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In this work, the electrochemical behavior of the glycosylated flavonoid kaempferitrin was studied, and an electroanalytical methodology was developed for its determination in infusions of Bauhinia forficata using a boron-doped diamond electrode (BDD). The electrochemical behavior of the flavonoid was studied by cyclic voltammetry, and two irreversible oxidation peaks at 0.80 and 1.0 V vs Ag/AgCl were observed. The influence of the pH on the voltammograms was examined, and higher sensitivity was found at pH 7.0. The electrochemical process corresponding to peak 1 at 0.80 V is predominantly diffusion-controlled, as the study shows at varying scan rates. An analytical plot was obtained by square wave voltammetry at optimized experimental conditions (frequency = 100 s -1 , amplitude = 90 mV, and step potential = 8 mV) in the concentration range from 3.4 μmol L -1 to 58 μmol L -1 , with a linearity of 0.99. The limit of detection and limit of quantification values were 1.0 μmol L -1 and 3.4 μmol L -1 , respectively. Three samples of Bauhinia forficata infusions (2 g of sample in 100 mL of water) were analyzed, and the KF values found were 5.0 × 10 -4  mol L -1 , 3.0 × 10 -4  mol L -1 , and 7.0 × 10 -4  mol L -1 , with recovery percentages of 98 %, 106 % and 94 %, respectively. Finally, experiments were performed with two other flavonoids (chrysin and apeginin) to compare and propose an electrochemical oxidation mechanism for kaempferitrin, which was supported by quantum chemical calculations., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Molecular dereplication and drug-like discovery are important tools for exploring the chemical profile of metabolites in a complex mixture. In order to establish a workflow for discovering novel acetylcholinesterase (AChE) ligands, we performed the chemical study of Myrsine guianensis (Aubl.) Kuntze (Primulaceae). To carry out the bioprospection, nine extracts were obtained from different parts of the plant. Through the dereplication approaches, seventeen metabolites were annotated. In order to confirm the putative inferences, a HPLC preparative method was developed to isolate three known myrsinoic acids, A(1), B(2) and C(3). Along with, we are reporting the obtention of two new congeners, G(5) and H(6), which their structures were elucidated by NMR and HRMS data. Besides that, two extracts were submitted to affinity assays to accelerate the discovery of AChE ligands. Desorbates were analyzed through LC-HRMS for calculating the affinity ratio (AR). Thus, (1) presented AR = 4.59, therefore was considered a potential ligand., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests. Thiago Andre Moura Veiga reports financial support was provided by Federal University of Sao Paulo. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

Although several studies have been conducted to elucidate the relationship between psychedelic consumption and cognition, few have focused on understanding the long-term use influence of these substances on these variables, especially in ritualistic contexts.  To verify the influence of ritualistic ayahuasca consumption on the cognition of experienced ayahuasca religious users (> 20 years) and beginners (< 3 years), which participated in rituals of the Centro Luz Divina (CLD), a Santo Daime church in Brazil. Observational, descriptive, and cross-sectional study was carried out in which 48 people participated divided into three groups: (a) experienced ayahuasca users (n = 16), (b) beginner ayahuasca users (n = 16) and (c) control group (n = 16). All groups were matched by sex, age, and education and contained 8 women and 8 men. Cognition was assessed with the WASI (intelligence quotient), Digit Span (verbal working memory), Corsi Block-Tapping Task (visuospatial-related and working memory), Rey-Osterrieth Complex Figure test (visual perception, immediate memory), and Wisconsin Card Sorting and Five Digit Test (executive functions). Groups were homogenous in terms of sociodemographic characteristics, with participants presenting average intellectual performance. There was no evidence of cognitive decline amongst ayahuasca users. The experienced group showed higher scores compared to the less experienced group in the Digit Span and Corsi Block-Tapping tasks, which assess working verbal and visuospatial memories respectively. We confirmed the botanical identities of Psychotria viridis and Banisteriopsis caapi and the presence of the alkaloids both in the plants and in the brew. Short and long-term ayahuasca consumption does not seem to alter human cognition, while long-term use seems to be associated with improvements in aspects of working memory when compared with short-term use., (© 2024. Springer-Verlag GmbH Germany, part of Springer Nature.)

L-Cysteine (Cys) is a non-essential sulfur-containing amino acid, crucial for protein synthesis, detoxification, and several metabolic functions. Cys is widely used in the agricultural, food, cosmetic, and pharmaceutical industries. So, a suitable sensitive and selective sensing approach is of great interest, and a low-cost sensor would be necessary. This article presents silver nanoparticles (EuAgNPs) synthesized by a green synthesis method using Eugenia uniflora L. extracts and photoreduction. The nanoparticles were characterized by UV/VIS, transmission electron microscopy, high-performance liquid chromatography (HPLC), FTIR, and Zeta potential. With the addition of Cys in the EuAgNPs solution, the terminal thiol part of L-cysteine binds on the surface of nanoparticles through Ag-S bond. The EuAgNPs and CysAgNPs coexist until flavonoids bound the amino group of Cys, enhancing the red color of solutions. The EuAgNPs provided selectivity to detect Cys among other amino acids, and its detection limit was found to be 3.8 nM. The sensor has the advantages of low-cost synthesis, fast response, high selectivity, and sensitivity., (© 2022 Wiley-VHCA AG, Zurich, Switzerland.)

The incessant search for new natural molecules with biological activities has forced researchers in the field of chemistry of natural products to seek different approaches for their prospection studies. In particular, researchers around the world are turning to approaches in metabolomics to avoid high rates of re-isolation of certain compounds, something recurrent in this branch of science. Thanks to the development of new technologies in the analytical instrumentation of spectroscopic and spectrometric techniques, as well as the advance in the computational processing modes of the results, metabolomics has been gaining more and more space in studies that involve the prospection of natural products. Thus, this chapter summarizes the precepts and good practices in the metabolomics of microbial natural products using mass spectrometry and nuclear magnetic resonance spectroscopy, and also summarizes several examples where this approach has been applied in the discovery of bioactive molecules., (© 2023. The Author(s), under exclusive license to Springer Nature Switzerland AG.)

Penicillium setosum represents a Penicillium species recently described, with little up-to-date information about its metabolic and biological potential. Due to this scenario, we performed chemical and biological studies of P. setosum CMLD18, a strain isolated from Swinglea glutinosa (Rutaceae). HRMS-MS guided dereplication strategies and anti-leukemia assays conducted the isolation and characterization of six compounds after several chromatographic procedures: 2-chloroemodic acid ( 2 ), 2-chloro-1,3,8-trihydroxy-6- (hydroxymethyl)-anthraquinone ( 7 ), 7-chloroemodin ( 8 ), bisdethiobis(methylthio)acetylaranotine ( 9 ), fellutanine C ( 10 ), and 4-methyl-5,6-diihydro-2H-pyran-2-one ( 15 ). From the assayed metabolites, ( 10 ) induced cellular death against Kasumi-1, a human leukemia cell line, as well as good selectivity for it, displaying promising cytotoxic activity. Here, the correct NMR signal assignments for ( 9 ) are also described. Therefore, this work highlights more detailed knowledge about the P. setosum chemical profile as well as its biological potential, offering prospects for obtaining natural products with anti-leukemia capabilities.

The aim of this study was to investigate the cytotoxic activity of the Coriandrum sativum ( C. sativum ) ethanolic extract (CSEE) in neuroblastoma cells, chemically characterize the compounds present in the CSEE, and predict the molecular interactions and properties of ADME. Thus, after obtaining the CSEE and performing its chemical characterization through dereplication methods using UPLC/DAD-ESI/HRMS/MS, PM6 methods and the SwissADME drug design platform were used in order to predict molecular interactions and ADME properties. The CSEE was tested for 24 h in neuroblastoma cells to the establishment of the IC50 dose. Then, the cell death was evaluated, using annexin-PI, as well as the activity of the effector caspase 3, and the protein and mRNA levels of Bax and Bcl-2 were analyzed by ELISA and RT-PCR, respectively. By UHPLC/DAD/HRMS-MS/MS analysis, the CSEE showed a high content of isocoumarins-dihydrocoriandrin, coriandrin, and coriandrones A and B, as well as nitrogenated compounds (adenine, adenosine, and tryptophan). Flavonoids (apigenin, hyperoside, and rutin), phospholipids (PAF C-16 and LysoPC (16:0)), and acylglicerol were also identified in lower amount as important compounds with antioxidant activity. The in silico approach results showed that the compounds 1 to 6, which are found mostly in the C. sativum extract, obey the "Five Rules" of Lipinski, suggesting a good pharmacokinetic activity of these compounds when administered orally. The IC50 dose of CSEE (20 µg/mL) inhibited cell proliferation and promoted cell death by the accumulation of cleaved caspase-3 and the externalization of phosphatidylserine. Furthermore, CSEE decreased Bcl-2 and increased Bax, both protein and mRNA levels, suggesting an apoptotic mechanism. CSEE presents cytotoxic effects, promoting cell death. In addition to the promising results predicted through the in silico approach for all compounds, the compound 6 showed the best results in relation to stability due to its GAP value.

The dichloromethane extract of the cashew nuts from Anacardium occidentale was fractionated by rotation locular countercurrent chromatography aimed at discovering metabolites that could be useful as new models for photosynthesis inhibitors. The chemical fractionation afforded a complex mixture of anacardic acids, which upon catalytic hydrogenation yielded anacardic acid (1). Methylation of 1 via reaction with diazomethane afforded an ester 2. Both compounds were evaluated using polarographic approaches and fluorescence studies of chlorophyll a (ChL a). The in vitro assays informed the decision for the classification of 1 and 2 as Hill reaction inhibitors. Besides that, 1 inhibited the donor side of the PSII, while 2 acted as an energy transfer inhibitor. Therefore, this study is important for the development of herbicides., (© 2022 Wiley-VHCA AG, Zurich, Switzerland.)

Penicillium is a widely explored genus due to its chemical diversity and associated biological properties; in addition, it represents an important source for cytotoxic compounds with good application perspectives. Based on these aspects, in this review, Penicillium compounds that presented activity against human leukemia cell lines are being listed and discussed. For this, a careful bibliographic survey was carried out in the main electronic databases, i.e. Scopus, SciFinder, Web of Science and Pubmed. Between 1984 and 2020, thirty seven original papers were selected, when using the search terms Penicillium and leukemia. The occurrence of l-asparaginase produced by some Penicillium spp. was also highlighted since this enzyme is being employed for acute lymphoblastic leukemia and lymphosarcoma therapies. Therefore, this overview aims to demonstrate the potential of metabolites biosynthesized by Penicillium fungi which can be applied in human leukemia therapies and opportunities for designing new lead compounds.

Objective: This in vitro study evaluated the influence of bioactive plant extracts as dentin biomodifying agents to improve the longevity of bonded restorations. For that, plant extracts were applied to the dentin surface prior to the adhesive system., Materials and Methods: Bovine incisors were ground flat to obtain 2 mm thick slices in which conical preparations were made ( N  = 10). Tannin-containing plant extracts were applied to dentin before the application of the restorative system, as follows: control group (untreated, CTL), chlorhexidine 0.12% (CHX), mastruz ( Dysphania ambrosioides, MTZ), cat's claw ( Uncaria tomentosa, CTC), guarana ( Paullinia cupana , GUA), galla chinensis ( Rhus chinensis , GCH), and tannic acid (extracted from Acacia decurrens , TNA). The push-out bond strength test was conducted (0.5 mm/min). Dentin biomodification was assessed by the modulus of elasticity and mass change in bovine tooth sections (0.5 × 1.7 × 7.0 mm). The dentin staining after extract treatments of dentin slices was compared. The dentin surface wettability was also evaluated by means of the contact angles of the adhesive system with the dentin surface and compared with the untreated control group. Data were subjected to ANOVA/Tukey's test ( α  = 0.05)., Results: The bond strength of the restoratives to dentin was not significantly improved by the plant extracts, irrespective of the evaluation time ( p > 0.05). Except for TNA, the elastic modulus of demineralized dentin significantly reduced after treatment with the plant extracts ( p < 0.05). The dentin staining correlated with the tannin content of the extracts. The contact angle was significantly reduced when treated with CTC, GCH, and TNA., Conclusions: The tannin-containing extracts had a questionable effect on the longevity of bonded restorations. The dentin modulus was negatively affected by the extract treatments. Although some of the extracts changed the contact angle, which seems to improve the adhesive monomer permeation, the tannin-rich plant extract application prior to adhesive application was proven to be clinically unfeasible due to dentin staining., Competing Interests: The authors declare that there are no conflicts of interest regarding the publication of this study., (Copyright © 2021 Mackeler Ramos Polassi et al.)

Several molecules extracted from natural products exhibit different biological activities, such as ion channel modulation, activation of signaling pathways, and anti-inflammatory or antitumor activity. In this study, we tested the antitumor ability of natural compounds extracted from the Raputia praetermissa plant. Among the compounds tested, an alkaloid, here called compound S4 (4-Deoxyraputindole C), showed antitumor effects against human tumor lineages. Compound S4 was the most active against Raji, a lymphoma lineage, promoting cell death with characteristics that including membrane permeabilization, dissipation of the mitochondrial potential, increased superoxide production, and lysosomal membrane permeabilization. The use of cell death inhibitors such as Z-VAD-FMK (caspase inhibitor), necrostatin-1 (receptor-interacting serine/threonine-protein kinase 1 inhibitor), E-64 (cysteine peptidases inhibitor), and N-acetyl- L-cysteine (antioxidant) did not decrease compound S4-dependent cell death. Additionally, we tested the effect of cellular activity on adherent human tumor cells. The highest reduction of cellular activity was observed in A549 cells, a lung carcinoma lineage. In this lineage, the effect on the reduction of the cellular activity was due to cell cycle arrest, without plasma membrane permeabilization, loss of the mitochondrial potential or lysosomal membrane permeabilization. Compound S4 was able to inhibit cathepsin B and L by a nonlinear competitive (negative co-operativity) and simple-linear competitive inhibitions, respectively. The potency of inhibition was higher against cathepsin L. Compound S4 promoted cell cycle arrest at G 0 and G 2 phase, and increase the expression of p16 and p21 proteins. In conclusion, compound S4 is an interesting molecule against cancer, promoting cell death in the human lymphoma lineage Raji and cell cycle arrest in the human lung carcinoma lineage A549., (© 2018 Wiley Periodicals, Inc.)

Twenty-one isovanillin derivatives were prepared in order to evaluate their cytotoxic properties against the cancer cell lines B16F10-Nex2, HL-60, MCF-7, A2058 and HeLa. Among them, seven derivatives exhibited cytotoxic activity. We observed that for obtaining smaller IC 50 values and for increasing the index of selectivity, two structural features are very important when compared with isovanillin (1); a hydroxymethyl group at C-1 and the replacement of the hydroxyl group at C-3 by different alkyl groups. As the lipophilicity of the compounds was changed, we decided to investigate the interaction of the cytotoxic isovallinin derivatives on cell membrane models through Langmuir monolayers by employing the lipids DPPC (1,2-diplamitoyl-sn-glycero-3-phosphocoline) and DPPS (1,2-diplamitoyl-sn-glycero-3-phosphoserine). The structural changes on the scaffold of the compounds modulated the interaction with the phospholipids at the air-water interface. These results were very important to understand the biophysical aspects related to the interaction of the cytotoxic compounds with the cancer cell membranes., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Four compounds were isolated from roots and aerial parts of Pluchea sagittalis (Asteraceae), 3, 5-dihydroxy-6, 7, 3', 4'-tetramethoxiflavunol (1), 5-hydroxymethylfurfural (2), 3, 4-dimethoxybenzaldehyde (3) and 2, 3, 4-trihydroxybenzaldeyde (4). Their herbicidal potential was detected by polarographic techniques. All of them inhibited the non-cyclic electron transport on basal, phosphorylating and uncoupled conditions from H 2 O to methylviologen (MV); thus, they act as Hill reaction inhibitors. Studies on fluorescence of chlorophyll a (ChL a) indicated they have different modes of interaction and inhibition sites on the photosystem II electron transport chain; 1-3 have interacted with the acceptor side while 4 has interacted at the donor side.

Cyanogenic glucosides are a class of specialized metabolites widespread in the plant kingdom. Cyanogenic glucosides are α-hydroxynitriles, and their hydrolysis releases toxic hydrogen cyanide, providing an effective chemical defense against herbivores. Eucalyptus cladocalyx is a cyanogenic tree, allocating up to 20% of leaf nitrogen to the biosynthesis of the cyanogenic monoglucoside, prunasin. Here, mass spectrometry analyses of E. cladocalyx tissues revealed spatial and ontogenetic variations in prunasin content, as well as the presence of the cyanogenic diglucoside amygdalin in flower buds and flowers. The identification and biochemical characterization of the prunasin biosynthetic enzymes revealed a unique enzyme configuration for prunasin production in E. cladocalyx This result indicates that a multifunctional cytochrome P450 (CYP), CYP79A125, catalyzes the initial conversion of l-phenylalanine into its corresponding aldoxime, phenylacetaldoxime; a function consistent with other members of the CYP79 family. In contrast to the single multifunctional CYP known from other plant species, the conversion of phenylacetaldoxime to the α-hydroxynitrile, mandelonitrile, is catalyzed by two distinct CYPs. CYP706C55 catalyzes the dehydration of phenylacetaldoxime, an unusual CYP reaction. The resulting phenylacetonitrile is subsequently hydroxylatedby CYP71B103 to form mandelonitrile. The final glucosylation step to yield prunasin is catalyzed by a UDP-glucosyltransferase, UGT85A59. Members of the CYP706 family have not been reported previously to participate in the biosynthesis of cyanogenic glucosides, and the pathway structure in E. cladocalyx represents an example of convergent evolution in the biosynthesis of cyanogenic glucosides in plants., (© 2018 American Society of Plant Biologists. All rights reserved.)

Eight alkaloids ( 1 ⁻ 8 ) were isolated from Ruta graveolens , and their herbicide activities were evaluated through in vitro, semivivo, and in vivo assays. The most relevant results were observed for Compounds 5 and 6 ⁻ 8 at 150 μM, which decreased dry biomass by 20% and 23%, respectively. These are significant results since they presented similar values with the positive control, commercial herbicide 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU). Based on the performed assays, Compound 5 (graveoline) is classified as an electron-transport inhibitor during the light phase of photosynthesis, as well as a plant-growth regulator. On the other hand, Compounds 6 ⁻ 8 inhibited electron and energy transfers, and are also plant-growth inhibitors. These phytotoxic behaviors based on acridone and quinolone alkaloids may serve as a valuable tool in the further development of a new class of herbicides since natural products represent an interesting alternative to replace commercial herbicides, potentially due their low toxicity.

A phytochemical study of Pavonia multiflora A. St-Hil. (Malvaceae) led to the isolation through chromatographic techniques of 10 secondary metabolites: vanillic acid (1), ferulic acid (2), p-hydroxybenzoic acid (3), p-coumaric acid (4), loliolide (5), vomifoliol (6), 4,5-dihydroblumenol A (7), 3-oxo-α-ionol (9), blumenol C (10), and taraxerol 4-methoxybenzoate (8), the latter being a novel metabolite. Their structures were identified by (1) H- and (13) C-NMR, using one- and two-dimensional techniques, and X-ray crystallography. In this work, we report the effect of compounds 5 and 8 on several photosynthetic activities in an attempt to search for new compounds as potential herbicide agents that affect photosynthesis. Both compounds inhibited the electron flow from H2 O to methyl viologen; therefore, they act as Hill reaction inhibitors. Using polarographic techniques and studies of the fluorescence of chlorophyll a, the interaction sites of these compounds were located at photosystem II., (© 2016 Verlag Helvetica Chimica Acta AG, Zürich.)