Rheological characterization in shear of a model dumbbell polymer concentrated solution

We investigate the linear and non-linear rheological behavior in shear of a concentrated solution of ??dumbbell?? polystyrene with long linear backbone and dense short brushes at both ends and compare it with corresponding linear polymers. This type of dumbbells has never been rheologically characterized before. In linear viscoelasticity, the dumbbell polymers show significant differences with conventional linear polymers. In particular, the reptation relaxation of the dumbbell is strongly slowed down. Furthermore, the addition of the side chains increases the friction so that the dumbbell lies above the ?? ₀ vs. number of entanglements relation of linear samples. Transient shear rheology experiments on weakly entangled solutions show a retardation of the chain stretch relaxation of the dumbbell by a factor 2.5 vs. a linear polymer with the same Rouse time. Additionally, a second peak in the transient viscosity is observed at high shear rates.     

A new half-condensed Schiff base compound: highly selective and sensitive pH-responsive fluorescent sensor

A new probe, 3-[(3-benzyloxypyridin-2-ylimino)methyl]-2-hydroxy-5-methylbenzaldehyde (1-H) behaves as a highly selective fluorescent pH sensor in a Britton-Robinson buffer at 25 °C. The pH titrations show a 250-fold increase in fluorescence intensity within the pH range of 4.2 to 8.3 with a pK(a) value of 6.63 which is valuable for studying many of the biological organelles.     

A highly selective fluorescent chemosensor for zinc ion and imaging application in living cells

A new 2,6-bis(5,6-dihydrobenzo[4,5]imidazo[1,2-c]quinazolin-6-yl)-4-methylphenol (1) serves as a highly selective and sensitive fluorescent probe for Zn(2+) in a HEPES buffer (50 mM, DMSO:water = 1:9 (v/v), pH = 7.2) at 25 °C. The increase in fluorescence in the presence of Zn(2+) is accounted for by the formation of dinuclear Zn(2+) complex [Zn(2)(C(35)H(25)N(6)O)(OH)(NO(3))(2)(H(2)O)] (2), characterized by X-ray crystallography. The fluorescence quantum yield of the chemosensor 1 is only 0.019, and it increases more than 12-fold (0.237) in the presence of 2 equiv of the zinc ion. Interestingly, the introduction of other metal ions causes the fluorescence intensity to be either unchanged or weakened. By incubation of cultured living cells (A375 and HT-29) with the chemosensor 1, intracellular Zn(2+) concentrations could be monitored through selective fluorescence chemosensing.     

Differential electrochemical behaviour of phytofabricated and chemically synthesized silver nanoparticles towards hydrogen peroxide sensing**

Silver nanoparticles (AgNPs) are one of the most widely used nanomaterials for biomedical applications. However, the impact of its synthesis by chemical and plant-mediated routes on its differential electrochemical behaviour has not been examined till date. Here, we report for the first time the differential study of the electrochemical behaviour of the AgNPs synthesized by different routes. First, the AgNPs were obtained by different routes (chemical and phytofabrication) and extensively characterized to compare their physical properties. Thereafter, a comparison of electron transfer kinetics between chemically synthesized (Ag−C) and phyto-fabricated (Ag-Phy) nanoparticles (NPs) has been studied by electrochemical techniques such as potentiodynamic cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). To further investigate the electrocatalytic properties of both types of AgNPs, we have used the peroxide moieties (H₂O₂), and the Ag−C NPs-based sensor probe has been reported to have four times better sensitivity than the Ag−Phy NPs-based sensor. The AgNPs modified sensor probes have also been tested in real-world environments to explore the consistency of their performance in complex matrices by using clinical urine samples, where we found comparable sensitivity to the standard conditions.     

Efficient electrocatalytic oxidation and selective determination of isoniazid by Fe(tmphen) 3 2+ -exchanged Nafion?-modified electrode

Cyclic voltammetry and electrochemical impedance studies of Fe(tmphen) ₃ ²⁺ (where tmphen?=?3,4,7,8-tetramethyl-1,10-phenanthroline)-immobilized Nafion?-modified glassy carbon electrode (GC/Nf/Fe(tmphen) ₃ ²⁺ ) are carried out in 0.1?M Na₂SO₄ solution. Nafion–Fe(tmphen) ₃ ²⁺ complex exhibits efficient electrocatalytic oxidation of isoniazid. The linear double reciprocal plot of current and concentration of isoniazid shows a Michaelis–Menten-type catalytic process. The catalytic oxidation currents are proportional to the concentration of isoniazid and show a wide linear calibration range for the quantitative determination of isoniazid. Detection limit and sensitivity are found to be 13?μM and 2.5?μA?mM^?1, respectively.     

In situ three-dimensional characterization of membrane fouling by protein suspensions using multiphoton microscopy

Fouling of microfiltration membranes leads to severe flux declines and the need to clean or replace the membrane. In situ 3D characterization of protein fouling both on the surface and within the pores of the membrane was achieved using multiphoton microscopy. Time-lapse images of the fouled membrane were obtained for single suspensions and mixtures of fluorescently labeled bovine serum albumin and ovalbumin. Deposited protein aggregates were visible on the membrane and evidently play an important role in fouling. A combination of 3D images and resistance versus time data was used to identify the dominant fouling mechanism. Fouling is initially internally dominated, but after 1 and 15 min for ovalbumin and bovine serum albumin, respectively, the fouling becomes externally dominated. This is in good agreement with two-stage protein fouling models.     

Synthesis of 2‐aryl and coumarin substituted benzothiazole derivatives

A facile and effective method for the synthesis of some benzothiazole derivatives is described. The method involves the action of aryl aldehyde and o‐aminothiophenol in acetic acid resulting into in situ formation of the thiol substituted Schiff's base and its cyclization to 2‐aryl benzothiazole upon prolonged heating.     

Hydroxyl-terminated dendritic oligomers from bile acids: synthesis and properties

[reaction: see text] The high reactivity of the chloroacetyl group has been exploited for the synthesis of bile acid based first and second generation dendrons with multiple hydroxyl groups. The synthesis involves only a few steps and avoids the use of protecting groups for the terminal hydroxyl groups. These dendritic structures with facially amphiphilic bile acid backbones on the periphery were able to solubilize cresol red, a hydrophilic dye, in a nonpolar solvent. HPLC analysis of the dendrons suggests that hydrophobicity increases with increase in oligomer size, but in each generation, the dendrons with a higher degree of branching are less hydrophobic.     

Numerical integration in Galerkin meshless methods, applied to elliptic Neumann problem with non-constant coefficients

In this paper, we explore the effect of numerical integration on the Galerkin meshless method used to approximate the solution of an elliptic partial differential equation with non-constant coefficients with Neumann boundary conditions. We considered Galerkin meshless methods with shape functions that reproduce polynomials of degree k?≥?1. We have obtained an estimate for the energy norm of the error in the approximate solution under the presence of numerical integration. This result has been established under the assumption that the numerical integration rule satisfies a certain discrete Green’s formula, which is not problem dependent, i.e., does not depend on the non-constant coefficients of the problem. We have also derived numerical integration rules satisfying the discrete Green’s formula.     

A total reflection X‐ray fluorescence method for the determination of chlorine at trace levels in nuclear materials without sample dissolution

A total reflection X‐ray fluorescence (TXRF) method for the determination of chlorine at trace levels in nuclear fuel samples is described. Chlorine present in trace concentrations in nuclear fuel materials such as U₃O₈, (U,Pu)C, PuO₂ and Pu‐alloys was first separated from the solid matrix by pyrohydrolysis as HCl and was collected in 5 mM NaOH solution. This solution was analyzed for chlorine by TXRF spectrometry using Cl Kα analytical line excited by W Lα. Cobalt was used as internal standard. The precision for such chlorine determination was found to be within 27% (n = 4) when the analysis was carried out in air atmosphere. This could be improved to 8% by making TXRF measurement in flowing helium atmosphere. The results obtained from TXRF determinations were also compared with those obtained from ion chromatography (IC) and were in good agreement. The collection of distillate during pyrohydrolysis in NaOH helped in counterchecking loss of chlorine during TXRF sample preparation. The average deviation of TXRF‐determined values in helium‐purged TXRF measurements with IC determined values (as chloride) was 15% at a chlorine concentration level in the range of 1–70 µg/mL. Copyright © 2012 John Wiley & Sons, Ltd.