RESUMO
This study aims to evaluate the toxicity of ZnS nanoparticles (ZnS NP50 = 50 µg/L and ZnS NP100 = 100 µg/L) and diethyl (3-cyano-1-hydroxy-2-methyl-1-phenylpropyl)phosphonate or P (P50 = 50 µg/L and P100 = 100 µg/L) in the clams Ruditapes decussatus using chemical and biochemical approaches. The results demonstrated that clams accumulate ZnS NPs and other metallic elements following exposure. Moreover, ZnS NPs and P separately lead to ROS overproduction, while a mixture of both contaminants has no effect. In addition, data showed that exposure to P100 resulted in increased levels of oxidative stress enzyme activities catalase (CAT) in the gills and digestive glands. A similar trend was also observed in the digestive glands of clams treated with ZnS100. In contrast, CAT activity was decreased in the gills at the same concentration. Exposure to ZnS100 and P100 separately leads to a decrease in acetylcholinesterase (AChE) levels in both gills and digestive glands. Thus, AChE and CAT after co-exposure to an environmental mixture of nanoparticles (ZnS100) and phosphonate (P100) did not show any differences between treated and non-treated clams. The outcome of this work certifies the use of biomarkers and chemical assay when estimating the effects of phosphonate and nanoparticles as part of an ecotoxicological assessment program. An exceptional focus was given to the interaction between ZnS NPs and P. The antioxidant activity of P has been demonstrated to have an additive effect on metal accumulation and antagonistic agents against oxidative stress in clams treated with ZnS NPs.
Assuntos
Bivalves , Nanopartículas Metálicas , Organofosfonatos , Poluentes Químicos da Água , Animais , Catalase/farmacologia , Acetilcolinesterase/farmacologia , Organofosfonatos/farmacologia , Antioxidantes/farmacologia , Nanopartículas Metálicas/toxicidade , Poluentes Químicos da Água/toxicidade , Brânquias , BiomarcadoresRESUMO
An efficient, versatile, and one-pot method for the preparation of novel fluorinated thiazolo- and oxazolo[3,2-a]pyrimidin-7-ones is described from 2-aminothiazoles or 2-amino-oxazoles and fluorinated alkynoates. This transformation, performed under transition-metal-free conditions, offers new fluorinated cyclized products with good to excellent yields. Moreover, the functionalization of these N-fused scaffolds via the Suzuki-Miyaura and Sonogashira cross-coupling reactions led to the synthesis of highly diverse thiazolo- and oxazolo[3,2-a]pyrimidin-7-ones.
Assuntos
Oxazóis , Paládio , CatáliseRESUMO
The present study objective was to assess polycyclic aromatic hydrocarbons in Bizerte and Ghar El Melh Lagoons Solea solea and to assess the potential risk to human health from its consumption. To reach these objectives twenty fish samples from each site were collected and 15 priority polycyclic aromatic hydrocarbons (PAHs) were analyzed in their muscles using high-performance liquid chromatography with a fluorescence detector. Total PAH sole concentrations from Bizerte and Ghar El Melh Lagoons were similar or lower to those recorded in other species from other regions across the world. In the studied fish species, the 2 and 3 ring PAHs are the dominated compounds that enter to the composition of PAHs which indicates that PAHs could be principally derived from a petrogenic origin for the both studied lagoons. The human health risk by sole consumption was evaluated and revealed to exhibit no hazard to the local population health concerning PAH intakes. The findings of this biomonitoring study will help in the implementation of sustainable environmental policies for effective water pollution control and the two investigated lagoons management.
Assuntos
Linguados , Hidrocarbonetos Policíclicos Aromáticos , Poluentes Químicos da Água , Animais , Bioacumulação , Monitoramento Ambiental , Humanos , Hidrocarbonetos Policíclicos Aromáticos/análise , Medição de Risco , Tunísia , Poluentes Químicos da Água/análiseRESUMO
A series of novel α-(diphenylphosphoryl)- and α-(diphenylphosphorothioyl)cycloalkanone oximes have been synthesized in search for novel bioactive molecules. Their structures were characterized by various spectroscopic methods including IR, NMR (1 H, 31 P, 13 C), mass spectrometry and single crystal X-ray diffraction. The newly synthesized phosphorus-containing oximes were screened for their inâ vitro antimicrobial activity against Gram-positive bacteria (Staphylococcus aureus and Bacillus subtilis), Gram-negative bacteria (Escherichia coli and Salmonella typhimurium) and fungal strains (Candida albicans and Candida glabrata). The biological assays showed that all the studied compounds exhibited high antibacterial and antifungal activities at only 0.1-2.1â µg/mL. In silico molecular docking studies in FabH enzyme active site were performed in order to predict the possible interaction modes and binding energies of the drug candidates at the molecular level.
Assuntos
Anti-Infecciosos/farmacologia , Oximas/química , Oximas/farmacologia , Anti-Infecciosos/química , Candida/efeitos dos fármacos , Cristalografia por Raios X , Bactérias Gram-Negativas/efeitos dos fármacos , Bactérias Gram-Positivas/efeitos dos fármacos , Testes de Sensibilidade Microbiana , Simulação de Acoplamento Molecular , Oximas/síntese química , Análise Espectral/métodos , Relação Estrutura-AtividadeRESUMO
Occurrence of traditional (PBDEs) and novel (HBB, PBEB, DBDPE) brominated flame retardants, as well as the natural compounds of MeO-PBDEs, were studied in a shellfish species (Hexaplex trunculus) sampled from Bizerte Lagoon. PBDE and MeO-PBDE mean concentrations in murex soft tissues were 187 and 264 ng g-1 lw respectively. The alternative flame retardants were not identified. The sum of PBDE and MeO-PBDE levels recorded in murex from the investigated aquatic ecosystem were comparable or a relatively lower than those reported for other organisms from other regions across the world. The amount of PBDE and MeO-PBDE concentrations from the Bizerte Lagoon recorded in murex were comparable or a relatively lower than those recorded from other areas across the world for other species. There is not a danger to the population health with regard to PBDE intakes associated with the consumption of murex in Bizerte city. We believe that this is the first study of the analysis of these pollutants in marine gastropod mollusks from Tunisian aquatic areas.
Assuntos
Monitoramento Ambiental/métodos , Retardadores de Chama/análise , Gastrópodes/química , Éteres Difenil Halogenados/análise , Hidrocarbonetos Bromados/análise , Poluentes Químicos da Água/análise , Animais , Ecossistema , Humanos , Medição de Risco , Frutos do Mar/análise , TunísiaRESUMO
Based on the broad spectrum of biological activities associated with organophosphates, a novel type of this class of compounds was synthesized, bearing a nitrile group, from the sodium alkoxide-catalyzed reaction of dialkylphosphites with γ-ketonitriles at 80°C under solvent-free conditions. A reaction mechanism involving a phospha-Brook type rearrangement is proposed. Eight title compounds were investigated for their in vitro inhibitory potency and selectivity against acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) using Ellman's spectrophotometric method. The synthesized derivatives exhibited mostly a moderate activity against both cholinesterases. The IC50 values for BChE were in a smaller concentration range (5.96-23.35µM) compared to those for AChE inhibition (9.61-53.74µM). The diethyl-3-cyano-1-p-tolylpropylphosphate which displayed the higher dual inhibitory potency towards both cholinesterases could be considered as a potential candidate for developing new drugs to treat Alzheimer's disease.
Assuntos
Acetilcolinesterase/metabolismo , Inibidores da Colinesterase/farmacologia , Organofosfatos/farmacologia , Inibidores da Colinesterase/síntese química , Inibidores da Colinesterase/química , Relação Dose-Resposta a Droga , Humanos , Simulação de Acoplamento Molecular , Estrutura Molecular , Organofosfatos/síntese química , Organofosfatos/química , Relação Estrutura-AtividadeRESUMO
The aims of the present study were to investigate the current exposure levels of persistent organochlorine compounds (OCs) in adipose tissues intraoperatively collected from 40 patients over 20 years undergoing non-cancer-related surgery residing in Northern region of Tunisia (Bizerte), which constitutes an exemplary case, and examined association between levels of contamination and both socio-demographic characteristics and dietary habits. Concentration of hexachlorobenzene (HCB), hexachlorocyclohexane isomers (α-HCH, ß-HCH, γ-HCH and δ-HCH), dichlorodiphenyltrichloroethane isomers (p,p'-DDT and o,p'-DDT) and metabolites (p,p'-DDE, o,p'-DDE, p,p'-DDD and o,p'-DDD) and 12 polychlorinated biphenyls (PCBs) congeners were measured using capillary gas chromatography with electron capture detector. Overall, residue levels of OCs followed the decreasing order of DDTs > PCBs > HCB > HCHs. DDTs levels ranged from 74.49 to 1834.76ngg-1 lipid and contributing to more than 90% to the sum of organochlorine pesticides (OCPs). p,p'-DDE was the most abundant in all samples and the p,p'-DDT/p,p'-DDE ratio (range between 1.85% and 58.45%) suggesting recent and ongoing exposure to banned commercial DDT products. PCB concentrations varied from 29.27 to 322.58ngg-1 lipid and PCB-180, PCB-153 and PCB-138 were the dominant congeners accounting for 70% of total PCBs. We did not find significant correlations between OC exposure levels and sex, parity, habitat areas and smoking habits. In females, the adipose tissue concentrations of DDTs, HCB and PCB-118 were positively correlated with age. There was statistically significant relationship between body mass index (BMI) changes and the adipose tissue levels of HCB and HCHs. No association was found between OCPs levels and dietary factors. However, our study suggests that fish consumption may be an important contributor of PCBs adipose tissue content of PCBs in Tunisian people. The presented work is highly significant, being the first study pointing out the chronic exposure to OCs in Bizerte.
Assuntos
Tecido Adiposo/química , Poluentes Ambientais/análise , Hidrocarbonetos Clorados/análise , Praguicidas/análise , Adulto , Fatores Etários , Idoso , Idoso de 80 Anos ou mais , Animais , Índice de Massa Corporal , Demografia , Monitoramento Ambiental , Comportamento Alimentar , Feminino , Peixes , Contaminação de Alimentos , Humanos , Masculino , Pessoa de Meia-Idade , Tunísia , Adulto JovemRESUMO
The present study investigates the quality of surface sediments from the Bizerte lagoon (North Tunisia) using an integrated approach including chemical contaminant analysis, bioassays and sediment quality guidelines (SQGs). Sediment samples were collected at 9 sites and analyzed for eight heavy metals (Hg, Cd, Cr, Cu, Pb, Zn, Ni, Fe and Mn). PAHs, PCBs, OCPs were measured previously in the same sediment samples. Our results indicated that the highest concentrations of metals were found near urban areas due to the municipial and industrial wastewater discharges. Sediment pollution assessment was carried out using geoaccumulation index and enrichment factor, which indicate a widespread pollution by Cd, Pb, Ni and Zn in the studied sediments. For bioassays, aqueous and organic extracts were used to assess toxicity and genotoxicity in sediments by using Microtox(®) and SOS Chromotest, respectively. Toxicity levels were compared to metallic and organic pollutants contents. Our results highlight differences in the pattern of responses between the different assays and show no correlation with all the studied contaminants, emphasizing the influence of other contaminants not analyzed in the present study. Based on SQGs, the results of toxicity assessment indicated that adverse effects caused by Ni and Zn would be expected frequently. Nickel was found to have the highest predicted acute toxicity, followed by Zn, Pb, Cd, Cu and Cr. There was no significant relationship between sediment toxicity calculated from heavy metal concentrations (SQG approach) and those measured with bioassays. These findings support the use of integrated approachs for evaluating the environmental risks of sediments.
Assuntos
Monitoramento Ambiental/métodos , Sedimentos Geológicos/química , Poluentes Químicos da Água/análise , Metais Pesados/análise , Bifenilos Policlorados/análise , Hidrocarbonetos Policíclicos Aromáticos/análise , Água do Mar/química , TunísiaRESUMO
Methoxylated polybrominated diphenyl ethers (MeO-PBDEs) were determined in 36 human milk samples collected in 2010 from healthy mothers living in Bizerte region from Tunisia. Gas chromatography coupled to mass spectrometry working with negative ion chemical ionization (GC-NCI-MS) was used to identify and quantify residue levels on a lipid basis of organo-brominated compounds. Among the 8 examined MeO-PBDE congeners 6-MeO-BDE-47, 2'-MeO-BDE-68, 4'-MeO-BDE-49 and 5'-MeO-BDE-100 were detected in human milk at different levels and frequencies. This is the first study reporting 5'-MeO-BDE-100 and 4'-MeO-BDE-49 levels in human milk samples. Levels of ∑MeO-PBDEs ranged from 0.23 to 4.70ngg(-)(1) lipid weight (lw) in the samples, with a mean and median value of 1.52 and 1.11ngg(-1)lw respectively. Concentrations of ∑MeO-PBDEs in human milk were negatively correlated with age of primapara mothers (p<0.05) and no age-dependency was observed for multipara mothers. Primapara mothers had higher levels of MeO-PBDEs than multipara mothers however no statistical significance was observed. A weak correlation between ∑PBDEs and ∑MeO-PBDEs was found but not between BDE-47 and its methoxylated analog 6-MeO-BDE-47, suggesting differences in exposure pathways for these contaminants in humans and further supporting the hypothesis that MeO-PBDEs were likely not only originated from PBDE precursors.
Assuntos
Exposição Ambiental , Éteres Difenil Halogenados/análise , Éteres Difenil Halogenados/metabolismo , Hidrocarbonetos Bromados/análise , Hidrocarbonetos Bromados/metabolismo , Leite Humano/química , Adulto , Fatores Etários , Monitoramento Ambiental , Poluentes Ambientais/análise , Poluentes Ambientais/metabolismo , Feminino , Cromatografia Gasosa-Espectrometria de Massas , Humanos , ParidadeRESUMO
The effects of exposure to a novel synthetic organophosphorus compound, 2-(4-Methoxyphenyl)-5, 6-trimethylene-4H-1, 3, 2-oxathiaphosphorine-2-sulfide (OMTOS) concentrations (Control=0, C1=0.01, C2=0.1, C3=1 and C4=10µg/L) were investigated in the clam Ruditapes decussatus. Vitellogenin (Vg)-like protein levels in haemolymph from males and females were investigated. Concentrations of 1µg/L and 10µg/L significantly decreased Vg levels in male haemolymph after 7 days, whereas significant variations were only found in females treated with 10µg/L. On the other hand, superoxide dismutase (SOD), catalase (CAT) and acetylcholinesterase activities (AChE) in whole soft tissue were measured after 2, 4 and 7 days of exposure to the same series of concentrations. After 2 days of exposure, 0.1, 1, and 10µg/L of OMTOS increased SOD activity significantly, but this decreased with 10µg/L after 4 and 7 days. No changes in CAT activity were observed after 2 days compared to controls. OMTOS significantly reduced AChE activity after 4 and 7 days in treated clams with the highest concentration 10µg/L, but it did not induce significant variations at the other concentrations tested. Our study demonstrates that OMTOS alters biochemical parameters in R. decussatus, even at low concentrations, and suggests differing modes of action of the contaminant. Using clams is a powerful tool to provide valuable insights into possible mechanisms of environmental toxicity of novel synthetic organic products both in non-target organisms and the marine ecosystem. Additionally, our results highlight that biomarker responses facilitate elucidation of putative mechanisms of action of OMTOS in non-target species.
Assuntos
Biomarcadores/metabolismo , Bivalves/efeitos dos fármacos , Compostos Organofosforados/toxicidade , Poluentes Químicos da Água/toxicidade , Acetilcolinesterase/metabolismo , Animais , Bivalves/metabolismo , Catalase/metabolismo , Fenômenos Químicos , Monitoramento Ambiental , Feminino , Hemolinfa/efeitos dos fármacos , Hemolinfa/metabolismo , Masculino , Compostos Organofosforados/química , Medição de Risco , Superóxido Dismutase/metabolismo , Tunísia , Vitelogeninas/metabolismo , Poluentes Químicos da Água/químicaRESUMO
Betaxolol (Bx) is a selective ß1 receptor blocker used in the treatment of hypertension and glaucoma. The aim of the present work was to demonstrate an approach involving use of liquid chromatography (LC) and liquid chromatography-electrospray ionization mass spectrometry (LC-ESI/MS) for the simultaneous separation, identification and characterization of impurities and of degradation products of betaxolol without their isolation from the reaction mixtures. At optimum condition, and according to ICH guidelines, the limit of detection (LOD) and limit of quantification (LOQ) for Bx are found to be 5.46 and 16.54 µg mL-1, respectively. However, the LOD and LOQ for the major degradation product P6 were 2.15 and 6.53 µg mL-1. Betaxolol was subjected to hydrolytic (acidic and basic) and oxidative, stress conditions according to International Conference on Harmonization (ICH) guideline Q1A (R2), and as results, the drug was found to be labile in acidic, basic and oxidative stress conditions. Based on LC-ESI/MS analysis, the found results revealed that Bx decomposes in acidic, basic and oxidizing environments. All degradation products were identified with the help of their fragmentation pattern and the masses obtained upon the MS analysis.
RESUMO
BACKGROUND: Mannich bases are an important class of compounds in medicinal chemistry with a wide spectrum of biological activities, however, knowledge on their toxicity is limited. MATERIALS AND METHODS: Two Mannich base hydrochlorides 1a (2-thienyl-ß-dimethylaminoethyl ketone hydrochloride) and 1b (ß-dimethylaminopropiophenone hydrochloride) were synthesized and characterized on the basis of their infrared and nuclear magnetic resonance spectral data. The potential effects of the synthesized compounds (5 mg/kg, i.p, during 30 days) on relative weight, hematological parameters, biochemical parameters, and neurotoxicity were tested using male Wistar rat. RESULTS: The results showed that compound 1b alters body weight on the first 10 days (182%, P < 0.01) and on the last 10 days (107%, P < 0.01) of treatment. The same treatment decreases food intake (P < 0.01) and increases water intake (P < 0.05). Both compounds induced a deficit on rotarod test manifested by a decrease of grasping time (1a: 65.33%, P < 0.01; 1b: 60.55%, P < 0.01) and fall time (1a: 59.75%, P < 0.01; 1b: 56.81%, P < 0.01) only on the last day of training. Moreover, Mannich base 1b decreases the liver relative weight (22.24%, P < 0.01). It was also observed that both products decrease the total serum cholesterol (Ch) levels (1a: 52.87%, P < 0.01; 1b: 64.70%, P < 0.01). Interestingly, compounds 1a and 1b affect hematological parameters manifested by an increase of the number of white blood cells (1a: 32.29%, P < 0.05; 1b: 20.64%, P < 0.05) and red blood cells (RBCs) (1a: 12.57%, P < 0.05; 1b: 20.11%, P < 0.05), an increase of red cell hemoglobin concentration (1a: 10.48%, P < 0.05; 1b: 16.12%, P < 0.05) and of the volume occupied by RBCs or hematocrit (1a: 18.28%, P < 0.05; 1b: 15.56%, P < 0.05), and an increase of the number of platelets (1a: 16.80%, P < 0.05; 1b: 39.96%, P < 0.05) accompanied by a decrease in hemoglobin level only with the compound 1a (7.41%, P < 0.05). CONCLUSION: These results show that both compounds 1a and 1b induced a hypoxia status associated to low level of Ch and liver toxicity. The deficit observed by rotarod could be explained by the myorelaxant effect of the used products.
RESUMO
Many studies have focused on aliphatic hydrocarbons and polycyclic aromatic hydrocarbons (AHs and PAHs) in different environmental compartments, especially atmospheric particles (aerosols), due to their adverse effects on the environment and human health. However, much less information is currently available on the content of AHs and PAHs in the atmospheric gas phase, which is a major reservoir of volatile and photoreactive compounds. Here, for the first time, we assessed the levels, gas-particle partitioning, human health risks and seasonal variations of AHs and PAHs in the atmospheric gas-phase of Bizerte city (Tunisia, North Africa) over a one-year period (March 2015-January 2016). Σ34PAH concentration in the gas phase over the period ranged from 6.7 to 90.6 ng m-3 and on average was 2.5 times higher in the cold season than in the warm season. Σ28AH concentration in the gas phase over the period ranged from 14.0 to 35.9 ng m-3, with no clear seasonal variations. In the gas phase, hydrocarbons were dominated by low-molecular-weight (LMW) compounds, i.e. 3- and 4-ring for PAHs and < n-C24 for AHs. Gas-phase concentrations of PAHs and AHs accounted for up to 80 % of the total (gas + particle phases) atmospheric concentrations of PAHs and AHs. Further analysis of gas-particle partitioning showed that LMW hydrocarbons preferential accumulated in the gas phase, and that gas-particle partitioning was not in equilibrium but dominated by absorption processes into the aerosol organic matter. Benzo[a]pyrene toxic equivalency quotient (BaP-TEQ) in the gas phase represented on average 37 % of the total atmospheric BaP-TEQ concentration, which was always higher in the cold season. Atmospheric gas is a significant factor in the risks of cancer associated with inhalation of ambient air. The Monte Carlo simulation-based exposure assessment model predicted that outdoor air exposure to PAHs does not pose a cancer risk to infants, but the children, adolescent, and adult populations may face a lower cancer risk during the warm season and a higher risk in the cold season.
Assuntos
Poluentes Atmosféricos , Neoplasias , Hidrocarbonetos Policíclicos Aromáticos , Adulto , Criança , Humanos , Adolescente , Poluentes Atmosféricos/análise , Monitoramento Ambiental , Tunísia , Hidrocarbonetos Policíclicos Aromáticos/análise , Medição de Risco , Aerossóis/análise , Material Particulado/análiseRESUMO
In spite of the fact that bromophenols (BPs) and hexabromocyclododecanes (HBCDs) are widely used as flame retardants, no data was available until now on the levels of these two chemicals in North Africa biota. Seafood products might represent one of the main sources of dietary exposure to persistent organic pollutants such as non-dioxin-like polychlorinated biphenyls (ndl-PCBs), brominated flame retardants (BFRs), and polycyclic aromatic hydrocarbons (PAHs). In this study, the concentrations of the ndl-PCBs, PAH4, and BFRs were determined in seafood products from a North African lagoon (Bizerte lagoon). Almost all the compounds were detected (15 out of 18) in the analyzed marine organisms. The accumulation of the contaminants followed the order BFRs > ndl-PCB > PAH4. Mean contaminants concentrations ranged from 0.35 to 28.7 ng g-1 ww for ∑ndl-PCBs; from below limit of quantification to 476 ng g-1 ww for ∑BFRs and from below limit of quantification to 5.30 ng g-1 ww for ∑PAH4. PCB 138, 153, and 180 were the most frequently detected ndl-PCB congeners due to their high resistance to metabolic degradation. 2,4-dibromophenol (2,4-DBP) was the predominant BFR. Chrysene (Chr) was found to be the main contributor to the total PAH4 concentration. Contaminant profiles varied significantly among seafood which may be due to the difference in lipid content, trophic level, feeding behavior, and metabolism. To assess the human health risks, the average daily dose exposure of ndl-PCBs, the dietary daily intake of PAHs and the estimated dietary intake of 3,3-,5,5-tetrabromobisphenol A (TBBPA) and HBCD from seafood were estimated. Findings indicated no adverse effects for human health from any of the analyzed contaminants, except for ndl-PCBs in eel.
Assuntos
Dioxinas , Retardadores de Chama , Bifenilos Policlorados , Humanos , Bifenilos Policlorados/análise , Tunísia , Retardadores de Chama/análise , Contaminação de Alimentos/análise , Alimentos Marinhos/análiseRESUMO
Microplastics (MPs) are emerging pollutants of global concern due to their pervasiveness, high sorption ability for persistent organic pollutants (POPs) and direct and indirect toxicity to marine organisms, ecosystems, as well as humans. As one of the major coastal interfaces, beaches are considered among the most affected ecosystems by MPs pollution. The morphological characteristics of MPs (pellets and fragments) collected from four beaches along the Tunisian coast and sorbed POPs, including polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs), were investigated in this study. The results showed that the MPs varied greatly in color, polymer composition and degradation degree. The color varied from colored to transparent and the most prevalent polymer identified using Raman spectroscopy was polyethylene. Scanning electron microscope (SEM) images exhibited various surface degradation features including cavities, cracks, attached diatom remains, etc. The concentrations of Σ12PCBs over all beaches ranged from 14 to 632 ng g-1 and 26 to 112 ng g-1 in the pellets and fragments, respectively, with a notable presence and dominance of highly-chlorinated PCBs such as CB-153 and -138. Among the OCPs, γ-HCH is the only compound detected with concentrations ranging from 0.4 to 9.7 ng g-1 and 0.7 to 4.2 ng g-1 in the pellets and fragments, respectively. Our findings indicate that MPs found on the Tunisian coast may pose a chemical risk to marine organisms as the concentrations of PCBs and γ-HCH in most of the analysed samples exceeded the sediment-quality guidelines (SQG), especially the effects range medium (ERM) and the probable effects level (PEL). As the first report of its kind, the information gathered in this study can serve as the baseline and starting point for future monitoring work for Tunisia and neighbouring countries, as well as for stakeholders and coastal managers in decision-making processes.
Assuntos
Poluentes Ambientais , Hidrocarbonetos Clorados , Praguicidas , Bifenilos Policlorados , Poluentes Químicos da Água , Humanos , Ecossistema , Monitoramento Ambiental/métodos , Poluentes Ambientais/análise , Hexaclorocicloexano/análise , Hidrocarbonetos Clorados/análise , Mar Mediterrâneo , Microplásticos , Poluentes Orgânicos Persistentes , Praguicidas/análise , Plásticos/análise , Bifenilos Policlorados/análise , Tunísia , Poluentes Químicos da Água/análise , AnimaisRESUMO
We investigated the occurrence, origin, and potential ecological risk of dissolved polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyl (PCBs) and organochlorine pesticides (OCPs) in 27 surface water samples collected from a highly anthropized and industrialized area in the Gulf of Gabès (Tunisia, Southern Mediterranean Sea) in October-November 2017. The results demonstrated a wide range of concentrations (ng L-1) with the following decreasing order: Æ©16 PAHs (17.6-71.2) > Æ©20 PCBs (2.9-33.7) > Æ©6 DDTs (1.1-12.1) > Æ©4 HCHs (1.1-14.8). Selected diagnostic ratios indicated a mixture of both pyrolytic and petrogenic sources of PAHs, with a predominance of petrogenic sources. PCB compositions showed distinct contamination signatures for tetra- to hepta-chlorinated PCBs, characteristic of contamination by commercial (Aroclor) PCB mixtures. The dominant OCP congeners were γ-HCH, 2,4'-DDD and 2,4'-DDE, reflecting past use of Lindane and DDTs in the study area. Agricultural, industrial and domestic activities, as well as atmospheric transport are identified as potential sources of PAHs, PCBs and OCPs in surface waters of the Gulf of Gabès. Toxic equivalents (TEQs) suggested a low carcinogenic potential for PAHs in seawater samples (mean of 0.14 ng TEQ L-1). Evaluation of risk coefficients revealed low risk for PAHs and PCBs, and moderate to severe risk for OCPs.
Assuntos
Hidrocarbonetos Clorados , Praguicidas , Bifenilos Policlorados , Hidrocarbonetos Policíclicos Aromáticos , Poluentes Químicos da Água , Monitoramento Ambiental , Hexaclorocicloexano/análise , Hidrocarbonetos Clorados/análise , Mar Mediterrâneo , Praguicidas/análise , Bifenilos Policlorados/análise , Hidrocarbonetos Policíclicos Aromáticos/análise , Tunísia , Poluentes Químicos da Água/análiseRESUMO
An efficient and simple approach has been developed for the synthesis of unprecedented 4,5-diphosphonyldihydropyridazines and 3,4-diphosphonylpyrroles, through the condensation of bisphosphonylallenes with hydrazines and primary amines, respectively. The reactions proceed under operationally simple, mild, and catalyst-free conditions, for a wide substrate scope. The synthesized compounds were screened for their antiproliferative activity against melanoma cancer cells, and they showed promising growth inhibition.
RESUMO
An efficient and simple approach has been developed for the synthesis of eight dialkyl/aryl[(5-phenyl-1,3,4-oxadiazol-2-ylamino)(aryl)methyl]phosphonates through the Pudovik-type reaction of dialkyl/arylphosphite with imines, obtained from 5-phenyl-1,3,4-oxadiazol-2-amine and aromatic aldehydes, under microwave irradiation. Five of them were hydrolyzed to lead to the corresponding phosphonic acids. Selected synthesized compounds were screened for their in vitro antiviral activity against the avian bronchitis virus (IBV). In the MTT cytotoxicity assay, the dose-response curve showed that all test compounds were safe in the range concentration of 540-1599 µM. The direct contact of novel synthesized compounds with IBV showed that the diethyl[(5-phenyl-1,3,4-oxadiazol-2-ylamino)(4-trifluoromethoxyphenyl)methyl]phosphonate (5f) (at 33 µM) and the [(5-phenyl-1,3,4-oxadiazol-2-ylamino)(4-trifluoromethylphenyl)methyl] phosphonic acid (6a) (at 1.23 µM) strongly inhibited the IBV infectivity, indicating their high virucidal activity. However, virus titers from IBV-infected Vero cells remained unchanged in response to treatment with the lowest non-cytotoxic concentrations of synthesized compounds suggesting their incapacity to inhibit the virus replication inside the host cell. Lack of antiviral activity might presumably be ascribed to their polarity that hampers their diffusion across the lipophilic cytoplasmic membrane. Therefore, the interactions of 5f and 6a were analyzed against the main coronavirus protease, papain-like protease, and nucleocapsid protein by molecular docking methods. Nevertheless, the novel 1,3,4-oxadiazole-based α-aminophosphonic acids and α-amino-phosphonates hold potential for developing new hygienic virucidal products for domestic, chemical, and medical uses.
RESUMO
A selective molecularly imprinted polymer (MIP) adsorbent was synthesised and used in a batch micro-solid phase extraction format for isolating aflatoxins (AFB1, and AFB2) from non-dairy beverages before liquid chromatography-tandem mass spectrometry determination. MIP synthesis (precipitation polymerization in 3 : 1 acetonitrile/toluene as a porogen) was performed with 5,7-dimethoxycoumarin (DMC), methacrylic acid (MAA) and divinylbenzene-80 (DVB) as a dummy template, functional monomer and cross-linker, respectively (1 : 4 : 20 molar ratio). 2,2'-Azobisisobutyronitrile (AIBN) was used as a polymerization initiator. The adsorbent MIP (50 mg) was enclosed in a cone-shaped polypropylene membrane (porous membrane protected molecularly imprinted micro-solid phase extraction), and parameters such as sample pH, mechanical (orbital-horizontal) shaking, the extraction time (loading stage), the composition of the eluting solution, and the desorption time were optimised. The highest extraction yields were obtained by using 5 mL of non-dairy beverages (pH adjusted at 6.0), and mechanical shaking (150 rpm) for 15 min. Elution was performed with 5 mL of an acetonitrile/formic acid (97.5 : 2.5) mixture under ultrasound (325 W, 35 kHz) for 15 min. After eluate evaporation to dryness and re-dissolution in 150 µL of the mobile phase, the pre-concentration factor of the method was 33.3, which yields limits of detection within the 0.085-0.207 µg L-1 range. In addition, the current proposal was shown to be an accurate and precise method through relative standard deviation of intraday and inter-day assays below 18% and analytical recoveries in the range of 91-104%. However, the method was found to suffer from matrix effects.
Assuntos
Aflatoxinas , Impressão Molecular , Aflatoxinas/análise , Bebidas , Cromatografia Líquida de Alta Pressão , Cromatografia Líquida , Polímeros Molecularmente Impressos , Polímeros , Extração em Fase Sólida , Espectrometria de Massas em TandemRESUMO
Organophosphorus derivatives are widely used in human health care and have been detected in aquatic ecosystems. These compounds may pose significant risks to non-target exposed organisms and only limited studies are available on bioconcentration and the effects of organophosphorus derivatives on marine organisms. The aim of this work was to evaluate the possible toxic effects of two concentrations (20 and 40 µg/L) of γ-oximo- and γ-amino-phosphonates and phosphine oxides in mediterranean clams Ruditapes decussatus exposed for 14 days using different biomarkers and the changes of filtration and respiration rate. The use of clams in ecotoxicity evaluation is thus mandatory to assess the feasibility of assessing oxidative stress on R. decussatus after being exposed to γ-oximo- and γ-amino-phosphonates and phosphine oxides. The oxidative status was analyzed by measuring oxidative stress biomarkers RNS and ROS production in mitochondria, superoxide dismutase (SOD), catalase (CAT), glutathione-S-transferases (GSTs), lipid peroxidation (LPO) and acetylcholinesterase (AChE), whose alteration was indicative of organophosphorus exposure, in both gills and digestive gland of the clams. No significant alterations in RNS, ROS production, SOD, CAT and AChE activities and MDA content were observed in both organs of clams treated with γ-oximophosphine oxides. It was possible then to hypothesize that γ-oximophosphine oxides may have probably exerted an incomplete alteration of antioxidant defenses and damage, which was changed by the activation of defense mechanisms. On the contrary, oxidative stress parameters were changed after exposure to γ-amino-phosphonates and phosphine oxides. In addition, metals accumulation, filtration and respiration rates were altered following exposure to all the studied organophosphorus compounds.