world legislation. In this work, methodologies were used to detect BEA using HPLC-DAD and MALDI-FT-ICR MS. The results of HPLC-DAD allowed the detection of BEA in the tissues of the samples with F. guttiforme, evidenced by chromatographic peaks in the retention time, 6.1 min, similar to the standard, however, in the samples of visibly healthy tissue the mycotoxin was not detected. With MALDI-FT-ICR MS, BEA was detected with mass errors of less than 1 ppm in all samples (tissues infected with F. guttiforme and in healthy tissues), showing that, in addition to the greater sensitivity of the method, there is the possibility of mycotoxin diffusion in the healthy tissues of fruits inoculated with F. guttiforme, when these tissues are also contaminated. Pineapple worldwide fusariosis BEA, , (BEA) consumers urgent legislation work HPLCDAD HPLC DAD MALDIFTICR MALDI FT ICR MS F time 61 6 6. min standard however tissues, tissues) that method contaminated (BEA

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. sphere invisible eye objects developers developer FTICR FT ICR PS (PS this 241 24 1 24- developed signals 2 acids squalene Finally efficiently minutiae line them System

The aim of this work was to extract and characterize pectin from lyophilized noni pulp (Morinda citrifolia Linn.) at three different pHs using different extractor agents and to evaluate anti-viral activity. The extraction of high yield (acid extraction) was subjected to sulfation procedure. Fourier transform infrared spectroscopy and proton nuclear magneticresonance analysis were used to calculate the degree of methylation of pectin from acid extraction and its sulfated derivative. The data obtained for the degree of methylation of noni pectin and sulfated pectin were 30.3 and 30.7, respectively. Pectin was subjected to acute oral toxicity testing in mice. The results showed that pectin had a pro-inflammatory effect, and sulfated pectin had an anti-inflammatory effect. Both pectins were also evaluated for herpes simplex virus activity in vitro, and although they successfully inhibited virus replication, the sulfated pectins were cytotoxic. Morinda Linn. Linn antiviral anti viral procedure derivative 303 30 3 30. 307 7 30.7 respectively mice proinflammatory pro inflammatory effect antiinflammatory vitro replication cytotoxic

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. Multidrugresistant Multi drug resistant (MDR time mortality context 1,2,3triazole 123triazole 1,2,3 1 2 3 copperIcatalyzed copper I catalyzed azidealkyne azide alkyne (CuAAC activities two unpublished NMR, NMR , (NMR) FTIR, FTIR (FTIR) Fouriertransform FTICR FT ICR MS Xrays, Xrays X rays, rays X-rays coli MIC (MIC 10 mL1. mL1 mL 1. mL-1 213 21 21. 985 98 5 98.5% high impurities 3triazole 123 1,2, (NMR (FTIR mL- 9 98.5 12 1,2 98. 1,

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. years vigorously society spectrometry technique simpler faster underway days probesubstrate probe collect store TSI (TSI used TSI, , needles swabs sticks FSI, FSI (FSI) substrates (FSI

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.

RESUMO: Brucella ovis é responsável por perdas econômicas e reprodutivas em rebanhos ovinos. O objetivo deste trabalho foi caracterizar a infecção com as cepas isoladas de campo de B. ovis em modelo murino e avaliar a eficiência vacinal da mutante B. ovis ΔabcAB para proteção contra desafio com as cepas isoladas de campo. Foram utilizadas sete cepas isoladas de campo foram capazes de colonizar e provocar lesões no fígado e no baço de camundongos após sete dias pós-infecção. Após triagem, duas cepas foram selecionadas para a melhor caracterização (B. ovis 94 AV and B. ovis 266L). Ambas apresentaram crescimento em placa de cultivo semelhante ao da cepa de referência B. ovis ATCC 25840. A vacinação com a cepa de Brucella ovis ΔabcBA encapsulada com alginato a 1% foi capaz de proteger camundongos desafiados com as cepas isoladas de campo, com os seguintes índices de proteção: 0,751, 1,736 e 2,746, para camundongos desafiados com B. ovis ATCC 25840, B. ovis 94 AV e B. ovis 266 L, respectivamente. Estes resultados demonstraram que as cepas isoladas de campo de B. ovis são capazes de infectar e induzir lesão em camundongos experimentalmente infectados. O uso da cepa mutante atenuada B. ovis ΔabcBA para vacinação de fêmeas C57BL/6 desafiados com diferentes cepas de B. ovis induziu proteção nos camundongos desafiados com diferentes cepas de B. ovis. Deste modo, mostrando-se eficiente na proteção das cepas de campo de B. ovis.

ABSTRACT: Brucella ovis causes economic and reproductive losses in sheep herds. The goal of this study was to characterize infection with B. ovis field isolates in a murine model, and to evaluate protection induced by the candidate vaccine strain B. ovis ΔabcBA in mice challenged with these field isolates. B. ovis field strains were able to colonize and cause lesions in the liver and spleen of infected mice. After an initial screening, two strains were selected for further characterization (B. ovis 94 AV and B. ovis 266 L). Both strains had in vitro growth kinetics that was similar to that of the reference strain B. ovis ATCC 25840. Vaccination with B. ovis ΔabcBA encapsulated with 1% alginate was protective against the challenge with field strains, with the following protection indexes: 0.751, 1.736, and 2.746, for mice challenged with B. ovis ATCC25840, B. ovis 94 AV, and B. ovis 266 L, respectively. In conclusion, these results demonstrated that B. ovis field strains were capable of infecting and inducing lesions in experimentally infected mice. The attenuated vaccine strain B. ovis ΔabcBA induced protection in mice challenged with different B. ovis field isolates, resulting in higher protection indexes against more pathogenic strains.

RESUMO: O histograma em escala de cinza (HEC) possibilita a mensuração da quantidade e distribuição da frequência de tonalidades de cinza, fornecendo informações quantitativas, tanto sobre a ecogenicidade quanto a ecotextura dos tecidos. Havendo a necessidade de diminuir a subjetividade das imagens ultrassonográficas do ligamento nucal (LN), esse trabalho propôs avaliar o LN por imagens ultrassonograficas modo-B pelo HEC em diferentes idades de cavalos da raça Quarto de Milha. Utilizou 15 cavalos da raça Quarto de Milha saudáveis os quais foram classificados por idade em três grupos diferentes: “baby” (1), “sobreano” (2) e “adulto” (3). Os animais foram submetidos a contenção química para a realização do exame ultrassonográfico. Posteriormente, a ferramenta HEC foi empregada em cada imagem para análise estatística. Houve diferença significativa entre as variáveis “Mean” e “Mode” entre os grupos. O Grupo 1 diferenciou significativamente quando comparado ao Grupo 2 e 3. O Grupo 2 apresentou ecogenicidade superior ao Grupo 1 e 3. Quanto à altura do LN não teve variação considerável entre os grupos. O HEC indicou que a ecogenicidade do LN em cavalos Quarto de Milha varia conforme a idade.

ABSTRACT: The gray scale histogram (GSH) makes it possible to measure the amount and distribution of gray shade frequencies, providing quantitative information on both echogenicity and echotexture of tissues. There is a need to diminish the subjectivity of the ultrasound images of the nuchal ligament (NL). This work proposes to evaluate the NL by ultrasound B-mode GSH images in different ages of Quarter horses. It used 15 healthy Quarter horses, which were classified by age into three different groups: “baby” (1), “sobreano” (2) and “adult” (3). The animals were submitted to chemical restraint for the ultrasound examination. Subsequently, the GSH tool was used in each image for statistical analysis. There was a significant difference between Mean and Mode between groups. Group 1 differed significantly when compared to Group 2 and 3. Group 2 presented superior echogenicity to Group 1 and 3. The height of the NL did not vary considerably between groups. GSH indicated that the echogenicity of NL in Quarter horses varies with age.

The Cannabis sativa L. plant has a complex chemical composition, containing various chemical compounds such as terpenes, sugars, hydrocarbons, steroids, flavonoids, and amino acids. Few works have attempted to identify the constitutional isomers of cannabinoids that are found in the plant. The present study reported the analysis of seven cannabinoid standards: five neutral and two acidic, as well as Cannabis products (hashish and marijuana) and parts of the Cannabis plant (flower and leaf) using mono-dimensional gas chromatography coupled with mass spectrometry (GC-MS) and two-dimensional gas chromatography coupled with quadrupole MS (GC × GC-QMS), ultra performance liquid chromatography coupled with electrospray ionization-quadrupole-time of flight (UPLC-ESI-QTOF)-MS and UPLC-ESI-travelling wave ion mobility (TWIM)-MS. The results of GC-MS demonstrated close retention times (∆tR = 1.303 min) in separation of the five cannabinoid standards, whereas GC × GC-QMS provided a substantially better identification and distinction of constitutional isomers of cannabinoids, where a total of 11 cannabinoids were identified in the hashish sample. UPLC-QTOF-MS and UPLC-TWIM-MS data obtained complete chemical information, in which ESI(+) revealed the presence of seven constitutional isomers of ∆9-tetrahydrocannabinol (∆9-THC), whereas ESI(-) proved the presence of four isomers of ∆9-tetrahydrocannabinolic acid A (∆9-THCA A).

RESUMO A diversidade e distribuição de moluscos na Costa Amazônica do Estado do Maranhão, Brasil, são pobremente conhecidas. O objetivo deste estudo foi investigar como os moluscos em dois igarapés de manguezal (Buenos Aires e Tronco) na Baía de São Marcos, costa do Estado do Maranhão, respondem a variações espaciais e temporais no ambiente. A amostragem foi conduzida no entre-marés ao longo de três zonas estabelecidas a partir de um transecto em linha reta de 100 m. As variáveis abióticas de água e sedimento foram medidas para cada igarapé. Foram contabilizados 5.912 espécimes pertencentes a 23 espécies e 15 famílias na epifauna e endofauna. Os padrões de distribuição de moluscos foram distintos entre os dois igarapés. Salinidade, oxigênio dissolvido e precipitação foram as principais variáveis que influenciaram a distribuição temporal dos moluscos. Observou-se baixa riqueza de espécies na composição geral de moluscos. A diversidade no igarapé Buenos Aires foi menor do que a observada no igarapé Tronco, possivelmente por causa das atividades portuárias nas proximidades do primeiro. A distribuição espacial vertical de moluscos ao longo das zonas seguiu um gradiente de abundância e diversidade influenciado principalmente pelo tempo de exposição durante a maré baixa. As atividades portuárias podem estar influenciando os padrões de distribuição de moluscos nos manguezais do entorno, portanto destacamos a importância do manejo e monitoramento dessas áreas.

ABSTRACT The diversity and distribution of molluscs from the Amazon Coast of Maranhão State, Brazil, are poorly understood. The aim of this study was to investigate how molluscs in two mangrove creeks (Buenos Aires and Tronco) at the São Marcos Bay, coast of the Maranhão State, respond to spatial and temporal variations in the environment. Sampling was performed in the intertidal area along three zones established using a straight line transect of 100 m. Abiotic variables of water and sediment were measured at each creek. We found 5,912 specimens belonging to 23 species and 15 families of epifaunal and infaunal molluscs. The patterns of their distribution in the two creeks were different. Salinity, dissolved oxygen, and rainfall were the main variables that affected the temporal distribution of molluscs. We found low species richness in the overall mollusc composition. Diversity in the Buenos Aires Creek was lower than that observed in the Tronco Creek, possibly because of activities of a port located in proximity to the former. The spatial distribution of molluscs along the zones followed an abundance and diversity gradient, mainly influenced by exposure time during low tide. Port activities may influence the patterns of mollusc distribution in the surrounding mangroves, and we thus highlight the importance of management and monitoring of these areas.