Modification of polysulfones by click chemistry: Amphiphilic graft copolymers and their protein adsorption and cell adhesion properties

Well‐defined amphiphilic graft copolymer with hydrophobic polysulfone (PSU) backbone and hydrophilic poly(acrylic acid) (PAA) side chains were synthesized and characterized. For this purpose, commercially available PSU was converted to azido‐functionalized polymer (PSU‐N₃) by successive chloromethylation and azidation processes. Independently, poly(tert‐butyl acrylate) (PtBA) with an alkyne‐end‐group is obtained by using suitable initiator in atom transfer radical polymerization (ATRP). Then, this polymer was successfully grafted onto PSU‐N₃ by click chemistry to yield polysulfone‐graft‐poly(tert‐butyl acrylate), (PSU‐g‐PtBA). Finally, amphiphilic polysulfone‐graft‐poly(acrylic acid), (PSU‐g‐PAA), membranes were obtained by hydrolyzing precursor the PSU‐g‐PtBA membranes in trifluoroacetic acid. The final polymer and intermediates at various stages were characterized by ¹H NMR, FTIR, GPC, and SEM analyses. Protein adsorption and eukaryotic and prokaryotic cell adhesion on PSU‐g‐PAA were studied and compared to those of PSU‐g‐PtBA and unmodified PSU. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

New Amperometric Cholesterol Biosensors Using Poly(ethyleneoxide) Conducting Polymers

Accumulation of cholesterol in human blood can cause several health problems such as heart disease, coronary artery disease, arteriosclerosis, hypertension, cerebral thrombosis, etc. Therefore, simple and fast cholesterol determination in blood is clinically important. In this study, two types of amperometric cholesterol biosensors were designed by physically entrapping cholesterol oxidase in conducting polymers; thiophene capped poly(ethyleneoxide)/polypyrrole (PEO-co-PPy) and 3-methylthienyl methacrylate-co-p-vinyl benzyloxy poly(ethyleneoxide)/polypyrrole (CP-co-PPy). PEO-co-PPy and CP-co-PPy were synthesized electrochemically and cholesterol oxidase was immobilized by entrapment during electropolymerization. The amperometric responses of the enzyme electrodes were measured by monitoring oxidation current of H₂O₂ at +0.7 V in the absence of a mediator. Kinetic parameters, such as Km and Imax, operational and storage stabilities, effects of pH and temperature were determined for both entrapment supports. Km values were found as 1.47 and 5.16 mM for PEO-co-PPy and CP-co-PPy enzyme electrodes, respectively. By using these Km values, it can be observed that ChOx immobilized in PEO-co-PPy shows higher affinity towards the substrate.     

Electroanalysis of Caffeic Acid in Red Wine and Investigation of Thermodynamic Parameters Using an Ag Nanoparticles Modified Poly(Thiophene) Film Glassy Carbon Electrode

A silver nanoparticle decorated poly(thiophene) modified glassy carbon electrode (GCE) was prepared for determination of caffeic acid. The Ag/PTh/GCE surface was characterized by scanning electron microscopy (SEM) and energy‐dispersive X‐ray (EDX) spectroscopy. The modified electrode has shown higher electrocatalytic activity towards the oxidation of caffeic acid. The peak current of was found linear in the concentration range from 1.00×10^?8 to 4.83×10^?6 M with a detection limit of 5.3×10^?9 M (S/N=3). The modified electrode was used for determination of CA concentration in red wine samples. The thermodynamic constants, entropy change (ΔS), enthalpy change (ΔH) and Gibbs free energy change (ΔG) were calculated as ?166.34 J/(mol K), ?154.24 kJ/mol and ?104.75 kJ/mol at 25 °C, respectively.     

A New and Convenient Synthesis of Amino‐phthalimide (1H‐Isoindole‐1,3(2H)‐dione) Derivatives and Their Photoluminescent Properties

A new and convenient synthesis for amino‐phthalimide (1H‐isoindole‐1,3(2H)‐dione) derivatives has been developed starting from an α,β‐unsaturated ketone. The ketones were reacted with amines to give aromatic amine products. This is the first time that substituted amine groups have been incorporated in aromatic rings. The mechanism of the product formation is rationalized by the 1,2‐addition of amines to ketones. All aromatic compounds exhibited high fluorescence properties at the blue‐green region.     

One-Pot Synthesis of Mannich Bases Under Solvent-Free Conditions

A mild and practically convenient one-pot procedure for the Mannich reaction via condensation of amines, aldehydes and malonates, β-ketoesters, or β-dicarbonyl compounds has been carried out without using any organic solvent, metallic catalyst, or Lewis acids or bases at room temperature. The present protocol offers several advantages, such as goods yields, simple procedure with easy workup, and the absence of any volatile, hazardous organic solvents and metallic catalyst.     

Paal–Knorr Pyrrole Synthesis in Water

Water was a suitable medium for Paal–Knorr pyrrole cyclocondensation. Hexa-2,5-dione was reacted with several aliphatic and aromatic primary amines, affording N-substituted 2,5-dimethyl pyrrole derivatives in good to excellent yields. An efficient, green method using water either as environmentally friendly solvent or catalyst was presented.     

Feasibility of tetracycline,a common antibiotic,as chelating agent for spectrophotometric determination of UO2 2+ after cloud point extraction

A cloud point extraction (CPE) procedure was presented for the preconcentration of UO₂ ²⁺ ion in different water samples. Tetracycline (TC) is the second most widely used antibiotics in the world and is used as chelating agent. To the best of our knowledge, this is the first work that an antibiotic is used as a chelating agent for CPE of UO₂ ²⁺. Besides, the use of TC as complexing agent provides excellent chelating features. TC molecule has large numbers of functional groups (adjacent hydroxyl oxygen atoms and cyclohexanone oxygen atoms, amide groups) which can form stable complex with UO₂ ²⁺. After complexation with TC, UO₂ ²⁺ ions were quantitatively recovered in Triton X-100 after cooling in the ice bath. 3.0 mL of acetate buffer was added to the surfactant-rich phase prior to its analysis by UV–Vis spectrophotometer. The influence of analytical parameters including pH, buffer volume, TC, Triton X-100 concentrations, bath temperature, incubation time were optimized. The effect of the matrix ions on the recovery of UO₂ ²⁺ ions was investigated. The limit of detection was 0.0746 μg mL^?1 along with enrichment factor of 14.3 with a R.S.D. of 3.6 %. The proposed procedure was applied to the analysis of various environmental water samples. On the other hand, the electronic distribution of TC molecule is investigated with their frontier molecular orbital density distributions.     

Effects of Heavy Iodine Atoms and π-Expanded Conjugation on Charge Transfer Dynamics in Carboxylic Acid BODIPY Derivatives as Triplet Photosensitizers

Borondipyrromethene (BODIPY) chromophores are composed of a functional-COOH group at meso position with or without a biphenyl ring, and their compounds with heavy iodine atoms at −2, −6 positions of the BODIPY indacene core were synthesized. The photophysical properties of the compounds were studied with steady-state absorption and fluorescence measurements. It was observed that the absorption band is significantly red-shifted, and fluorescence signals are quenched in the presence of iodine atoms. In addition to that, it was indicated that the biphenyl ring does not affect the spectral shifting in the absorption as well as fluorescence spectra. In an attempt to investigate the effect of π-expanded biphenyl moieties and heavy iodine atoms on charge transfer dynamics, femtosecond transient absorption spectroscopy measurements were carried out in the environment of the tetrahydrofuran (THF) solution. Based on the performed ultrafast pump-probe spectroscopy, BODIPY compounds with iodine atoms lead to intersystem crossing (ISC) and ISC rates were determined as 150 ps and 180 ps for iodine BODIPY compounds with and without π-expanded biphenyl moieties, respectively. According to the theoretical results, the charge transfer in the investigated compounds mostly appears to be intrinsic local excitations, corresponding to high photoluminescence efficiency. These experimental findings are useful for the design and study of the fundamental photochemistry of organic triplet photosensitizers.     

Folic‐Acid‐Modified Conducting Polymer: Electrochemical Detection of the Cell Attachment

Here, postfunctionalization and bioapplication of a π‐conjugated polymer named 4‐[4H‐dithieno(3,2‐b:2′,3′‐d)pyrrol‐4‐yl]aniline (DTP‐aryl‐NH₂) are reported, which is successfully synthesized via electropolymerization onto the glassy carbon electrode. Folic acid (FA) is used to modify the amino functional polymer via N‐(3‐dimethylaminopropyl)‐N′‐ethylcarbodiimide hydrochloride/N‐hydroxysuccinimide chemistry for the further steps. The selective adhesion of folate receptor positive cells on the surface is followed by the electrochemical methods. Cyclic voltammetry and electrochemical impedance spectroscopy have been used to characterize stepwise modification of the electroactive surface. After optimization studies such as scan rate during the polymer deposition, FA amount for the efficient surface targeting, incubation time with the cells etc., analytical characterization is carried out. The surface morphologies at each step are imaged by using fluorescence microscopy.

     

Investigation of electrochemical behavior and development of a validated adsorptive stripping square wave voltammetry method for 3-nitrotyrosine in human plasma and cerebrospinal fluid

An adsorptive stripping square wave voltammetric (AdSqW) method was developed for the determination of 3-nitrotyrosine (3-NT), a biomarker of in vivo oxidative damage in Alzheimer, ALS, Parkinson’s, cardiovascular diseases and cancer, in some biological fluids. Voltammetric measurements were performed in 0.30 M (pH 9.0) phosphate solution as supporting electrolyte, a reduction peak was observed at–0.487 V (vs. Ag/AgCl–3 M KCl) with a hanging mercury drop electrode by square wave voltammetry. Cyclic voltammetric measurements showed that the current was adsorption-controlled. LOD and LOQ values were as 0.25 and 1.5 nM, respectively, for the AdSqW method. 3-NT was determined in plasma and cerebrospinal fluid using AdSqW method, which allowed to work at low concentrations. Recovery value was measured as 96.3 ± 2.3%.