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Molecular modification of compounds remains important strategy towards the discovery of new drugs. In this sense, this study presents a new pyrazole derivative 5-(1-(2-fluorophenyl)-1 H-pyrazol-4-yl)-1 H-tetrazole (LQFM039) and evaluated the anti-inflammatory, analgesic, and vasorelaxant effects of this compound as well the mechanisms of action involved in the pharmacological effects. For this, mice were orally treated with LQFM039 (17.5, 35, or 70 mg/kg) prior acetic acid-induced abdominal writhing, formalin, tail flick, and carrageenan-induced paw edema protocols. In addition, vascular reactivity protocols were made with aortic rings contraction with phenylephrine and stimulated with graded concentrations of LQFM039. Abdominal writhing and licking time in both neurogenic and inflammatory phases of formalin were reduced with LQFM039 without altering latency to nociceptive response in the tail flick test. Carrageenan-induced paw edema showed that LQFM039 reduces edema and cell migration. In addition, the mechanism of action of LQFM039 involves NO/cGMP pathway and calcium channels, since this new pyrazole derivate elicited concentration-dependent relaxation attenuated by Nω-nitro-l-arginine methyl ester and 1 H-[1,2,4] oxadiazolo [4,3-alpha]quinoxalin-1-one, and blockade of CaCl2-induced contraction. Altogether, our finding suggests anti-inflammatory, antinociceptive, and vasorelaxant effect of this new pyrazole derivative with involvement of NO/cGMP pathway and calcium channels.

Here, we present a new application of desorption electrospray ionization (DESI) and laser ablation electrospray ionization (LAESI) mass spectrometry imaging to assess the spatial location of organic compounds, both polar and nonpolar, directly from rock surfaces. Three carbonaceous rocks collected from an aquatic environment and a berea sandstone subjected to a small-scale oil recovery experiment were analyzed by DESI and LAESI. No rock pretreatment was required before DESI and LAESI analyses. DESI detected and spatially mapped several fatty acids and a disaccharide on the surfaces of carbonaceous rocks, and various nitrogenated and oxygenated compounds on the surfaces of berea sandstone. In contrast, LAESI using a 3.4 μm infrared laser beam was able to detect and map hydrocarbons on the surfaces of all rock samples. Both techniques can be combined to analyze polar and nonpolar compounds. DESI can be used first to detect polar compounds, as it does not destroy the rock surface, and LAESI can then be used to analyze nonpolar analytes, as it destroys a layer of the sample surface. Both techniques have the potential to be used in several scientific areas involving rocks and minerals, such as in the analysis of industry-derived contaminants in aquatic sediments or in small-scale rock-fluid interaction experiments.

The LQFM05 is a prototype drug designed for treatment of psychiatric disorders, such as schizophrenia, exhibiting anxiolytic- and antidepressant-like (12 or 24 µmol/kg) effects in classical behavioral tests. In order to evaluate its pharmacokinetic properties, a liquid chromatography method coupled to a quadrupole time of flight mass spectrometry system (LC-QTOF/MS) was developed and fully validated for LQFM05 analysis in rat plasma and tissue samples (brain, heart, liver, and kidneys). Liquid–liquid extraction, solid phase extraction and protein precipitation were assessed as clean-up procedures for biological samples and analyte enrichment. Plasma and tissue samples underwent protein precipitation as a preliminary step, using acetonitrile. Linearity was fully demonstrated for the dynamic range (10.0 to 900.0 ng/mL), with r2 values higher than 0.99 (RSDslope ≤ 2%, Fcal < Ftab, Ccal < Ctab). Biodistribution studies in rats revealed high brain tissue concentrations (12.4 µg/g), suggesting elevated drug affinity to the main therapeutic target tissue, showing a blood partition coefficient of 1.9. Kidneys also showed great exposure and tissue affinity, suggesting a potential extrahepatic clearance. Likewise, all examined tissues exhibited satisfactory LQFMF05 distribution. The mass fragmentation spectrum indicated the presence of its main metabolite, LQFM235, yielded by high hepatic hydroxylation route, an equally bioactive derivative. Lastly, the developed LC-QTOF/MS method was shown to be sensitive (LOQ = 10 ng/mL), precise and accurate for LQFM05 determination in tissue homogenates and plasma samples.

Naphthenic acids comprise one of the most toxic compounds of the produced water released from offshore oil platforms. Therefore, developing and applying faster, simpler, and more efficient analytical methods for analyzing naphthenic acids are urgently needed. Electromembrane extraction (EME) uses the electrokinetic migration of target ions through a porous membrane. Herein, the EME method was applied to extract naphthenic acids from produced water. The EME method was optimized, and the optimal conditions encompassed decanol as the organic solvent, the sample with pH 10.0, 5 min of extraction at 200 V, and the ratio 4:1 (borate buffer/matrix, v/v). Electrochemical impedance spectroscopy confirmed charged species' migration from produced water through the EME. Subsequently, all extracts were analyzed by ultra-high-resolution mass spectrometry. The EME efficiency was assessed by comparing the extraction results to the liquid-liquid extraction (LLE) method results. Analytical results showed good linearity for both solvent and matrix curves (

Background: Privileged scaffolds are of high importance for molecules containing the pyrazole subunit due to their broad spectrum of pharmacological activities. For this reason, a method that is more efficient needs to be developed for the preparation of pyrazole derivatives. Objective: The purpose of this study was the optimisation of the conventional synthesis of the pyrazole ring and the oxidation of phenyl-1H-pyrazole-4-carbaldehyde to phenyl-1H-pyrazole-4-carboxylic acid through Microwave- Assisted Organic Synthesis (MAOS). Methods: We performed a comparison between conventional synthesis and conventional synthesis with microwave heating using the synthesis method of pyrazole ring described by Finar and Godfrey and for the oxidation of phenyl-1H-pyrazole-4-carbaldehyde, the method described by Shriner and Kleiderer was used. Results: : MAOS reduces the reaction time to obtain all compounds compared to conventional heating. At a temperature of 60°C, 5 minutes of reaction time, and power of 50 W, the yield of phenyl-1H-pyrazoles (3a-m) compounds was in the range of 91 - 98% using MAOS, which is better than conventional heating (72 - 90%, 75ºC, 2 hours). An improvement in the yield for the oxidation reaction was also achieved with MAOS. The compounds (5a-m) were obtained with yields ranging from 62 - 92% (80ºC, 2 minutes, 150 W), while the yields with conventional heating were in the range of 48 - 85% (80ºC, 1 hour). The 26 compounds were achieved through an easy work-up procedure with no chromatographic separation. The pure products were characterised by the spectral data obtained from IR, MS, 1H and 13C NMR or HSQC/HMBC techniques. Conclusion: The advantages of MAOS include short reaction time and increased yield, due to which it is an attractive option for pyrazole compounds synthesis.

The initial objective of our work was to synthesize a series of 2-amino-4H-pyran-3-carbonitriles to be tested for their antifungal activities against economically relevant phytopathogenic fungi. Fourteen compounds were prepared in up to 94% yield and shown percentages of Botrytis cinerea inhibition above 70%. Despite the promising biological results, we observed that stock solutions prepared for biological tests showed color changing when kept for a few days on the laboratory bench, under room conditions, illuminated by common LED daylight tubes (4500–6000 k). This prompted us to investigate the possible photo-induced degradation of our compounds. FT-IR ATR experiments evidenced variations in the expected bands for functional of -amino-4H-pyran-3-carbonitriles stored under LED daylight. Following, HPLC–UV analysis showed reductions in the intensity of chromatographic peaks of 2-amino-4H-pyran-3-carbonitriles, and but not for solutions kept in the dark. A solution of (E)-2-amino-8-(4-nitrobenzylidene)-4-(4-nitrophenyl)-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile underwent 84.4% of conversion after 72 h of exposure to continuous LED daylight in a BOD chamber, and the reaction product was isolated in 36% yield and characterized as (E)-7-cyano-5-(4-nitrobenzylidene)-8-(4-nitrophenyl)bicyclo[4.2.0]oct-1(6)-ene-7-carboxamide (7*). Despite freshly prepared solutions of 2-amino-4H-pyran-3-carbonitriles produced antifungal activities, these solutions lost biological activity when left on the bench for a week. Besides, compound 7* formed from photo-induced degradation of 7 also showed no antifungal activity. With this, we hope to bring two contributions: (1) production of cyclobutenes through photochemical reactions of 2-amino-4H-pyran-3-carbonitriles can be carried out through exposure to simple white LED daylight; (2) biological applications of such 2-amino-4H-pyran-3-carbonitriles may be impaired by their poor photostability.

This work describes the development of a system that combines a derivatization protocol based on the Katritzky reaction with paper spray ionization mass spectrometry (PSI-MS) for the analysis of amino acid neurotransmitters in mouse brain tissues. The system is relatively simple, consisting of spraying the derivatization solution onto a mouse brain section mounted on a glass slide, applying a small volume of solvent to moisten the sample, pressing a triangular paper onto the sample surface to transfer the sample constituents to the paper surface, and using the paper as a substrate for PSI-MS analysis. The Katritzky reaction facilitated the ionization of the amino acids by reacting a pyrylium salt with the amino group of the analytes, forming very stable pyridinium cations, which greatly increased the sensitivity of the PSI-MS analysis. Most of the intensities of the amino acids modified by the Katritzky reaction were more than 10 times greater than the nonderivatized ones. The system was applied for the analysis of brain sections obtained from mice with Parkinson's disease, and the amino acids gamma-aminobutyric acid (GABA) and glycine (Gly), two compounds very well-known in studies of Parkinson's disease, were readily detected. The results suggest that the Katritzky reaction combined with PSI-MS might offer a significant advance in the knowledge on protocols that improve the sensitivity of detection of crucial biological compounds.

The antinociceptive and anti-inflammatory activities of a polysaccharide-free extract of the cashew gum obtained from Anacardium occidentale L., Anacardiaceae, in a chronic model of complete Freund’s adjuvant-induced arthritis were investigated, as well as the possible adverse effects caused by continued administration of this extract. The cashew gum extract was obtained after the precipitation and removal of polysaccharides using acetone. The chemical characterization of this extract was performed with liquid chromatography coupled to mass spectrometry and tandem mass spectrometry analyses. In the complete Freund’s adjuvant-induced arthritis model, the experimental groups (number = 8) were orally treated once daily for 15 days with vehicle (5 ml/kg) or extract (75 mg/kg). Pain, edema joint, and cell migration to synovial fluid were assessed. Alterations in the body weight and organ weight of the animals were evaluated and histopathological analyses of the stomach, liver, and kidney were performed. Liquid chromatography coupled to mass spectrometry basically identified and quantified seven anacardic acids as the predominant constituents of the extract. The polysaccharide-free cashew gum reduced the prostration, joint edema, and migration of polymorphonuclear cells; in addition, this extract did not alter body or organ weight. The histopathological analysis showed promoted gastroprotective and hepatoprotective effects against damage caused by adjuvant injection. These findings support the use of cashew gum in popular medicine and demonstrate that part of its effects is independent of the presence of polysaccharides, evidencing its therapeutic potential for the future development of new analgesic and anti-inflammatory drugs.

This work describes the surface coating of wooden toothpicks with amino groups (NH2) for electrospray ionization mass spectrometry (MS) analysis of naphthenic acids (NAs) in produced water samples and crude oil fractions. NH2 was introduced into the cellulosic material through a silanization reaction using aminopropyltriethoxysilane. An NH2-modified toothpick was inserted into the analyte extraction sample and was subsequently used as an electrospray emitter for MS analysis. The extraction conditions were optimized by analyzing NAs (benzoic acid, 1-naphthoic acid, decanoic acid, 3,5-dimethyladamantane-1-carboxylic acid, and 3,5-dimethyladamantane-1-acetic acid) in pure water, and the best condition was using 5 min of extraction time with the samples under agitation. Modified and unmodified wooden toothpicks were compared, and the intensities of all NAs were higher when using the modified substrates than when using the unmodified ones. Limit of detection (LOD), limit of quantification (LOQ), linearity, precision, and recovery were determined by analyzing decanoic acid in seawater samples. The LOD and LOQ were 2 and 5 μg mL-1, respectively, and a linear correlation (R2 = 0.9927) was obtained with concentrations ranging from 5 to 250 μg mL-1. Precision values ranged from 6 to 13% and recoveries from 89 to 106%. The technique was also employed to analyze three produced water samples, in which decanoic acid was semi-quantified, and the concentrations ranged from 10 to 13 μg mL-1. High abundances of acidic compounds of class O2 with DBEs (double bond equivalents) ranging from 1 to 3 and carbon numbers going from 8 to 12 were detected in the produced water samples. The results suggest that the modification of wooden toothpicks with NH2 might offer a significant advancement in the knowledge of cheap substrates that can improve the sensitivity of analysis of NAs in water samples.

The indiscriminate utilization of agrochemicals causes environmental and animal life impacts. In this regard, methodologies have been developed to offer efficiency and quickness for agrochemicals detection. Due to their selectivity and molecular recognition sites, Molecular Imprinted Polymer (MIPs) have been widely employed in some areas, including biotechnology, waste analyses, foodstuff, biological fluids, and others. This work proposed developing a method to determine aminocarb, pirimicarb, dimethoate, omethoate, pyridaphenthion, and fenitrothion pesticides using molecularly imprinted polymer combined with solid-phase extraction (MIP-SPE) for clean-up and paper spray ionization mass spectrometry for their analysis. Extractions analysis for Aminocarb, Pirimicarb, and Omethoate using MIP-SPE showed better performance when compared with MIP and NIP. The R(2) values were found with R(2) > 0.98 for all pesticides, and LODs and LOQs values were 50 and 100 µg kg(−1), respectively. The precision and accuracy were assessed at three concentration levels—low, medium, and high. The precision values (interday and intraday) were below 10%, and the variation of recovery was between 80 and 120% for all pesticides. Therefore, it was possible to verify the presence of two carbamates and five organophosphorus without the necessity of preconcentration samples with precision and good recovery. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s13197-022-05464-7.

This study reports for the first time the use of a microchip electrophoresis (ME) device with integrated capacitively coupled contactless conductivity detection (C

Activated carbon from coconut shell (Elaeis guineensis), in both crude and chemically modified forms, was evaluated as an adsorbent for removing nitrogen compounds of samples from synthetic and rea...

This study investigated the antinociceptive and anti-inflammatory effects of new pyrazole compounds LQFM011(5), LQFM043(6) and LQFM044(7) as well as the mechanisms of action and acute in vitro toxicity. The antinociceptive activity was evaluated using the acetic acid-induced abdominal writhing test, formalin-induced pain test and the Randall–Selitto test. The anti-inflammatory activity was evaluated using models of paw oedema and pleurisy induced by carrageenan; cell migration, the levels of tumour necrosis factor α (TNF-α) and myeloperoxidase (MPO) enzyme activity were evaluated. In addition, the ability to inhibit phospholipase A2 (PLA2) in vitro and docking in PLA2 were used. Acute oral systemic toxicity in mice was evaluated through the neutral red uptake assay. The synthesised compounds (5–7), delivered via gavage (p.o.) at 70, 140 or 280 µmol/kg, decreased the number of writhings induced by acetic acid; the three compounds (280 µmol/kg p.o.) reduced the paw licking time in the first and second phase of the formalin test and decreased the nociceptive threshold variation in the Randall–Selitto test. Furthermore, this dose reduced oedema formation, leucocyte migration (specifically through reduction in polymorphonuclear cell movement) and increased mononuclear cells. MPO activity and the levels of pro-inflammatory cytokines TNF-α were decreased. Evaluation of PLA2 inhibition via the docking simulation revealed more interactions of LQFM043R(6) and LQFM044(7), data that corroborated the half-maximal inhibitory concentration (IC50) of PLA2 inhibition in vitro. Therefore, LQFM011(5), LQFM043(6) and LQFM044(7) were classified with the Globally Harmonized System of Classification and Labelling of Chemicals (GHS) as category 4.

Growing concerns on free radicals are the oxidative processes associated with physiological damage. The consumption of functional foods and use of plants with antioxidant capacity are widespread. Given the importance of determining antioxidant capacity in relation to the therapeutic effect, this study was aimed at evaluating cinnamon extract (Cinnamomum sp.) in commercial samples by spectrophotometric and voltammetric methods and assessing the vascular activity of some samples. The spectrophotometric methods performed were DPPH (1,1-diphenyl-2-picrihydrazine), ABTS (2,21-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid)), and Folin-Ciocalteu radical sequestration assays. For the electrochemical experiments, a three-electrode system was used, consisting of carbon paste electrode, platinum wire, and Ag/AgCl/KClsat, representing the working, auxiliary, and reference electrodes, respectively. The electroanalytical methods used were differential pulse, square wave, and cyclic voltammetries. The extracts were prepared in hydroalcoholic solution. A calibration curve with gallic acid was calculated to quantify their equivalent amounts in the analyzed extract. The correlation between the electrochemical approach and the total phenols calculated by the ABTS, DPPH, and Folin-Ciocalteu methods was 0.63, 0.7, and 0.73, respectively, with 1 being an ideal directly proportional correlation. The correlation between spectrophotometric methods was 0.83. A biosensor was developed in a carbon paste electrode using the enzyme laccase, obtained by the fungus Marasmiellus colocasiae. It was observed that the antioxidant profile of the cinnamon samples had an analytical sign improvement of up to 4 times when compared with the electrode without the modification. The samples were analyzed by mass spectrometer, and the main chemical markers found were coumarin, cinnamaldehyde, and eugenol. Pharmacological trials showed that these samples also induce a significant vasorelaxant effect associated to antioxidant potential on vascular injury induced by oxidative stress. Thus, cinnamon showed a high antioxidant capacity, in agreement with the results obtained in other studies, emphasizing its importance as a functional food.

This work describes the surface coating of wooden toothpicks with amino groups (NH

Mass spectrometry (MS) is one of the most effective analytical methods that provide information about molecular weights and chemical structures of analytes with high sensitivity and specificity. The requirement for in situ MS analysis has increased over the years. The hindrance preventing MS from in situ applications can be overcome by the coupling of ambient mass spectrometry (AMS) techniques to portable mass spectrometers. Paper spray ionization (PSI) is a well-established and easy-to-use AMS technique. In PSI, triangular paper is used as a substrate to generate analyte ions by applying a high voltage and a spray solvent onto the paper. Coupling the simplicity of PSI to the portability of mass spectrometers may take MS out of the laboratory and make feasible the MS analysis in demanding environments. Therefore, in this review, we will discuss the state of the art, applications, and advances of the PSI technique as well as the development of portable mass spectrometer systems and the coupling of PSI to portable mass spectrometers to enable real-time field analysis.

The use of conductive polymers (CPs) as a substrate in ambient paper spray ionization was achieved under high DC voltage. Some pharmaceuticals, drugs of abuse, adulterants, metabolites, and impurities showed a signal that was higher in absolute intensity compared to that of uncoated papers. Surface characterization of the coated paper confirmed that the modified features on the paper surface were responsible for high electrical fields, signal stability, and reusability. The linearity and performance of CP-coated papers were demonstrated for a range of forensically relevant analytes, proving that CP-coated papers are an easy and cheap alternative for use in both qualitative and quantitative analyses.

It is herein described the preparation and evaluation of antimetastatic activity of twenty-six cinnamic acid derivatives containing 1,2,3-triazolic portions. The compounds were prepared using as the key step the Copper(I)-catalyzed azide (A)-alkyne (A) cycloaddition (C) (CuAAC reaction), also known as click reaction, between alkynylated cinnamic acid derivatives and different benzyl azides. The reactions were carried in CH2Cl2/H2O (1:1 v/v) at room temperature, and the triazole derivatives were obtained in yields ranging from 73% 99%. Reaction times varied from 5 to 40 min. The identity of the synthesized compounds was confirmed by IR and NMR (1H and 13C) spectroscopic techniques. They were then submitted to in vitro bioassays to investigate how they act over metastatic behavior of murine melanoma. The most potent compound, namely 3-(1-benzyl-1H-1,2,3-triazol-4-yl)propyl cinnamate (9a), showed significant antimetastatic and antiproliferative activities against B16-F10 cells. In addition, gelatin zymography and molecular docking analyses pointed to the fact that this compound has potential to interact with matrix metalloproteinase 9 (MMP-9) and MMP-2, which are directly involved in melanoma progression. Therefore, these findings suggest that cinnamic acid derivatives containing 1,2,3-triazolic portions may have potential for development of novel candidates for controlling malignant metastatic melanoma.

3D printing is a technology that has revolutionized traditional rapid prototyping methods due to its ability to build microscale structures with customized geometries in a simple, fast, and low-cost way. In this sense, this article describes the development of a microfluidic mixing device to monitor chemical reactions by mass spectrometry (MS). Microfluidic mixers were designed containing 3D serpentine and Y-shaped microchannels, both with a pointed end for facilitating the spray formation. The devices were fabricated entirely by 3D printing with fusion deposition modeling (FDM) technology. As proof-of-concept, micromixers were evaluated through monitoring the Katritzky reaction by injecting simultaneously 2,4,6-triphenylpropyllium (TPP) and amino acid (glycine or alanine) solutions, each through a different reactor inlet. Reaction product was monitored online by MS at different flow rates. Mass spectra showed that the relative abundances of the products obtained with the device containing the 3D serpentine channel were three times greater than those obtained with the Y-channel device due to the turbulence generated by the barriers created inside microchannels. In addition, when compared to the conventional electrospray ionization mass spectrometry (ESI-MS) technique, the 3D serpentine mixer offered better performance measured in relation to the relative abundance values for the reaction products. These results as well as the instrumental simplicity indicate that 3D printed microfluidic mixer is a promising tool for monitoring organic reactions via MS.

Morita-Baylis-Hillman adducts (MBHA) is a class of polyfunctional molecules that has been standing out due to their versatility and expressive biological activities. Therefore, this paper describes the synthesis and antiproliferative activity of some new MBHA/7-choroquinoline hybrids. The Michael acceptors were obtained starting from 4,7-dichloroquinoline which were submitted to the Morita-Baylis-Hillman reaction with ortho, meta and para-nitrobenzaldehyde. The in vitro screening of the synthetized MBHA against NCI-H292, HCT-116 and MCF-7 cancer cells suggests the influence of the spacer chain in its inhibition potential. The 50% inhibitory concentration (IC50) obtained in the antiproliferative assay using MCF-7, HCT-116, HL-60 and NCI-H292 cancer cells indicate expressive cytotoxic potential of the adducts containing nitro group in the ortho position, with IC50 of 4.60 µmol L-1. MBHA/7-choroquinoline hybrids were more active than MBHA described in literature, indicating the improvement of the cytotoxic effect due to 7-chloroquinoline moiety in the molecular structure, with maximum selectivity index values of 11.89.

The usefulness of molecularly imprinted polymer assisted paper spray ionization mass spectrometry (MIP-PSI-MS) for the determination of methamphetamine in urine has been demonstrated. MIP-PSI-MS is a method in which a MIP is synthesized on the surface of a paper, producing a chemically selective paper surface with molecular recognition sites for a target analyte. The analyte is extracted by the MIP substrate, which is posteriorly used for conventional PSI-MS analysis. As methamphetamine is one of the most widely used drugs of abuse in the world, it was selected to be studied in synthetic urine by the MIP-PSI-MS method. Methamphetamine was detected at higher ion signals compared to other different drugs, such as lysergic acid diethylamide (LSD) and cocaine, suggesting that MIP-PSI-MS has a chemical affinity for methamphetamine. In experiments to validate the method, a linear calibration curve was achieved with R-squared (R2) > 0.99. Limit of detection (LOD) and limit of quantification (LOQ) were determined to be 0.8 and 2.8 µg L-1, respectively. Precision (relative standard deviation) and accuracy (relative error) were less than 10%, and the recoveries were close to 100%. The matrix effect was below 10%. These data demonstrate the possibility of using MIP-PSI-MS as an analytical tool for a specific/selective analysis of methamphetamine in forensic sciences.

This study proposes a new, efficient, and selective method for the analysis of cocaine in oral fluid. For this purpose, an extractive phase with restricted access materials (RAM) capable of extract and pre-concentrate low molecular weight analytes and simultaneously exclude macromolecules was developed for disposable pipette extraction (DPX) followed by liquid chromatography coupled to mass spectrometry (LC-MS) analyses. The proposed method was optimized using a 24 factorial design which pointed higher extraction efficiency under the following conditions: pH 9, 10 cycles of extraction (aspirate/dispense), 3 cycles of desorption (aspirate/dispense) and acetonitrile as desorption solvent. The DPX-RAM/LC-MS method showed linearity range from 10 to 100 ng mL-1 with determination coefficient (R2) = 0.999, accuracy values ranged from -0.9 to 4.3%, precision values ranged from 1.7 to 9.1% and recovery values ranged from 97.9 to 101.1%. The benefits of this method are that it can be performed in few minutes and that the analytical performances, including the limit of detection (3.13 ng mL-1), limit of quantitation (10 ng mL-1) and linear range were found to be in agreement with other methods used for similar analysis.

This work describes the use of laser ablation electrospray ionization mass spectrometry imaging (LAESI imaging) to investigate the diffusion of the mycotoxin patulin from rotten to healthy areas of fruits. Slices of mold-infected and uninfected (control) apples and strawberries were prepared, and this was the only sample preparation step used. An infrared laser beam (2.94 μm) was used to irradiate the slices, resulting in the ablation of sample compounds directly ionized by electrospray and analyzed by mass spectrometry. Multivariate curve resolution – alternating least squares was applied in unfolded LAESI images to obtain relative quantity information. Patulin was not detected in the control samples but was seen in all mold-infected fruits. LAESI images showed the diffusion of patulin from the rotten area to unaffected parts of the fruits. This study points out the advantage of LAESI imaging over traditional analytical methods used to study the diffusion of mycotoxins in fruits.

Here we discovered an unprecedented giant octahedral coordination compound bearing 16 Zn2+, 12 Na+, 8 O2-, 4 OH-, 13 H2O and 6 L4- ligands [L4- = fully deprotonated tetra(carboxymethoxy)calix[4]arene]. Its structure was elucidated by single-crystal X-ray diffraction, wavelength-dispersive X-ray spectroscopy and MALDI-TOF mass spectrometry. This compound, Zn8Na6L6⊃Zn8Na6O8(OH)4(H2O)13 (external⊃internal), has eight tetrahedral zinc ions forming the coordination vertices of an outermost cube where carboxylate groups from the sodium calixarenes are anchored. Its core consists of eight Zn2+, six Na+, eight O2-, and four OH- distributed over three layers, besides thirteen coordinated H2O molecules.

A new approach using paper spray ionization mass spectrometry (PSI-MS) for the analysis of steroid hormones in wastewater samples has been demonstrated. Triangular papers containing paraffin barriers as microfluidic channels were used to direct the sample solution to the paper tip, preventing the sample from spreading over the corners of the paper. The method was used to analyze the hormones levonorgestrel and algestone acetophenide in industrial wastewaters. Analytical curves presented a correlation coefficient (R2) above 0.99. Limits of quantification were below 2.3 ppm and limits of detection below 0.7 ppm. Values of precision (coefficient of variation) and accuracy (relative error) were less than 15% for all analyses. Recovery results ranged from 82% to 102%. Levonorgestrel was also analyzed by high-performance liquid chromatography coupled to mass spectrometry in order to compare the analytical performance with PSI-MS. No statistically significant differences were found between both methods. This study demonstrates the usefulness of PSI-MS for rapid analysis of hormones in industrial wastewater samples and also indicates its potential to be employed as a simple and reliable analytical method in environmental sciences.

LQFM219 is a molecule designed from celecoxibe (COX-2 inhibitor) and darbufelone (inhibitor of COX-2 and 5-LOX) lead compounds through a molecular hybridisation strategy. Therefore, this work aimed to investigate the antinociceptive and anti-inflammatory activities of this new hybrid compound. The acute oral systemic toxicity of LQFM219 was evaluated via the neutral red uptake assay. Acetic acid-induced abdominal writhing and CFA-induced mechanical hyperalgesia were performed to evaluate the antinociceptive activity, and the anti-oedematogenic activity was studied by CFA-induced paw oedema and croton oil-induced ear oedema. Moreover, the acute anti-inflammatory activity was determined by carrageenan-induced pleurisy. In addition, cell migration, myeloperoxidase enzyme activity, and TNF-α and IL-1β levels were determined in pleural exudate. Moreover, a redox assay was conducted using electroanalytical and DPPH methods. The results demonstrated that LQFM219 was classified as GHS category 4, and it showed better free radical scavenger activity compared to BHT. Besides, LQFM219 decreased the number of writhings induced by acetic acid and the response to the mechanical stimulus in the CFA-induced mechanical hyperalgesia test. Furthermore, LQFM219 reduced oedema formation, cell migration, and IL-1β and TNF-α levels in the pleural cavity and inhibited myeloperoxidase enzyme activity. Thus, our study provides that the new pyrazole derivative, LQFM219, demonstrated low toxicity, antinociceptive and anti-inflammatory potential in vitro and in vivo.