High-resolution Electrospray Ionization Mass Research Articles

Characterization of the fragmentation mechanisms in electrospray ionization tandem mass spectrometry of chloroquinoline derivatives with larvicidal activity against Aedes aegypti.

4,7-Dichloroquinoline (DCQ) represents a group of synthetic molecules inspired by natural products with important roles in biological and biomedical areas. This work aimed to characterize DCQ and its derivatives by high-resolution electrospray ionization (ESI) mass spectrometry and tandem mass spectrometry (ESI-MS/MS), supported by theoretical calculations. Biological assays were carried out with DCQ and its derivatives to determine LC50 values against Aedes aegypti larvae. Five DCQ derivatives were synthesized by using previously described protocols. ESI-MS/MS analyses were carried out with a quadrupole/time-of-flight and ion-trap instrument. The proposed gas-phase protonation sites and fragmentation were supported by density functional theory calculations. The larvicidal tests were performed with the Ae. aegypti Rockefeller strain, and the LC50 values were determined by employing five test concentrations. Larval mortality was determined after treatment for 48 h. DCQ bromides or aldehydes (C-3 or C-8 positions), as well as the trimethylsilyl derivative (C-3 position), were prepared. Detailed ESI-MS/MS data revealed heteroatom elimination through an exception to the even-electron rule, to originate open-shell species. Computational studies were used to define the protonation sites and fragmentation pathways. High activity of DCQ and its derivatives against Ae. aegypti larvae was demonstrated. Our results provided a well-founded characterization of the fragmentation reactions of DCQ and its derivatives, which can be useful for complementary studies of the development of a larvicidal product against Ae. aegypti.

Stochastic dynamics mass spectrometric structural analysis of poly(methyl methacrylate)

Polymers such as poly(methyl methacrylate), comprising of all-carbon backbones are regarded as ubiquitous functional materials mainly due to their low cost, unique physical properties, and impressive robustness. The latter properties are results from relative chemical inertness of the polymer backbone carbon–carbon bonds. The highlighted stability crucially challenges not only innovations to plastic recycling polymer materials, but also developments of reliable analytical protocols for determining both quantitatively and structurally polymers. Despite, the fact that there are numerous applications of mass spectrometric methods to polymer science, the analysis involves chiefly annotation of monomers of polymers and additives, owing to the fact that the additives are low molecular weight analytes. The exact structural determining of end-chain groups, particularly highlighting chemically substituted end carbon–carbon bond represents significant challenge even utilizing the superior features of the analytical mass spectrometric instrumentation. This study, in the latter context, illustrates innovative stochastic dynamics approach and model equations capable of not only determining unambiguously substituted carbon–carbon end chain of the entitled polymer but also to predict mass spectra of its derivatives: thus, extending crucially the applicability of the method to many fields of the fundamental scientific and industrial research. The latter claim is argued still at the beginning of the study with the achieved method performances showing |r|=0.99998. The study utilizes experimental and theoretical mass spectrometric data on high resolution electrospray ionization mass spectrometry; high accuracy quantum chemical static methods, molecular dynamics; and chemometrics.

Synthesis and structural determination of some 1,5-disubstituted-4-ethoxycarbonyl-3-hydroxy-3-pyrroline-2-one derivatives containing nitro group

2-Pyrrolidinone is a γ-lactam heterocycle consisting of four carbon atoms and one nitrogen atom. In the family of 2-pyrrolidinone heterocycles, 3-pyrroline-2-ones, also named as 1,5-dihydro-2H-pyrrol-2-ones are important substructures of various natural products with promising biological activities. In addition, this γ-lactam heterocyclic ring also exists in synthetic medicinal compounds. In this manuscript, multi-component reactions (MCRs) were applied to synthesize three 1,5-disubstituted-4-ethoxycarbonyl-3-hydroxy-3-pyrroline-2-ones containing nitro group from aromatic aldehydes, 4-nitroaniline and sodium diethyl oxalacetate in absolute ethanol. Furthermore, the molecular structure of products has been proven via modern spectroscopic methods: nuclear magnetic resonance spectroscopy (1H NMR, 13C NMR) and electrospray ionization-high resolution mass spectrometry (ESI – HRMS).

Distribution, chemical, and molecular composition of high and low molecular weight humic-like substances in ambient aerosols

Abstract. Humic-like substances (HULIS) encompass a continuum of molecular weight (MW) ranges, yet our understanding of how HULIS characteristics vary with MW is still limited and not well established. In this study, a combination of ultrafiltration and solid-phase extraction protocols was employed to fractionate the high MW (HMW; > 1 kDa) and low MW (LMW; < 1 kDa) HULIS fractions from ambient aerosols collected during summer and winter at a rural site. Subsequently, comprehensive characterization using total organic carbon, high-performance size exclusion chromatography (HPSEC), UV-visible (UV-vis) and fluorescence spectroscopy, Fourier transform infrared spectroscopy (FTIR), and negative electrospray ionization high-resolution mass spectrometry (ESI–HRMS) were conducted. The results revealed that HMW HULIS were dominated by larger-sized chromophores, substantially constituting a higher fraction of total organic carbon and UV absorption at 254 nm than LMW HULIS. While both HMW and LMW HULIS shared similar fluorophore types and functional groups, the former exhibited higher levels of humification and a greater presence of polar functional groups (e.g., −COOH; > C=O). HRMS analysis further unveiled that molecular formulas within HMW HULIS generally featured smaller sizes but higher degrees of unsaturation and aromaticity compared to those within LMW HULIS fractions. This observation suggests the possibility of small molecules assembling to form the HMW HULIS through intermolecular weak forces. Moreover, HMW HULIS contained a higher proportion of CHON but fewer CHO compounds than LMW HULIS. In both HMW and LMW HULIS, the unique molecular formulas were primarily characterized by lignin-like species, yet the former displayed a prevalence of N-enriched and highly aromatic species. Additionally, HMW HULIS contained more unique lipid-like compounds, while LMW HULIS exhibited a distinct presence of tannin-like compounds. These findings provide valuable insights into the distribution, optical properties, and molecular-level characteristics of HULIS in atmospheric aerosols, thereby advancing our understanding of their sources, composition, and environmental implications.

Investigation of the Behavior of Hydrocarbons during Crude Oil Fouling by High-Resolution Electrospray Ionization Mass Spectrometry

Crude oil is probably the most complex natural chemical mixture processed in various ways to make fuel and fine chemicals among a wide range of products in industrial processing. The conditions of those industrial processes often include high temperatures, which often cause undesired chemical reactions. One of those reaction sequences is crude oil fouling, which finally results in the formation of undesired solid deposits of carbon material, a calamity that costs millions of dollars worldwide each year and produces toxic waste. However, the compounds involved in fouling, let alone the underlying reaction mechanisms, are not understood to date. Here, in order to investigate chemical fouling, the process was simulated under laboratory conditions, focusing on hydrocarbons as the main constituents of crude oil. The results demonstrate large differences within the hydrocarbon class of compounds before and after thermal treatment, even for a very light crude oil fraction, which initially does not contain any bigger or heavier compounds. Here, the fouling reaction is simulated and studied on the molecular level using high-resolution mass spectrometry. After thermal treatment, new, higher molecular weight hydrocarbon compounds with high aromaticity were detected. Results indicate that a radical reaction leads to the formation of larger and more aromatic compounds. The findings were verified by the use of a model hydrocarbon compound to study the mechanism.

Functional Group Analysis of α-Pinene Oxidation Products Using Derivatization Reactions and High-Resolution Electrospray Ionization Collision-Induced Dissociation Mass Spectrometry.

Oxidation products of monoterpenes (C10H16) play a significant role as precursors for secondary organic aerosol formation. They contain several structural isomers with multifunctional groups. However, only a few of these isomers have been identified experimentally. We describe a measurement technique for identifying oxygen-containing functional groups (carbonyl, carboxyl, and hydroxyl groups) included in monoterpene oxidation products. This technique involves (i) three derivatization reactions (oximation of carbonyls by O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine, methyl esterification of carboxylic acids by trimethylsilyl diazomethane, and acylation of alcohols by acetic anhydride), (ii) no preseparation high-resolution electrospray ionization mass spectrometry, and (iii) collision-induced dissociation. This technique was applied to functional group analysis of ozonolysis products for α-pinene. Multifunctional groups of known ozonolysis products were accurately identified. Furthermore, we successfully estimated the multifunctional groups of products that have not been previously reported.

Cycloartane-type triterpenoids from the leaves of Sandoricum koetjape and their efficacy on α-glucosidase inhibition activity.

The preliminary α-glucosidase inhibitory activity of the methanol extract of the leaves of Sandoricum koetjape Merr. exhibited promising results. The leaves was extracted with methanol to obtain the methanol extract that was continuedly partitioned with hexane and ethyl acetate. Those fractions were further purified by various chromatographic techniques. The isolation of the potent fractions furnished two new cycloartane-type triterpenoids (1 and 2) along with ten known compounds (3-12). Their chemical structures were unambiguously established by interpretation of NMR (1 D & 2 D) and high-resolution electrospray ionization mass spectrometry (HRESIMS) data. Furthermore, the configurations of two new compounds were determined by using NOESY spectrum as well as comparing their NMR data to the reference. These compounds were evaluated against α-glucosidase. All tested compounds revealed potent activity with IC50 value in the range of 2.17-49.2µM compared to that of acarbose (IC50 100.6µM). Compound 10 showed the lowest IC50 value. This compound was reported as a mixed-type inhibitor. Compound 3 possessed the second strong activity with an IC50 value of 14.0μM and was further investigated on kinetic analysis which revealed as a mixed-type inhibitor with Ki and Ki' values of 59.1 and 155.2μM, respectively.

Ent-labdane-type diterpene glycosides obtained from Rubus chingii Hu and their inhibitory effects on PDE5A activity

In this study, 16 new ent-labdane-type diterpene glycosides, designated as goshonosides J1–J16 (1–16), along with nine previously known diterpene glycosides (17–25) were extracted from the fruits of Rubus chingii Hu. The structures of goshonosides J1–J16 were elucidated using various analytical techniques, such as nuclear magnetic resonance, electron capture detector ECD, high-resolution electrospray ionization mass spectrometry HREIMS, single-crystal X-ray diffraction, and hydrolysis. Furthermore, the isolates' efficacy in inhibiting the activity of phosphodiesterase type 5 A was evaluated. Goshonosides J1, J2, and G effectively inhibited the activity of the aforementioned enzyme (IC50 values: 6.15 ± 1.76, 3.27 ± 0.65, and 9.61 ± 2.36 μM, respectively). Our findings highlight the remarkable structural diversity of bioactive compounds in R. chingii Hu and offer insights into the use of this shrub.

Gas-phase F-atom migration reaction of deprotonated N-fluoroarenesulfonamides.

Recently N-Fluoroarenesulfonamides (ArSO2 NHF) were found to be promising precursors for the preparation of N-fluorobenzenesulfonimide derivatives without applying F2 . However, very few studies have discussed the mass spectrometric behaviors of ArSO2 NHF with N-F structure. In this article, we applied high-resolution electrospray ionization tandem mass spectrometry (HR-ESI-MS/MS) to study the effect on the mass spectrometric behaviors of ArSO2 NHF after the introduction of the F-atom to the N-atom of ArSO2 NH2 . High-resolution electrospray ionization mass spectrometry (HR-ESI-MS) experiments showed that ArSO2 NHF produced only good signals in negative ion mode, and the dominating product ion SO2 F- at m/z 83 was observed in all HR-ESI-MS/MS of ArSO2 NF- with different substituents in the Ar group. The formation of the product ion SO2 F- was proof of the gas-phase F-atom migration rearrangement from the N-atom to the S-atom in ESI-MS/MS of ArSO2 NF- . To fully explain the gas-phase reaction mechanism from ArSO2 NF- to SO2 F- , we studied the HR-ESI-MS/MS of deprotonated ArSO2 NHF and also performed theoretical calculations. Both results confirmed that ArSO2 NF- first underwent Smiles rearrangement to yield intermediate I (INT1) ArNFSO2 - , and then the F-atom of ArNFSO2 - migrated from the N-atom to the S-atom to form intermediate II (INT2) ArN- SO2 F, which finally dissociated to SO2 F- at m/z 83 with loss of a neutral nitrene (ArN). All these results showed that the formation of the product ion SO2 F- from ArSO2 NF- was a common and intrinsic gas-phase reactivity of ArSO2 NF- .

Chaenomelin, a New Phenolic Glycoside, and Anti-Helicobacter pylori Phenolic Compounds from the Leaves of Salix chaenomeloides.

Salix chaenomeloides Kimura, commonly known as pussy willow, is a deciduous shrub and tree belonging to the Salicaceae family. The genus Salix spp. has been known as a healing herb for the treatment of fever, inflammation, and pain relief. The current study aimed to investigate the potential bioactive natural products from S. chaenomeloides leaves and evaluate their antibacterial activity against Helicobacter pylori. A phytochemical investigation of the ethanol (EtOH) extract of S. chaenomeloides leaves led to the isolation of 13 phenolic compounds (1-13) from the ethyl acetate (EtOAc) fraction, which showed antibacterial activity against H. pylori strain 51. The chemical structure of a new phenolic glycoside, chaenomelin (1), was established by a detailed analysis of 1D and 2D (1H-1H correlation spectroscopy (COSY), heteronuclear single-quantum coherence (HSQC), and heteronuclear multiple-bond correlation (HMBC)) nuclear magnetic resonance (NMR), high-resolution electrospray ionization mass spectroscopy (HR-ESIMS), and chemical reactions. The other known compounds were identified as 5-O-trans-p-coumaroyl quinic acid methyl ester (2), tremulacin (3), citrusin C (4), benzyl 3-O-β-d-glucopyranosyl-7-hydroxybenzoate (5), tremuloidin (6), 1-[O-β-d-glucopyranosyl(1→2)-β-d-glucopyranosyl]oxy-2-phenol (7), arbutin cinnamate (8), tremulacinol (9), catechol (10), 4-hydroxybenzaldehyde (11), kaempferol 3-rutinoside (12), and narcissin (13), based on the comparison of their NMR spectra with the reported data and liquid chromatography/mass spectrometry (LC/MS) analysis. The isolated compounds were evaluated for antibacterial activity against H. pylori strain 51. Among the isolates, 1-[O-β-d-glucopyranosyl(1→2)-β-d-glucopyranosyl]oxy-2-phenol (7) and arbutin cinnamate (8) exhibited antibacterial activity against H. pylori strain 51, with inhibitions of 31.4% and 33.9%, respectively, at a final concentration of 100 μM. These results were comparable to that of quercetin (38.4% inhibition), which served as a positive control. Generally, these findings highlight the potential of the active compounds 7 and 8 as antibacterial agents against H. pylori.

Chemometric Analysis Combined with GC × GC-FID and ESI HR-MS to Evaluate Ultralow-Sulfur Diesel Stability.

Diesel has been the most employed fuel in highway and nonhighway transportation systems. Many studies over the past years have attempted to classify diesel as a stable or unstable composition since this fuel can still degrade during storage or thermal oxidative processes. Products generated because of such degradation are the reason for the formation of soluble gums and insoluble organic particulates, which in turn cause a negative influence on engine performance. This work reports a detailed composition of nonpolar and polar compounds in many ultralow-sulfur diesel (ULSD) samples by comprehensive two-dimensional gas chromatography with a flame ionization detector (GC × GC-FID) and electrospray ionization high-resolution mass spectrometry (ESI HR-MS). In addition, chemometric approaches were applied for ULSD storage stability investigation. GC × GC-FID experiments achieved the nonpolar chemical characterization for the ULSD samples, including all main hydrocarbon classes: paraffins, mono- and dinaphthenics and olefins, and aromatics. The GC × GC-FID data combined with principal component analysis (PCA) described that the separation of the samples' concerning storage stability was mainly due to the contents of mono- and diaromatic compounds in the unstable ULSD samples. Moreover, PCA was also applied to the ESI (±) data set, and the results highlight the presence of compounds belonging to O class (natural antioxidants), which decrease the rate of oxygen consumption in the fuel, characterizing it as stable composition. The basic nitrogen compounds are mostly present in the stable ULSD samples indicating that they did not affect the stability of the fuel. On the other hand, the HC classes presented pronounced abundance among unstable ULSD samples suggesting that the fuel degradation may go through the oxidation of hydrocarbons and the formation of Ox compounds as byproducts. Furthermore, MS/MS experiments point to the formation of CcHhNnOo-like precursor species, which can react with each other and lead to the formation of gums and insoluble sediments in the fuel. In summary, the results express the potential of using the GC × GC-FID and ESI (±) Orbitrap MS techniques as valuable tools for diesel stability evaluations.

Aculeatiols A-G: Lovastatin Derivatives Extracted from Aspergillus aculeatus.

In this study, we isolated lovastatin derivatives, including aculeatiols A-G (1-7) and three known compounds (8-10), from Aspergillus aculeatus. Their structures and absolute configurations were experimentally determined by high-resolution electrospray ionization mass spectrometry, nuclear magnetic resonance spectroscopy, and X-ray diffraction analyses, and the results were corroborated by quantum-chemical calculations. As members of the lovastatin derivatives, aculeatiols A-C (1-3) possess a γ-lactone functional group in the side chain. Compound 6 represents the first example that features an undescribed aromatized heterotetracyclic 6/6/6/6 ring system. Biologically, the lipid-lowering effects of all of these compounds were evaluated by analyzing the free fatty acid-induced intracellular lipid accumulation. In addition, compound 5, which regulated the transcription of genes associated with lipid uptake and synthesis, inhibited the accumulation of lipids.

Secondary metabolites and their bioactivities from Paecilomyces gunnii YMF1.00003.

Four new polyketides (1-4) and seven known compounds (5-11) including three polyketides and four sterols were isolated from the fermented extracts of Paecilomyces gunnii YMF1.00003. The new chemical structures were determined through the analysis of the nuclear magnetic resonance and high-resolution electrospray ionization mass spectrometry, and their configurations were subsequently confirmed by nuclear overhauser effect spectroscopy, the calculated electronic circular dichroism (ECD) spectra, and quantum chemical calculations of the NMR data (qcc NMR). Based on the results of pre-activity screening and compound structure target prediction, certain metabolites were assayed to evaluate their cytotoxic and protein kinase Cα inhibitory activities. Results indicated that 3β-hydroxy-7α-methoxy-5α,6α-epoxy-8(14),22E-dien-ergosta (8) exhibited potent cytotoxic activity, with half-maximal inhibitory concentration values of 3.00 ± 0.27 to 15.69 ± 0.61 μM against five tumor cells, respectively. The new compound gunniiol A (1) showed weak cytotoxic activity at a concentration of 40 μM. At a concentration of 20 μg/mL, compounds 1, 6, and 7 exhibited protein kinase Cα inhibition by 43.63, 40.93, and 57.66%, respectively. This study is the first to report steroids demonstrating good cytotoxicity and polyketides exhibiting inhibitory activity against protein kinase Cα from the extracts of P. gunnii.

Chalcogen- and Halogen-Bond-Donating Cyanoborohydrides Provide Imine Hydrogenation.

Sulfonium, selenonium, telluronium, and iodonium cyanoborohydrides have been synthesized, isolated, and fully characterized by various methods, including single-crystal X-ray diffraction (XRD) analysis. The quantum theory of atoms in molecules' analysis based on the XRD data indicated that the hydride···σ-hole short contacts observed in the crystal structures of each compound have a purely noncovalent nature. The telluronium and iodonium cyanoborohydrides provide a significantly higher rate of the model reaction of imine hydrogenation compared with sodium and tetrabutylammonium cyanoborohydrides. Based on the NMR and high-resolution electrospray ionization mass spectrometry data indicating that the reaction progress is accompanied by the cation reduction, a mechanism involving intermediate formation of elusive onium hydrides has been proposed as an alternative to conventional electrophilic activation of the imine moiety by its ligation to the cation's σ-hole.

Identification and nitric oxide production inhibitory activity of phenolic derivatives from the trunks of Gnetum latifolium

Phytochemical investigation of the trunks from Gnetum latifolium led to the isolation of a novel phenolic glucoside, 2E-2,4-di-(3,4-dihydroxyphenyl)but-2-en-1-yl-O-β-D-glucopyranoside (1), along with five known stilbene derivatives (2–6). Their structures were determined mainly using high-resolution electrospray ionisation mass spectrometry and nuclear magnetic resonance spectroscopic analyses, followed by comparisons of observed spectral data with reported values. The novel compound 1 in G. latifolium was found to be useful as a chemotaxonomic marker. Biological evaluation revealed that compound 6 had remarkable inhibitory effects on nitric oxide production, with a half-maximal inhibitory concentration (IC50) value of 4.85 ± 0.20 µM, which was much higher than that of the positive control dexamethasone (IC50 = 14.20 ± 0.54 µM).

Unveiling the Anticancer Mechanism of Echinops davuricus: Isolation and Evaluation of AKR1B10 Inhibitors.

Five compounds (1-5), one long-chain fatty acid (1), two thiophenes (2 and 3), one alkaloid (4), and one phenyl ester (5), were isolated from the aerial part of Echinops davuricus. The structures of the products were established by performing detailed nuclear magnetic resonance (NMR) analysis, and the structure of compound 1 was determined via high-resolution electrospray ionization mass spectrometry (HRESIMS) and NMR. Compounds 1, 4, and 5 were isolated from Echinops davuricus for the first time. Based on network pharmacology methods, AKR1B10 was selected as a key anticancer target. Compounds 1 and 5 exhibited significant AKR1B10 inhibitory activities, with IC50 values of 156.0±1.00 and 146.2±1.50 nM, respectively, with epalrestat used as the positive control (81.09±0.61 nM). Additionally, the interactions between the active compounds and AKR1B10 were evaluated via molecular docking. Ultimately, the GO and KEGG enrichment analysis indicated that the key signaling pathways associated with the active compounds may be related to the PI3K-Akt, MAPK, apoptotic, cellular senescence, and TNF signaling pathways and the human diseases corresponding to the targets are cancer. Our study reveals for the first time the anticancer properties of Echinops davuricus and provides a comprehensive understanding of its application in traditional medicine.

Apium extract alleviates indomethacin-induced gastric ulcers in rats via modulating the VEGF and IK-κB/NF-κB p65 signaling pathway: insights from in silico and in vivo investigations

BackgroundGastric ulcers represent a worldwide health problem, characterized by erosions that affect the mucous membrane of the stomach and may even reach the muscular layer, leading to serious complications. Numerous natural products have been assessed as anti-ulcerogenic agents, and have been considered as new approaches for treatment or prevention of gastric ulcers. The present research investigated the preventive benefits of Apium graveolens L. (Apiaceae), known as celery, seed extract towards indomethacin-induced ulceration of the stomach in rats.MethodsMetabolomic profiling, employing liquid chromatography coupled to high-resolution electrospray ionization mass spectrometry (LC-HR-ESI–MS), was implemented with the aim of investigating the chemical profile of the seeds. Histopathological analysis of gastric tissues, as well as assessment of numerous inflammatory cytokines and oxidative stress indicators, confirmed the in vivo evaluation.ResultsThe prior treatment with A. graveolens seed extract resulted in a substantial reduction in the ulcer index when compared to the indomethacin group, indicating an improvement in stomach mucosal injury. Moreover, the gastroprotective effect was demonstrated through examination of the oxidative stress biomarkers which was significantly attenuated upon pre-treatment with A. graveolens seed extract. Vascular endothelial growth factor (VEGF), a fundamental angiogenic factor that stimulates angiogenesis, was markedly inhibited by indomethacin. A. graveolens seed extract restored this diminished level of VEGF. The dramatic reductions in NF-κB protein levels indicate a considerable attenuation of the indomethacin-induced IKκB/NF-κB p65 signaling cascade. These activities were also correlated to the tentatively featured secondary metabolites including, phenolic acids, coumarins and flavonoids, previously evidenced to exert potent anti-inflammatory and antioxidant activities. According to our network pharmacology study, the identified metabolites annotated 379 unique genes, among which only 17 genes were related to gastric ulcer. The PTGS2, MMP2 and PTGS1 were the top annotated genes related to gastric ulcer. The top biological pathway was the VEGF signaling pathway.ConclusionA. graveolens seed extract possesses significant anti-ulcer activity, similar to famotidine, against gastric lesions induced by indomethacin in rats. It is worth highlighting that the extract overcomes the negative effects of conventional chemical anti-secretory drugs because it does not lower stomach acidity.

Synthesis and Spectroscopic Characterization of Schiff Base Metal Complexes, Biological Activity, and Molecular Docking Studies.

New cobalt(II), copper(II), and zinc(II) Schiff metal complexes were synthesized by the condensation reaction of 4-nitrobenzene-1,2-diamine with 3-4-(diethylamino)-2-hydroxybenzaldehyde. Fourier transform infrared, nuclear magnetic resonance, ultraviolet-visible, electron paramagnetic resonance, and high-resolution electrospray ionization mass spectrometry and powder X-ray diffraction were used to characterize the synthesized H2L and its metal complexes. Conductance measurements, magnetic moment estimation, and metal estimation have all been determined and discussed. The electrochemical properties of the synthesized compounds have been determined and discussed using cyclic voltammetry. The molecular structures of H2L and its metal complexes have been optimized using the B3LYP functional and the 6-31G (d,p) basis set, and their parameters have been discussed. The quantum chemical properties of these synthesized compounds have been predicted through charge distribution and molecular orbital analysis. The biological properties of the synthesized compounds' antioxidant, antifungal, and antibacterial activity have been studied and discussed. Furthermore, H2L and its complexes have been docked with HER2-associated target proteins in breast cancer.

Cytotoxic metabolites from Sinularia levi supported by network pharmacology.

The in-vitro anti-proliferative evaluation of Sinularia levi total extract against three cell lines revealed its potent effect against Caco-2 cell line with IC50 3.3 μg/mL, followed by MCF-7 and HepG-2 with IC50 6.4 μg/mL and 8.5 μg/mL, respectively, in comparison to doxorubicin. Metabolic profiling of S. levi total extract using liquid chromatography coupled with high-resolution electrospray ionization mass spectrometry (LC-HR-ESI-MS) revealed the presence of phytoconstituents clusters consisting mainly of steroids and terpenoids (1-20), together with five metabolites 21-25, which were additionally isolated and identified through the phytochemical investigation of S. levi total extract through various chromatographic and spectroscopic techniques. The isolated metabolites included one sesquiterpene, two steroids and two diterpenes, among which compounds prostantherol (21) and 12-hydroperoxylsarcoph-10-ene (25) were reported for the first time in Sinularia genus. The cytotoxic potential evaluation of the isolated compounds revealed variable cytotoxic effects against the three tested cell lines. Compound 25 was the most potent with IC50 value of 2.13 ± 0.09, 3.54 ± 0.07 and 5.67 ± 0.08 μg/mL against HepG-2, MCF-7 and Caco-2, respectively, followed by gorgosterol (23) and sarcophine (24). Additionally, network analysis showed that cyclin-dependent kinase 1 (CDK1) was encountered in the mechanism of action of the three cancer types. Molecular docking analysis revealed that CDK1 inhibition could possibly be the reason for the cytotoxic potential.

African Under-Utilized Medicinal Leafy Vegetables Studied by Microtiter Plate Assays and High-Performance Thin-Layer Chromatography-Planar Assays.

Biological activities of six under-utilized medicinal leafy vegetable plants indigenous to Africa, i.e., Basella alba, Crassocephalum rubens, Gnetum africanum, Launaea taraxacifolia, Solanecio biafrae, and Solanum macrocarpon, were investigated via two independent techniques. The total phenolic content (TPC) was determined, and six microtiter plate assays were applied after extraction and fractionation. Three were antioxidant in vitro assays, i.e., ferric reducing antioxidant power (FRAP), cupric reduction antioxidant capacity (CUPRAC), and 2,2-diphenyl-1-picrylhydrazyl (DPPH) scavenging, and the others were enzyme (acetylcholinesterase, butyrylcholinesterase, and tyrosinase) inhibition assays. The highest TPC and antioxidant activity from all the methods were obtained from polar and medium polar fractions of C. rubens, S. biafrae, and S. macrocarpon. The highest acetyl- and butyrylcholinesterase inhibition was exhibited by polar fractions of S. biafrae, C. rubens, and L. taraxacifolia, the latter comparable to galantamine. The highest tyrosinase inhibition was observed in the n-butanol fraction of C. rubens and ethyl acetate fraction of S. biafrae. In vitro assay results of the different extracts and fractions were mostly in agreement with the bioactivity profiling via high-performance thin-layer chromatography-multi-imaging-effect-directed analysis, exploiting nine different planar assays. Several separated compounds of the plant extracts showed antioxidant, α-glucosidase, α-amylase, acetyl- and butyrylcholinesterase-inhibiting, Gram-positive/-negative antimicrobial, cytotoxic, and genotoxic activities. A prominent apolar bioactive compound zone was tentatively assigned to fatty acids, in particular linolenic acid, via electrospray ionization high-resolution mass spectrometry. The detected antioxidant, antimicrobial, antidiabetic, anticholinesterase, cytotoxic, and genotoxic potentials of these vegetable plants, in particular C. rubens, S. biafrae, and S. macrocarpon, may validate some of their ethnomedicinal uses.