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Multiple protocols have been reported to fabricate paper-based analytical devices (PADs). However, some of these techniques must be revised because of the instrumentation required. This paper describes a versatile and globally affordable method to fabricate PADs using office paper as a substrate and a laser printing technique to define hydrophobic barriers on paper surfaces. To demonstrate the feasibility of the alternatives proposed in this study, the fabrication of devices for three types of detection commonly associated with using PADs was demonstrated: colorimetric detection, electrochemical detection, and mass spectrometry associated with a paper-spray ionization (PSI-MS) technique. Besides that, an evaluation of the type of paper used and chemical modifications required on the substrate surface are also presented in this report. Overall, the developed protocol was suitable for using office paper as a substrate, and the laser printing technique as an efficient fabrication method when using this substrate is accessible at a resource-limited point-of-need. Target analytes were used as a proof of concept for these detection techniques. Colorimetric detection was carried out for acetaminophen, iron, nitrate, and nitrite with limits of detection of 0.04 μg, 4.5 mg mL -1 , 2.7 μmol L -1 , and 6.8 μmol L -1 , respectively. A limit of detection of 0.048 fg mL -1 was obtained for the electrochemical analysis of prostate-specific antigen. Colorimetric and electrochemical devices revealed satisfactory performance when office paper with a grammage of 90 g m -2 was employed. Methyldopa analysis was also carried out using PSI-MS, which showed a good response in the same paper weight and behavior compared to chromatographic paper.

There is an increasing need for developing a strategy to analyze the penetration of pesticides in cultures during postharvest control with minimal or no sample preparation. This study explores the combined use of laser ablation electrospray ionization mass spectrometry imaging (LAESI imaging) and tissue spray ionization mass spectrometry (TSI-MS) to investigate the penetration of thiabendazole (TBZ) in fruits, simulating a postharvest procedure. Slices of guava and apple were prepared, and an infrared laser beam was used, resulting in the ablation of TBZ directly ionized by electrospray and analyzed by mass spectrometry. The experiments were conducted for 5 days of fruit storage after TBZ administration to simulate a postharvest treatment. During postharvest treatment, TBZ is applied directly to the fruit peel after harvesting. Consequently, TBZ residues may remain on the peel if the consumer does not wash the fruit properly before its consumption. To evaluate the effectiveness of household washing procedures, TSI-MS was employed as a rapid and straightforward technique to monitor the remaining amount of TBZ in guava and apple peels following fruit washing. This study highlights the advantages of LAESI imaging for evaluating TBZ penetration in fruits. Moreover, the powerful capabilities of TSI-MS are demonstrated in monitoring and estimating TBZ residues after pesticide application, enabling the comprehensive unveiling of pesticide contaminants in fruits.

This study performs a chemical investigation of blood plasma samples from patients with and without fibromyalgia, combined with some of the symptoms and their levels of intensity used in the diagnosis of this disease. The symptoms evaluated were: visual analogue pain scale (VAS); fibromyalgia impact questionnaire (FIQ); Hamilton anxiety rating scale (HAM); Tampa Scale for Kinesiophobia (TAMPA); quality of life Questionnaire-physical and mental health (QL); and Pain Catastrophizing Scale (CAT). Plasma samples were analyzed by paper spray ionization mass spectrometry (PSI-MS). Spectral data were organized into datasets and related to each of the symptoms measured. The datasets were submitted to multivariate classification using supervised models such as principal component analysis with linear discriminant analysis (PCA-LDA), successive projections algorithm with linear discriminant analysis (SPA-LDA), genetic algorithm with linear discriminant analysis (GA-LDA) and their versions with quadratic discriminant analysis (PCA/SPA/GA-QDA) and support vector machines (PCA/SPA/GA-SVM). These algorithm combinations were performed aiming the best class separation. Good discrimination between the controls and fibromyalgia samples were observed using PCA-LDA, where the spectral data associated with the CAT symptom achieved 100% classification sensitivity, and associated with the VAS symptom achieved 100% classification specificity, with both symptoms at the moderate level of intensity. The spectral variable at 579 m/z was found to be substantially significant for classification according to the PCA loadings. According to the human metabolites database, this variable can be associated with a LysoPC compound, which comprises a class of metabolites already evidenced in other studies for fibromyalgia diagnosis. This study proposed an investigation of spectral data combined with clinical data to compare the classification ability of different datasets. The good classification results obtained confirm this technique is as a good analytical tool for the detection of fibromyalgia, and provides theoretical support for other studies about fibromyalgia diagnosis., (© 2023. The Author(s).)

Employing a combination of liquid chromatography electrospray ionization and paper spray ionization high-resolution tandem mass spectrometry, extracts from cupuassu ( Theobroma grandiflorum ) pulp prepared with either water, methanol, acetonitrile or combinations thereof were subjected to metabolite fingerprinting. Among the tested extractors, 100% methanol extracted preferentially phenols and cinnamic acids derivatives, whereas acetonitrile and acetonitrile/methanol were more effective in extracting terpenoids and flavonoids, respectively. And while liquid chromatography- mass spectrometry detected twice as many metabolites as paper spray ionization tandem mass spectrometry, the latter proved its potential as a screening technique. Comprehensive structural annotation showed a high production of terpenes, mainly oleanane triterpene derivatives. of the mass spectra Further, five major metabolites with known antioxidant activity, namely catechin, citric acid, epigallocatechin-3'-glucuronide, 5,7,8-trihydroxyflavanone, and asiatic acid, were subjected to molecular docking analysis using the antioxidative enzyme peroxiredoxin 5 (PRDX5) as a model receptor. Based on its excellent docking score, a pharmacophore model of 5,7,8-trihydroxyflavanone was generated, which may help the design of new antioxidants.

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.

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., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

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., 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 © 2021 Elsevier B.V. All rights reserved.)

Fibromyalgia is a rheumatological disorder that causes chronic pain and other symptomatic conditions such as depression and anxiety. Despite its relevance, the disease still presents a complex diagnosis where the doctor needs to have a correct clinical interpretation of the symptoms. In this context, it is valid to study tools that assist in the screening of this disease, using chemical work techniques such as mass spectroscopy. In this study, an analytical method is proposed to detect individuals with fibromyalgia (n = 20, 10 control samples and 10 samples with fibromyalgia) from blood plasma samples analyzed by mass spectrometry with paper spray ionization and subsequent multivariate classification of the spectral data (unsupervised and supervised), in addition to the treatment of selected variables with possible associations with metabolomics. Exploratory analysis with principal component analysis (PCA) and supervised analysis with successive projections algorithm with linear discriminant analysis (SPA-LDA) showed satisfactory results with 100% accuracy for sample prediction in both groups. This demonstrates that this combination of techniques can be used as a simple, reliable and fast tool in the development of clinical diagnosis of Fibromyalgia., (© 2021. The Author(s).)

A method named imprint paper spray ionization mass spectrometry (imprint-PSI-MS) has been developed and employed for the determination of pungency of peppers. A pepper fruit was cut into a triangular shape, deposited onto a triangular paper, and compressed by a homemade press tool aiming to imprint and transfer the pepper constituents onto the paper surface. Subsequently, the triangular paper was submitted to conventional PSI-MS analysis. Twelve peppers were analyzed, ranging from highly pungent to lowly pungent taste. Pepper pungency values from the Scoville scale (in Scoville heat units, SHU) were compared with the ion intensities of the capsaicin and dihydrocapsaicin compounds obtained from the imprint-PSI-MS analysis, and a correlation coefficient of 0.97 was achieved. In addition, the ion intensities of a sugar compound were monitored in all peppers, and the results were compared with the Scoville scale. Low sugar ion intensities were detected in pungent peppers, while high ion intensities were achieved in low-pungent peppers, suggesting that the pepper pungency may be determined by inversely relating pungency to sugar contents. This work demonstrates the utility of the imprint-PSI-MS method to perform rapid qualitative analyses of peppers and estimate the pungency by monitoring the pepper metabolites. Graphical abstract.