Selective crystallization of calcium salts by poly(acrylate)-grafted chitosan

The biopolymer chitosan was chemically modified by grafting polyacrylamide or polyacrylic acid in a homogeneous aqueous phase using potassium persulfate (KPS) as redox initiator system in the presence of N,N-methylene-bis-acrylamide as a crosslinking agent. The influence of the grafted chitosan on calcium salts crystallization in vitro was studied using the sitting-drop method. By using polyacrylamide grafted chitosan as substrate, rosette-like CaSO4 crystals were observed. This was originated by the presence of sulfate coming from the initiator KPS. By comparing crystallization on pure chitosan and on grafted chitosan, a dramatic influence of the grafted polymer on the crystalline habit of both salts was observed. Substrates prepared by combining sulfate with chitosan or sulfate with polyacrylamide did not produce similar CaSO4 morphologies. Moreover, small spheres or donut-shaped CaCO3 crystals on polyacrylic acid grafted chitosan were generated. The particular morphology of CaCO3 crystals depends also on other synthetic parameters such as the molecular weight of the chitosan sample and the KPS concentration.     

Syntheses of 1-substituted 1,2,4-triazoles,imidazoles and benzimidazoles

Substituted 2-phenethyl-1,2,4-triazoles, 1-phenethylimidazoles 3 and 1-phenethylbenzimidazoles 5 were synthesized from the reaction of compound 8 with tri-n-butyltin hydride in good yield. The reaction of substituted-2-phenethyl halide with 1H-1,2,4-triazoles, imidazoles and benzimidazoles gave a low yield. The yield was increased by the use of substituted-2-phenethyl p-toluensulfonate.     

Synthesis and Evaluation of Biocompatible pH‐Sensitive Hydrogels as Colon‐Specific Drug Delivery Systems

Because of the growing importance of pH‐sensitive hydrogels as drug delivery systems, biocompatible copolymeric hydrogels based N‐vinyl‐2‐pyrrolidinone (NVP) and methacrylic acid (MAA) were designed and synthesized. These hydrogels were investigated for oral drug delivery. Radical copolymerizations of N‐vinyl‐2‐pyrrolidinone (NVP) and methacrylic acid (MAA) with the various ratios of cross‐linking agent were carried out at 70 °C. Azabisisobutyronitrile (AIBN) was the free‐radical initiator employed and Cubane‐1,4‐dicarboxylic acid (CDA) linked to two 2‐hydroxyethyl methacrylate (HEMA) group was the crosslinking agent (CA) used for hydrogel preparations. The hydrogels were characterized by differential scanning calorimetry and FT‐IR. Equilibrium swelling studies were carried out in enzyme‐free simulated gastric and intestinal fluids (SGF and SIF, respectively). A model drug, olsalazine [3,3′‐azobis (6‐hydroxy benzoic acid)] (OSZ) as an azo derivative of 5‐aminosalicylic acid (5‐ASA), was entrapped in these gels and the in‐vitro release profiles were established separately in both enzyme‐free SGF and SIF. The drug‐release profiles indicated that the amount of drug released depended on the degree of swelling. The swelling was modulated by the amount of crosslinking of the polymer bonded drug (PBDs) prepared. Based on the great difference in hydrolysis rates at pH 1 and 7.4, these pH‐sensitive hydrogels appear to be good candidates for colon‐specific drug delivery.     

Role of reactive species in processing materials at laboratory temperature by spray plasma devices

Processing the aerosol of metal salts in non-equilibrium plasma represents a promising technique that combines the advantages of spray pyrolysis with the high reactivity of plasmas at nearlaboratory temperature in order to produce mixed-oxides and perovskite materials. The aim of this paper is to describe the principles of this new technique and to present the various applications and latest developments. This technique’s capacity to deposit various mixed metal oxides with precise stoichiometry is demonstrated. It is shown that oxidant plasma species play a key role in the chemical transformation of starting materials into oxides at laboratory temperature, while the configuration of the reactor determines the morphology and texture of the deposited layers. Two different reactor configurations are presented. The porous layers of La _x Sr_1−x MnO₃ as the cathode for fuel cells were synthesised in a wave shock reactor configuration, while nanostructured ZnO-Al layers to form a transparent conductive cathode for photovoltaic cells were deposited in the spray plasma reactor of the latest generation for this technique. The experimental results emphasise the role of plasma species in the rate of chemical reactions and in the chemical composition of the deposited layers.     

Microfunnel‐filter‐based emulsification microextraction followed by gas chromatography for simple determination of organophosphorus pesticides in environmental water samples

A simple and fast method named microfunnel‐filter‐based emulsification microextraction is introduced for an efficient determination of some organophosphorus pesticides including diazinon, malathion, and chlorpyrifos in the environmental samples including the river, sea, and well water. This method is based upon the dispersion of a low‐toxicity organic solvent (dihexyl ether), as the extractant, in a high volume of an aqueous sample solution (45 mL). It is implemented without a centrifugation step, and using a syringe filter and a micro‐funnel, the phase separation and transfer of the enriched analytes to the gas chromatograph are simply achieved. By filtration of the extractant phase, a suitable sample clean‐up is obtained, and the total extraction time is just a few minutes. The factors influencing the extraction efficiency are optimized, and under the optimal conditions, the proposed method provides a good linearity (in the range of 15–1500 ng/mL (R² > 0.996). A high enrichment factor is obtained (in the range of 306–342), and the method provides low limits of detection and quantification (in the ranges of 4–8 and 15–25 ng/mL, respectively).     

New pH-Sensitive Hydrogels for Oral Delivery of Hydrophobic Drugs

A series of acrylic copolymers containing silyl pendant groups was prepared by free radical cross-linking copolymerization. Me₃Si, Et₃Si, and Ph₃Si together with cubane-1,4-dicarboxylic acid (CDA) were covalently linked with 2-hydroxyethyl methacrylate (HEMA). CDA linked to two HEMA group is the cross-linking agent (CA). Free radical cross-linking copolymerization of the methacrylic acid (MAA) and organosilyl monomers with two different molar ratios of CA was carried out at 60–70°C. The compositions of the cross-linked three-dimensional polymers were determined by FT-IR spectroscopy. The glass transition temperature of the network polymers was determined calorimetrically. Equilibrium swelling studies were carried out in enzyme-free simulated gastric and intestinal fluids (SGF and SIF, respectively). A model hydrophobic drug, the steroid hormone estradiol, was entrapped in these gels, and the in vitro release profiles were established separately in both SGF (pH 1) and SIF (pH 7.4). Incorporation of silyl groups in a new macromolecule system modified network polymers for drug delivery.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Synthesis,Characterization and Properties of a Novel Environmentally Friendly Mono Azo Disperse Dye and Its Application on Polyethylene Terephthalate (PET)

The aim of this research is to achieve the synthesis of a novel mono azo disperse dye containing both a β‐naphthyl acetate group and carboxylic acid ester group and application on PET fabric. In this study the dyeing properties have also been investigated. The synthesized dye was characterized using UV‐Vis, FTIR, ¹H NMR and ¹³C NMR spectroscopic techniques. To investigate alkali‐clearability, both alkali‐hydrolysis behavior and the effect of its fastness properties with regard to PET fabric were examined. This dye showed a reasonable level of hydrolysis under relatively mild alkaline conditions. The application of the dye to PET fabric showed good leveling and building up properties. Estimating fastness properties of the dyed fabric showed excellent wash, rubbing fastness, good light and sublimation fastness. The results furthermore displayed that the synthesized dye offers the option of alkali‐clearing process over that of a conventional reduction‐clearing process. Therefore, the value of Chemical Oxygen Demand (COD), Biological Oxygen Demand (BOD) and water pollution as well as the expenditure of production were decreased.     

Theoretical analysis of the local orientation effect and the lift‐hyperlayer mode of rodlike particles in field‐flow fractionation

We investigated theoretically the effects of the cross‐stream migration and the local average orientation of rodlike particles on the shape‐based separation using field‐flow fractionation. The separation behavior was analyzed by comparing the retention ratios of spheres and rods. The retention ratio of a rod was evaluated through the derivation of its cross‐sectional concentration profile by considering the rod migration and the local average orientation. Our study in various flow conditions showed that the rod migration, caused by the hydrodynamic interaction with a wall, can affect the separation behavior as a lift‐hyperlayer mode. We also demonstrated that the local average orientation, which is a function of a local shear rate and a rotational diffusivity, results in the transverse diffusivity that is different from its perpendicular diffusivity. These results suggest that the experimental separation behaviors of rods in field‐flow fractionation may not be fully explained by the current theory based on the normal mode and the steric mode. We also characterized each condition where one of the normal mode, the steric mode of spheres, and the lift‐hyperlayer mode of rods is dominant.