Picric acid (2,4,6-Trinitrophenol) is a high-power explosive and a common environmental pollutant found in wastewaters generated from leather, pharmaceutical, and dye industries. It can form a fluorescent Meisenheimer complex with nucleophiles like N,N'-Diisopropylcarbodiimide (DPC). Based upon this unique Meisenheimer complex, a miniaturized fluorescence sensor has been designed for highly selective and sensitive detection of picric acid from environmental samples and commercial samples. The sensor probe equipped with a portable 532 nm DPSS green laser could detect picric acid concentrations as low as 100 nM (25 ppb) with excellent reproducibility. It shows promise for real time evaluation of picric acid contamination in environmental and commercial samples with excellent discrimination against other structurally related nitroaromatics. The validation results for picric acid concentrations in spiked environmental and commercial samples were in good agreement with high performance liquid chromatography analysis. The fluorescence method is simple, selective, sensitive and amenable to high throughput screening. The design of the portable sensor and its working principle has been discussed. (C) 2017 Elsevier B.V. All rights reserved.

Moringa oleifera trees grow well in Jamaica and their parts are popularly used locally for various purposes and ailments. Antioxidant activities in Moringa oleifera samples from different parts of the world have different ranges. This study was initiated to determine the antioxidant activity of Moringa oleifera grown in Jamaica. Dried and milled Moringa oleifera leaves were extracted with ethanol/water (4:1) followed by a series of liquid–liquid extractions. The antioxidant capacities of all fractions were tested using a 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay. IC50 values (the amount of antioxidant needed to reduce 50% of DPPH) were then determined and values for the extracts ranged from 177 to 4458 μg/mL. Extracts prepared using polar solvents had significantly higher antioxidant capacities than others and may have clinical applications in any disease characterized by a chronic state of oxidative stress, such as sickle cell anemia. Further work will involve the assessment of these extracts in a sickle cell model of oxidative stress.

Response surface methodology (RSM) using a Box-Behnken design was used to optimize the extraction conditions for obtaining pancreatic lipase inhibitory and antioxidant principles from Ilex paraguariensis leaves. Three influencing factors: extraction time (min), the liquid–solid ratio, and ethanol concentration (%, v/v) were investigated in the ultrasonic extraction process. Optimization of the extraction conditions to obtain a product with minimum PL activity, maximum antioxidant activity, and maximum yield was performed using RSM by focusing on the three target influencing factors. The optimum conditions were established as the ethanol concentration (54.8 %), liquid–solid ratio (35.4), and extraction time (70.0 min). Under these conditions, the 2,2-diphenyl-1-picrylhydrazyl scavenging activity, PL activity, extraction yield were 59.3 ± 3.5, 35.3 ± 3.0, and 34.4 ± 0.4 %, respectively, similar to the theoretical predicted values of 59.7, 35.2, and 34.3 %, respectively.

A series of 1-aryl-3-(cyclicamino)-prop-2-en-1-one analogs was synthesized from commercial acetophenones in 2 or 3 steps. Compound 6, (E)-3-(piperidinyl)-1-(2′-hydroxyphenyl)-prop-2-en-1-one, exhibited the unique shape and intensity of the Csp2NCH2 peaks in the 1H and 13C NMR spectra. Variable temperature (VT) nuclear magnetic resonance (NMR) and X-ray diffraction (XRD) studies of 6 revealed that the piperidine ring has a lower energy barrier to rotation than the 5-membered pyrrolidine 9 due to the less effective π electron delocalization along the Csp2N bond.

Agmatine is an endogenous brain metabolite, decarboxylated arginine, which has neuroprotective properties when injected intraperitoneally (i.p.) into rat pups following hypoxic-ischemia. A previous screen for compounds based on rat brain lysates containing agmatinase with assistance from computational chemistry, led to piperazine-1-carboxamidine as a putative agmatinase inhibitor. Herein, the neuroprotective properties of piperazine-1-carboxamidine are described both in vitro and in vivo. Organotypic entorhinal-hippocampal slices were firstly prepared from 7-day-old rat pups and exposed in vitro to atmospheric oxygen depletion for 3 h. Upon reoxygenation, the slices were treated with piperazine-1-carboxamidine or agmatine (50 μg/ml agents), or saline, and 15 h later propidium iodine was used to stain. Piperazine-1-carboxamidine or agmatine produced substantial in vitro protection compared to post-reoxygenated saline-treated controls. An in vivo model involved surgical right carotid ligation followed by exposure to hypoxic-ischemia (8 % oxygen) for 2.5 h. Piperazine-1-carboxamidine at 50 mg/kg i.p. was given 15 min post-reoxygenation and continued twice daily for 3 days. Cortical agmatine levels were elevated (+28.5 %) following piperazine-1-carboxamidine treatment with no change in arginine or its other major metabolites. Histologic staining with anti-Neun monoclonal antibody also revealed neuroprotection of CA1-3 layers of the hippocampus. Until endpoint at 22 days of age, no adverse events were observed in treated pups’ body weights, rectal temperatures, or prompted ambulation. Piperazine-1-carboxamidine therefore appears to be a neuroprotective agent of a new category, agmatinase inhibitor.

Objective: A sesquiterpene lactone, vernodalinol, was isolated from VA leaves. The first reported source of vernodalinol was in 2009 from a different plant, only <SU1</SUH NMR spectrum and no detailed structural analysis were carried out. No whole spectroscopic data were provided.Materials and methods: VA dried leaves were extracted with 85% ethanol followed by further separation into four fractions by liquid--liquid extraction technique using various solvents: hexane, chloroform, and n-butanol. Vernodalinol was separated from the n-butanol fraction by column chromatography. The biological activity of vernodalinol was evaluated in estrogen receptor-positive (ER<SU++</SU) human breast carcinoma cells (MCF-7) in vitro.Results: Results indicated that vernodalinol (25 and 50 mu mu g/mL) inhibited breast cancerous cell growth (DNA synthesis) by 34% (P < 0.025) and 40% (P < 0.025), respectively. It is reasonable to expect an LC50 of 70--75 mu mu g/mL for vernodalinol in MCF-7 cells.Discussion and conclusion: Vernodalinol structure was confirmed using a battery of spectroscopic methods, 1D and 2D NMR, high-resolution mass spectrometry (HR-MS), UV, IR, and X-ray. These results suggest that vernodalinol, although it has some biological activity, is likely to work in concert with other ingredients responsible for the anticancer activity exhibited of VA.

Structural characterization of a hydrogen sulfate complex with a tren-based urea suggests that the anion is coordinated with six NH···O bonds (d(N···O) = 2.857 (3) to 3.092 (3) Å) and one OH···O bond (d(O···O) = 2.57 (2) Å) from three receptors; however, in solution the anion is bound within the pseudo-cavity of one receptor.

Vernonia amygdalina (VA) is widely used for medicinal and food purposes in tropical Africa. Many health benefits (antioxidant, antimicrobial, anticancer activities and more) of VA extracts have been reported. The mechanisms of actions have also been described. We have previously reported that VA extracts elicited growth inhibitory activities in human estrogen receptor-positive (ER+) cells (MCF-7 cells) and ductal carcinoma cells (BT-549) in vitro. The active components in the organic solvent (chloroform)-extracted VA have been previously determined. However, the active components in the ethanolic extracts of VA have not been previously studied. Hence, the objectives of this study are to isolate and characterize the active components of the ethanolic extracts of VA using liquid–liquid extraction, thin layer chromatography and column techniques. Fractionation of the ethanolic extracts of VA yielded three fractions named A1, A2 and A3, and A2 retained the DNA synthesis-inhibitory activity of the extracts. Subsequent fractionation of A2 yielded fraction A2B whose activity was 16 and three times more potent than the ethanolic fraction and fraction A2, respectively. The treatment of cells with 100 μg/mL of either the ethanolic VA extracts, fraction A2 or fraction A2B resulted in a 23% (P < 0.01), 86% (P < 0.0001) and 97% (P < 0.0001) inhibition of DNA synthesis compared with vehicle-treated controls, respectively. Further purification of A2B by high-speed countercurrent chromatography and confirmed by spectroscopic analysis revealed that the major active components of A2B (65% by weight) were steroid glucosides.

Vernonia amygdalina (VA) is an edible plant of the Asteraceae family used in many herbal formulations prescribed by herbalists for many diseases. We have previously reported that aqueous VA extracts inhibit the growth of estrogen receptor-positive human breast cancerous cells in vitro. Activity markers of the VA extracts have not been previously identified or characterized. Hence, the objective of this study was to identify activity markers of the VA extracts associated with cell growth inhibition. Extraction of VA with multiple solvents of various polarity indexes yielded three fractions (A-1-2, B-1-3) that significantly inhibited cell growth (P < 0.05) at 0.1 mg/ml concentration. At a higher concentration of 1 mg/ml, six fractions of hexane, chloroform, butanol, and ethyl acetate (A-1-3, B-1-4) inhibited DNA synthesis by 76%, 98%, 94%, 98%, 98%, and 96%, respectively. These fractions were UV-detected from 250-730 nm; and all showed three distinct peaks around 410, 431, and 664 nm. Furthermore, HPLC analysis of the fractions revealed similar retention times of 2.213, 2.167, and 2.151 min, respectively. Bioactivity assays showed that HPLC retention of approximately 2 min is required for cell growth-inhibitory activity of VA fractions. Interestingly, all active fractions exhibited HPLC peaks at approximately 2 min. Therefore, the UV and HPLC peaks may be used as predictive tools to determine VA extracts activities.

To assess the effectiveness of anion exchange resins (Dowex M43 and Dowex monosphere 66) in neutralization and detoxification of an acid hydrolyzate solution, a fermentation medium containing inhibitors was inoculated with Saccharomyces cerevisiae. When treated with resins at a 1:1 ratio (vol:wt) for up to 20 min, 55-67% of furan and more than 95% of phenolic compounds were removed. Ethanol fermentation activity in resin-treated fermentation medium was the same as the control. There was 21-43% of the total sugar loss after one resin treatment, depending on the sugar concentration. Additional treatments increased sugar retention rate to 95%.

The present work was carried out to determine the optimum culture conditions of Phanerochaete chrysosporium (ATCC 20696) for maximizing ligninolytic enzyme production. Additionally, separation of its lignin peroxidase was conducted. After experiments, an optimized culture medium/condition was constructed (per liter of Kirk’s medium): dextrose 10 g, ammonium tartrate 0.11 g, Tween-80 0.5 g, MnSO4 7 mg, and veratryl alcohol 0.3 g in 10 mM acetic acid buffer pH 4.5. Under the optimized experimental condition, both lignin peroxidase (LiP) and manganese peroxidase (MnP) were detected and reach the highest yield at 30°C on the 8th day culture. Salt precipitation methods was used in the extraction and purification processes. Results show that salt precipitation with 60% (NH4)2SO4 yielded the best result, especially toward LiP. Enzyme separation was conducted and two fractions with LiP activity. LiP1 and LiP2 were produced using three columns sequentially: desalting column, Q FF ion exchange column and Sepharyl S-300 HR gel filtration. LiP1 and LiP2 had been purified by 9.6- and 7.6-fold with a yield of 22.9% and 18.6%, respectively. According to the data of sodium dodecyl sulfate polyacrilamide gel electrophoresis (SDS-PAGE), the molecular weights of the enzymes are 38 kDa and 40 kDa, respectively.

In reports from WHO, cancer is a leading cause of death worldwide and the breast cancer is one of most frequent cancer types, among women: one out of every eight women will be diagnosed with cancer in her lifetime. Our interest is in finding a novel and effective breast cancer chemotherapeutics from the natural resources like a folk medicine. An aqueous extract of an African edible plant, Vernonia amygdalina (VA) leaf, has been reported to be potent to breast tumor cell line MCF-7. We used 85% EtOH to extract active organic components from VA leaves. And then, the condensate was separated by the liquid—liquid method (Method A). Three fractions, A1, A2, and A3 were obtained from Method A, and the fraction A2 shows better activity than A and aqueous extract in the bioassay. Column Chromatography was used to separate A2 into five parts, A2A, A2B, A2C, A2D, and A2E, in methanol—chloroform solvent system with various ratios between two solvents. The cell proliferation assay data indicated that active compounds still kept in A2B. The yield of A2B from raw VA powder is about 5%. Column Chromatography was used again to separate A2B in methanol—chloroform solvents system. In this separation, same volume solutions, washed out from the column, were collected and condensed. The condensates were kept in the vials numbered in sequence. After that, TLC was used to analyze the condensates. It gave five fractions, A2B5, A2B15, A2B25, A2B35 and A2B45, and the fractions of A2B15 and A2B25 showed the better activity towards the cancer cell in the bioassay. A2B25 were analyzed by the MS and it shows that there is a carboxylic group in the molecule, which the molecular weight is 552. Acknowledgement: This research was supported by NIH (RCMI: NIH-NCRR G12RR13459 and NCMHD: P20MD000534-01).

An extensive theoretical study of berberine has been performed at the ab initio HF/6-31G**, FW/6-311G**, and B3LYP/6-311G** levels with and without solvent effects. The optimized structures are compared with X-ray data. We found that the optimized structures with solvent effects are in slightly better agreement with X-ray data than those without solvent effects. The H-1 and C-13 nuclear magnetic resonance (NMR) chemical shifts of berberine were calculated by using the gauge-independent atomic orbital (GIAO) (with and without solvent effects), CSGT, and IGAIM methods. The calculated chemical shifts were compared with the two-dimensional NMR experimental data. Overall, the calculated chemical shifts show very good agreement with the experimental results. The harmonic vibrational frequencies for berberine were calculated at the B3LYP/6-311G** level. (c) 2005 Wiley Periodicals, Inc. Int J Quantum Chem 105: 396 - 409, 2005.

An extensive theoretical study of two agmatine analogues, ( 3- aminopropyl) guanidine and ( trans-4-aminocyclohexyl) guanidine, has been performed at the ab initio HF/6-31G**, HF/6-311G**, B3LYP/6-311G** and B3LYP/6-311G**/IEFPCM levels. Bond lengths, bond angles and dihedral angles of the optimized structures of ( 3- aminopropyl) guanidine and ( trans-4-aminocyclohexyl) guanidine are very close to each other. The H-1 and C-13 NMR chemical shifts of ( 3- aminopropyl) guanidine and ( trans-4-aminocyclohexyl) guanidine were calculated by using GIAO ( with and without solvent effects), CSGT and IGAIM methods. The calculated chemical shifts were compared with the two-dimensional NMR experimental data. Overall, the calculated chemical shifts show very good agreement with the experimental results. The harmonic vibrational frequencies for ( 3- aminopropyl) guanidine and ( trans-4-aminocyclohexyl) guanidine were calculated at the B3LYP/6-311G** level.

The synthetic steroid 9α-fluoro-11β,17α,21-trihydroxy-1,4-pregnadiene-3,20-dione-21-acetate (9-fluoroprednisolone-21-acetate), formula C23H29O6F, is related to substances which are potent inducers of hepatic microsomal enzymes and anti-inflammatory agents. The structure was determined at 294 K from counter-collected data by direct methods. Crystals are tetragonal, space groupP41212,a, b=9.214(2),c=49.452(39) Å,V=4198(4), Å,D x =1.33μg/m3 forZ=8;R (onF) 0.063 for 915 independent intensities (I>2σ1). The structure shows H-bonding and packing of the mean molecular plane approximately perpendicular to the crystallographic 4-fold axis.