Bioactive Hydrogel Layers on Microdisk Electrode Arrays: Impedimetric Characterization and Equivalent Circuit Modeling

Microfabricated microdisk electrode arrays (MDEAs) of 50 μm (5184 disks), 100 μm (1296 disks) and 250 μm (207 disks) (d/r=4; A= 0.1 cm²) were coated with poly(hydroxyethylmethacrylate)‐based hydrogel membranes and studied by electrochemical impedance spectroscopy (EIS) in 1.0 mM ferrocene monocarboxylic acid (FcCO₂H). Equivalent circuit modeling showed an approximate three‐fold increase in solution resistance, R_sol, and an order of magnitude increase in charge transfer resistance, R_ct, resulting from a reduction in apparent diffusivity of FcCO₂H. Additionally, both resistive parameters decreased while the capacitance (Q) increased with decreasing microdisk diameter; consistent with an increase in effective electroactive area. The hydrogel layer did not compromise enhanced mass transport achieved by the MDEA and thus may be used to advantage in biosensors.     

Strategies for the elimination of matrix effects in the liquid chromatography tandem mass spectrometry analysis of the lipophilic toxins okadaic acid and azaspiracid-1 in molluscan shellfish

Considerable efforts are being made worldwide to replace in vivo assays with instrumental methods of analysis for the monitoring of marine biotoxins in shellfish. Analysis of these compounds by the preferred technique of liquid chromatography tandem mass spectrometry (LC-MS/MS) is challenged by matrix effects associated with the shellfish tissues. In methods validation, assessment of matrix interferences is imperative to ensure the validity and accuracy of results being produced. Matrix interferences for the analysis of okadaic acid (OA) and azaspiracid 1 (AZA1) were assessed using acidic methods on electrospray triple stage quadrupole (TSQ) and hybrid quadrupole time of flight (QToF) instruments by the use of matrix matched standards for different tissue types. Using an acidic method no matrix interference and suppression was observed on the TSQ for OA and AZA1 respectively, whilst the opposite was observed on the QToF; matrix enhancement for OA and no matrix interference for AZA1. The suppression of AZAs on the TSQ was found to be due to interfering compounds being carried over from previous injections. The degree of suppression is very much dependant on the tissue type ranging from 15 to 70%. Several strategies were evaluated to eliminate these interferences, including the partitioning of the extract with hexane, optimisation of the chromatographic method and the use of on-line SPE. Hexane clean up did not have any impact on matrix effects. The use of an alkaline method and a modified acidic method eliminated matrix suppression for AZA1 on the TSQ instrument while an on-line SPE method proved to be effective for matrix enhancement of OA on the QToF.     

Ionic liquids supported on magnetic nanoparticles as a sorbent preconcentration material for sulfonylurea herbicides prior to their determination by capillary liquid chromatography

A magnetic material based on N-methylimidazolium ionic liquid and Fe(3)O(4) magnetic nanoparticles incorporated in a silica matrix has been used to extract and preconcentrate sulfonylurea herbicides, such as thifensulfuron methyl (TSM), metsulfuron methyl (MSM), triasulfuron (TS), tribenuron methyl (TBM) and primisulfuron methyl (PSM) from polluted water samples, prior to their analysis by capillary liquid chromatography with a diode array detector (DAD). Under the optimum conditions, this method allows the determination of TSM, MSM, TS, TBM and PSM in a linear range between 5 and 100 ng mL(-1), with relative standard deviation values lower than 5.3% (n = 10), in all cases. Detection limits ranging between 1.13 and 2.95 ng mL(-1) were achieved. The usefulness of the proposed method was demonstrated by the analysis of river water samples, obtaining recoveries higher than 91%.     

Phase synchronization of bursting neural networks with electrical and delayed dynamic chemical couplings

Diffusive electrical connections in neuronal networks are instantaneous, while excitatoryor inhibitory couplings through chemical synapses contain a transmission time-delay.Moreover, chemical synapses are nonlinear dynamical systems whose behavior can bedescribed by nonlinear differential equations. In this work, neuronal networks withdiffusive electrical couplings and time-delayed dynamic chemical couplings are considered.We investigate the effects of distributed time delays on phase synchronization of burstingneurons. We observe that in both excitatory and Inhibitory chemical connections, the phasesynchronization might be enhanced when time-delay is taken into account. This distributedtime delay can induce a variety of phase-coherent dynamical behaviors. We also study thecollective dynamics of network of bursting neurons. The network model presents theso-called Small-World property, encompassing neurons whose dynamics have two time scales(fast and slow time scales). The neuron parameters in such Small-World network, aresupposed to be slightly different such that, there may be synchronization of the bursting(slow) activity if the coupling strengths are large enough. Bounds for the criticalcoupling strengths to obtain burst synchronization in terms of the network structure aregiven. Our studies show that the network synchronizability is improved, as itsheterogeneity is reduced. The roles of synaptic parameters, more precisely those of thecoupling strengths and the network size are also investigated.     

In Situ Synthesis of Self‐Assembled Gold Nanoparticles on Glass or Silicon Substrates through Reactive Inkjet Printing

A facile and low cost method for the synthesis of self‐assembled nanoparticles (NPs) with minimal size variation and chemical waste by using reactive inkjet printing was developed. Gold NPs with diameters as small as (8±2) nm can be made at low temperature (120 °C). The size of the resulting NPs can be readily controlled through the concentration of the gold precursor and oleylamine ink. The pure gold composition of the synthesized NPs was confirmed by energy‐dispersive X‐ray spectroscopy (EDXS) analysis. High‐resolution SEM (HRSEM) and TEM (HRTEM), and X‐ray diffraction revealed their size and face‐centered cubic (fcc) crystal structure, respectively. Owing to the high density of the NP film, UV/Vis spectroscopy showed a red shift in the intrinsic plasmonic resonance peak. We envision the extension of this approach to the synthesis of other nanomaterials and the production of tailored functional nanomaterials and devices.     

Stereoselective and Convenient Synthesis of Diethyl (E)-α-Triphenylstannyl or (Z)-α-Tributylstannyl α-Alkenylphosphonates

Diethyl (E)-α-triphenylstannyl or (Z)-α-tri-n-butylstannyl α-alkenylphosphonates are conveniently and stereoselectively prepared using a “tin-Peterson-like” reaction. Protonolysis of the carbon-tin bond of α-tributylstannyl derivatives proved to be easy and stereospecific.     

Bioactive Hydrogel Layers on Microdisk Electrode Arrays: Cyclic Voltammetry Experiments and Simulations

Poly(hydroxyethylmethacrylate)‐based hydrogel membranes were applied to microfabricated, microdisk electrode arrays (MDEAs) of 50 μm (5184 disks), 100 μm (1296 disks) and 250 μm (207 disks) (d/r=4; A= 0.1 cm²) and studied by cyclic voltammetry (CV) in 1.0 mM ferrocene monocarboxylic acid (FcCO₂H). The membrane produced an order of magnitude decrease in current densities and a shift to quasi reversibility due to a decrease in the D_appt of FcCO₂H, from 4.51×10^?6 cm² s^?1 to 1.42×10^?8 cm² s^?1, (2.18×10^?8 cm² s^?1 from release experiments). The MDEA050 (comprising 50 μm disks) maintained its enhanced current density attributes confirming its value as an effective electrode for biosensors. Finite element modeling (FEM) simulations successfully replicated the voltammograms of the MDEAs.     

Sawdust for the Removal of Heavy Metals from Water: A Review

The threat of the accumulation of heavy metals in wastewater is increasing, due to their abilities to inflict damage to human health, especially in the past decade. The world’s environmental agencies are trying to issue several regulations that allow the management and control of random disposals of heavy metals. Scientific studies have heavily focused on finding suitable materials and techniques for the purification of wastewaters, but most solutions have been rejected due to cost-related issues. Several potential materials for this objective have been found and have been compared to determine the most suitable material for the purification process. Sawdust, among all the materials investigated, shows high potential and very promising results. Sawdust has been shown to have a good structure suitable for water purification processes. Parameters affecting the adsorption mechanism of heavy metals into sawdust have been studied and it has been shown that pH, contact time and several other parameters could play a major role in improving the adsorption process. The adsorption was found to follow the Langmuir or Freundlich isotherm and a pseudo second-order kinetic model, meaning that the type of adsorption was a chemisorption. Sawdust has major advantages to be considered and is one of the most promising materials to solve the wastewater problem.     

Numerical simulation of flow over urban-like topographies and evaluation of turbulence temporal attributes

We have used large-eddy simulation with an immersed boundary method to study turbulent flows over distributions of uniform height, staggered cubes. The computational domains were designed such that both the roughness sublayer and a region of the inertial layer are resolved. With this, we record vertical profiles of time series of fluctuating streamwise and vertical velocity at different locations throughout the domain. Contour images of these fluctuating quantities shown relative to elevation and time are studied; contour images of Reynolds shear stresses owing to ‘sweeps’ and ‘ejections’ are also studied. These images show that periods of momentum excess (deficit) in the inertial-layer precede excitation (subdual) of cube-scale coherent vortices in the roughness sublayer. We compute this time lag (termed advective lag) and demonstrate that it scales linearly with wall-normal elevation. The advective lag is attributed to coherent, low- and high-momentum regions in the aloft inertial layer. Vortex identification is used to illustrate the presence of hairpin packets encapsulating low-momentum regions. Based on this, the reported inclination angle associated with hairpin packets is used to guide the development of a model for prediction of advective lag with height. The model captures the advective lag profiles reasonably well. In the interest of generality, additional cases of flow over homogeneous roughness (aerodynamic drag imposed with the equilibrium logarithmic law) are considered. We again observe that advective lag scales linearly with wall-normal elevation. Advective lag predictions from the aforementioned model agree well with results for these cases.