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The major goal of the paper is to provide empirical proof of view that innovative stochastic dynamic mass spectrometric equation D″

The study provides new function tested on labetalol in large infusion volumes (Vinf = 80-115 µL) via electrospray ionization mass spectrometry, tandem MS2–MS7 operation modes and collision energy: 0, 0.1, 10, 20, 25, 26, 30 and 35 eV, respectively. It is derived from the stochastic dynamic mass spectrometric equation D”SD = 2.6388.10-17.(2>-2), which exactly quantifies analyte concentration in solution. Also, it determines 3D conformations and electronic structures. The description of mass spectrometric intensity data as random variables and the shown relation, there are written two new linear functions among D”SD parameters, average total intensity values of fragmentation peaks, infusion volume, and collision energy. They introduce covariance of datasets of variables per short span of scan time of ions in any experimental conditions “l” and “m”. They are: D”SD;m,l = D”SD,l + D”SD,m + 5.2776.10-17.{l.Im>–l>.m>}≈l>+m> and l>+m>≈|rl,m|.sd(yEr±)1.sd(yEr±)m. Those relations yields to new formula D”SD,l+ D”SD,m = |rl,m|.sd(yEr±)l.sd(yEr±)m, providing exact function of mass spectrometric variable intensity of any peaks of analyte ion in any two sets of experimental conditions of measurements and diffusion parameters according to the first formula. Correlation between theory and experiment of fragmentation processes of labetalol shows |r|=1–0.99999. Chemometrics is used.

Complete theoretical and experimental data on the entitled contribution.

During production of diethylenetriaminepentaacetic acid (DTPA), process waste water is generated in several production stages. Process wastewater is usually disposed of via waste water treatment pl...

The content support new function tested on labetalol in large infusion volumes (Vinf = 80–115 mL) via electrospray ionization mass spectrometry, tandem MS2–MS7 operation modes and collision energy values of: 0, 0.1, 10, 20, 25, 26, 30 and 35 eV. The new function is derived from stochastic dynamic mass spectrometric equation D”SD = 2.6388.10-17.(2>-2).

Three new bufadienolides, namely, paulliniogenin A (1), paulliniogenin B (2), and 16β-formyloxybersamagenin 1,3,5-orthoacetate (3), together with two known bufadienolides and six known phenolic substances, were isolated from the stem bark of Bersama abyssinica subsp. abyssinica and B. abyssinica subsp. paullinioides. The structures of the compounds were elucidated based on their NMR and HRMS data analyses. The relative configurations were defined by single-crystal X-ray crystallography and NOESY correlations. Cytotoxicity against the L929 and KB3.1 cancer cell lines of the isolated compounds was investigated using an MTT assay. Paulliniogenin A (1) and 16β-hydroxybersamagenin-1,3,5-orthoacetate (4) showed cytotoxicity against the KB3.1 cell line with IC50 values of 1.4 ± 0.77 and 1.6 ± 0.81 μM, respectively. Moreover, paulliniogenin A (1) and paulliniogenin B (2) demonstrated weak activity against Staphylococcus aureus.

Chemical investigation of the root of Zanthoxylum paracanthum afforded 1 new alkamide derivative, (2E,4E)-6-oxo-N-isobutyldeca-2,4-dienamide (1) together with 10 known congeners including one pheno...

Endocrine-disrupting chemicals (EDCs) interfere with the mammalian hormone system and alter its endo- and paracrine regulation. The goal of the present study was to examine the presence of 14 EDCs, including the technical mixture of nonylphenols and Mirex, in human follicular fluid (FF) and to find a potential correlation between endocrine active substances and a possible impact on female fertility. Furthermore, potential sources of EDC exposition regarding patients’ lifestyle and socioeconomic factors were investigated. Human FF was collected from a total of 210 women undergoing intracytoplasmic sperm injection-treatment cycles because of male subfertility. The presence of EDCs was analyzed using gas chromatography coupled with mass spectrometry. Thirteen of the 14 investigated EDCs were present in every FF sample; compounds with the highest concentrations in FF were nonylphenol and Mirex. Nearly all kinds of EDCs led to significantly reduced maturation and fertilization rate. No significant influence of EDC concentration on the clinical pregnancy rate was observed for neither of the analyzed EDCs. Patients who obtained their clothes and textiles at fashion discounters displayed a higher amount of EDCs in their FF. In contrast, patients’ residential area, source of food products, and nicotine or caffeine consumed were not associated with EDC accumulation. Clinicaltrials.gov NCT01385605 (11 July 2011)

Melianthus major is a medicinal plant endemic to South Africa. Its leaf extract led to the isolation of five new bufadienolides, 2β-acetoxy-3,5-di-O-acetylhellebrigenin (1), 2β-acetoxy-3-O-acetylhellebrigenin (2), 2β-acetoxy-14-deoxy-15β,16β-epoxymelianthugenin (4), 2β-acetoxy-14-deoxy-15β,16β-epoxymelianthusigenin (5), and 2β-hydroxymelianthusigenin (6), and four known analogues. The structures of the compounds were elucidated using NMR and HRESIMS data analyses. The relative configurations were defined by single-crystal X-ray crystallography and NOESY correlations. The isolated compounds exhibited strong cytotoxicity against MCF-7 breast cancer cells and sensitive CCRF-CEM and multidrug-resistant CEM/ADR5000 leukemia cells. Compound 1 showed the most potent activity, with IC50 values of 0.1 μM toward CCRF-CEM and CEM/ADR5000 and 0.3 μM toward MCF-7.

Introduction Kaurane diterpenes, notably xylopic acid, have demonstrated important biological activities including analgesia, anti-oxidant, antimicrobial and cytotoxicity. The fruits of Xylopia aethiopica have been reported to be a rich source of kaurane diterpenes. Objective An analytical approach for detailed imaging and characterisation of selected kaurane diterpenes was developed using matrix-assisted laser desorption/ionisation high-resolution mass spectrometry (MALDI-HRMS) imaging techniques and high-performance liquid chromatography-high resolution electrospray ionisation-tandem mass spectrometry (HPLC-HRESI-MSn ) studies, respectively. Methods The images of the compounds were constructed based on selected ions from their HRESI-MS spectra. The matrix employed comprised a solution of α-cyano-4-hydroxycinnamic acid (HCCA) in acetonitrile-water with trifluoroacetic acid (TFA). HPLC-HRESI-MSn measurements were conducted on an LTQ-Orbitrap spectrometer equipped with a heated electrospray ionisation (HESI)-II source. Results The analytical strategy adopted showed the spatial distribution of the compounds in the fruits of X. aethiopica based on the dominant ions at m/z 301.2163 [M + H - HOCOCH3 ]+ and m/z 399.1932 [M + K]+ for xylopic acid, m/z 317.2111 [M + H]+ and m/z 355.1670 [M + K]+ for 15-oxo-ent-kaur-16-en-19-oic acid and m/z 303.2319 [M + H]+ for ent-kaur-16-en-19-oic acid. The fragmentation patterns of the compounds were proposed based on the HRESI-MSn measurements. Conclusions The study revealed the spatial variability, differential behaviours and specificity of the selected kaurane diterpenes in the fruit, seed and pericarp. The compounds under study were predominantly restricted to the pericarp of the fruit with trace amounts in the seed.

Investigations of the root extract of Dracaena usambarensis Engl. for anticancer principles led to the characterization of one new homoisoflavonoid, (3S)-3,4ʹ,5,6-tetrahydroxy-7-methoxyhomoisoflavanone (1) and a new retrodihydrochalcone, 4ʹ,4-dihydroxy-2,3-dimethoxydihydrochalcone (2) along with six previously reported compounds, including two homoisoflavonoids, 7-O-methyl-8-demethoxy-3-hydroxy-3,9-dihydropunctatin (3) and loureiriol (4); a phenolic amide, 3-(4ʹʹʹ-hydroxyphenyl)-N-[2ʹ-(4ʹʹ-hydroxyphenyl)-2ʹ-methoxyethyl]acrylamide (5); a spirostane, 25S-spirosta-1,4-dien-3-one (6) and two steroids, stigmasterol (7) and stigmasterol 3-O-β-D-glucopyranoside (8). The structures of 1-8 were determined using spectroscopic and spectrometric techniques. The absolute configurations of compounds 1 and 3 were achieved using circular dichroism spectroscopy. Using the resazurin reduction assay and doxorubicin as reference anticancer drug, 1 showed moderate cytotoxicity against drug sensitive CCRF-CEM but was inactive against all the other tested drug sensitive, resistance phenotypes and normal cells. The crude extract and 2-8 were inactive in the preliminary screening against CCRF-CEM and drug resistant CEM/ADR5000 cell lines. Interestingly, the activity of the standard drug, doxorubicin was comparable to those of inactive compounds against CEM/ADR5000 cells. Future studies should focus on structure modifications of 1-3, in order to obtain more potent analogues.

A new flavone, named hildeflavone (1) along with 7 other known flavonoids were isolated from the aerial parts of Tephrosia hildebrandtii Vatke. Their characterisation was based on NMR and MS data analysis. The anti-inflammatory properties of the crude extract, isolated compounds and combination of the compounds were investigated in lipopolysaccharide (LPS)-stimulated peripheral blood mononuclear cells (PBMCs). Treatment of the LPS-stimulated PBMCs with the isolated flavonoids at a concentration of 100 µM significantly reduced the production of interleukins (IL-1β, IL-2 and IL-6), interferon-gamma (IFN-γ), granulocyte macrophage-colony stimulating factor (GM-CSF) and tumour necrosis factor-alpha (TNF-α). It was also found that the combination of a flavone and flavanones exhibited remarkable synergistic anti-inflammatory effects on the production of the cytokines.

Phytochemical analysis of a methanol–dichloromethane (1:1) extract of the aerial parts of Tephrosialinearis led to the isolation of 18 compounds. Seven of these, namely, lineaflavones A–D (1–4), 6-...

The study reports quantification of metronidazole (MTZ) in clinical human urine employing our innovative stochastic dynamic equation D”SD =2.6388.10-17.(2>–2>). There are direct analysis without presence of internal standard, using ultra-high accuracy nano-electrospray ionization (ESI) mass spectrometry (MS), quantum chemistry and chemometrics, respectively. The linear calibration D”SD =f(conc.) equations are obtained for concentration range 2.5 to 25000 ng.(mL)-1 of spiked urine samples, examining analyte MS ions at m/z 171.0998, 172.0718, 172.04081, 213.1463, 181.0722 and 151.1114, respectively. There is achieved exact coefficient of linear correlation (|r|=1) between theory and experiment of ion at m/z 172.04081. The major challenge to quantify MTZ in urine sample is that it stabilizes cations [M+H]+ of two tautomers, which equilibrium varies drastically within the standard linear calibration dynamic range. The fragmentation patterns depend on analyte tautomers and it unambiguous assignment in multicomponent samples with complex sample matrix effect (SME) is unable to be made without mediation to an independent physico-chemical law. To solve the problem, herein, is used, again, above equation, which is designed a bridge between quantitative and multidimensional structural analytical chemistry, when is used complementary with Arrhenius’s quantum chemical diffusion parameter (DQC.) There is achieved |r|=0.98 of D”SD=f(DQC’) examining tautomeric molecular and fragment ions of MTZ.

Even though maytansine was first discovered from Celastraceae plants, it was later proven to be an endophytic bacterial metabolite. However, a pure bacterial culture cannot synthesize maytansine. Therefore, an exclusive interaction between plant and endophytes is required for maytansine production. Unfortunately, our understanding of plant-endophyte interaction is minimal, and critical questions remain. For example: how do endophytes synthesize maytansine inside their plant host, and what is the impact of maytansine production in plant secondary metabolites? Our study aimed to address these questions. We selected

There is explored, herein, functional relation: Experimental mass spectrometric phenomenon, obeying a certain scientific law ⇔ 3D molecular conformations and electronic structures of analytes obtained for quantum chemical theories. The paper answers to questions: (a) What evidence claims these actual relations among measurable and theoretical parameters, experimental factors and molecular properties; (b) how the provided evidence is collected and used; and (c) how empirical proof relates to assign and explain mass spectrometric phenomena of steroids afforded by our innovative stochastic dynamic mass spectrometric formula, D″

This paper details with design, synthesis, isolation, spectroscopic and structural elucidation of seven crystals of organic barbiturates (a red phase of bis(5-(hydroxyimino)pyrimidine-2,4,6(1H,3H,5H)-trione) 4H-1,2,4-triazol-4-amine co-crystal (1y), 2-methylamino-1-phenyl-propan-1-ol 2-thioxo-dihydro-pyrimidine-4,6-dione (2), 4-phenylpyridine thiobarbituric acid co-crystal (3), new monoclinic polymorph of violuric acid monohydrate (4), 2-pyrrolidin-1-yl-ethylammonium bis(violurate) dihydrate (5) and redetermination of barbituric acid dihydrate (6) and noncentrosymmetric orthorhombic violuric acid monohydrate (7)). The noncentrosymmetric crystals (1r) (2) and (7) can efficiently be employed in the field of nonlinear optical (NLO) materials research. We aim at studying relationship between molecular, respectively, crystal structure and NLO properties within a relatively large range of temperatures (T = 273–500 K). The single crystal X-ray diffraction, electronic absorption, conventional and linear polarized infrared spectroscopies have been used to provide experimental structural and spectroscopic data. The deuterated derivatives of (4) and (7) have been analysed, as well. The theoretical description of linear and NLO properties of crystals (1)–(7) is based on quantum chemical ab initio methods and density functional theory (DFT). The work contributes, importantly, to the fields of nonlinear optics, crystal engineering or materials research, reflecting in mind frequency conversion of lasers, electro-optics, modulators, waveguides and more.

The kernel idea for this paper came from our more recent development of a mass spectrometric model equation, based on stochastic dynamics. It treats quantitatively the experimental intensity of analytes and their fragment ions under soft ionization conditions. The effort has resulted to exact universally applicable and empirically testable relationship, between mass spectrometric stochastic dynamic diffusion and the intensity. A linear correlation at high level of statistical significance occurs between DSD and the corresponding quantum chemical diffusions, obtained within the Arrhenius' approximation. It provides bridge between experimental MS parameters and 3D structure of analyte ions. Furthermore, we have claimed that the total intensity of the ions is proportional to their DSD parameter according to our model equation; or Itot ~ DSD. As evident from the small–scale of our contributions, so far, the simplistic theoretical concept and corresponding model equation need to be translated into a broad practical employment, because of; there is extended the capability of mass spectrometry beyond its routine application as irreplaceable method for quantitative analysis to the analytical practice. The superior features of the mass spectrometric instrumentation can offer us a new perspective of looking at the implementation of the method to exact 3D structural analysis in condense phase. As far as any such statement should be strongly quantified from the point of view of the chemometrics, this work deals with application of our stochastic dynamic concept of mass spectrometric diffusion to structural analysis of complex ions of CuII–ion with glycylhomopentapeptide and its dimeric associates. The large difference in the coordination fashion of oligopeptides, and competitive fragment paths together with the variety of the coordination modes of CuII–ion; and accounting, in parallel, for the different oxidation states of copper allows for us to demonstrate the great capability of our theoretical concept, studying so challenging research area. The experimental design is based on high resolution electrospray ionization mass spectrometric data in positive operation mode. High accuracy ab initio and methods based on theory on functional of density are used. Both static and molecular dynamic methods are employed.

The focus on this paper is on to continue the research line taken in our more recent studies of mass spectrometric approaches treating quantitatively the intensity of analyte fragment peaks with respect to time within the own model equation, based on stochastic dynamics, and correlating between experimental diffusion parameters of ions and their 3D structures, when this approach is used complementary with high accuracy methods of quantum chemistry. Accordingly, the aims at the work will be undeniably presented. First, we will explore ESI–MS in solution, operating under positive mode and crystallographic data of a CuII–complex of glycine (cis–{[CuII(Gly)2].H2O} (1)) in determining experimental MS diffusions of ions according to the aforementioned methodology. The correlative analysis to quantum chemical diffusions will be carried out, using the Arrhenius' approximation to the theoretical diffusion of charged species under soft–ionization MS conditions. Second, on the base on experimentally observed complex isotope shape of coordination species of ions of copper, a theoretical description of redox processes under ESI–MS conditions will be detailed. There is nothing irreconcilable between both goals, as far as, the experimental data convincingly argued that the relation to MS stochastic dynamic diffusions ⇔ quantum chemical diffusion parameters has direct bearing on how the analysis of the MS intensity of isotope sub–peaks within the aforementioned method can provide direct information about experimental 3D structure of the analyte in condense phase. The cis/trans isomerization of {[CuII(Gly)2]} complex is discussed in detail correlating crystallographic data of (1) with ESI(+)–MS ones. A process of isomerization cis–{[CuII(gly)2]0} → trans–{[CuII(gly)2+H]+} is proposed on the base on crystallographic and mass spectrometric data on (1).

Knowledge about translocation of plant protection products (PPP's) in plants is important to understand the uptake via the root system. Here we report the combination of analysis of tissue extracts by LC-HRMSn, autoradiography of 14C-labeled compounds and MALDI-MSI, which combine qualitative and quantitative information of chemical composition and the spatial distribution of PPP's and their metabolites in situ. Therefore, the uptake of the phenylamide fungicide metalaxyl was studied in tomato plants (Solanum lycopersicum) using a hydroponic system. The plants have been cultivated in perlite until the two-leaf stage and were transferred into the hydroponic test system afterwards. The radioactive labeled fungicide was readily taken up by the roots during the normal water consumption and radioactivity was translocated uniformly to the aboveground part of the tomato plants, while only small proportion of the applied radioactivity were observed in the roots. The distribution of metalaxyl after the plant uptake experiment in the primary roots where analyzed by a transversal tissue section in the zone of maturation. Metalaxyl is mainly localized in root xylem and in cortex located at the epidermis. With LC-HRMSn and radiochemical analyses of stem and leaf, no parent compound was detectable. Four polar metabolites were the main identified components of the residue and could be visualized by MALDI-imaging mass spectrometry. With these results we could show, that the fungicide metalaxyl is taken up by the plant via the roots during the regular water consumption and transported to xylem.

Tetrapleura tetraptera is a medicinal plant used in East and West Africa to treat inflammation and related diseases. From the stem bark of the plant, three previously undescribed flavan-3-ol derivatives named (2R,3S)-3,3',5',7-tetrahydroxy-4'-methoxyflavane (1), (2R,3S)-3',5',7-trihydroxy-4'-methoxyflavane-3-O-β-D-glucopyranoside (2), and (2R,3S,4S)-3,3',4,5',7-pentahydroxy-4'-methoxyflavane (3) were isolated with three known analogues. The structural elucidation of the compounds was performed based on NMR spectroscopy and HRMS data analyses. The absolute configurations around the stereogenic carbons were determined using Circular Dichroism (ECD) and density functional theory (DFT) calculations. The cytotoxicity of the isolated compounds was tested using resazurin reduction assay. Compound 1 was moderately active against both recalcitrant leukemia cell lines with IC

In this work we discuss certain consideration for quantum chemical and chemometric assessing in the crystallographic polymorphism. It is aimed primarily at researchers in ‘Analytical chemistry’ and is designed to help readers’ understanding of the implications of the different quantum chemical theories in the chemical crystallography. The focal part of the discussion sets out the polymorphism of aspirin. The other parts of the paper extend the scope of the contribution considering crystallographic, quantum chemical and chemometric data about pharmaceutics. In the corresponding results–sections we present discussion concentrating on subtle electronic effects in polymorphs, thus illustrating the great capability of the computational quantum chemistry to distinguish between modifications showing perturbations of the atomic positions in the crystals. (The content of the book isunedited by the Publisher version.)

Three new bufadienolides, namely, paulliniogenin A (

Chemical investigation of the root of

In the current paper, we further search for certainty of our innovative stochastic dynamic (SD) simplistic model formula D”SD = 2.6388.10-17. (2>-2) connecting among the so-called mass spectrometric SD diffusion parameter DSD parameter, the mass spectrometric measurable variable intensity, and the analyte concentration in solution. Since this equation has been derived more recently from our basic, but a more complex, formula for a large number of practical purposes of the analytical chemistry such a simplistic relationship is sufûcient significantly. Therefore, the motivation behind this work is further experimental justiûcation of the validity of this formula that is required in order to successfully apply the new model to the analytical practice. The quantification is carried out by studying reserpine (1) in solution at an analyte concentration of ng.(mL)-1. The capability of the model equation to express quantitatively the analyte concentration in solution is tested with independent chromatographic analysis. Correlation between chromatographic and mass spectrometric (MS) data is carried out by means of chemometrics. The diffusion parameters according to our stochastic dynamic concept and the simplistic model formula presented above and the corresponding diffusion data according to the current monitoring method (CMM) are correlated mutually, as well.

Background & Aims Acute liver failure (ALF) represents an unmet medical need in Western countries. Although the link between intestinal dysbiosis and chronic liver disease is well-established, there is little evidence for a functional role of gut-liver interaction during ALF. Here we hypothesized that intestinal dysbiosis may affect ALF. Methods To test this hypothesis, we assessed the association of proton pump inhibitor (PPI) or long-term antibiotics (ABx) intake, which have both been linked to intestinal dysbiosis, and occurrence of ALF in the 500,000 participants of the UK BioBank population-based cohort. For functional studies, male Nlrp6-/- mice were used as a dysbiotic mouse model and injected with a sublethal dose of acetaminophen (APAP) or lipopolysaccharide (LPS) to induce ALF. Results Multivariate Cox regression analyses revealed a significantly increased risk (odds ratio, 2.3–3) for developing ALF in UK BioBank participants with PPI or ABx. Similarly, dysbiotic Nlrp6-/- mice displayed exacerbated APAP- and LPS-induced liver injury, which was linked to significantly reduced gut and liver tissue microbiota diversity and correlated with increased intestinal permeability at baseline. Fecal microbiota transfer (FMT) from Nlrp6-/- mice into wild-type (WT) mice augmented liver injury on APAP treatment in recipient WT mice, resembling the inflammatory phenotype of Nlrp6-/- mice. Specifically, FMT skewed monocyte polarization in WT mice toward a Ly6Chi inflammatory phenotype, suggesting a critical function of these cells as sensors of gut-derived signals orchestrating the inflammatory response. Conclusions Our data show an important yet unknown function of intestinal microbiota during ALF. Intestinal dysbiosis was transferrable to healthy WT mice via FMT and aggravated liver injury. Our study highlights intestinal microbiota as a targetable risk factor for ALF., Graphical abstract

From the leaves of Kenyan medicinal plant Bersama abyssinica Subspecies abyssinica, four previously undescribed compounds namely, three bufadienolides, 10β-formylpaulliniogenin B, 10β-formylpaulliniogenin A and 1β-acetoxy-3β,5β-dihydroxy-15-methoxy-16,19-dioxobufa-14(15),20,22-trienolide, and a phenolic compound 2,6,4'-trihydroxybenzophenone-4-O-(6‴-cinnamoyl)-β-D-glucoside were isolated together with four known compounds. The structural elucidation of the compounds was based on 1D and 2D NMR spectroscopy and HRMS data analyses. The relative configurations were defined by NOESY correlations. Cytotoxic activities on L929 and KB3.1 cell lines of the isolated compounds were investigated using MTT assay. The 1β-acetoxy-3β,5β-dihydroxy-15-methoxy-16,19-dioxobufa-14(15),20,22-trienolide showed significant cytotoxic activity against KB3.1 cell lines with IC

The leaves of Dracaena steudneri yielded 6 new flavonoids–3,5,7-trihydroxy-6-methyl-3′,4′-methylenedioxyflavone (1), 5,7-dihydroxy-3-methoxy-6-methyl-3′,4′-methylenedioxyflavone (2), 3,5,7-trihydroxy-6-methoxy-3′,4′-methylenedioxyflavone (3), (2S,3S)-3,7-dihydroxy-6-methoxy-3′,4′-methylenedioxyflavanone (4), 4′,5,7-trihydroxy-3,3′,8-trimethoxy-6-methylflavone (5), (2R) 7-hydroxy-2′,8-dimethoxyflavanone (6)–together with 13 known congeners. Their structures were established using spectroscopic and spectrometric methods including NMR, CD, and HRMSn measurements. The compounds were evaluated for their anti-inflammatory potential through measurement of the levels of cytokines IL-1β, IL-2, GM-CSF, and TNF-α in the supernatant of human peripheral blood mononuclear cells stimulated by lipopolysaccharide. Flavones derivatives 1–4 with a C-3′/4′ methylenedioxy substituent led to a substantial increase in the production of IL-1β and GM-CSF out of 4 pro-inflammatory cytokines relative to LPS control. Quercetin derivatives 5, 11, and 13 with a hydroxyl group at C-4′ inhibited the production of IL-2, GM-CSF, and TNF-α. The presence of a C-2/C-3 double bond in 14 was pivotal to the significantly stronger (0.4 to 27.5% of LPS control) inhibitory effect compared to its dihydro derivative 8 (36.2 to 262.7% of LPS control) against all tested cytokines. It is important to note that the inhibitory activity of 14 was substantially higher than that of the standard drug used, ibuprofen.

Four new steroidal sapogenins, dracaenogenins C F (1–4), a new conjugated chalcone-stilbene, 3′′-methoxycochinchinenene H (5) together with eight known compounds namely, (25S)-spirosta-1,4-dien-3-one (6), trans-resveratrol (7), 4,4′-dihydroxy-3′-methoxychalcone (8), N-trans-coumaroyltyramine (9), N-trans-p-coumaroyloctopamine (10), N-trans-feruloyloctopamine (11), 7-hydroxy-1-(4-hydroxy-3-methoxyphenyl)-N2,N3-bis(4-hydroxyphenethyl)-6-methoxy-1,2-dihydronaphthalene-2,3-dicarboxamide (12) and grossamide (13) were isolated from the stems of Dracaena usambarensis Engl. from Kenya. It is important to note that compounds 12 and 13 are being reported from this genus for the first time. Structural elucidation of the isolated compounds was done using spectroscopic (NMR, UV, IR, optical rotation) and spectrometric (HRESIMS) techniques. The absolute and relative configurations of the isolated compounds were determined by employing single crystal X-ray crystallography analysis, NOESY correlations and coupling constants. The anti-inflammatory potencies of the isolated compounds were evaluated by measuring the levels of four cytokines (IL-1β, IL-2, GM-CSF and TNF-α) in the supernatant media of human peripheral blood mononuclear cells (PBMCs) stimulated by lipopolysaccharide (LPS). At the tested concentration of 100 μM, the new conjugated chalcone-stilbene 5, the dihydrochalcone, 8 and the lignanamide, 13 were substantially more potent than the standard drug, ibuprofen, inhibiting the release of all the cytokines, IL-1β, IL-2, GM-CSF and TNF-α from 0.06–58.04% compared to LPS control. These compounds should therefore be considered for development into anti-inflammatory drug candidates. Compound 7 significantly decreased the release of GM-CSF (6.11% of LPS control) and TNF-α (18.35% of LPS control). The cytokine TNF-α was sensitive to all the tested compounds 1-13.

This paper deals with quantification of the following steroids in mixture: hydrocortisone (1), deoxycorticosterone (2), progesterone (3) and methyltestosterone (4) by means of mass spectrometry and implementing our innovative stochatic dynamic functional relationship between the analyte concentration in solution and the experimental variable intensity. The mass spectrometric data are correlated independently using chromatography. Chemometric analysis is carried out.

A new flavone, named hildeflavone (

The data analyzed in this paper are on quantitative and 3D structural determination of ionic ensembles and multiply charged solvates ions of type [(Cl)(H2O)x(H3O)y(CH3CN)z]+, [(Cl)(O2)x(CH3OH)y(NH4)z]+, [(O2)x(H2O)(H3O)(CH3CN)]+n and [(Cl)(H2O)2(H3O)(CH3CHN2)]+ observable under electrospray ionization conditions in presence of ZnII-ion containing metal-organics, where x = y = z = 1–3 are the number of molecules, respectively, ions participating into each of the interacting ensemble, while “n” denotes the number of interacting ensembles forming the more complex ionic clusters. The major theoretical problem we have to deal with is the applicability of our more recently developed stochastic dynamic concept and formulas connecting among the mass spectrometric variable intensity, the so-called stochastic dynamic diffusion parameters (DSD), the temperature (T) and the analyte concentration in solution to such challenging molecular/ionic systems from the perspective of molecular structure. The DSD parameters of analyte ions correlate linearly with the so-called quantum chemical diffusion parameters (DQC) according to the Arrhenius’s theory. The work has demonstrated persuasively that these equations are capable of providing reliable analytical information about so complex ensembles of interacting species. It shows their significant advantages as analytical approaches, amongst other rival concepts, to quantify the mass spectrometric outcome intensity highly accurately, selectively, precisely and sensitively. The thermodynamics parameters of common reactions of the following ionic species observable under electrospray ionization experimental conditions of some tetrachlrozinc(II) complex ions of metal-organics are examined. These are the ions [(Cl)(H2O)(H3O)2(CH3CN)3]+ (m/z 214/216), [(Cl)(H2O)(H3O)2(CH3CN)2]+ (m/z 173/175), [(Cl)(H2O)2(H3O)2(CH3CN)]+ (m/z 150/152), [(Cl)(H2O)(H3O)2(CH3CHNH]+ (m/z 134/136,) [(Cl)(H2O)2(H3O)(CH3CHNH2]+, [(Cl)(H2O)(H3O)2(CH3CN]+ (m/z 132/134,) [(Cl)(H2O)2(H3O)2(CH3CN]+ (m/z 183/185), [(CH3OH)(H2O)5(NH4)(CH3CN)3]+3 (m/z 263,) and [(CH3OH)(H2O)(H3O)(CH3CN)]+31 (m/z 110,) respectively.

Phytochemical analysis of a methanol-dichloromethane (1:1) extract of the aerial parts of

From the leaves of South African medicinal plant Melianthus comosus, four previously undescribed bufadienolides, 16β-formyloxymelianthugenin (1), 2β-acetoxymelianthusigenin (2), 2β-hydroxy-3β,5β-di-O-acetylhellebrigenin (3), and 2β-acetoxy-5β-O-acetylhellebrigenin (4) were isolated together with two known bufadienolides. The structural elucidation of the compounds was based on 1D and 2D NMR spectroscopy, high-resolution mass spectrometry, and other spectroscopic methods. The relative configurations were determined by single-crystal X-ray crystallography analysis and NOESY correlations. The isolated compounds displayed strong cytotoxicity against MCF-7 breast cancer cells, sensitive CCRF-CEM and multidrug-resistant CEM/ADR5000 leukemia cells. Compound 1 showed the most potent activity, with IC50 values of 0.07 μM towards CCRF-CEM, 0.06 μM towards CEM/ADR5000 and 0.36 μM towards MCF-7 followed by compound 4 with IC50 values of 0.13 μM towards CCRF-CEM, 0.08 μM towards CEM/ADR5000 and 0.53 μM towards MCF-7.