Synthesis and X-Ray Crystal Structure Study of ]2-Methyl-4-(2-methylbenzoyl)-phenoxy] Acetic Acid Hydrazide

Benzophenone analog 3 has been synthesized and characterized by the X-ray diffraction (XRD) method. The compound crystallizes in a monoclinic space group P2₁/c with cell parameters a = 7.701(8) Å, b = 7.151(5) Å, c= 28.323(3) Å, = 104.639(4)°, Z = 4. The structure exhibits intra- and intermolecular hydrogen bonding of the type N–HO, C–HO, and N–HN. The molecules are interlinked through hydrogen bonds forming an infinite chain. This polymeric-like structure may play an important role in biological activity.     

Synthesis and Crystal Structure of a Novel Polymeric Thiocyanato-Bridged Heteronuclear Complex of Copper(II) and Cadmium(II)

The title polymeric complex of Cu(II) and Cd(II) bridged by thiocyanate, Cu(en)₂[Cd(SCN)₃]₂, has been prepared and its structure determined by X-ray diffraction (XRD) methods. The crystal structure reveals that the Cu(II) atom is in an elongated octahedral coordination formed by two SCN^– anions and two en molecules. The Cd(II) atom is in a distorted octahedral coordination formed by six bridging SCN^– anions. Two different bridging thiocyanate anions exist in the complex. Both 1,1--SCN^– and 1,3--SCN^– anion act a role of bridge ligand and link Cu(II), Cd(II) atoms, and adjacent Cd(II). Cd(II) atoms form the three-dimensional (3-D) network polymeric structure. The IR and UV-Vis spectra have also been investigated.     

Resistance properties of a macroporous silica-based N,N,N′,N′-tetraoctyl-3-oxapentane-1,5-diamide-impregnated polymeric adsorption material against nitric acid, temperature and γ-irradiation

The resistance of a novel silica-based N,N,N′,N′-tetraoctyl-3-oxapentane-1,5-diamide (TODGA) polymeric adsorption material (TODGA/SiO₂-P) against nitric acid, temperature and γ-irradiation had been investigated. The adsorption property of the treated TODGA/SiO₂-P was evaluated by a 3 M HNO₃ solution containing 0.01 M Nd(III). It was found that both 3 and 0.01 M HNO₃ concentrations did not decrease the stability of TODGA/SiO₂-P at 25°C. The quantity of TODGA leaked from TODGA/SiO₂-P was equivalent to its solubility in the corresponding HNO₃ aqueous solution. The effect of 3 M HNO₃ on the leakage of TODGA at 80°C was significantly higher than that in 0.01 M HNO₃ as well as in all cases at 25°C. The amount of Nd(III) adsorbed towards the treated TODGA/SiO₂-P was determined in the range of 0.143–0.148 mmol/g for the HNO₃ concentration effect and 0.142–0.0506 mmol/g for the temperature effect. γ-Irradiation showed a more noticeable destruction effect on TODGA/SiO₂-P. The content of TODGA leaked increased with an increase in the γ-irradiation dose (ID) from 1.06 to 3.72 MGy in terms of the linear equation [TODGA]=794.5ID+84.0. The amount of Nd(III) adsorbed onto the irradiated TODGA/SiO₂-P decreased rapidly from 0.134 to 0.0438 mmol/g, which was lower than 0.153 mmol/g, the adsorption of fresh TODGA/SiO₂-P for Nd(III), according to the equation Q_Nd(III)=−0.0301ID+0.160, showing that a large quantity of TODGA leaked from TODGA/SiO₂-P. The adsorbed amount of Nd(III) decreased obviously in this order: the HNO₃ concentration effect, temperature effect and γ-irradiation.     

Electrochemically formed fullerene-based polymeric films

The recent results of investigations involving the electrochemical formation of polymers containing fullerenes and studies of their properties and applications are critically reviewed. From a structural point of view, these polymers can be divided into four main categories including (1) polymers with fullerenes physically incorporated into the foreign polymeric network without forming covalent bonds, (2) fullerene homopolymers formed via [2+2] cycloaddition, (3) “pearl necklace” polymers with fullerenes mutually linked covalently to form polymer chains, and (4) “charm bracelet” polymers containing pendant fullerene substituents. The methods of electrochemical polymerization of these systems are described and assessed. The structural features and properties of the electrochemically prepared polymers and their chemically synthesized analogs are compared. Polymer films containing fullerenes are electroactive in the negative potential range due to electroreduction of the fullerene moieties. Related films made with fullerenes derivatized with electron-donating moieties as building blocks are electroactive in both the negative and positive potential range. These can be regarded as “double cables” as they exhibit both p- and n-doping properties. Fullerene-based polymers may find numerous applications. For instance, they can be used as charge-storage and energy-converting materials for batteries and photoactive units of photovoltaic cell devices, respectively. They can be also used as substrates for electrochemical sensors and biosensors. Films of the C₆₀/Pt and C₆₀/Pd polymers containing metallic nano-particles of platinum and palladium, respectively, effectively catalyze the hydrogenation of olefins and acetylenes. Laser ablation of electrochemically formed C₆₀/M and C₇₀/M polymer films (M=Pt or Ir) results in fragmentation of the fullerenes leading to the formation of hetero-fullerenes, such as [C₅₉M]⁺ and [C₆₉M]⁺.Dedicated to Professor Dr. Alan M. Bond on the occasion of his 60th birthday.     

Hydrophobic cryogels for DNA adsorption: Effect of embedding of monosize microbeads into cryogel network on their adsorptive performances

As alternative hydrophobic adsorbent for DNA adsorption, supermacroporous cryogel disks were synthesized via free radical polymerization. In this study, we have prepared two kinds of cryogel disks: (i) poly(2‐hydroxyethyl methacrylate‐N‐methacryloyl‐l ‐tryptophan) [p(HEMA‐MATrp)] cryogel containing specific hydrophobic ligand MATrp; and (ii) monosize p(HEMA‐MATrp) particles synthesized via suspension polymerization embedded into p(HEMA) cryogel structure to obtain p(HEMA‐MATrp)/p(HEMA) composite cryogel disks. These cryogel disks containing hydrophobic functional group were characterized via swelling studies, Fourier transform infrared spectroscopy, elemental analysis, surface area measurements and scanning electron microscopy. DNA adsorption onto both p(HEMA‐MATrp) cryogel and p(HEMA‐MATrp)/p(HEMA) composite cryogels was investigated. Maximum adsorption of DNA on p(HEMA‐MATrp) cryogel was found to be 15 mg/g polymer. Otherwise, p(HEMA‐MATrp)/p(HEMA) composite cryogels significantly increased the DNA adsorption capacity to 38 mg/g polymer. Composite cryogels could be used repeatedly without significant loss on adsorption capacity after 10 repetitive adsorption–desorption cycles. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis and photovoltaic properties of main chain polymeric metal complexes containing 1,10‐phenanthroline metal complexes conjugating alkyl fluorene or alkoxy benzene by C═C bridge for dye‐sensitized solar cells

Four main chain polymeric metal complexes (P1–P4) based on 1,10‐phenanthroline metal complexes via the Heck coupling have been synthesized and characterized by Fourier transform infrared spectroscopy, ¹H NMR, UV–Vis absorption, photoluminescence spectroscopy, gel permeation chromatography, thermogravimetric analysis, differential scanning calorimetry, elemental analysis, and cyclic voltammetry. To investigate their photovoltaic properties, the dye‐sensitized solar cells based on these polymers dyes are studied, under the illumination of AM 1.5G, 100 mW/cm². The study results show the four polymers exhibit good thermally stable and the solar cells based on them have good device performance, and the maximum power conversion efficiency is up to 0.735% for the solar cells based on P3 with a short‐circuit current (J_sc) of 1.68 mA/cm² and an open‐circuit voltage (V_oc) of 0.62 V. Copyright © 2012 John Wiley & Sons, Ltd.     

Polymerization and Copolymerization of Some Monomers as Adducts with β-Cyclodextrin

The feasibility of chemical bond formation, especially in the chain-transfer reaction between polymer and β-cyclodextrin (β-CD) molecules in the products of the radiation polymerization of β-CD with vinylidene chloride (VDC) its adducts has been considered. The lack of these bonds in the polymerization products of similar β-CD adducts with methyl methacrylate (MM), styrene (St), a mixture of VDC and allyl chloride (AC) and a mixture of VDC and MM (10:90 molar ratio) has been established. On the basis of the results obtained the lack of chemical bonds in the polymerization product of β-CD· VDC adduct is suggested.     

Synthesis by Emulsion Polymerization of Poly(butyl acrylate-co-silver acrylate) Ionomers and Evaluation of their Possible Applications

The synthesis by emulsion polymerization and the characterization by a battery of techniques of poly(butyl acrylate-co-silver acrylate) [poly(BuAc-co-AgAc)] ionomers are reported here. Reaction rates were fast and conversions around 90% were obtained in less than one hour, regardless of the initial ratio of butyl acrylate and silver acrylate employed (BuAc/AgAc = 90/10, 80/20, 70/30). Particle size was in the range of 176 to 200 nm, depending on the BuAc/AgAc ratio. Ionomers’ formation was corroborated by infrared spectroscopy and inferred by differential scanning calorimetry (DSC). DSC disclosed that the poly(BuAc-co-AgAc) has two glass transition temperatures: one at ca. ?49°C due to relaxation of the ionomer backbone domains rich in BuAc and another ca. 35°C due to the relaxation of the backbone domains where the AgAc-units content was higher. Young moduli increased as the copolymers became richer in AgAc. Antibacterial tests against Escherichia coli with the 90/10 (BuAc/AgAc) ionomer revealed that the bacteria population diminishes from 5 log CFU/mL to less than 0.3 MPN/mL after one hour of contact with the ionomers. Also, we demonstrated that the ionomers are excellent compatibilizers for making semiconductive films of n-dodecylbenzene sulfonic acid-doped polyaniline (PANIDBSA)-poly(BuAc-co-AgAc) and poly(n-butyl methacrylate) (PBMA) blends. The electrical conductivity of the blend films, which were homogeneous, rose as the AgAc content in the films increased.     

Towards predicting the solubility of CO2 and N2 in different polymers using a quasi-SMILES based QSPR approach

The solubility of gases in various polymers plays an important role for the design of new polymeric materials. Quantitative structure–property relationship (QSPR) models were designed to predict the solubility of gases such as CO₂ and N₂ in polyethylene (PE), polypropylene (PP), polystyrene (PS), polyvinyl acetate (PVA) and poly (butylene succinate) (PBS) at different temperatures and pressures by using quasi-SMILES codes. The dataset of 315 systems was split randomly into training, calibration and validation sets; random split 1 led to 214 training (r² = 0.870 and RMSE = 0.019), 51 calibration (r² = 0.858 and RMSE = 0.020) and 50 validation (r² = 0.869 and RMSE = 0.017) sets. The suggested approach based on the quasi-SMILES, which are analogues of the traditional SMILES gives reasonable good predictions for solubility of CO₂ and N₂ in different polymers. The described methodology is universal for situations where the aim is to predict the response of an eclectic system upon a variety of physicochemical and/or biochemical conditions.     

Stabilization of zeylenone in rat plasma by the presence of esterase inhibitors and its LC‐MS/MS assay for pharmacokinetic study

Six esterase inhibitors, namely EDTA·2Na⁺, NaF, phenylmethanesulfonyl fluoride, dichlorvos, bis‐nitrophenyl phosphate (BNPP) and thenoyltrifluoroacetone, and the mixture of NaF and BNPP, were evaluated for the stabilization of labile benzoate containing zeylenone in rat plasma. The mixture appeared to exhibit the most effectively stabilizing effect with the degraded content of zeylenone decreasing from >60% (in the absence of inhibitors) to <6%. Following the stabilization by the addition of NaF (5 mm ) and BNPP (5 mm ), the analytes in rat plasma were acidified by formic acid and extracted into ethyl acetate at 0°C. After chromatographic separation, the detection of zeylenone was performed on a 3200 Q‐Trap with positive ion electrospray mode, monitoring the ion transition m/z 383.2 → 105.0. The method was validated over the range from 2.68 to 1340 ng/mL with inter‐ and intra‐run precision for the quality control samples being less than 6.8%. The assay accuracy was within 100 ± 7.0%. The validated method was successfully applied to a pharmacokinetic study in rats after the intratracheal administration of zeylenone in free drug or polymeric micellar solutions. The results showed that the pulmonary absorption of zeylenone loaded in micelles was significantly retarded compared with that of free drug solutions. Copyright © 2012 John Wiley & Sons, Ltd.