Electrochemical determination of nitrate with nitrate reductase-immobilized electrodes under ambient air

Nitrate monitoring biosensors were prepared by immobilizing nitrate reductase derived from yeast on a glassy carbon electrode (GCE, d = 3 mm) or screen-printed carbon paste electrode (SPCE, d = 3 mm) using a polymer (poly(vinyl alcohol)) entrapment method. The sensor could directly determine the nitrate in an unpurged aqueous solution with the aid of an appropriate oxygen scavenger: the nitrate reduction reaction driven by the enzyme and an electron-transfer mediator, methyl viologen, at -0.85 V (GCE vs Ag/AgCl) or at -0.90 V (SPCE vs Ag/AgCl) exhibited no oxygen interference in a sulfite-added solution. The electroanalytical properties of optimized biosensors were measured: the sensitivity, linear response range, and detection limit of the sensors based on GCE were 7.3 nA/microM, 15-300 microM (r2 = 0.995), and 4.1 microM (S/N = 3), respectively, and those of SPCE were 5.5 nA/microM, 15-250 microM (r2 = 0.996), and 5.5 microM (S/N = 3), respectively. The disposable SPCE-based biosensor with a built-in well- or capillary-type sample cell provided high sensor-to-sensor reproducibility (RSD < 3.4% below 250 microM) and could be used more than one month in normal room-temperature storage condition. The utility of the proposed sensor system was demonstrated by determining nitrate in real samples.     

In-fiber reflection mode interferometer based on a long-period grating for external refractive-index measurement

We present two novel schemes for refractometry based on a long-period fiber grating- (LPG-) based Michelson interferometer. These schemes are designed to overcome the measurement dependence of previously demonstrated LPG-based refractometry on the immersion depth. The first utilizes an unshielded LPG and the second, a shielded one. Both schemes were tested over a certain refractive-index range, and the measurement of glucose concentration in water was experimentally demonstrated. In addition, the temperature sensitivity of the two schemes is discussed.     

Rheology of unsaturated polyester resins. I. Effects of filler and low-profile additive on the rheological behavior of unsaturated polyester resin

Measurements were taken of the bulk rheological properties of concentrated suspensions of particulates in unsaturated polyester resins, using a cone-and-plate rheometer. The particulates used were clay, calcium carbonate, and milled glass fiber. With clay and milled glass fibers, shear-thinning behavior of suspensions was observed at low shear rates or low shear stresses as the concentration of particulates was increased, whereas concentrated suspensions of calcium carbonate exhibited Newtonian behavior over the range of shear stresses or shear rates investigated. The cone-and-plate rheometer was also used for measurements of the bulk rheological properties of various mixtures of polyester resin and low-profile additives. For low-profile additives, solutions, in styrene, of poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA) were used. It was found that the bulk viscosities of all mixtures of polyester resin and PVAc solution lie between those of the individual components, whereas the bulk viscosities of some mixtures of polyester resin and PMMA solution go through a minimum and a maximum, depending on the composition of the mixture. While all mixtures of polyester resin and PVAc solution exhibited negligible normal stress, some mixtures of polyester resin and PMMA solution exhibited noticeable normal stresses. It should be mentioned that polyester resin follows Newtonian behavior. It turned out that all mixtures of polyester resin and PVAc solution exhibited clear, homogeneous solutions, whereas mixtures of polyester resin and PMMA solution exhibited optical heterogeneity, i.e., turbidity. When polyethylene powders were used as low-profile additives, suspensions of polyester resin and polyethylene powders exhibited negative values of normal stress as the concentrations of suspension reached a critical value. When both filler and low-profile additive were put together in polyester resin, the rheological behavior became quite complex, indicating that some interactions exist between the filler and the low-profile additive.     

Prediction and screening of solubility of pharmaceuticals in single‐ and mixed‐ionic liquids using COSMO‐SAC model

In this work, we investigated the prediction of solubility (x_d) of drug molecules in single‐ and mixed‐ionic liquid (IL) solutions using the COSMO‐SAC activity coefficient model. In particular, the effect of dissociation of IL on solubility is examined. The prediction accuracy is found to be 91% in x_d (root‐mean‐square deviation in ln x_d is 0.65) for a total of 442 data points with solubility ranging from 0.93 to 2.84 × 10^?4 (mole fraction) and temperature ranging from 248.9 to 488.3 K. The solubility of drug is found not sensitive to the treatment of dissociation of IL in the calculations. The method is used to determine the solubility of paracetamol in 2624 single IL made from combination of 82 cations and 32 anions. The solubility of paracetamol can vary by 4 orders of magnitude in different ILs, indicating that this is a powerful method for screening for solvents with desired solubility power. The solubility of a drug in binary IL solution can be significantly higher or lower than those in pure IL components. For the 3,441,376 binary IL mixtures, about 8% of the mixtures exhibit higher solubility for paracetamol and 6% exhibit lower solubility. Our results indicate that mixing ILs can be a viable approach for tuning drug solubility. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3096–3104, 2017     

Studies on multilayer film coextrusion II. Interfacial instability in flat film coextrusion

An experimental study was carried out to investigate the phenomenon of interfacial instability in multilayer flat-film coextrusion. For the study, a sheet-forming die with a feed block was used to coextrude three-and five-layer flat films. Polymers coextruded were: (a) low-density polyethylene with polystyrene, and (b) high-density polyethylene with polystyrene. It was observed that, for a given polymer system, there is a critical value of wall shear stress at which an irregular (i.e., unstable) interface between the layers sets in, giving rise to a pattern similar to that usually found in a wood panel. Once the instability sets in, the severity of interfacial instability is found to depend on both the total volumetric flow rate (hence wall shear stress) of the combined streams and the ratio of the individual layer thicknesses. An attempt is made to correlate the critical conditions for the onset of interfacial instability in terms of the layer thickness ratio, and the viscosity and elasticity ratios of the two polymers being coextruded.     

Measurement of stress birefringence patterns in molten polymers flowing through geometrically complex channels

Measurements were taken of stress birefringence patterns in molten polymers flowing through geometrically complex channels. Six different flow channels were constructed for experiment, some representing the flow geometries of spinnerettes encountered in fiber spinning, and others representing mold cavities encountered in injection molding. All the flow channels had two glass windows, which permitted one to take photographs of the flow birefringence patterns of molten polymers with the aid of a polariscope. Quantitative information on the stress distributions in a flow channel was obtained, with the aid of the stress-optical laws, from the pictures taken of both isochromatic and isoclinic fringe patterns. The significance of flow birefringence measurement is discussed from the standpoint of die design for extrusion operation and mold design for injection molding operation.     

Studies on multilayer film coextrusion I. The rheology of flat film coextrusion

Multilayer flat film coextrusion was studied, both experimentally and theoretically. For the experimental study, a sheet-forming die with a feedblock was designed, and plastic films of three and five layers were coextruded. The die was provided with three pressure transducers in the axial direction in order to determine the pressure gradient in the die, allowing the determination of the reduction in pressure drop when different combinations of two polymer melts were coextruded. Polymers used for coextrusion were: (1) low density polyethylene and ethylene-vinyl acetate; (2) low density-polyethylene and high density polyethylene; (3) low density polyethylene and polystyrene. For the theoretical study, the z-component of the equations of motion for steady fully-developed flow were solved using a power law non-Newtonian model, Comparisons were made between the experimental and the theoretically predicted volumetric flow rates. Predictions of the velocity distributions, shear rate profiles, and shear stress distributions were made as functions of the processing conditions and the rheological properties of the individual polymers concerned.     

Rubber modified epoxy resin. II: Phase separation behavior

DGEBA (diglycidyl ether of bisphenol A)–ATBN (amine terminated butadiene acrylonitrile copolymer) blends exhibited upper critical solution temperature (UCST) behavior. Triethylene tetramine (TETA) was introduced as an amine curing agent of epoxy. The real-time phase separation behavior of ATBN-added epoxy system during cure was investigated using laser light scattering. SEM (scanning electron microscopy) and optical microscopy were also employed to observe the morphology of the epoxy blends. Since the DGEBA–ATBN blends showed UCST behavior, the degree of phase separation when cured at low temperature was higher than that when cured at high temperature. The domain correlation length increased as the curing temperature was lowered. Dynamic mechanical analysis (DMA) results indicated that the phase inversion occurred above 20 wt% of ATBN composition.