Potentiometric Determination of Dopamine Using a Solid-Contact Polymeric Membrane Ion-Selective Electrode

A simple solid-contact polymeric membrane ion-selective electrode for determination of dopamine was developed. The electrode is fabricated with polymeric membranes incorporating heptakis(2,3,6-tri-o-methyl)-beta-cyclodextrin as ionophore and sodium trakis[3,5-bis(trifluoromethyl)phenyl]borate as ionic additive. Using hydrophobic poly(3-octylthiophene) as solid-contact transducer, the sensor displays a stable potential response for detection of dopamine in 2 mM HAc-NaAc buffer solution (pH 4.4) within a wide concentration range of 3.0 x 10(-5) M-1.0 x 10(-3) M with a sub-Nernstian slope of 43.8 +/- 0.5 mV/dec. The detection limit calculated as the intersection of the two slope lines is 1.3 x 10(-5) M. The electrode exhibits good selectivity over inorganic ions, pharmaceutical excipients and ascorbic acid. In addition, the electrode shows a stable potential response over a wide pH range of 4.0 to 8.5, fast response time (less than 10 s) and excellent repeatability. The proposed electrode has been successfully applied for direct potentiometric determination of dopamine in pharmaceutical formulation without pretreatment procedures

Proteomic responses reveal the differential effects induced by cadmium in mussels Mytilus galloprovincialis at early life stages

Cadmium (Cd) has become an important metal contaminant and posed severe risk on the organisms in the coastal environments of the Bohai Sea. Marine mussel Mytilus galloprovincialis is widely distributed along the Bohai coast and consumed as seafood by local residents. Evidences indicate that the early stages of marine organisms are more sensitive to metal contaminants. In this study, we applied two-dimensional electrophoresis-based proteomics to characterize the biological effects of Cd (50 mu g L-1) in the early life stages (D-shape larval and juvenile) of mussels. The different proteomic responses demonstrated the differential responsive mechanisms to Cd exposure in these two early life stages of mussels. In details, results indicated that Cd mainly induced immune and oxidative stresses in both D-shape larval and juvenile mussels via different pathways. In addition, the significant up-regulation of triosephosphate isomerase and metallothionein confirmed the enhanced energy demand and mobilized detoxification mechanism in D-shape larval mussels exposed to Cd. In juvenile mussels, Cd exposure also induced clear apoptosis. Overall, this work suggests that Cd is a potential immune toxicant to mussel M. galloprovincialis at early life stages. (C) 2016 Elsevier Ltd. All rights reserved

An integrated proteomic and metabolomic study on the gender-specific responses of mussels Mytilus galloprovincialis to tetrabromobisphenol A (TBBPA)

Tetrabromobisphenol A (TBBPA), accounting for the largest production of brominated flame-retardants (BFRs) along the Laizhou Bay in China, is of great concern due to its diverse toxicities. In this study, we focused on the gender-specific responses of TBBPA in mussel Mytilus galloprovincialis using an integrated proteomic and metabolomic approach. After exposure of TBBPA (10 mu g L-1) for one month, a total of 9 metabolites and 67 proteins were altered in mussel gills from exposed group. The significant changes of metabolites in female mussel gills from exposed group exhibited the disturbances in energy metabolism and osmotic regulation, while in male samples only be found the variation of metabolites related to osmotic regulation. iTRAQ-based proteomic analysis showed biological differences between male and female mussel gills from solvent control group. The higher levels of proteins related to primary and energy metabolism and defense mechanisms in male mussel gills meant a greater anti-stress capability of male mussels. Further analysis revealed that TBBPA exposure affected multiple biological processes consisting of production and development, material and energy metabolism, signal transduction, gene expression, defense mechanisms and apoptosis in both male and female mussels with different mechanisms. Specially, the responsive proteins of TBBPA in male mussels signified higher tolerance limits than those in female individuals, which was consistent with the biological differences between male and female mussel gills from solvent control group. This work suggested that the gender differences should be considered in ecotoxicology. (C) 2015 Elsevier Ltd. All rights reserved

In Situ ATR-FTIR Investigation of Photodegradation of 3,4-Dihydroxybenzoic Acid on TiO2

The catalytic photo-oxidation of 3,4-dihydroxybenzoic acid on TiO2 has been studied by in situ ATR-FTIR in flowing water and in flowing wet air/nitrogen gas. In flowing water it was difficult to observe photodegradation intermediates despite photocatalytic action during UV illumination. In the flowing wet air/nitrogen system carboxylic acids and carbonates were observed. It was shown that water plays an important role in the formation of oxidation active species. Oxygen shows a prominent role for carboxylic acid degradation, but the photogenerated hole plays the important role for the 3,4-dihydroxybenzoic acid ring cleavage

Removal of phenanthrene from coastal waters by green tide algae Ulva prolifera

Ulva prolifera (U. prolifera) has been frequently involved in terrible algal proliferation in coastal areas. Although it is known to be associated with green tide, its contribution to the natural attenuation of the polycyclic aromatic hydrocarbons (PAHs) in seawater has not been evaluated. In this study, the removal of phenanthrene using U. prolifera collected from coastal water with green tide blooming was investigated. The results showed that phenanthrene could be removed efficiently in the presence of both the live and heat-killed U. prolifera. The phenanthrene concentrations of the live algae treatment decreased smoothly from 10.00 to 0.80 mu g L-1 through the whole process, while those of the heat-killed algae treatment decreased sharply from 10.0 to 2.71 mu g L-1 in one day and kept constantly after that. The in situ monitoring and visualizing using laser confocal scanning microscopy (LCSM) confirmed the accumulation of phenanthrene in U. prolifera. The increase in nutrient and temperature led to the increase of phenanthrene removal rate, while the salinity had less influence on the removal of phenanthrene. The removal efficiency by U. prolifera had a good linear relationship with phenanthrene initial concentration (r(2) = 0.999) even at 100 mu g L-1 which was higher than its environmentally relevant concentrations. High removal efficiency (91.3%) was observed when the initial phenanthrene concentration was set at environmental relevant concentration (5 mu g L-1). Results of this study demonstrate a potential new natural attenuation process for typical PAHs in coastal water during the outbreak of green tide. These findings indicate that the outbreak of harmful green tide algae may bring positive environmental benefits in the terms of the removal of harmful organic pollutants from coastal waters. (C) 2017 Elsevier B.V. All rights reserved.</p

Ultrasensitive surface-enhanced Raman scattering detection of trypsin based on anti-aggregation of 4-mercaptopyridine-functionalized silver nanoparticles: an optical sensing platform toward proteases

In this work, a simple and sensitive surface-enhanced Raman scattering (SERS) strategy was developed for recognition and detection of trypsin, by using anti-aggregation of 4-mercaptopyridine (4-MPY)-functionalized silver nanoparticles (AgNPs) based on the interaction between protamine and trypsin. The polycationic protamine not only served as a substrate for enzyme hydrolysis but also worked as a medium for SERS enhancement, which could bind negatively charged 4-MPY-functionalized AgNPs and induce their aggregation. The hydrolysis catalyzed with trypsin in sample solution decreased the concentration of free protamine, resulting in the dispersion of AgNPs and thus decreasing the Raman intensity of 4-MPY, by which the trypsin could be sensed optically. A detection level down to 0.1 ng mL(-1) for trypsin was obtained. The induced accumulation of AgNPs modified with Raman reporter 4-MPY largely enhanced the SERS responses. A good linearity was found within the wide range over five orders of magnitude and reasonable relative standard deviations (between 2.4 and 11.6%) were attained. By using trypsin as a model, the new concept can provide an excellent platform for ultrasensitive SERS measurements of various proteases/enzymes which can lead to nanoparticles stability change through catalyzed hydrolysis toward substrate.In this work, a simple and sensitive surface-enhanced Raman scattering (SERS) strategy was developed for recognition and detection of trypsin, by using anti-aggregation of 4-mercaptopyridine (4-MPY)-functionalized silver nanoparticles (AgNPs) based on the interaction between protamine and trypsin. The polycationic protamine not only served as a substrate for enzyme hydrolysis but also worked as a medium for SERS enhancement, which could bind negatively charged 4-MPY-functionalized AgNPs and induce their aggregation. The hydrolysis catalyzed with trypsin in sample solution decreased the concentration of free protamine, resulting in the dispersion of AgNPs and thus decreasing the Raman intensity of 4-MPY, by which the trypsin could be sensed optically. A detection level down to 0.1 ng mL(-1) for trypsin was obtained. The induced accumulation of AgNPs modified with Raman reporter 4-MPY largely enhanced the SERS responses. A good linearity was found within the wide range over five orders of magnitude and reasonable relative standard deviations (between 2.4 and 11.6%) were attained. By using trypsin as a model, the new concept can provide an excellent platform for ultrasensitive SERS measurements of various proteases/enzymes which can lead to nanoparticles stability change through catalyzed hydrolysis toward substrate

Per- and poly-fluoroalkyl substances (PFASs) in the urban, industrial, and background atmosphere of Northeastern China coast around the Bohai Sea: Occurrence, partitioning, and seasonal variation

Air samples were collected using high-volume samplers at two coastal towns on the Bohai Sea in China, 320 km apart, and at a background site (North Huangcheng Island) in the Bohai Sea, 50 km from the coast. A suite of neutral and ionic per- and poly-fluoroalkyl substances (PFASs) was investigated. Urban activity was related to high levels of neutral PFASs at Tianjin while perfluorooctanoic carboxylic acid (PFOA) was dominant in the atmosphere at Weifang, possibly due to industrial sources. Polyfluoroalkyl phosphoric acid diesters (diPAPs) occurred in the particle phase only, with a total concentration range of 0.02-6.72 pg m(-3). The dominant homologue was 6:2 diPAP. PFASs profiles at NHI suggested direct atmospheric transport of neutral and ionic PFASs from source regions. Temperature-dependent partitioning of fluorotelomer alcohols (FTOHS) was observed in winter, when total concentrations and particle-phase fractions of FTOHs were significantly higher as compared to those in summer. Correlation analyses suggested more active gas-phase degradation of FTOHs in summer and likely heterogeneous degradation in both seasons. Overall, it is necessary to account for ionic PFASs in both gas and particle phases and particulate matter was important for atmospheric transport and for determining the fate of PFASs, especially in areas close to a source region. (C) 2017 Elsevier Ltd. All rights reserved.</p

A Potentiometric Flow Biosensor Based on Ammonia-Oxidizing Bacteria for the Detection of Toxicity in Water

A flow biosensor for the detection of toxicity in water using the ammonia-oxidizing bacterium (AOB) Nitrosomonas europaea as a bioreceptor and a polymeric membrane ammonium-selective electrode as a transducer is described. The system is based on the inhibition effects of toxicants on the activity of AOB, which can be evaluated by measuring the ammonium consumption rates with the ammonium-selective membrane electrode. The AOB cells are immobilized on polyethersulfone membranes packed in a holder, while the membrane electrode is placed downstream in the flow cell. Two specific inhibitors of the ammonia oxidation. allylthiourea and thioacetamide. have been tested. The IC50 values defined as the concentration of an inhibitor causing a 50% reduction in the ammonia oxidation activity have been measured as 0.17 mu M and 0.46 mu M for allylthiourea and thioacetamide, respectively. The proposed sensor offers advantages of simplicity, speed and high sensitivity for measuring toxicity in water.A flow biosensor for the detection of toxicity in water using the ammonia-oxidizing bacterium (AOB) Nitrosomonas europaea as a bioreceptor and a polymeric membrane ammonium-selective electrode as a transducer is described. The system is based on the inhibition effects of toxicants on the activity of AOB, which can be evaluated by measuring the ammonium consumption rates with the ammonium-selective membrane electrode. The AOB cells are immobilized on polyethersulfone membranes packed in a holder, while the membrane electrode is placed downstream in the flow cell. Two specific inhibitors of the ammonia oxidation. allylthiourea and thioacetamide. have been tested. The IC50 values defined as the concentration of an inhibitor causing a 50% reduction in the ammonia oxidation activity have been measured as 0.17 mu M and 0.46 mu M for allylthiourea and thioacetamide, respectively. The proposed sensor offers advantages of simplicity, speed and high sensitivity for measuring toxicity in water

Occurrences and distribution characteristics of organophosphate ester flame retardants and plasticizers in the sediments of the Bohai and Yellow Seas, China

Concentrations and distribution characteristics of organophosphate esters (OPEs) in surface sediment samples were analyzed and discussed for the first time in the open Bohai Sea (BS) and YellowSea (YS). Three halogenated OPEs [ tris-(2-chloroethyl) phosphate (TCEP), tris-(1-chloro-2-propyl) phosphate (TCPP), and tris-(1,3-dichloro2- propyl) phosphate (TDCPP)] and five non-halogenated OPEs [ tri-isobutyl phosphate (TiBP), tri-n-butyl phosphate (TnBP), tripentyl phosphate (TPeP), triphenyl phosphate (TPhP) and tris-(2-ethylhexyl) phosphate (TEHP)] were detected in this region. The concentrations of eight OPEs in total (Sigma 8OPEs) ranged from 83 to 4552 pg g(-1) dry weight (dw). The halogenated OPEs showed higher abundances than the non-halogenated ones did, with TCEP, TCPP, and TEHP the main compounds. Generally, concentrations of OPEs in the BS were higher than those in the YS. Riverine input (mainly the Changjiang DilutedWater (CDW)) and deposition effect in the mud areas might have influenced the spatial distributions of OPEs. Correlation between OPE concentrations and total organic carbon (TOC) indicated TOC was an effective indicator for the distribution of OPEs. Inventory analysis of OPEs implied that sea sediment might not be the major reservoir of these compounds. (C) 2017 Elsevier B.V. All rights reserved.</p

Dual cloud point extraction coupled with hydrodynamic-electrokinetic two-step injection followed by micellar electrokinetic chromatography for simultaneous determination of trace phenolic estrogens in water samples

A dual cloud point extraction (dCPE) off-line enrichment procedure coupled with a hydrodynamic-electrokinetic two-step injection online enrichment technique was successfully developed for simultaneous preconcentration of trace phenolic estrogens (hexestrol, dienestrol, and diethylstilbestrol) in water samples followed by micellar electrokinetic chromatography (MEKC) analysis. Several parameters affecting the extraction and online injection conditions were optimized. Under optimal dCPE-two-step injection-MEKC conditions, detection limits of 7.9-8.9 ng/mL and good linearity in the range from 0.05 to 5 mu g/mL with correlation coefficients R (2) a parts per thousand yenaEuro parts per thousand 0.9990 were achieved. Satisfactory recoveries ranging from 83 to 108 % were obtained with lake and tap water spiked at 0.1 and 0.5 mu g/mL, respectively, with relative standard deviations (n = 6) of 1.3-3.1 %. This method was demonstrated to be convenient, rapid, cost-effective, and environmentally benign, and could be used as an alternative to existing methods for analyzing trace residues of phenolic estrogens in water samples.A dual cloud point extraction (dCPE) off-line enrichment procedure coupled with a hydrodynamic-electrokinetic two-step injection online enrichment technique was successfully developed for simultaneous preconcentration of trace phenolic estrogens (hexestrol, dienestrol, and diethylstilbestrol) in water samples followed by micellar electrokinetic chromatography (MEKC) analysis. Several parameters affecting the extraction and online injection conditions were optimized. Under optimal dCPE-two-step injection-MEKC conditions, detection limits of 7.9-8.9 ng/mL and good linearity in the range from 0.05 to 5 mu g/mL with correlation coefficients R (2) a parts per thousand yenaEuro parts per thousand 0.9990 were achieved. Satisfactory recoveries ranging from 83 to 108 % were obtained with lake and tap water spiked at 0.1 and 0.5 mu g/mL, respectively, with relative standard deviations (n = 6) of 1.3-3.1 %. This method was demonstrated to be convenient, rapid, cost-effective, and environmentally benign, and could be used as an alternative to existing methods for analyzing trace residues of phenolic estrogens in water samples