Synthesis,characterization, and biological activity of [2‐oxo‐2‐(4‐acetyl) phenyl amino] ethylene methacrylate and its derivatives

A new type of methacrylate monomer, [2‐oxo‐2‐(4‐acetyl) phenyl amino] ethylene methacrylate (APEMA), was synthesized. The oxime, 2,4‐dinitrophenylhydrazone, and thiosemicarbazone derivatives of poly{[2‐oxo‐2‐(4‐acetyl) phenyl amino] ethylene methacrylate} [poly(APEMA)] were prepared with hydroxylamine hydrochloride, 2,4‐dinitrophenylhydrazine, and thiosemicarbazone hydrochloride, respectively. The radical homopolymerization of APEMA was performed at 65 °C in a 1,4‐dioxane solution with benzoyl peroxide as an initiator. The monomer and its homopolymer were characterized with Fourier transform infrared and NMR techniques. The thermal stabilities of poly(APEMA) and its derivatives were investigated with thermogravimetric analysis and differential scanning calorimetry. The ultraviolet stability of the polymers were compared. The solubility and inherent viscosity of the polymers were also determined. The number‐average and weight‐average molecular weights and polydispersity index of the polymers were determined with gel permeation chromatography. The antibacterial and antifungal effects of the monomer and the polymer and its derivatives were also investigated on various bacteria and fungi. The activation energies of the thermal degradation of the polymers were calculated with the Ozawa method. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3157–3169, 2004     

Analytical TEM examinations of CoPt-TiO2 perpendicular magnetic recording media.

For this analytical TEM study, nonmagnetic oxygen-rich boundaries were introduced into Co-Pt-alloy perpendicular recording media by cosputtering Co and Pt with TiO2. Increasing the TiO2 content resulted in changes to the microstructure and elemental distribution within grains and boundaries in these films. EFTEM imaging was used to generate composition maps spanning many tens of grains, thereby giving an overall depiction of the changes in elemental distribution occurring with increasing TiO2 content. Comparing EFTEM with spectrum-imaging maps created by high-resolution STEM with EDXS and EELS enabled both corroboration of EFTEM results and quantification of the chemical composition within individual grain boundary areas. The difficulty of interpreting data from EDXS for these extremely thin films is discussed. Increasing the TiO2 content of the media was found to create more uniformly wide Ti- and O-rich grain boundaries as well as Ti- and O-rich regions within grains.     

Charge transfer efficiency in hybrid bulk heterojunction composites

On the basis of recently published electrochemical measurements, the charge transfer efficiency within CdSe nanocrystal/conducting polymer heterojunction composites was investigated by means of luminescence interaction strength. It was found that poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene] and poly-9-vinylcarbazole luminescence was not totally quenched by nanocrystals, whereas poly-3-octylthiophene and polyvinylpyrrolidone was completely quenched. In case of poly-3-hexylthiophene, the nanocrystal luminescence was quenched. The results are in complete agreement with the electrochemical findings and thus, the CdSe nanocrystal/Polyvinylpyrrolidone composite should be a promising material for electroluminescent devices.     

Synthesis, spectral and thermal properties of homo- and copolymers of 2-[(5-methylisoxazol-3-yl)amino]-2-oxo-ethyl methacrylate with styrene and methyl methacrylate and determination of monomer reactivity ratios

The methacrylate monomer, 2-[(5-methylisoxazol-3-yl)amino]-2-oxo-ethyl methacrylate (IAOEMA), was synthesized by reacting 2-chloro-N-(5-methylisoxazol)acetamide dissolved in acetonitrile with sodium methacrylate in the presence of triethylbenzylammoniumchloride (TEBAC). The free-radical-initiated copolymerization of IAOEMA, with styrene (ST) and methyl methacrylate (MMA) was carried out in dimethylsulphoxide (DMSO) solution at 65 °C using 2,2^′-azobisisobutyronitrile (AIBN) as an initiator with different monomer-to-monomer ratios in the feed. The monomer (IAOEMA) and copolymers were characterized by FTIR, ¹H- and ¹³C-NMR spectral studies. The copolymer composition was evaluated by nitrogen content in polymers led to the determination of reactivity ratios. The reactivity ratios of the monomers were determined by the application of Fineman-Ross and Kelen-Tüdös methods. The analysis of reactivity ratios revealed that ST and MMA are more reactive than IAOEMA, and copolymers formed are statisticalle in nature. The molecular weights (M_w and M_n) and polydispersity index of the polymers were determined using gel permeation chromagtography. Glass transition temperatures of the copolymers were found to increase with an increase in the mole fraction of IAOEMA in the copolymers. The apparent thermal decomposition activation energies (E_d) were calculated by Ozawa method using the SETARAM Labsys TGA thermobalance.     

Two-step polymerization approach for synthesis of macroporous surface ion-imprinted cryogels

Today, the surface imprinted polymers emerge in various fields as synthetic adsorbents gaining attention in a variety of application areas. In this study, Cu(II) ion surface imprinted poly(2-hydroxyethyl methacrylate-glycidyl methacrylate), poly(HEMA-GMA), cryogels were synthesized via modified two-step polymerization which is different from given in literature and the adsorption of Cu(II) ion from aqueous solution was investigated batch wise. In this respect, the method applied in this study is new in the literature despite heavy metal removal studies reported. The polyethyleneimine (PEI) molecule was used in polymeric structure as a ligand. The poly(HEMA-GMA) cryogels prepared was characterized via Fourier transform infrared spectroscopy (FTIR), inductively coupled plasma optical emission spectrometry (ICP-OES), elemental analysis, scanning electron microscopy (SEM) and the micro-computed tomography (μCT).     

Interactions of Imidazolium Based Ionic Liquids with Water Studied by Density and Speed of Sound Measurements: Effect of the Chain Length of an Alkyl Substituent on the Imidazolium Ion

Densities and speeds of sound of three ionic liquids (ILs), 1-ethyl-3-methyl imidazoliumtetrafluoroborate (C₂mimBF₄), 1-butyl-3-methylimidazoliumtetrafluoroborate (C₄mimBF₄) and 1-hexyl-3-methylimidazoliumtetrafluoroborate (C₆mimBF₄) were measured in aqueous solutions at (288.15, 293.15, 298.15, 303.15 and 308.15) K. These data were used to calculate the volumetric properties apparent molar volume and apparent molar isentropic compression as a function of molality. Infinite dilution values for these properties were evaluated by an extrapolation procedure based on Redlich–Meyer type equations. Apparent molar isobaric expansions at infinite dilution were also obtained from the slopes of the apparent molar volume at infinite dilution versus temperature. All these properties are interpreted in terms of IL–water interactions. The hydrolysis of the \( {\text{BF}}_{4}^{ - } \) anion of the ILs and its effects on the results is discussed.     

Substrates with discretely immobilized silver nanoparticles for ultrasensitive detection of anions in water using surface-enhanced Raman scattering

Positively charged silver nanoparticles, Ag [+], obtained by UV-assisted reduction of silver nitrate using branched poly(ethyleneimine) (BPEI) and 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) solutions as reducing agents, were immobilized on glass surfaces to produce substrates active in surface-enhanced Raman scattering (SERS). Negatively charged silver nanoparticles, Ag [-], synthesized via a modified citrate reduction method, were also investigated for comparison. At a sparse surface coverage of 30 nanoparticles/microm(2), substrates with immobilized Ag [+] showed increasing SERS sensitivity to a variety of anions in water in the order SO(4)(2-) < CN(-) < SCN(-) approximately ClO(4)(-), with corresponding binding constants of 10(5), 3.3 x 10(5), and 10(7) (for both SCN- and ClO(4)(-)) M(-1), respectively. This order followed the Hofmeister series of anion binding in water. Significantly, substrates with Ag [+] allowed limit of detection values of 8.0 x 10(-8) M (8 ppb) and 2.7 x 10(-7) M (7 ppb) for environmentally relevant perchlorate (ClO(4)(-)) and cyanide (CN(-)) anions, respectively. In contrast, substrates with immobilized Ag [-], even upon subsequent modification by a monolayer of BPEI for positive surface charge of the nanoparticles, showed a drastically lower sensitivity to these anions. The high sensitivity of substrates with Ag [+] for anion detection can be attributed to the presence of two types of functional groups, amino and amide, on the nanoparticle surface resulting from UV-assisted fragmentation of BPEI chains. Both amino and amide provide strong binding of anions with Ag [+] nanoparticles due to the synergistic effect through a combination of electrostatic, hydrogen bonding, and dispersive interactions.     

New Methacrylate Copolymers Based on the Benzofurane Ring: Synthesis,Characterization, Monomer Reactivity Ratios and Biological Activity

The free radical copolymerization of (5-bromo-1-Benzofuran-2-yl)(phenyl)-O-methacrylketoxime (BPMKO) with 2-(4-acetylphenoxy)-2-oxoethyl-2-methylacrylate(AOEMA) has been carried out in 1, 4-dioxane at 65°C ± 1 and was analyzed by Fourier transform infrared, ¹H-NMR, ¹³C-NMR and gel permeation chromatography. Elemental analysis was used to determine the molar fractions of BPMKO and AOEMA in the copolymers. The monomer–reactivity ratios were calculated according to the general copolymerization equation using Kelen-Tüdõs and Finemann-Ross linearization methods. The reactivity ratios indicated a tendency toward random copolymerization. The polydispersity indices of the polymers were determined by gel permeation chromatography and suggested a strong tendency for chain termination by disproportionation. The thermal behaviors of copolymers with various compositions were investigated by differential scanning calorimetry and thermogravimetric analysis. The glass-transition temperature of the copolymers increased with increasing BPMKO content in the copolymers. All the products showed moderate activity against different strains of bacteria and fungi.     

Investigation of metal activation of a partially purified polyphenol oxidase enzyme electrode

Biosensors can be developed using different biological materials and immobilization technologies. Enzymes are generally used in biosensor construction, and some enzymes need metal ions or small organic molecules as a cofactor for their activation. Polyphenol oxidases can be activated by several metal ions such as Cu²⁺, Mg²⁺, Zn²⁺, Mn²⁺, and Ni²⁺. In this study, a new measurement method has been developed that is based on the metal ion activation of the polyphenol oxidase enzyme used in the biosensor preparation, especially to determine the concentration of Mg²⁺ ions. Polyphenol oxidase (PPO) (EC 1.10.3.1) was partially purified from potato (Solanum tuberosum) by using (NH₄)₂SO₄ precipitation, dialysis, and lyophylization processes. As a result of this processes, approximately 30-fold purification was achieved for PPO. For construction of the biosensor, the enzyme was immobilized on the dissolved oxygen probe membrane using gelatin and glutaraldehyde (2.5%). Using the biosensor, we obtained responses for catechol in the absence and presence of Mg²⁺ ions. Differences between the biosensor responses were related to the concentration of Mg²⁺ ions. The biosensor response depends linearly on concentration of Mg²⁺ ions between 0.05 and 7.5?mM. In the optimization studies, phosphate buffer (pH 7.0, 50?mM) and 35°C were determined to be the optimum conditions. This project will be a novel biosensor study and it might bring a new term, ‘activation based biosensor’ into the biosensor area.     

Molar conductance of aqueous solutions of sodium, potassium, and nickel trifluoromethanesulfonate at 25‡C

The electrical conductivities of aqueous solutions of NaCF₃SO₃, KCF₃SO₃, and Ni(CF₃SO₃)₂ have been measured at 25‡C in the concentration range 1 to 25X 10^-3 mol-dm^-3 The data approach the Onsager limiting law at low concentrations, leading to a limiting molar ion conductivity for the CF₃SO ₃ ⁻ ion of 44.5±0.2 S-cm²-mol^-1, based on standard values for the cations. Using a simple size parameter for unsymmetrical polyatomic ions, based on the ion geometry, it is shown that the well known empirical relation between the molar conductivities of symmetrical ions and their radii can be extended to include certain polyatomic anions including CF₃SO ₃ ⁻ . The results suggest that the CF₃SO ₃ ⁻ ion is either a weak structure breaker in aqueous solution or neutral in this respect.