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Human genomic DNA contains a number of diverse repetitive sequence motifs, often identified as fragile sites leading to genetic instability. Among them, expansion events occurring at triplet repeats have been extensively studied due to their association with neurological disorders, including Huntington’s disease (HD). In the case of HD, expanded CAG triplet repeats in the HTT gene are thought to cause the onset. The expansion of CAG triplet repeats is believed to be triggered by the emergence of stem-loops composed of CAG triplet repeats, while the underlying molecular mechanisms are largely unknown. Therefore, identifying proteins recruited on such stem loops would be useful to understand the molecular mechanisms leading to the genetic instability of CAG triplet repeats. We previously developed a plasmid DNA pull-down methodology that captures proteins specifically assembled on any sequence of interest using nuclear extracts. Analysis by Mass Spectrometry revealed that among the proteins specifically bound to a stem-loop composed of CAG triplet repeats, many turned out to belong to DNA repair pathways. We expect our data set to represent a useful entry point for the design of assays allowing the molecular mechanisms of genetic instability at CAG triplet repeats to be explored.

The Mars Organic Molecule Analyzer (MOMA) is a key scientific instrument on the ExoMars Rover mission. MOMA is designed to detect and characterize organic compounds, over a wide range of volatility and molecular weight, in samples obtained from up to 2 m below the martian surface. Thorough analog sample studies are required to best prepare to interpret MOMA data collected on Mars. We present here the MOMA characterization of Mars analog samples, microbial streamer communities composed primarily of oxygenic and anoxygenic phototrophs, collected from an alkaline silica-depositing hot spring in Yellowstone National Park, Wyoming, USA. Samples of partly mineralized microbial streamers and their total lipid extract (TLE) were measured on a MOMA Engineering Test Unit (ETU) instrument by using its laser desorption/ionization mass spectrometry (LDI-MS) mode. MOMA LDI-MS detected a variety of lipids and pigments such as chlorophyll

The composition and structural characteristics of Shengli lignite were characterized by ultimate analysis, 13C-NMR, and FTIR. Pyrolysis volatiles products of lignite were studied by TG-FTIR-GC/MS. Solid 13C-NMR analysis showed that the most abundant in Shengli lignite skeleton structure was aromatic carbon, followed by aliphatic carbon, and some carbonyl carbon. TG-FTIR-GC/MS analysis indicated that the main components of the small molecular gas released by Shengli lignite were CO2, CO, CH4, light arenes, etc., mainly from the carboxyl, carbonyl, aliphatic chains and aromatic structure in the lignite. Normalization method was used to describe the distribution of volatiles products. The release temperature of aliphatic, aromatic, phenolic and naphthalene substances is concentrated around 450–600 °C. The relative content of CO released at 540 °C is the highest, mainly from the pyrolysis of phenol. And the initial release temperature of CO is about 300 °C which is higher than that of CO2 and lower than that of CH4.

The method of voltammetric determination of nitroimidazoles in honey is developed. This method is based on the reduction of nitroimidazoles nitro group on the mercury drop indicator electrode. The obtained values of LODs for nitroimidazoles are as follows: 1.5 × 10−7 M, 8.6 × 10−8 M and 2.0 × 10−7 M for metronidazole, dimetridazole, and ipronidazole, and the linear correlation coefficients are 0.99974, 0.99987 and 0.99849, respectively, which tend towards to 1. The minimum amount of metronidazole that can be detected by means of our method, using simple dissolving of honey sample in water is 300 µg of metronidazole per 1 kg of honey. The developed voltammetric technique’s accuracy was confirmed by the “added-found” method and by HPLC-MS/MS analysis. The calculated amount of metronidazole in the tested model solution is in good agreement with the amount, introduced into honey. The calculated values of texp are 0.52, 0.48 and 0.43 for three different concentrations. Significant advantages of the method are effortless sample preparation, fast procedure of analysis, the possibility of miniaturization, low cost, not necessary use of organic solvents.

Alternariol (AOH) and alternariol-9-monomethyl ether (AME) are two secondary metabolites of Alternaria fungi which can be found in various foodstuffs like tomatoes, nuts, and grains. Due to their toxicity and potential mutagenic activity the need for the development of high-throughput methods for the supervision of AOH and AME levels is of increasing interest. As the availability of both native and labeled AOH and AME analytical standards is very limited, we herein present a novel and concise approach towards their synthesis by employing a ruthenium-catalyzed ortho-arylation as the key step. Finally, we demonstrate their suitability as internal standards in stable-isotope dilution assay (SIDA)-HPLC-MS/MS analysis, a technique commonly used for the quantification of natural products in food and feed.

Black aspergilli are some of the most common mycotoxigenic fungi in vineyards worldwide. The aims of this research were to assess the occurrence of fumonisin-producing black aspergilli in Australian wine grapes and the effects of environmental factors on fumonisin production by A. niger and A. welwitschiae (syn. A. awamori). Thirty-eight Aspergillus isolates (black aspergilli) were collected from six wine grape varieties grown in Australian vineyards. LC-MS/MS analysis of culture extracts revealed that six isolates produced fumonisins FB2 and FB4. Molecular data revealed that all fumonisin-producing isolates were A. niger and A. welwitschiae. None of the reference isolates, A. carbonarius, A. tubingensis, A. japonicus, and A. foetidus, were positive for fumonisin production. The effects of temperature and water activity on the growth and production of fumonisins were studied using two A. niger and an isolate of A. welwitschiae on synthetic grape juice medium (SGJM) at 20 °C, 25 °C, 30 °C, and 35 °C, and 0.92 aw, 0.95 aw, and 0.98 aw levels. All isolates produced FB2 and FB4 at 0.95 aw and 0.98 aw and 20 °C, 25 °C, and 30 °C. The highest growth rate observed was 14.89 mm/day for A. welwitschiae at 0.98 aw and 35 °C, whereas the highest fumonisin production observed was 25.3 mg/kg at 0.98 aw and 20 °C for A. welwitschiae. None of the isolates produced fumonisins at 35 °C at any water activity levels. To our knowledge, this is the first report on the occurrence of fumonisin-positive isolates of Aspergillus from Australian wine grapes and the impact of the environmental factors on fumonisin production by A. welwitschiae.

Limonoids are bioactive plant specialized metabolites found in the Meliaceae family. The basic limonoids, i.e., azadiradione, epoxyazadiradione, and gedunin have been exploited for various bioactivities and therefore are the potential drug leads for tomorrow. However, their low abundance, structural similarity, and lack of adequate mass fragmentation data have hampered their accurate identification and quantification from various sources. In the present study, basic limonoids such as azadirone, azadiradione, epoxyazadiradione, and gedunin isolated from Neem were utilized for the synthesis of their derivatives and isotopologs. A total of 30 one compounds were used in this study among which five were isolated, two were biotransformed, and 24 were synthesized. Among the synthesized compounds nine are novel compounds including six deuterated analogs/isotopologs which are (1,3-2H)-1,2-dihydro-3β-hydroxyazadiradione (9), (1,3,16-2H)-1,2-dihydro-3β-16β-dihydroxyazadiradione (10), 3β-hydroxyazadiradione (11), 3β-16β-dihydroxyazadiradione (12), (3-2H)-3β-hydroxyazadiradione (13), (3,16-2H)-3β-16β-dihydroxyazadiradione (14), (1,3,7-2H)-1,2-dihydro-3β-hydroxy-7-deacetylazadiradione (15), 1,2,20,21,22,23-hexahydroazadiradione (17), and (1,3-2H)-1,2-dihydro-3β-hydroxygedunin (29). These limonoids along with their semisynthesized derivatives were subjected to ultra high performance liquid chromatography mass spectrometry (UHPLC–MS/MS) and the fragmentation pathway was established based on structure–fragment relationships (SFRs), utilizing high resolution MS/MS data. We have developed a most reliable and easily reproducible protocol describing in depth analysis of SFRs based on the structural modifications and synthesis of isotopologs. Also, the MS/MS fragment library of these basic limonoids generated in this study acts as a fingerprint for accurate identification and quantification of limonoids by MS/MS analysis in various plant tissue extracts, phytopharmaceutical formulations and biological samples.

OBJECTIVE To report the clinicopathologic and proteomic characteristics of a novel form of amyloidosis derived from the precursor protein somatostatin. MATERIALS AND METHODS Cases were identified by searching the Mayo Clinic amyloid liquid chromatography and tandem mass spectrometry (LC-MS/MS) typing database from 1 January 2008 to 1 September 2020 for specimens with the amyloid signature proteins and abundant somatostatin, in the absence of other amyloid precursor proteins. All available medical records and pathologic materials were examined. RESULTS Somatostatin-derived amyloid deposits were found in four patients, two females and two males, with a median age of 61.5 years (range 47-73 years). One patient also had neurofibromatosis-1. The amyloid in each case was associated with a well-differentiated, somatostatin-producing neuroendocrine tumour arising in the small bowel or pancreas. The amyloid deposits were Congo Red-positive and were readily identified by LC- MS/MS analysis. Somatostatin was present exclusively in somatostatin-associated amyloid cases (p

In this report, we perform structure validation of recently reported RNA phosphorothioate (PT) modifications, a new set of epitranscriptome marks found in bacteria and eukaryotes including humans. By comparing synthetic PT‐containing diribonucleotides with native species in RNA hydrolysates by high‐resolution mass spectrometry (MS), metabolic stable isotope labeling, and PT‐specific iodine‐desulfurization, we disprove the existence of PTs in RNA from E. coli, S. cerevisiae, human cell lines, and mouse brain. Furthermore, we discuss how an MS artifact led to the initial misidentification of 2′‐O‐methylated diribonucleotides as RNA phosphorothioates. To aid structure validation of new nucleic acid modifications, we present a detailed guideline for MS analysis of RNA hydrolysates, emphasizing how the chosen RNA hydrolysis protocol can be a decisive factor in discovering and quantifying RNA modifications in biological samples., For discovery of novel RNA modifications, a stringent workflow for structure validation is necessary to avoid misinterpretation of artifacts. The comparison of the synthetic standard to the native compound's retention time, full mass spectrum, high‐resolution mass spectrum and metabolic isotope labeling allow for confident identification of RNA modifications.

In-source fragmentation-based high-resolution mass spectrometry (ISF-HRMS) is a potential analytical technique, which is usually used to profile some specific compounds that can generate diagnostic neutral loss (NL) or fragment ion (FI) in ion source inherently. However, the ISF-HRMS method does not work for those compounds that cannot inherently produce diagnostic NL or FI in ion source. In this study, a derivatization-based in-source fragmentation-information-dependent acquisition (DISF-IDA) strategy was proposed for profiling the metabolites with easily labeled functional groups (submetabolomes) by liquid chromatography-electrospray ionization-quadrupole time-of-flight mass spectrometry (LC-ESI-Q-TOF MS). As a proof-of-concept study, 36 carboxylated compounds labeled with N,N-dimethylethylenediamine (DMED) were selected as model compounds to examine performance of DISF-IDA strategy in screening the carboxylated metabolites and acquiring their MSn spectra. In ESI source, the DEMD-derived carboxylated compounds were fragmented to produce characteristic neutral losses of 45.0578, 63.0684, and/or 88.1000 Da that were further used as diagnostic features for screening the carboxylated metabolites by DISF-IDA-based LC-Q-TOF MS. Furthermore, high-resolution MSn spectra of the model compounds were also obtained within a single run of DISF-IDA-based LC-Q-TOF MS analysis, which contributed to the improvement of the annotation confidence. To further verify its applicability, DISF-IDA strategy was used for profiling carboxylated submetabolome in mice feces. Using this strategy, a total of 351 carboxylated metabolites were detected from mice feces, of which 178 metabolites (51% of the total) were positively or putatively identified. Moreover, DISF-IDA strategy was also demonstrated to be applicable for profiling other submetabolomes with easily labeled functional groups such as amino, carbonyl, and cis-diol groups. Overall, our proposed DISF-IDA strategy is a promising technique for high-coverage profiling of submetabolomes with easily labeled functional groups in biological samples.

Made available in DSpace on 2022-04-29T08:31:35Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-01-01 We evaluated the use of MALDI-TOF MS for the identification of 3 major, dairy-associated Prototheca species, namely, Prototheca bovis (formerly P. zopfii genotype 2), P. blaschkeae, and P. ciferrii (formerly P. zopfii genotype 1). The MALDI-TOF MS spectra established for those species were introduced into the reference spectra library of the Bruker Biotyper MALDI-TOF MS analysis software. Next, 31 Prototheca isolates from Holstein cows with mastitis, from herds located in the midwestern area of São Paulo State, Brazil, were subjected to MALDI-TOF MS profiling. MALDI-TOF MS allowed identification of 22 of 27 P. bovis and 3 of 4 P. blaschkeae isolates with scores >2.0, with 5 of 27 P. bovis and 1 of 4 P. blaschkeae isolates identified only to the genus level. With our extended algae database, MALDI-TOF MS can contribute to quick and effective speciation of Prototheca from mastitis cases. Department of Animal Nutrition and Production School of Veterinary Medicine and Animal Science University of São Paulo-USP Department of Medical Microbiology Institute of Microbiology Faculty of Biology University of Warsaw Department of Animal Production and Preventive Veterinary Medicine School of Veterinary Medicine and Animal Sciences São Paulo State University-UNESP Department of Animal Production and Preventive Veterinary Medicine School of Veterinary Medicine and Animal Sciences São Paulo State University-UNESP

The quantitative analysis of substances in dried blood spots (DBS) has gained vast popularity in the past decade. The World Anti-Doping Agency (WADA) also recently committed to implementing DBS. Currently, DBS sampling mainly has focused on various volumetric sampling devices such as Hemaxis, Capitainer, and Mitra. These devices are designed to collect a specific sample volume, independent of the hematocrit (HCT), to enable quantitative DBS analysis. Here, we present an automated solution that makes the necessity of volumetric sampling for quantitative DBS analysis obsolete. Combining automated reflectance-based HCT correction in combination with fully automated DBS LC-MS/MS analysis, the novel strategy permits high-throughput analysis in combination with HCT independence. Studying the model compound phosphatidylethanol 16:0/18:1, which is HCT-dependent due to incorporation into red blood cells, an implementation of DBS HCT normalization is presented. First, the performance of the automated HCT module with DBS is demonstrated compared to standardized HCT analysis from whole blood using a centrifuge. Second, the HCT dependency of fully automated PEth analysis from DBS is evaluated. Third, a solution to correct for the HCT dependency of PEth using the HCT scanner is presented. The study demonstrates that as soon as the HCT dependence of an analyte is known, a correction factor can be applied for the normalization of HCT levels. In the context of PEth, a linear increase in PEth concentration was observed, as the analyte is primarily located within the cellular fraction. Based on the obtained results, the use of a common correction factor for PEth DBS is possible.

Lignin is currently one of the most promising biologically derived resources, due to its abundance and application in biofuels, materials and conversion to value aromatic chemicals. The need to better characterize and understand this complex biopolymer has led to the development of many different analytical approaches, several of which involve mass spectrometry and subsequent data analysis. This review surveys the most important analytical methods for lignin involving mass spectrometry, first looking at methods involving gas chromatography, liquid chromatography and then continuing with more contemporary methods such as matrix assisted laser desorption ionization and time-of-flight-secondary ion mass spectrometry. Following that will be techniques that directly ionize lignin mixtures—without chromatographic separation—using softer atmospheric ionization techniques that leave the lignin oligomers intact. Finally, ultra-high resolution mass analyzers such as FT-ICR have enabled lignin analysis without major sample preparation and chromatography steps. Concurrent with an increase in the resolution of mass spectrometers, there have been a wealth of complementary data analyses and visualization methods that have allowed researchers to probe deeper into the “lignome” than ever before. These approaches extract trends such as compound series and even important analytical information about lignin substructures without performing lignin degradation either chemically or during MS analysis. These innovative methods are paving the way for a more comprehensive understanding of this important biopolymer, as we seek more sustainable solutions for our human species’ energy and materials needs.

Mass spectrometry (MS) was considered as the most informative technique for components identification and has been widely adopted in plant sciences. However, spatial distribution of compounds in plant, which is vital for the exploration of plant physiological mechanism, is missed in MS analysis. Recent years mass spectrometry imaging has brought great breakthrough in plant analysis, because it can determine both the molecular compositions and spatial distributions, which is conducive to understand functions and regulation pathways of specific components in plants. Mass spectrometry imaging analysis of plant tissue is toward high sensitivity, high spatial resolution, and even single cell analysis. Despite of many challenges and technical barriers, such as difficulties of sample pretreatment caused by morphological diversity of plant tissues, obstacles for high spatial resolution imaging, and so on, lots of researches have contribute to remarkable progresses, including improvement in tissue preparation, matrix innovation, and ionization mode development. This review focuses on the advances of mass spectrometry imaging analysis of plant in the last 5 years, including commonly used ionization techniques, technical advances, and recent applications of mass spectrometry imaging in plants. This article is protected by copyright. All rights reserved.

Honey varies depending on plant origin and environmental conditions. Chemical constituents can be used to determine the origins, characteristics, and storage period of a specific honey. Styrax japonica (snowbell) honey has excellent flavor, but very few studies have been carried out on its chemical constituents. Therefore, the present study was aimed to identify chemical constituents containing in snowbell honey and to screen candidate marker compounds for predicting the storage period of snowbell honey using the identified compounds. Twelve compounds including three new compounds were purified and isolated from the snowbell honey. Three new compounds were elucidated as 1α,3β,5β-bornetriol, 7-hydroxy-2,2,6-trimethyl-1-oxaspiro[2.5]oct-5-en-4-one, and 2-benzyl-2,3-dihydroxybutanoic acid, based on ESI-MS and NMR experiments. 6,7-Dihydroxylinalool and 6,7-dihydroxygeraniol isolated as known compounds in this study were identified for the first time in snowbell honey as well as in other honeys. The isolated compounds were qualified and quantified by LC-ESI-Q-TOF-MS/MS analysis. All compounds were detected in snowbell honeys of different production years. The levels of tyrosol, 7-hydroxy-2,2,6-trimethyl-1-oxaspiro[2.5]oct-5-en-4-one, and (–)-dihydroxyphaseic acid were lower in snowbell honey with long storage period than in short storage period, which is suggested to be used as candidate marker compounds for predicting the storage period of snowbell honey.

Previous studies suggest that squalene (SQ) in sebum is oxidized by a photooxidation mechanism (i.e., singlet oxygen oxidation) to create SQ hydroperoxide (SQOOH), a compound that causes adverse skin conditions. However, oxidation of other lipids in sebum, such as linoleic acid (LA), has not been fully understood. Elucidating their oxidation, especially its mechanisms, may lead to a further understanding of the relationship between sebum oxidation and skin conditions. In this study, using HPLC-MS/MS, we aimed to detect LA hydroperoxide (LAOOH) directly from sebum and identify the oxidation mechanism of LA in sebum through analysis of LAOOH isomers. We developed extraction and HPLC-MS/MS analysis conditions that can sufficiently quantify each LAOOH isomer in sebum. Using this method, LAOOH was detected in samples from healthy individuals, demonstrating the presence of LAOOH in human sebum. Moreover, isomer analysis of LAOOH and SQOOH indicated that LA and SQ are oxidized in sebum by discrete oxidation mechanisms (LA oxidized by free radical oxidation, whereas SQ oxidized by singlet oxygen oxidation). Such results may further lead to the development of mechanism-specific ways to prevent oxidation of sebum via a selection of appropriate antioxidants, ultimately leading to the promotion of skin health.

In recent years there have been increasing complaints from staff working in UK prisons of secondary exposure to psychoactive drug fumes, often believed to be synthetic cannabinoids. Our pilot study aimed to provide an initial evidence base for this issue and reveal compounds of interest within indoor prison air. Here we present a new method for the detection of synthetic cannabinoids in air, and demonstrate its application in a UK prison. Air sampling was conducted using a fixed sequential sampler, alongside personal air sampling units worn by prison officers within an English prison. Air samples were collected onto thermal desorption (TD) tubes and analysed via comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC-TOF MS). This study is the first of its kind in a prison setting and the approach is of importance to analytical scientists, policy makers and public health employees tasked with the health and safety of prison staff. GC×GC-TOF MS analysis was able to separate and identify a range of compounds present in the prison air samples. Analysis of the TD tubes did not reveal any synthetic cannabinoids from the fixed pump air samples or the personal pump samples worn by prison officers. Air monitoring in prisons presents a challenge of logistics as well as science. Fixed sequential air sampling combined with personal air monitoring devices allowed air from multiple locations within a prison to be collected, providing a comprehensive approach to evaluating the air that prison staff are exposed to during a fixed time period.

The present study aims for quantitative analysis of citronella essential oil followed by its antifungal evaluation on maize fungi. GC/MS analysis of Cymbopogon nardus essential oil indicated the pr...

In the current study, the chemical constituents of leaf essential oil from Cananga odorata (Lam.) Hook. F. & Thomson were identified by GC/MS analysis. A total of 25 components (91.1 %) in the esse...

Microstructural and biomolecular preservation is reported in fossils as old as the Triassic. Such preservation suggests unusual taphonomic conditions. We collected fragments of fossil whale bone from silty, tuffaceous, and diatomaceous rocks of the middle-upper Miocene portion of the Pisco Formation. The whale fossils within the region are generally well-preserved and mostly articulated, including some specimens with in situ baleen. Due to the depositional setting associated with the preservation of these fossils, they could be expected to be favorable candidates for the preservation of cellular microstructures and/or original biomolecules. To test this hypothesis, fossil whale bone fragments were subjected to microscopic analysis and EDTA-mediated demineralization to release extractable materials. Microscopy of partially demineralized fossil bones revealed quartz-permineralized osteocyte-like and vessel-like structures. Protein assay (micro-Bicinchoninic Acid Assay) of the supernatants obtained from demineralized fossils yielded 12 to 19.5 μg of protein per gram of bone. MALDI-TOF analysis of the extracted protein demonstrated the presence of approximately 5 kD molecules in one fossil sample, consistent with the presence of highly fragmented polypeptides. An LC-MS/MS analysis of the fragmentation pattern of the tryptic digest of extracted protein was performed. However, attempted protein identification was unsuccessful. Nevertheless, this study first documents the microstructural preservation with some silicification of the fossil whale bones of the Pisco Formation, and then quantifies extractable protein from these bones. It adds to the growing body of reports of microstructural and organic preservation in fossils.

The human genome is sequenced and comprised of ~30,000 genes, making humans just a little bit more complicated than worms or flies. However, complexity of humans is given by proteins that these genes code for because one gene can produce many proteins mostly through alternative splicing and tissue-dependent expression of particular proteins. In addition, post-translational modifications (PTMs) in proteins greatly increase the number of gene products or protein isoforms. Furthermore, stable and transient interactions between proteins, protein isoforms/proteoforms and PTM-ed proteins (protein-protein interactions, PPI) add yet another level of complexity in humans and other organisms. In the past, all of these proteins were analyzed one at the time. Currently, they are analyzed by a less tedious method: mass spectrometry (MS) for two reasons: 1) because of the complexity of proteins, protein PTMs and PPIs and 2) because MS is the only method that can keep up with such a complex array of features. Here, we discuss the applications of mass spectrometry in protein analysis..

Salvadora persica L. (Sp) has been widely used as folk medicine. This study aimed to identify and assess the significant phenolics' antioxidant activities in young (S1) and old (S2) leaves of Sp. Six flavonoids; isoquercitrin, kaempferol-3-neohesperidoside, myricetin-3-galactoside, apigenin-O-hexoside, isorhamnetin and isorhamnetin-3-neohesperidoside, were identified for the first time in Sp leaves using LC-ESI-QTOF MS/MS analysis. The flavonoid-rich fraction obtained after purification of S1 (S1TF7) has the highest TFC (358.88 ± 0.12 mg rutin equivalent/g) and TPC (180.82 ± 0.82 mg gallic acid equivalent/g) and exhibits significant (p 0.05). The study concludes that S1TF7 can serve as a mean to prevent oxidative diseases, and it merits further pharmacological investigations.

The emergence of bacteria resistant to several families of antibiotics is nowadays a public health problem in the world. To overcome this, it appeared necessary to explore sources of active molecules from natural substances. Thus, the objective of this study was to carry out the phytochemical sorting of hydromethanol extracts from Ximenia americana stems and to evaluate their antibacterial activities on the in-vitro growth of methicillin-resistant Staphylococcus aureus. The phytochemical screening performed allowed us to identify saponins, sterols and polyterpenes, polyphenols, tannins and flavonoids. HPLC-MS/MS analysis lead to the identification of a variety of flavan-3ol, quercetin and derivatives. The study of antibacterial activity carried out on 5 multi-resistant clinical strains and on a reference strain by the Muller-Hinton agar medium diffusion and dilution method showed that the extracts were active on all the strains with MICs ranging from 6.25 to 100 mg and MBCs ranging from 12.5 to 100 mg. The antibacterial potential of these extracts highlighted in this study could make this plant a candidate for in-depth investigations that could lead to the discovery of new antibacterial molecules. L’apparition de bactéries résistantes à plusieurs familles d’antibiotiques constitue, de nos jours, un problème de santé publique dans le monde. Pour y remédier, l’exploration de sources de molécules actives à partir des substances naturelles s’est avérée nécessaire. Ainsi, l’objectif de cette étude était de réaliser le tri phytochimique des extraits hydrométhanoliques de tiges de Ximenia americana et d’évaluer leurs activités antibactériennes sur la croissance in-vitro des Staphylococcus aureus résistant à la méticilline. Le screening phytochimique réalisé a permis d’identifier des saponines, des stérols et polyterpènes, des polyphénols, des tanins et des flavonoïdes. L’analyse à la HPLC-MS/MS a permis d’identifier une variété de flavan-3ol, de la quercétine et dérivées. L’étude de l’activité antibactérienne réalisée sur 5 souches cliniques multirésistantes et sur une souche de référence par la méthode de diffusion et de dilution en milieu gélosé Muller-Hinton a montré que les extraits étaient actifs sur toutes les souches avec des CMI variant de 6,25 à 100 mg et des CMB variant de 12,5 à 100 mg. Le potentiel antibactérien de ces extraits mis en évidence dans cette étude pourrait faire de cette plante une candidate à des investigations approfondies pouvant aboutir à la découverte de nouvelles molécules antibactériennes.

Longicatenamides A-D, two diastereomeric pairs of new cyclic hexapeptides, were isolated from the combined-culture of Streptomyces sp. KUSC_F05 and Tsukamurella pulmonis TP-B0596. Their planar structures were determined by spectroscopic analysis including extensive 2D NMR and MS analysis. The absolute configurations of their component amino acids were determined by the use of highly sensitive reagents we recently developed; the highly sensitive-advanced Marfey's method (HS-advanced Marfey's method), which led us to reduce the sample loss and prevent incorrect structural determination. Particularly, the Cβ-stereochemistry of hyGlu in longicatenamides A and C was assigned without any use of Cβ-Marfey's methods. Longicatenamide A exhibited weak but preferential antimicrobial activity against Bacillus subtilis.

The demand for food has been increasing day by day. In the scenario of the blind use of pesticides and fertilizers, it becomes important to deliver quality food products to individuals. Analytical ...

The chemical composition of essential oils (EOs) isolated by hydrodistillation from Pterocarpus soyauxii Taub. root wood and root bark were determined for the first time by GC/MS analysis. The EOs ...

This paper presents the results of the research on the influence of catalytic activity of iron(II) octacarboxyphthalocyanines (FePcOC) on the transformation of diclofenac (DCF) which is the most popular anti-inflammatory analgesic. Diclofenac poses a serious threat to the natural environment. The paper demonstrates that diclofenac, in the presence a monomeric form of iron octacarboxyphthalocyanine and hydroxyl radicals (HO•) (from H2O2), undergoes a transformation into diclofenac-2,5-iminoquinone (DCF-2,5-IQ), causing distinct changes in the UV–Vis absorption spectrum. In the presence of iron octacarboxyphthalocyanine and H2O2, the previously colourless diclofenac solution becomes intense orange. As a result, a new band at approx. 450 nm appears in the absorption spectrum. HPLC analysis has shown that the concentration of diclofenac decreases with time. TD-DFT calculations using the CAM-B3LYP/6-31+G (d, p) method have been conducted to confirm experimental data concerning the formation of a new band at λmax = 450 nm.

Diffusion-ordered NMR spectroscopy (DOSY) can be used to analyze mixtures of compounds since resonances deriving from different compounds are distinguished by their diffusion coefficients (D). Previously, DOSY has mostly been used for organometallic and polymer analysis, we have now applied DOSY to investigate diffusion coefficients of structurally diverse organic compounds such as natural products (NP). The experimental Ds derived from 55 diverse NPs has allowed us to establish a power law relationship between D and molecular weight (MW) and therefore predict MW from experimental D. We have shown that D is also affected by factors such as hydrogen bonding, molar density and molecular shape of the compound and we have generated new models that incorporate experimentally derived variables for these factors so that more accurate predictions of MW can be calculated from experimental D. The recognition that multiple physicochemical properties affect D has allowed us to generate a polynomial equation based on multiple linear regression analysis of eight calculated physicochemical properties from 63 compounds to accurately correlate predicted D with experimental D for any known organic compound. This equation has been used to calculate predicted D for 217 043 compounds present in a publicly available natural product database (DEREP-NP) and to dereplicate known NPs in a mixture based on matching of experimental D and structural features derived from NMR analysis with predicted D and calculated structural features in the database. These models have been validated by the dereplication of a mixture of two known sesquiterpenes obtained from Tasmannia xerophila and the identification of new alkaloids from the bryozoan Amathia lamourouxi. These new methodologies allow the MW of compounds in mixtures to be predicted without the need for MS analysis, the dereplication of known compounds and identification of new compounds based solely on parameters derived by DOSY NMR., We report accurate DOSY NMR based molecular weight and diffusion coefficient prediction tools. These tools can be used to dereplicate known natural products from databases using structurally rich NMR data as a surrogate for mass spectrometric data.

The investigation of technologically critical elements (TCEs) as emerging pollutants is a constantly growing field of environmental research and societal concern. Nevertheless, existing data for most TCEs are still unsatisfactory for an accurate assessment of their potential (eco)toxicological effects on humans and the environment. The limited availability of data mainly results from the technically challenging analysis of selected TCEs. Low concentrations of TCEs in environmental matrices (μg kg−1 or lower) and the associated complex and time-consuming sample preparation pose the greatest challenges. This work aims at developing a new ICP-MS/MS-based multi-elemental approach targeting the analysis of all major TCEs (Sc, Ga, Ge, Nb, In, Te, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Yb, Lu, and Ta) in sediment, which represents one of the most important matrices for environmental research. N2O is applied as a reaction gas to overcome possible spectral interferences during ICP-MS/MS analysis. The use of N2O as a reaction gas for ICP-MS/MS analysis enabled higher oxide-product ion yields for many TCEs in comparison to the frequently used O2 cell gas. Hence, the selectivity and sensitivity of the method were improved. The presented multi-element method using N2O as a reaction gas achieved LODs between 0.00023 μg L−1 (Eu) and 0.13 μg L−1 (Te) for all analyzed TCEs. Likewise, for all analyzed elements, except for Te, recoveries between 80% and 112% were obtained for at least one of the analyzed reference materials (GBW 07313, GBW 07311, and BCR-2).

Traditional analysis methods are susceptible to interference caused by the complexity of sample matrices, and detector surface fouling arising from nonspecific adsorption of microorganisms (in biological samples) which leads in particular to a gradual loss of sensitivity. Imprinted materials can be used to effectively reduce interference originating in the matrices. However, the poor reproducibility and multicomponent quantification of trace antibiotics represent significant challenges to the detection process. Meanwhile, the high biological risk presented by bacterial antibiotic immunity and the persistence of antibiotics in foodstuffs, especially meat, both caused by the overuse of sulfonamide antibiotics, remain urgent issues. Here, we present the first example of a method for the accurate quantification of trace sulfa antibiotics (SAs) based on multi-template imprinted polymers (MMIPs). Levels of multiple SAs have been simultaneously successfully quantified by applying MMIP extraction coupled with UPLC-MS/MS analysis. This method shows excellent linearity of detection in the range of 0.1-500 μg L-1, and ultrasensitivity with low limits of detection of 0.03 μg L-1. The maximum SA residue recovered from sample tissues by using MMIPs was 5.48 μg g-1. MMIP-coupled UPLC-MS/MS quantification of SAs is an accurate and repeatable method for the monitoring of SA accumulation in mouse tissue samples. It also provides an effective strategy for the tracking and quantification of drugs in other biological samples.

Mass spectrometry (MS) based analysis has received intense attention in diverse biological fields. However, direct MS interrogation of target biomolecules in complex biological samples is still challenging, due to the extremely low abundance and poor ionization potency of target biological species. Innovations in nanomaterials create new auxiliary tools for deep and comprehensive MS characterization of biomolecules. More recently, growing research interest has been directed to the compositional and structural engineering of nanomaterials for enriching target biomolecules prior to MS analysis, enhancing the ionization efficiency in MS detection and designing biosensing nanoprobes in sensitive MS readout. In this review, we mainly focus on the recent advances in the engineering of nanomaterials towards their applications in sample pre-treatment, desorption/ionization matrices and ion signal amplification for MS profiling of biomolecules. This review will provide a toolbox of nanomaterials for researchers devoted to developing analytical methods and practical applications in the biological MS field.

SARS-CoV-2, the etiologic agent of the COVID-19 pandemic, emerged as the cause of a global crisis. Rapid and reliable clinical diagnosis is essential for effectively controlling transmission. The gold standard assay for SARS-CoV-2 identification is the highly sensitive real-time quantitative polymerase chain reaction (RT-qPCR); however, this assay depends on specialized reagents and may suffer from false results. Thus, additional assays based on different approaches could be beneficial. Here, we present a novel method for SARS-CoV-2 identification based on mass spectrometry. The approach we implemented combines a multistep procedure for the rational down-selection of a set of reliable markers out of all optional in silico derived tryptic peptides in viral proteins, followed by monitoring of peptides derived from tryptic digests of purified proteins, cell-cultured SARS-CoV-2, and nasopharyngeal (NP) swab matrix spiked with the virus. The marker selection was based on specificity to SARS-CoV-2 and on analytical parameters including sensitivity, linearity, and reproducibility. The final assay is based on six unique and specific peptide markers for SARS-CoV-2 identification. The simple and rapid (2.5 h) protocol we developed consists of virus heat inactivation and denaturation, tryptic digestion, and identification of the selected markers by liquid chromatography coupled to high-resolution mass spectrometry (LC-MS/MS). The developed assay enabled the identification of 104 PFU/mL SARS-CoV-2 spiked into buffer. Finally, the assay was successfully applied to 16 clinical samples diagnosed by RT-qPCR, achieving 94% concordance with the current gold standard assay. To conclude, the novel MS-based assay described here is specific, rapid, simple, and is believed to provide a complementary assay to the RT-qPCR method.

Five new compounds, dalpulapans A–E (1–5), were isolated from the hexane extract of the roots of Dalbergia stipulacea Roxb. Five new compounds, dalpulapans A–E (1–5), were isolated from the hexane extract of the roots of Dalbergia stipulacea Roxb. An evaluation of cytotoxic activity against HeLa, A549 and normal cell lines using MTT assay was performed. The results showed that R,R-velucarpin A (6) was the most active against HeLa cells with an IC50 value of 10.9 ± 0.42 μM, while fortunately this compound exhibited weak cytotoxicity against normal cells (29.20 ± 1.16 μM). Structures of all isolates were identified from their 1D and 2D NMR spectroscopic data and MS analysis. Experimental and calculated ECD spectra were studied to define the absolute configurations.

Background/Purpose: Although illicit substance use-induced toxicity or complication is a frequent cause of visit to the emergency department (ED), there are limited data on cases confirmed by liquid chromatography tandem-mass spectrometry (LC-MS/MS) analysis. This study aimed to describe clinical presentations of patients who visited the ED because of acute illicit substance-related complications. Methods: We performed a retrospective study between May 2017 and August 2018 on patients presenting to the ED with positive urine illicit substance analysis by LC-MS/MS. Results: Of 203 patients with at least one illicit substance detected in their urine, 162 (79.8%) showed traditional illicit substances, and 56 (32.0%) showed new psychoactive substances (NPS). Methamphetamine was the most common illicit substance (67.9%). The most common NPS was ketamine (21.7%), followed by synthetic cathinones (14.8%). We divided patients into traditional, NPS and combined (both traditional illicit substance and NPS) groups. Polysubstance use was more common in the NPS group than in the traditional group (P