Fenugreek hydrogel–agarose composite entrapped gold nanoparticles for acetylcholinesterase based biosensor for carbamates detection

A biosensor was fabricated to detect pesticides in food samples. Acetylcholinesterase was immobilized in a novel fenugreek hydrogel–agarose matrix with gold nanoparticles. Transparent thin films with superior mechanical strength and stability were obtained with 2% fenugreek hydrogel and 2% agarose. Immobilization of acetylcholinesterase on the membrane resulted in high enzyme retention efficiency (92%) and a significantly prolonged shelf life of the enzyme (half-life, 55 days). Transmission electron microscopy revealed that, gold nanoparticles (10–20 nm in diameter) were uniformly dispersed in the fenugreek hydrogel–agarose–acetylcholinesterase membrane. This immobilized enzyme-gold nanoparticle dip-strip system detected various carbamates, including carbofuran, oxamyl, methomyl, and carbaryl, with limits of detection of 2, 21, 113, and 236 nM (S/N = 3), respectively. Furthermore, the fabricated biosensor exhibited good testing capabilities when used to detect carbamates added to various fruit and vegetable samples.     

An innovative extensional viscometer for low-viscosity and low-elasticity liquids

A spinline-type extensional viscometer is described in which an innovative method of tensile stress measurement is employed. A limited amount of liquid flows through a vertical capillary at a constant flow rate under the influence of a constant pressure head. The drainage time decreases when the liquid stream leaving the capillary is stretched by the application of vacuum. These drainage times are measured in a manner similar to that used for intrinsic viscosity measurements. The measured difference in drainage times, with and without stretching, is trivially related to the extensional stress at the capillary exit, and this provides a very simple method of accurately determining fluid stretching forces having a magnitude as low as 10^-4 N; stresses at other axial locations in the stretched liquid jet are obtained by means of a force balance in the usual manner. The validity of the proposed technique is demonstrated by obtaining the expected results for a Newtonian oil having a shear viscosity of 56.2 mPa-s. Also presented are preliminary data on polyethylene oxide-in-water solutions having an even lower shear viscosity.     

Non-linear studies of orthotropic shallow spherical shells on elastic foundation

Governing non-linear integro-differential equations for cylindrically orthotropic shallow spherical shells resting on linear Winkler-Pasternak elastic foundations, undergoing moderately large deformations are presented. Three problems, namely, non-linear static deflection response, non-linear dynamic deflection response and dynamic snap-through buckling of orthotropic shells have been investigated. The influences of material orthotropy, foundation parameters and shell-material damping on the deflection response are determined for the clamped and the simply- supported immovable edge conditions accurately. Orthotropy, foundation interaction and material damping play significant roles in improving the load carrying capacity of the shell structures.     

A visual strip sensor for determination of iron

A visual strip has been developed for sensing iron in different aqueous samples like natural water and fruit juices. The sensor has been synthesized by UV-radiation induced graft polymerization of acrylamide monomer in microporous poly(propylene) base. For physical immobilization of iron selective reagent, the in situ polymerization of acrylamide has been carried out in the presence of 1,10-phenanthroline. The loaded strip on interaction with Fe(II) in aqueous solution turned into orange red color and the intensity of the color was found to be directly proportional to the amount of Fe(II) in the aqueous sample. The minimal sensor response with naked eye was found for 50 ng mL⁻¹ of Fe in 15 min of interaction. However, as low as 20 ng mL⁻¹ Fe could be quantified using a spectrophotometer. The detection limit calculated using the 3s/S criteria, where ‘s’ is the standard deviation of the absorbance of blank reagent loaded strip and ‘S’ is the slope of the linear calibration plot, was 1.0 ng mL⁻¹. The strip was applied to measure Fe in a variety of samples such as ground water and fruit juices.     

Aggregation and pH responsive disassembly of a new acid-labile surfactant synthesized by thiol-acrylate Michael addition reaction

Nucleophilic thiol-acrylate Michael reaction between a hydrophobic thiol and hydrophilic acrylate derivative generated a nonionic surfactant with acid-labile β-thiopropionate linker. Micellization of the surfactant, its ability to encapsulate hydrophobic dye, acid-induced disruption of the aggregate and pH-selective dye release profile have been revealed in this report. The micellar aggregates were found to be stable under neutral conditions, but they could be disrupted in acidic pH (5.3), and thus the encapsulated hydrophobic dye molecules could be selectively released. Appropriate control experiments revealed that the sulfur atom in the β-position is essential for acidic hydrolysis of the ester functionality of the surfactant.     

Protective Effect of Withania somnifera and Cardiospermum halicacabum Extracts Against Collagenolytic Degradation of Collagen

The irreversible destruction of extracellular matrix (ECM) such as cartilage, tendon, and bone that comprise synovial joints is the hallmark of both rheumatoid arthritis and osteoarthritis by over-expression of matrix metalloproteinase (MMP)-collagenases. We report herein the detailed study on the inhibitory effects of Withania somnifera extract (WSE) and Cardiospermum halicacabum extract (CHE) on Clostridium histolyticum collagenase (ChC) activity against the degradation of the ECM component of bovine Achilles tendon type I collagen by hydroxyproline assay method. Interaction of WSE and CHE with ChC exhibited 71% and 88% inhibition, respectively, to the collagenolytic activity of ChC against collagen degradation, and the inhibition was found to be concentration-dependent. The inhibition kinetics of ChC by both the extracts has been deduced from the extent of hydrolysis of N-[3-(2-furyl) acryloyl]-Leu-Gly-Pro-Ala. Both WSE and CHE are provided competitive and mixed type inhibition on ChC activity, respectively. Circular dichroism studies of ChC on treatment with WSE and CHE revealed changes in the secondary structure of collagenase. These results suggest that the WSE and CHE facilitated collagen stabilization through collagenase inhibition.     

CH···π interactions do not contribute to hydrogen transfer catalysis by glycerol dehydratase

The role of the nonbonded CH···π interaction in the hydrogen abstraction from glycerol by the coenzyme B(12)-independent glycerol dehydratase (GDH) was examined using the QM/MM (ONIOM), MP2, and CCSD(T) methods. The studied CH···π interaction included the hydrogen atom of the -C(2)H(OH)- group of the glycerol substrate and the tyrosine-339 residue of the dehydratase. A contribution of this interaction to the stabilization of the transition state for the transfer of a hydrogen atom from the adjacent terminal C(1)H(2)(OH) group to cysteine 433 was determined by ab initio HF, MP2, and CCSD(T) calculations with the aug-cc-pvDZ basis set for the corresponding methane/benzene, methanol/phenol, and glycerol radical/phenol subsystems. The calculated CH···π distance, defined as the distance between the H atom and the center of the phenol ring, shortened from 2.62 to 2.52 ? upon going from the ground- to the transition-state of the GDH-catalyzed reaction. However, this shortening was not accompanied by the expected lowering of the CH···π interaction free energy. Instead, this interaction remained weak (about -1 kcal/mol) along the entire reaction coordinate. Additionally, the mutual orientation of the CH group and the phenol ring did not change significantly during the reaction. These results suggest that the phenol group of the tyrosine-339 does not contribute to lowering the activation barrier in the enzyme, but do not exclude the possibility that tyrosine 339 facilitates proper orientation of glycerol for the electrostatic catalysis, or inhibits side-reactions of the reactive glycerol radical intermediate.     

The Tempered Aspirations solution for bargaining problems with a reference point

Gupta and Livne (1988) modified Nash’s (1950) original bargaining problem through the introduction of a reference point restricted to lie in the bargaining set. Additionally, they characterized a solution concept for this augmented bargaining problem. We propose and axiomatically characterize a new solution concept for bargaining problems with a reference point: the Tempered Aspirations solution. In Kalai and Smorodinsky (1975), aspirations are given by the so called ideal or utopia point. In our setting, however, the salience of the reference point mutes or tempers the negotiators’ aspirations. Thus, our solution is defined to be the maximal feasible point on the line segment joining the modified aspirations and disagreement vectors. The Tempered Aspirations solution can be understood as a “dual” version of the Gupta-Livne solution or, alternatively, as a version of Chun and Thomson’s (1992) Proportional solution in which the claims point is endogenous. We also conduct an extensive axiomatic analysis comparing the Gupta-Livne to our Tempered Aspirations solution.