Levels of dioxin-like PCBs in low-volume serum samples of male patients attending fertility clinics

An accurate and easy method for the extraction, cleanup, and HRGC-HRMS analysis of dioxin-like PCBs (DL-PCBs) in low-volume serum samples (1 mL) was developed. Serum samples were extracted several times using n-hexane and purified by acid washing. Recovery rates of labeled congeners ranged from 70 to 110 % and the limits of detection were below 1 pg/g on lipid basis. Although human studies are limited and contradictory, several studies have shown that DL-PCBs can have adverse effects on the male reproductive system. In this way, the present method was applied to 21 serum samples of male patients attending fertility clinics. The total levels obtained for the patients ranged from 6.90 to 84.1 pg WHO-TEQ/g lipid, with a mean value of 20.3 pg WHO-TEQ/g lipid. The predominant PCBs (the sum of PCB 118, 156, and 105) contributed 67 % to the mean concentration of total DL-PCBs in the samples analyzed.

Bioprospection of Petit Verdot grape pomace as a source of anti-inflammatory compounds.

The aim of this study was to evaluate the anti-inflammatory activity of Petit Verdot Extract and hexane, chloroform and ethyl acetate fractions obtained from grape pomace, in addition to identifying active compounds. The PVE and EAF reduced significantly paw edema and neutrophil migration when compared with control groups. The PVE reduced levels of TNF-α and IL1-β in the peritoneal fluid, whereas the EAF did not reduce cytokines significantly. Two hydroxybenzoic acids, two proanthocyanidins, three flavan-3-ol monomers and three anthocyanins were identified in the PVE and EAF by LC-MS/MS. The stilbene transresveratrol was identified only in the EAF. The phenolic compounds were quantified using HPLC-DAD analysis, except for the stilbenes, which were not sensible for the detection by the method. Since PVE and EAF showed significantly anti-inflammatory effects and high concentration of phenolic compounds, we concluded that Petit Verdot pomace could be an interesting source of anti-inflammatory bioactives.

Cytotoxic, anti-inflammatory and antioxidant activities of four different extracts of Galega officinalis L (Goat’s rue)

Purpose: To evaluate the cytotoxic, anti-inflammatory and antioxidant activities of four different solvent extracts obtained from the aerial parts of Galega officinalis L Methods: The hexane, DCM, methanol and water extracts of G. officinalis were successively obtained by soxhlet extraction method. The cytotoxic activity of the extracts was assessed against human lung carcinoma (A-549), human colorectal adenocarcinoma (HT-29), human brain glioblastoma (U-87), and colon adenocarcinoma (DLD-1) by Resazurine test. The antioxidant activity of extracts were determined by Folin-Ciocalteau, oxygen radical absorbing capacity (ORAC), and 2’.7’-dichlorofluorescin-diacetate (DCFH-DA) cell-based assay while their anti-inflammatory activity was determined by nitric oxide (NO) assay. Results: DCM extract showed strong cytotoxic activity against lung adenocarcinoma and brain glioblastoma cell lines, with IC50 (concentration inhibiting 50 % of cell growth) values of 11 ± 0.4 and 16 ± 3 μg/mL, respectively. The hexane extract showed moderate anticancer activity against the same cell lines (59 ± 13 and 63 ± 16 μg/mL, respectively). DCM extract also showed significant anti-inflammatory activity, inhibiting NO release by 86.7 % at 40 μg/mL in lipopolysaccharide (LPS) - stimulated murine RAW 264.7 macrophages. Of all test extracts, the methanol extract of G. officinalis showed the highest antioxidant activity with 2.33 ± 0.09 μmol Trolox/mg , 7.10 ± 0.9 g tannic acid equivalent (TAE), and IC50 of 44 ± 4 μg/mL. Conclusion: The findings of this study suggest that DCM extract may possess anticancer effect against lung adenocarcinoma and brain glioblastoma, as well as serve as an anti-inflammatory agent.

Phytochemical screening and evaluation of cytotoxicity of stem bark extracts of Genus dolichocarpa and Duguetia chrysocarpa (Annonaceae)

Purpose: To investigate the phytochemistry and cytotoxic activity of stem bark extracts from Genus dolichocarpa and Duguetia chrysocarpa - two species of the Annonaceae family. Methods: The crude ethanol bark extracts (EtOH) of the plants were obtained by maceration. The crude extracts were suspended in a mixture of methanol (MeOH) and water (H2O) (proportion 3:7 v/v) and partitioned with hexane, chloroform (CHCl3) and ethyl acetate (AcOEt) in ascending order of polarity to obtain the respective fractions. The extracts were evaluated on thin layer chromatography (TLC) plates of silica gel to highlight the main groups of secondary metabolites. Cytotoxicity was tested against human tumor cell lines - OVCAR-8 (ovarian), SF-295 (brain) and HCT-116 (colon) - using 3- (4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (MTT) assay. Results: The screening results demonstrated that all the extracts were positive for the presence of flavonoids and tannins. The presence of alkaloids also was detected in some extracts. The hexane extract of A. dolichocarpa showed the strongest cytotoxicity against HCT-116 with cell growth inhibition of 89.02 %. Conclusion: The findings demonstrate for the first time the cytotoxic activity of the extracts of A. dolichocarpa and D. chrysocarpa, thus providing some evidence that plants of the Annonaceae family are a source of active secondary metabolites with cytotoxic activity.

Larvicidal, pupicidal and insecticidal activities of Cosmos bipinnatus , Foeniculum vulgare and Tagetes minuta against Culex quinquefasciatus mosquitoes

Purpose: To evaluate the larvicidal, pupicidal and insecticidal activities of Cosmos bipinnatus , Foeniculum vulgare and Tagetes minuta against Culex quinquefasciatus mosquitoes. Methods: The leaves of the plants were extracted with distilled water, ethanol (95 %), and hexane and the extracts screened for their phytochemical profile. While larvicidal and pupicidal activities were assayed at concentrations ranging from 0.1 - 10 mg/mL, insecticidal property was tested at varying amounts (0.25 - 2 g) of the plant sample. The respective larval mortality was thereafter evaluated using Probit analysis. Results: Saponins, terpenoids, flavonoids and steroids were detected in the plant extracts. The ethanol extracts of F. vulgare, T. minuta and C. bipinnatus exhibited larvicidal activity half-maximal lethal concentration (LC50) of 0.10, 1.17 and 1.18 mg/mL, followed by hexane extracts with LC50 value of 1.03, 1.01 and 1.27 mg/mL, respectively, against the larvae of C. quinquefasciatus mosquito. Hexane extracts displayed pupicidal activity with LC50 of 1.07, 1.12 and 1.16 mg/mL against F. vulgare, T. minuta and C. bipinnatus, respectively, while the ethanol extracts of T. minuta, C. bipinnatus and F. vulgare displayed pupicidal activity at LC50 of 1.11, 1.14 and 1.31 mg/mL respectively, against pupa of C. quinquefasciatus mosquito. The aqueous extracts had no (p > 0.05) lethal effects on both larvae and pupa of C. quinquefasciatus at all evaluated concentrations. F. vulgare had the highest (p < 0.05) half-maximal knock-down effect (KD50 = 7.52 min-1), followed by T. minuta (KD50 = 8.64 min-1) on adult C. quinquefasciatus mosquitoes after 6 h of exposure. F. vulgare and T. minuta killed all evaluated mosquito adults within 12 h with LD99 = 0.25 g/air, while the leaves of C. bipinnatus had no (p > 0.05) knock-down or lethal effects on the adult mosquito. Conclusion: C. bipinnatus, F. vulgare and T. minuta possess larvicidal and pupicidal properties against C. quinquefasciatus, whereas only F. vulgare and T. minuta displayed insecticidal properties. Consequent upon these findings, all the plants can be considered naturally potent larvicidal and pupicidal agents against C. quinquefasciatus.

Leishmanicidal and cytotoxic activity of extracts and saponins from Ilex laurina (Aquifoliaceae)

Purpose: To evaluate the leishmanicidal and cytotoxic activity of alcohol and non-alcohol extracts and saponins from Ilex laurina . Methods: Extracts were obtained by percolation with solvents of different polarities: hexane, dichloromethane, ethyl acetate and ethanol. The ethyl acetate extract was subjected to silica gel column chromatography eluting with a step gradient of dichloromethane-methanol. All products were evaluated in vitro for leishmanicidal activity against amastigotes of leishmania panamensis and cytotoxicity on U- 937 cells. Results: Two saponins were isolated from the ethyl acetate extract. The ethyl acetate extract showed high leishmanicidal activity against intracellular amastigotes of L. panamensis (EC50, 7.5 ± 1.5 μg/mL) and low activity against axenic amastigotes (EC50, 52.8 ±1.6 μg/mL); this extract showed also high cytotoxicity (LC50, 57.7 ± 12.1 μg/mL). Saponin 2 exhibited high activity against intracellular amastigotes (EC50, 5.9 ± 0.5 μg/mL) but also showed high cytotoxicity on U-937 cells (EC50, 25.7 ± 6.1 μg/mL). This compound showed similar leishmanicidal activity and cytotoxicity to meglumine antimoniate and amphotericin B, respectively, drugs currently used for the treatment of leishmaniasis. Conclusions: Based on these results, Ilex laurina is a potential source of compounds that can lead to the development of new therapeutic alternatives against leishmaniasis.

Determination of acrylamide levels in selected commercial and traditional foods in Syria

Purpose: To determine acrylamide (AA) levels in different brands of commercial and traditional foodstuffs available in Syria by ultra-performance liquid chromatography-mass spectrometery (UPLCMS). Methods: A total of 63 samples were analyzed. Food samples were defatted by hexane and then extracted with methanol 98 % in a vortex mixer. Thereafter, Carrez I and Carrez II were added to precipitate proteins from the co-extractives and then centrifuged to obtain a clear aqueous extract that was evaporated to dryness. The extract was dissolved in 1 mL of water, eluted through a preconditioned Oasis HLB cartridge and then filtered. The filtrate was analyzed by UPLC-MS/MS to determine AA content. Results: Among the commercial foods tested, the highest acrylamide quantity was found in potato products (396 ± 3.59 – 1844 ± 5.29 μg kg−1) and the lowest in corn products (183 ± 2.64 – 366 ± 4.58 μg kg−1). This was followed by biscuits (57 ± 2.64 – 1433 ± 2.51 μg kg−1), breakfast cereals (121 ± 8.73 – 245 ± 3.60 μg kg−1), bread (119 ± 1.73 – 263 ± 3.60 μg kg−1) and then coffee (113 ± 2.64 - 64 ± 3.05 μg kg−1). Regarding traditional foods, the highest level of AA was found in AL- Mshabak (481 ± 2.08 μg kg−1) and AL-Awamat (421 ± 2.64 μg kg−1) followed by AL-Namora (282 ± 4.35 μg kg−1) and AL-Kenafa (242 ± 2.64 μg kg−1). It was also observed that the lowest amount of AA was in fried bread (230 μg kg−1), AL-Fatayer (192 ± 3.51 μg kg−1) and AL-Baqlawa (172 ± 4.35 μg kg−1) while Eid Aqras (130 ± 4.58 μg kg−1) and AL-Brazeq (167 ± 3.78 μg kg−1) contained the least amount of AA. Conclusion: The results indicate that the highest levels of AA are found in the most commonly consumed foods. There was significant difference (p < 0.05) in AA levels among different food items and within different brands of the same product.

Extração de metais (K, Mg, Ba, Ca, Cr, Mn, Li, Fe) de água produzida utilizando sistema microemulsionado

The produced water is a byproduct formed due to production of petroleum and carries with it a high amount of contaminants such as oil particles in suspension, organic compounds and metals. Thus, these latter pollutants are very difficult to treat because of its high solubility in water. The objective of this work is to use and evaluate a microemulsioned system to remove metals ( K , Mg , Ba , Ca , Cr , Mn , Li , Fe ) of synthetic produced water. For the extraction of metals, it was used a pseudoternary diagram containing the following phases: synthetic produced water as the aqueous phase (AP), hexane as organic phase (OP), and a cosurfactant/surfactant ratio equal to four (C/S = 4) as the third phase, where the OCS (saponified coconut oil) was used as surfactant and n-butanol as cosurfactant. The synthetic produced water was prepared in a bench scale and the region of interest in the diagram for the removal of metals was determined by experimental design called. Ten points located in the phase Winsor II were selected in an area with a large amount of water and small amounts of reagents. The samples were analyzed in atomic absorption spectrometer, and the results were evaluated through a statistical assesment, allowing the efficiency analysis of the effects and their interactions. The results showed percentages of extraction above 90% for the metals manganese, iron, chromium, calcium, barium and magnesium, and around 45% for metals lithium and potassium. The optimal point for the simultaneous removal of metals was calculated using statistical artifact multiple response function (MR). This calculation showed that the point of greatest extraction of metals occurs was the J point, with the composition [72% AP, 9% OP, 19% C/S], obtaining a global extraction percentage about 80%. Considering the aspects analyzed, the microemulsioned system has shown itself to be an effective alternative in the extraction of metals on synthetic produced water remediation

Microporous organic polymers based on hexaphenylbiadamantane:synthesis, ultra-high stability and gas capture

Hexaphenylbiadamantane-based microporous organic polymers (MOPs) were successfully synthesized by Suzuki coupling under mild conditions. The obtained MOPs show high surface area (891 m2 g−1), ultra-high thermal (less than 40% mass loss at temperatures up to 1000 °C) and chemical (no apparent decomposition in organic solvents for more than 7 days) stability, gas (H2, CO2, CH4) capture capabilities and vapor (benzene, hexane) adsorption. These combined abilities render the synthesized MOPs an attractive candidate as thermo-chemically stable adsorbents for practical use in gas storage and pollutant vapor adsorption.

Rhodium clusters: investigation of the reactivity towaeds phosphines and selected d- and p-metals

During my PhD we focused on different research projects concerning the synthesis and characterization of new rhodium carbonyl clusters. More specifically, we studied the reactivity between Rh4(CO)12 and different bidentate phosphines, obtaining seven different species: Rh4(CO)10(dppe), Rh4(CO)8(dppe)2, Rh4(CO)10(dppf), {Rh4(CO)10(dpp-hexane)}2, {Rh4(CO)10(t-dppe)}2, Rh2(CO)2(dppf)2 and Rh4(CO)9(μ2-dppe)(μ1-dppeO). The reactivity of [Rh7(CO)16]3- with [AuCl4]- and Au(Et2S)Cl led to the formation of seven bimetallic clusters, of which four new ones, namely [Rh16Au6(CO)36]6-, [Rh10Au(CO)26]3-, [Rh16Au6(CO)36]4-, [Rh16Au6(CO)36]5-, [Rh22Au3(CO)47]5-, [Rh19Au5(CO)40]4- and [Rh20Au7(CO)45]5-. The reactivity of [Rh16Au6(CO)36]6- and [Rh10Au(CO)26]3- was studied as well. The reactivity of [Rh7(CO)16]3- with AgBF4, AgNO3 and with Pt(Et2S)2Cl2 was investigated, yielding only to the already known [Rh6N(CO)15]-, [PtRh5(CO)15]- and [PtRh4(CO)14]2- compounds. [Rh7(CO)16]3- war reacted with SnCl2·2H2O in acetone obtaining [Rh7Sn4Cl10(CO)14]5-, and [Rh12Sn(CO)23Cl2]4- was reacted with H+ obtaining [Rh18Sn3Cl2(CO)44]4-. Reactivity of [Rh7(CO)16]3- with InCl3 resulted in the isolation of [Rh12In(CO)28]3- and [Rh11In3(CO)25Cl2]3-, already known in our research lab, and the new [HRh11In(CO)26]3-. Moreover, a more straightforward synthesis for [Rh6InCl3(CO)15]2- was found, and this also led to the isolation of the [Rh6InCl2(DMF)(CO)15]-. The recover or rhodium as valuable carbonyl compound was also studied, and starting from a mixture of by-products it was possible to obtain the starting material [Rh7(CO)16]3-.