Supramolecular chemosensor for selective detection of iron in aqueous medium

We have successfully developed a ‘turn-on’ colorimetric chemosensor for Fe³⁺ based on 1,10-phenanthroline. An amide derivative of 1,10-phenanthroline 4 was developed for the selective recognition of Fe³⁺ over Co²⁺, Cr³⁺, Cu²⁺, Mn²⁺, Ni²⁺, Ag⁺ and Zn²⁺ and could measure Fe³⁺ concentration in the range of 15–210 μM by UV–vis spectroscopy. Moreover, the addition of Fe³⁺ to a colourless solution of 4 turned its colour to light pink, indicating that 4 is capable of detecting Fe³⁺ by the naked eye. Compound 4 exhibits a major absorption band centred at 268 which shifted to 278 nm after addition of Fe³⁺, and a shoulder band around 514 nm was also observed. The complexation of Fe³⁺ with 4 was analysed at a different pH and favourable binding was observed at pH 6.2.     

A new class of fuzzy implications. Axioms of fuzzy implication revisited

Many different fuzzy implication operators have been proposed; most of them fit into one of the two classes: implication operations that are based on an explicit representation of implication A → B in terms of &, , and ¬ (e.g., S-implications that are based on the formula B ¬ A), and R-implications that are based on an implicit representation of implication A → B as the weakest C for which C&B implies A. However, some fuzzy implication operations (such as b^a) cannot be naturally represented in this form. To describe such operations, we propose a new (third) class of implication operations called A-implications whose relation to &, , and ¬ is described by (implicit) axioms.     

Chloro-Modified Magnetic Fe3O4@MCM-41 Core–Shell Nanoparticles for L-Asparaginase Immobilization with Improved Catalytic Activity,Reusability, and Storage Stability

This paper describes a new support that permits to efficient immobilization of L-asparaginase (L-ASNase). For this purpose, Fe₃O₄ magnetic nanoparticles were synthesized and coated by MCM-41. 3-chloropropyltrimethoxysilane (CPTMS) was used as a surface modifying agent for covalent immobilization of L-ASNase on the magnetic nanoparticles. The chemical structure; thermal, morphological, and magnetic properties; chemical composition; and zeta potential value of Fe₃O₄@MCM-41-Cl were characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential thermal analysis (DTA), differential scanning calorimetry (DSC), vibrating sample magnetometer (VSM), scanning electron microscope (SEM), energy dispersive X-ray (EDX), X-ray diffraction patterns (XRD), and zeta-potential measurement. The immobilization efficiency onto Fe₃O₄@MCM-41-Cl was detected as 63%. The reusability, storage, pH, and thermal stabilities of the immobilized L-ASNase were investigated and compared to that of soluble one. The immobilized enzyme maintained 42.2% of its original activity after 18 cycles of reuse. Furthermore, it was more stable towards pH and temperature compared with soluble enzyme. The Michaelis–Menten kinetic properties of immobilized L-ASNase showed a lower V_max and a similar K_m compared to soluble L-ASNase. Immobilized enzyme had around 47 and 32.5% residual activity upon storage a period of 28 days at 4 and 25 °C, respectively. In conclusion, the Fe₃O₄@MCM-41-Cl@L-ASNase core–shell nanoparticles could successfully be used in industrial and medical applications.

     

2-Morpholinoethyl-substituted <Emphasis Type="Italic">N</Emphasis>-heterocyclic carbene (NHC) precursors and their silver(I)NHC complexes: synthesis,crystal structure and in vitro anticancer properties

In this study, a series of unsymmetrically 2-morpholinoethyl-substituted benzimidazolium salts and their Ag(I)NHC complexes were synthesized. The 1,3-dialkylbenzimidazolium salts (1a–d) were synthesized in dimethylformamide at 80 °C temperature from the N-(2-morpholinoethyl)benzimidazole and alkyl halides. The Ag(I)NHC complexes (2a–d) were synthesized in dichloromethane at room temperature from the benzimidazolium salts and Ag₂O. All compounds were characterized by spectroscopic techniques (NMR and FT-IR) and elemental analyses. Also, the salt 1c and complex 2c were characterized by single-crystal X-ray crystallography. Anticancer activities of 2-morpholinoethyl-substituted benzimidazolium salts and Ag(I)NHC complexes were investigated against the MCF-7 breast cancer cell line, and the IC₃₀ and IC₅₀ values of these compounds were found to be in the range of 241–490 and 6–14 µM, respectively.     

Modeling and computer simulation of the identification problem related to the sludge concentration in a settler

The mathematical model of sludge particles settling in the water treatment plant (settler) is considered. In the case of the residence time of sludge particles in the settler the model leads to a nonlinear age-dependent transport–diffusion with a nonlocal additional condition. This problem is formulated as an identification/optimal control problem, where the sludge concentration is assumed to be a control. For the case of constant (“average”) velocity, as a characterization of the optimal control problem two necessary conditions are obtained. These conditions permit reducing the nonlinear coupled two-dimensional problem to the two-point boundary value problem for the second order nonlinear ordinary differential equation, and then, to a nonlinear equation, with respect to sludge concentration. For the solution of the problem an iteration algorithm is derived. Convergence of the iteration algorithm is analyzed theoretically, as well as on test examples. The numerical procedure for the considered problem is demonstrated on concrete examples.     

An experimental study on the effects of uniform injection through one perforated surface of a square cylinder on some aerodynamic parameters

It is well known that injection/suction (transpiration) through a perforated surface is an efficient way of influencing the characteristics of a turbulent boundary layer. Injection application creates a thicker boundary layer on a flat plate and it thus decreases drag. In aeronautical applications, suction is frequently used to delay boundary layer separation. This paper presents an experimental study on the effects of uniform injection through one perforated surface of a square cylinder on the pressure distribution and drag coefficient in a two-dimensional turbulent flow. For this purpose, surface pressure measurements around a square cylinder have been performed at three different Reynolds numbers in a wind tunnel. The parameters taken into account were injection rate, position of perforated surface (i.e., front, top, and rear), and pressure coefficient and drag coefficient. The results show that variation in pressure coefficient around the square cylinder and drag coefficient were influenced by the position of perforated surface and by injection rate.     

Return distributions in dog-flea model revisited

A recent study of coherent noise model for the system size independent case provides an exact relation between the exponent τ of avalanche size distribution and the q value of the appropriate q-Gaussian that fits the return distribution of the model. This relation is applied to Ehrenfest’s historical dog-flea model by treating the fluctuations around the thermal equilibrium as avalanches. We provide a clear numerical evidence that the relation between the exponent τ of fluctuation length distribution and the q value of the appropriate q-Gaussian obeys this exact relation when the system size is large enough. This allows us to determine the value of the q-parameter a priori from one of the well known exponents of such dynamical systems. Furthermore, it is shown that the return distribution in dog-flea model gradually approaches q-Gaussian as the system size increases and this tendency can be analyzed by a well defined analytical expression.     

A New HPLC Method with UV Detection for the Determination of Carnosol in Human Plasma and Application to a Pharmacokinetic Study

Chromatographia - This article aims to present a simple and sensitive, HPLC–UV method, which was developed to determine carnosol in human plasma samples. Chromatographic separation was...     

NO-NSAIDs. Part 3: nitric oxide-releasing prodrugs of non-steroidal anti-inflammatory drugs

In continuation of our efforts to discover novel nitric oxide-releasing non-steroidal anti-inflammatory drugs (NO-NSAIDs) as potentially "Safe NSAIDs," we report herein the design, synthesis and evaluation of 21 new NO-NSAIDs of commonly used NSAIDs such as aspirin, diclofenac, naproxen, flurbiprofen, ketoprofen, sulindac, ibuprofen and indomethacin. These prodrugs have NO-releasing disulfide linker attached to a parent NSAID via linkages such as an ester (compounds 9-16), a double ester (compounds 17-24), an imide (compounds 25-30) or an amide (compounds 31-33). Among these NO-NSAIDs, the ester-containing NO-aspirin (9), NO-diclofenac (10), NO-naproxen (11), and the imide-containing NO-aspirin (25), NO-flurbiprofen (27) and NO-ketoprofen (28) have shown promising oral absorption, anti-inflammatory activity and NO-releasing property, and also protected rats from NSAID-induced gastric damage. NO-aspirin compound 25, on further co-evaluation with aspirin at equimolar doses, exhibited comparable dose-dependent pharmacokinetics, inhibition of gastric mucosal prostaglandin E(2) (PGE(2)) synthesis and analgesic properties to those of aspirin, but retained its gastric-sparing properties even after doubling its oral dose. These promising NO-NSAIDs could therefore represent a new class of potentially "Safe NSAIDs" for the treatment of arthritic pain and inflammation.