Computer-assisted interpretation of atmospheric pressure chemical ionization mass spectra of triacylglycerols

Current lipidomics approaches require simple and rapid algorithms enabling the interpretation of mass spectra of lipids. Most lipids are complex mixtures of related components in which the composition of the aliphatic fatty acid chains varies from one molecule to the next. Triacylglycerols (TAGs) are an example of such a lipid class. Fatty acid chains are the only parts of the molecule to change from one species to another. Fatty acids, and consequently also TAGs, can be characterized by two parameters; the number of carbon atoms and the number of double bonds. All calculations reflecting relations among ions in the spectra can be easily made using these parameters. An algorithm for the automated interpretation of TAGs from atmospheric pressure chemical ionization mass spectra (TriglyAPCI) is presented in this paper. The algorithm first identifies diacylglycerol fragments and molecular adducts. In the next step, relations among the ions are searched and possible TAG structures are suggested. Individual features of the algorithm are described in detail and the software performance is demonstrated for the liquid chromatography/mass spectrometric (LC/MS) analysis of TAGs isolated from the termite Prorhinotermes canalifrons.     

Dispersion‐solidification liquid–liquid microextraction for volatile aromatic hydrocarbons determination: Comparison with liquid phase microextraction based on the solidification of a floating drop

Two microextraction techniques – liquid phase microextraction based on solidification of a floating organic drop (LPME‐SFO) and dispersive liquid–liquid microextraction combined with a solidification of a floating organic drop (DLLME‐SFO) – are explored for benzene, toluene, ethylbenzene and o‐xylene sampling and preconcentration. The investigation covers the effects of extraction solvent type, extraction and disperser solvents' volume, and the extraction time. For both techniques 1‐undecanol containing n‐heptane as internal standard was used as an extracting solvent. For DLLME‐SFO acetone was used as a disperser solvent. The calibration curves for both techniques and for all the analytes were linear up to 10 μg/mL, correlation coefficients were in the range 0.997–0.998, enrichment factors were from 87 for benzene to 290 for o‐xylene, detection limits were from 0.31 and 0.35 μg/L for benzene to 0.15 and 0.10 μg/L for o‐xylene for LPME‐SFO and DLLME‐SFO, respectively. Repeatabilities of the results were acceptable with RSDs up to 12%. Being comparable with LPME‐SFO in the analytical characteristics, DLLME‐SFO is superior to LPME‐SFO in the extraction time. A possibility to apply the proposed techniques for volatile aromatic hydrocarbons determination in tap water and snow was demonstrated.     

Circuit Covers of Signed Graphs

We introduce the concept of a signed circuit cover of a signed graph. A signed circuit cover is a natural analog of a circuit cover of a graph and is equivalent to a covering of the corresponding signed graphic matroid with circuits. As in the case of graphs, a signed graph has a signed circuit cover only when it admits a nowhere‐zero integer flow. In the present article, we establish the existence of a universal coefficient such that every signed graph G that admits a nowhere‐zero integer flow has a signed circuit cover of total length at most . We show that if G is bridgeless, then , and in the general case .     

Novel design of bicyclic beta-turn dipeptides on solid-phase supports and synthesis of [3.3.0]-Bicyclo([2,3])-leu-enkephalin analogues

[structure: see text] External bicyclic beta-turn dipeptide mimetics provide an excellent design approach that can offer a rich chiral ensemble of structures with different backbone conformations. We report herein a novel design of a convergent combinatorial synthetic methodology, which is illustrated by the solid-phase synthesis of a series of [3.3.0]-bicyclo([2,3])-Leu-enkephalin analogues. The reactions were optimized and the epimeric configurations were determined by 2D NMR spectroscopy. Biological assays show that these analogues have more potent delta binding affinity and bioactivity for delta vs micro opioid receptor, which may be related to the different conformations preferred by these analogues in our modeling studies.     

Note on independent sets in steiner systems

A partial Steiner (n, k, l)-system or briefly (n, k, l)-system is a pair (V, S), where V is an n-set and S is a collection of k-subsets of V, such that every l-subset of V is contained in at most one k-subset of S. A subset X ? V is called independent if [X]^k ∩ S = 0. The size of the largest independent set in S is denoted by α(S). Define The purpose of this note is to prove that for every k, l, k > l holds, where c, d are positive constants depending on k and l only.     

Multistrip Western blotting to increase quantitative data output

The qualitative and quantitative measurements of protein abundance and protein modification states are essential in understanding their role in diverse cellular processes. Traditional Western blotting technique, though sensitive, is prone to produce substantial errors and is not readily adapted to high-throughput technologies. We propose a modified immunoblotting procedure, which is based on simultaneous transfer of proteins from multiple gel-strips onto the same membrane, and is compatible with any conventional gel electrophoresis system. As a result, the data output per single blotting cycle can readily be increased up to ten-fold. In contrast to the traditional "one protein detection per electrophoresis cycle", this procedure allows simultaneous monitoring of up to nine different proteins. In addition to maintaining the ability to detect picogram quantities of protein, the modified system substantially improves data accuracy by reducing signal errors by two-fold. Multistrip Western blotting procedure allows making statistically reliable side-by-side comparisons of different or repeated sets of data. Compared to the traditional methods, this approach provides a more economical, reproducible, and effective procedure, facilitating the generation of large amounts of high-quality quantifiable data.     

Perfect Matchings of Regular Bipartite Graphs

Let G be a regular bipartite graph and . We show that there exist perfect matchings of G containing both, an odd and an even number of edges from X if and only if the signed graph , that is a graph G with exactly the edges from X being negative, is not equivalent to . In fact, we prove that for a given signed regular bipartite graph with minimum signature, it is possible to find perfect matchings that contain exactly no negative edges or an arbitrary one preselected negative edge. Moreover, if the underlying graph is cubic, there exists a perfect matching with exactly two preselected negative edges. As an application of our results we show that each signed regular bipartite graph that contains an unbalanced circuit has a 2‐cycle‐cover such that each cycle contains an odd number of negative edges.     

Supercritical CO2 extract and essential oil of aerial part of Ledum palustre L. – Chemical composition and anti-inflammatory activity

The anti-inflammatory activity of two extracts from the aerial parts of Ledum palustre has been reported. The volatile oil was obtained by supercritical fluid extraction (SFE) and the essential oil by hydrodistillation (HD). The oils were analysed by gas chromatography–mass spectrometry to monitor their composition. Both extracts shared as main compound (41.0–43.4%) ledol (23.3–26.7%) and ascaridole (15.1–4.5%). The anti-inflammatory activity was evaluated by the subcutaneous carrageenan injection-induced hind paw oedema. The treated animals received essential oil (SFE and HD), the reference group received ketoprofen or piroxicam and the control group received NaCl 0.9%. A statistical analysis was performed by the Student t-test. The results show that L. palustre essential oil enhanced a significant inhibition of oedema (50–73%) for HD oil and (52–80%) for SFE oil. These results were similar to those obtained with piroxicam (70%) and ketoprofen (55%).     

Plant Secondary Metabolites Produced in Response to Abiotic Stresses Has Potential Application in Pharmaceutical Product Development

Plant secondary metabolites (PSMs) are vital for human health and constitute the skeletal framework of many pharmaceutical drugs. Indeed, more than 25% of the existing drugs belong to PSMs. One of the continuing challenges for drug discovery and pharmaceutical industries is gaining access to natural products, including medicinal plants. This bottleneck is heightened for endangered species prohibited for large sample collection, even if they show biological hits. While cultivating the pharmaceutically interesting plant species may be a solution, it is not always possible to grow the organism outside its natural habitat. Plants affected by abiotic stress present a potential alternative source for drug discovery. In order to overcome abiotic environmental stressors, plants may mount a defense response by producing a diversity of PSMs to avoid cells and tissue damage. Plants either synthesize new chemicals or increase the concentration (in most instances) of existing chemicals, including the prominent bioactive lead compounds morphine, camptothecin, catharanthine, epicatechin-3-gallate (EGCG), quercetin, resveratrol, and kaempferol. Most PSMs produced under various abiotic stress conditions are plant defense chemicals and are functionally anti-inflammatory and antioxidative. The major PSM groups are terpenoids, followed by alkaloids and phenolic compounds. We have searched the literature on plants affected by abiotic stress (primarily studied in the simulated growth conditions) and their PSMs (including pharmacological activities) from PubMed, Scopus, MEDLINE Ovid, Google Scholar, Databases, and journal websites. We used search keywords: “stress-affected plants,” “plant secondary metabolites, “abiotic stress,” “climatic influence,” “pharmacological activities,” “bioactive compounds,” “drug discovery,” and “medicinal plants” and retrieved published literature between 1973 to 2021. This review provides an overview of variation in bioactive phytochemical production in plants under various abiotic stress and their potential in the biodiscovery of therapeutic drugs. We excluded studies on the effects of biotic stress on PSMs.     

Bioamperometric Systems with Fructose Dehydrogenase From Gluconobacter japonicus for D-Tagatose Monitoring

D-Tagatose is a rare natural sugar, which is promising alternative for popular dietary sweeteners. To optimize and make D-tagatose production more cost-effective, a portable (bio)sensor would be beneficial for D-tagatose quantification in bioreactor media during D-tagatose (bio)synthesis. In this study, a pilot study of D-tagatose quantification by a bioamperometric system is reported. A key feature of the system is usage of fructose dehydrogenase from Gluconobacter japonicus, widely known as a highly fructose-specific enzyme, and 2-arylamino-1,4-benzoquinone derivatives, as electron transfer mediators from the enzyme to carbon electrodes. The system has been validated as biosensor for D-tagatose quantification in the fermentation medium.