Bis(saccharinato)palladium(II) and platinum(II) complexes with 2,2′-bipyridine: Syntheses,structures, spectroscopic,fluorescent and thermal properties

New palladium(II) and platinum(II) complexes, cis-[Pd(bpy)(sac)₂] (1) and cis-[Pt(bpy)(sac)₂] (2), where sac = saccharinate, bpy = 2,2′-bipyridine, have been synthesized and characterized by elemental analysis, UV–Vis, IR, ¹H NMR and ¹³C NMR. The structures of the DMSO solvated complexes are determined by X-ray diffraction. Both complexes are isomorphous and the metal ions are coordinated by two N-bonded sac ligands, and two nitrogen atoms of pyridyl groups of bpy in a cis fashion. The mononuclear species interact each other through weak intermolecular C–H?O hydrogen bonds, C–H?π and π?π interactions leading to three-dimensional supramolecular networks. All complexes exhibit a high thermal stability in the solid state, and are fluorescent in the solution.     

Improvement of catalytic activity of lipase in the presence of wide rim substituted calix[4]arene carboxylic acid-grafted magnetic nanoparticles

Candida rugosa lipase immobilized on calix[4]arene carboxylic acid-grafted magnetic nanoparticles using a sol–gel encapsulation technique was tested for activity, which was assessed both in the enantioselective hydrolysis of racemic Naproxen methyl ester and that of p-nitrophenylpalmitate. It has also been noticed that, compared to the free enzyme (E = 137) with an ee value of >98 %, S-Naproxen calix[4]arene carboxylic acid-grafted magnetic nanoparticles based on encapsulated lipase (Calix-1-MN and Calix-2-MN) offer excellent enantioselectivity (E = 373 and E = 381). Moreover, the results indicated that after the fifth reuse in the enantioselective reaction, the encapsulated lipase (Calix-2-MN) still retained about 43 % of its conversion power.     

Influences of Co-60 gamma-ray irradiation on electrical characteristics of Al2O3 MOS capacitors

Effects of gamma-ray irradiation on the electrical characteristics of Al₂O₃ MOS capacitors such as barrier height, acceptor concentration, series resistance and interface state parameters have been studied by analyzing capacitance–voltage (C–V) and conductance–voltage (G/ω–V) measurements. The fabricated MOS capacitors were irradiated with gamma-rays at doses up to five grays. C–V and G/ω–V measurements were recorded prior to and after irradiation at high frequency. The results show that the measured capacitance and conductance values decreased with increasing in irradiation dose and C–V and G/ω curves has been shifted toward the negative voltages. Moreover, the series resistance (R _s) and density of interface states increased with increasing in irradiation dose and density of interface states (D _it) were calculated as order of 10¹² eV^?1cm^?2 prior to and after irradiation. Due to presence and variations in the R _s values, the corrected and the measured C–V and G/ω–V exhibited different behaviors. Therefore other electrical characteristics were assessed from corrected C _c characteristics. It was observed that acceptor concentration decreased with increasing in barrier height of device due to changes in interface states and diffusion potential.     

Polymerization of monoisocyanates by the Pruitt–Baggett adduct

n-Butyl isocyanate (nBIC) was polymerized in bulk by the Pruitt–Baggett adduct (PBA) at ?23, 0.0, and 25.0°C. Polymerization was accompanied by trimerization to the cyclicisocyanurates at all temperatures. Spectroscopic evidences supported the nylon-1 structure for both trimer and polymer. The polymer/trimer ratio and the molecular weight of produced polymers were found to increase with decreasing temperature. The Pruitt–Baggett catalyst (PBC), which is the reaction product of (PBA + H₂O) system, also polymerized nBIC, but with a relatively slower rate. In aromatic and etheric solutions, nBIC was only trimerized by PBA. Copolymerization of nBIC with propylene oxide by PBA and PBC failed. Some selected monoisocyanates were also polymerized by PBA. © 1993 John Wiley & Sons, Inc.     

Highly sensitive sensing of zinc(II) by development and characterization of a PVC-based fluorescent chemical sensor

A sensor membrane with excellent performance based on 1-methyl-1-phenyl-3-[1-hydroxyimino-2-(succinimido)ethyl]cyclobutane has been developed for the determination of zinc(II) ions. The sensing membrane is capable of determining zinc(II) with an outstanding high selectivity over a dynamic range between 8.0×10(-8) and 1.6×10(-4) mol L(-1) with a limit of detection of 2.5×10(-8) mol L(-1) (1.6 μg L(-1)). It can be easily and completely regenerated by using 0.1 mol L(-1) EDTA solution. The optical sensor developed here was found to be stable, cost effective, easy to prepare, and has unique selectivity towards Zn(2+) ion with respect to common metal ions. The proposed sensor was then applied for the determination of zinc in tap water and hair samples with satisfactory results.     

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     

Synthesis of pyrene end‐capped A6 dendrimer and star polymer with phosphazene core via “click chemistry”

Novel hexa‐armed and pyrene (Pyr) end‐capped phosphazene dendrimer [N₃P₃‐(Pyr)₆] and star polymer with poly(ε‐caprolactone) (PCL) arms [N₃P₃‐(PCL‐Pyr)₆] were prepared via two series of reactions. In these series, core‐first approach was used starting from a hexa‐hydroxy functional phosphazene derivative (N₃P₃‐(OH)₆). It was used as an initiator in the ring‐opening polymerization of ε‐caprolactone to prepare a hexa‐armed PCL star polymer (N₃P₃‐(PCL‐OH)₆). Hydroxyl functionalities of N₃P₃‐(OH)₆ and N₃P₃‐(PCL‐OH)₆ were then successfully converted into bromide and azide, in turn. Further end‐group modifications of azide functional dendrimer precursor (N₃P₃‐(N₃)₆) and star polymer (N₃P₃‐(PCL‐N₃)₆) were achieved quantitatively via the Cu(I) catalyzed click reaction between azide functional groups and 1‐ethynyl pyrene in the final step. Moreover, the pyrene end‐capped phosphazene dendrimer and star polymer were used in noncovalent functionalization of multiwalled carbon nanotubes. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis of a novel macroinimer based on thiophene and poly(ε‐caprolactone) and its use in electrochromic device application

Synthesis of a novel macroinimer comprising poly(ε‐caprolactone) (PCL) and thiophene (Th) and its use in electrochromic device (ECD) application have been reported. First, a novel Th monomer ( 5 ) with miktofuntional initiator groups (primary hydroxyl and tertiary bromide at the third position of the thiophene ring) was synthesized in a four‐step reaction sequence. Density functional theory‐predicted bond lengths, angles, and vibrations of 5 were in good agreement with available experimental vibrational spectra. Subsequently, ring‐opening polymerization of ε‐caprolactone (ε‐CL) was carried out in bulk using 5 as the initiator and tin(II) 2‐ethylhexanoate (Sn(Oct)₂) as the catalyst at 115 °C, which led to α‐thiophene end‐capped PCL macroinimer (PCL‐Th). Furthermore, PCL‐Th macroinimer was used in electrochemical copolymerization with pyrrole (Py) and Th. PCL‐Th/PTh copolymer film synthesized on indium tin oxide‐coated glass slide showed electrochromic behavior. Optical analyses of the PCL‐Th/PTh copolymer film indicated that the copolymer film was suitable to be used as an anodically coloring material for ECD applications. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Raman and Photoluminescence Spectroscopic Detection of Surface‐Bound Li+O2− Defect Sites in Li‐Doped ZnO Nanocrystals Derived from Molecular Precursors

We present a detailed study of Raman spectroscopy and photoluminescence measurements on Li‐doped ZnO nanocrystals with varying lithium concentrations. The samples were prepared starting from molecular precursors at low temperature. The Raman spectra revealed several sharp lines in the range of 100–200 cm^?1, which are attributed to acoustical phonons. In the high‐energy range two peaks were observed at 735 cm^?1 and 1090 cm^?1. Excitation‐dependent Raman spectroscopy of the 1090 cm^?1 mode revealed resonance enhancement at excitation energies around 2.2 eV. This energy coincides with an emission band in the photoluminescence spectra. The emission is attributed to the deep lithium acceptor and intrinsic point defects such as oxygen vacancies. Based on the combined Raman and PL results, we introduce a model of surface‐bound LiO₂ defect sites, that is, the presence of Li⁺O₂^? superoxide. Accordingly, the observed Raman peaks at 735 cm^?1 and 1090 cm^?1 are assigned to Li? O and O? O vibrations of LiO₂.     

Development of enhanced ultrafiltration methodologies for the resolution of racemic benzoin

In the scope of achieving the separation of chiral molecules, enzyme enhanced ultrafiltration (EEUF), a new method based on polymer enhanced ultrafiltration (PEUF), utilizing apoenzymes as ligands, was developed. Benzoin was chosen as the model chiral molecule. Bovine serum albumin (BSA) and apo form of benzaldehyde lyase (BAL) (E.C. 4.1.2.38) were used as chiral ligands in PEUF and EEUF experiments, respectively. In order to bind to the target enantiomer well, the addition of ligand to the benzoin solution was followed by ultrafiltration. With the use of BSA as ligand, adaptation of PEUF for chiral target molecules and process parameter optimization was carried out; whereas, in EEUF studies the effect of ligand concentration was focused on. In PEUF experiments, although total benzoin retention values reached to 48.7% and 41.3% at pH 10, for 15% (v/v) PEG 400 and 30% (v/v) DMSO cosolvents, respectively; obtained enantiomeric excess (ee) % values were all less than 20%. In EEUF experiments, at BAL concentrations greater than 158 ppm, total benzoin retention and ee% remained constant at ca. 75% and 60%, respectively. On the other hand, at 61 ppm BAL concentration, total benzoin retention was kept at ca. 75%, but ee% decreased to ca. 30%, probably due to the nonspecific binding of benzoin to DNA and other proteins. Thus, the method developed enzyme enhanced ultrafiltration, functioned with its intended purpose effectively in chiral separation.