Poly(p‐phenylene methylene)‐based block copolymers by mechanistic transformation

The synthesis of poly(p‐phenylene methylene) (PPM)‐based block copolymers such as poly(p‐phenylene methylene)‐b‐poly(ε‐caprolactone) and poly(p‐phenylene methylene)‐b‐polytetrahydrofuran by mechanistic transformation was described. First, precursor PPM was synthesized by acid‐catalyzed polymerization of tribenzylborate at 16 °C. Then, this polymer was used as macroinitiators in either ring‐opening polymerization of ε‐caprolactone or cationic ring‐opening polymerization of tetrahydrofuran to yield respective block copolymers. The structures of the prepolymer and block copolymers were characterized by GPC and ¹H NMR investigations. The composition of block copolymers as determined by ¹H NMR and TGA analysis was found to be in very good agreement. The thermal behavior and surface morphology of the copolymers were also investigated, respectively, by differential scanning calorimetry and atomic force microscopy measurements, and the contribution of the major soft segment has been observed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Soluble alkyl substituted poly(3,4‐propylenedioxyselenophene)s: A new platform for optoelectronic materials

Optical and electrochemical properties of regiosymmetric and soluble alkylenedioxyselenophene‐based electrochromic polymers, namely poly(3,3‐dibutyl‐3,4‐dihydro‐2H‐selenopheno[3,4‐b][1,4]dioxephine) (PProDOS‐C₄), poly(3,3‐dihexyl‐3,4‐dihydro‐2H‐selenopheno[3,4‐b][1,4]dioxephine) (PProDOS‐C₆), and poly(3,3‐didecyl‐3,4‐dihydro‐2H‐selenopheno[3,4‐b][1,4]dioxephine) (PProDOS‐C₁₀), are highlighted. It is noted that these unique polymers have low bandgaps (1.57–1.65 eV), and they are exceptionally stable under ambient atmospheric conditions. Polymer films retained 82–97% of their electroactivity after 5000 cycles. The percent transmittance of PProDOS‐C_n (n = 4, 6, 10) films found to be between 55 and 59%. Furthermore, these novel soluble PProDOS‐C_n polymers showed electrochromic behavior: a color change form pure blue to highly transparent state in a low switching time (1.0 s) during oxidation with high coloration efficiencies (328–864 cm² C^?1) when compared to their thiophene analogues. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Poly(cyclohexene oxide)/clay nanocomposites by photoinitiated cationic polymerization via activated monomer mechanism

Poly(cyclohexene oxide) (PCHO)/clay nanocomposites were prepared by in situ photoinitiated activated monomer cationic polymerization. The polymerization of cyclohexene oxide through the interlayer galleries of the clay can provide distribution of the clay layers in the polymer matrix homogenously and results in the formation of PCHO/clay nanocomposites. The exfoliated structures were characterized by X‐ray diffraction spectroscopy, thermogravimetric analysis, transmission electron microscopy, and atomic force microscopy. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5328–5335, 2009     

Orthogonal Synthesis of Block Copolymer via Photoinduced CuAAC and Ketene Chemistries

A novel route for the synthesis of poly(ethylene glycol)‐b‐polystyrene copolymer, starting from commercially available poly(ethylene glycol) methyl ether and azido terminated polystyrene prepared by atom transfer radical polymerization and subsequent nucleophilic substitution, is applied with simplicity and high efficiency. The combination of photoinduced copper (I)‐catalyzed alkyne‐azide cycloaddition (CuAAC) and ketene chemistry reactions proceeds either simultaneously or sequentially in a one‐pot procedure under near‐visible light irradiation. In both cases, excellent block copolymer formations are achieved, with an average molecular weight of around 7000 g mo1⁻¹ and a polydispersity index of 1.20.

     

Photopolymerized injectable RGD-modified fumarated poly(ethylene glycol) diglycidyl ether hydrogels for cell growth

In this study, photopolymerized hydrogels of fumarated poly(ethylene glycol) diglycidyl-co- poly(ethylene glycol) diacrylate have been synthesized and modified with cell adhesion peptide, Arg-Gly-Asp (RGD). The structural and mechanical properties of the hydrogels are found to be poly(ethylene glycol) diacrylate (PEGDA) dependent. The percentage of gelation is increased from 72 to 89 wt.-% when the amount of the crosslinker co-monomer (PEGDA) in the hydrogel formulation is increased from 20 to 40 wt.-%. In the present case, the equilibrium mass swelling is decreased from 216 to 93%. The viscosities of the uncured formulations have also been measured and likewise, the results were influenced by the increasing amount of PEGDA that reduced the value from 83 to 36 cP. The compressive modulus of the prepared hydrogels was improved with the addition of the PEGDA. Cell growth experiments have been performed by comparing the properties of the hydrogels with and without RGD units. The results show that RGD units enhance the adhesion of cells to the surface of the hydrogels. SEM-EDS studies reveal that nitrogen and calcium are produced on the osteoblast-seeded surface of the scaffold within the culture time period. [Figure: see text].     

Photoconductive novel mesomorphic oxotitanium phthalocyanines

The synthesis and photoconductivity properties of the alkylthia and triethyleneoxysulfonyl substituted oxotitanium(IV) phthalocyanines (1a and 2a) are reported for the first time. The new compounds have been characterized by elemental analysis, IR, ¹H and ¹³C NMR spectroscopy, electronic spectroscopy and mass spectroscopy. The mesogenic properties of these new materials were studied by differential scanning calorimetry and optical microscopy. The electrical dark conductivities (σ_d) and photoconductivities (σ_ph) of deposited films of 1a and 2a were investigated in various media with different concentrations of oxygen. Molecular oxygen increases photoconductivities (σ_ph) significantly. The photoconductivity mechanism and formation of Pc⁺ which is positive charge carrier under the light irradiation of the phthalocyanine molecules are demonstrated using the theoretical calculations. The geometries of the oxotitanium(IV) phthalocyanines (TiOPc) are optimized with PM3 semi-empirical method, and their visible absorption maxima are calculated with ZINDO/S method. The results agree well with the observed values. It was found that for the calculation of visible absorption of neutral and positively charged substituted TiOPc molecules using ZINDO/S method could rapidly yield excellent results. Dipole moment, HOMO, LUMO energies and atomic charges are also calculated for clarification of the oxygen effect on the photoconductivity using PM3 and ZINDO/S methods.     

Synthesis and characterization of liquid crystalline tetra- and octa-substituted novel phthalocyanines

Methylene-bridged tetra- and octa-(13,17-dioxa nonacosane-15 sulfanyl)-substituted metal free- and Ni(II) phthalocyanines were synthesized from the corresponding phthalonitrile (3, 4) derivatives in the presence of the anhydrous metal salt (NiCl₂) or a strong organic base. The new compounds were characterized by elemental analyses, UV/Vis, IR, NMR and mass spectra. The mesogenic properties of these materials were studied by differential scanning calorimetry (DSC), optical microscopy and X-ray diffraction investigations. X-ray diffraction patterns of the mesophase confirm that tetra- and octa-substituted compounds (3a–b, 4a–b) form hexagonal columnar mesophases (Col_h). We indicated that addition of the methylene-bridged phthalocyanine (Pc) core can either decrease the liquid crystal phase transition temperatures or extend the liquid crystal temperature range to include room temperature. Also, the Pc compounds (3a, 3b, 4a and 4b) are liquid crystals at room temperature. These properties of the Pc complexes provide some advantages such as easily obtaining an ordered film for sensor applications. Computational modelling work was combined with X-ray diffraction investigation to validate the diameter of the phthalocyanine molecule (3b).     

Atomistic Engineering of Chemiluminogens: Synthesis,Properties and Polymerization of 2,3-Dihydro-Pyrrolo[3,4-d]Pyridazine-1,4-Dione Scaffolds

Two chemiluminescent compounds containing 2,5-di(thien-2-yl)pyrrole and pyridazine units, namely 5,7-di(thiophen-2-yl)-2,3-dihydro-1H-pyrrolo[3,4-d]pyridazine-1,4(6H)-dione (5) and 6-phenyl-5,7-di(thiophen-2-yl)-2,3-dihydro-1H-pyrrolo[3,4-d]pyridazine-1,4(6H)-dione (6), were successfully synthesized and electrochemically polymerized. The compounds have chemiluminescent properties and glow in the presence of hydrogen peroxide in basic medium. The intensity of the glow can be increased dramatically by using Fe³⁺ ions, hemin (1.0 ppm) or blood samples (1.0 ppm) as catalyst. The compounds 5 and 6 have one well-defined irreversible oxidation peak at 1.08 V and 1.33 V vs Ag/AgCl, respectively. Electrochemical polymerization of both 5 and 6 were carried out successfully by repeating potential scanning in the presence of BF₃. Et2O in an electrolyte solution of 0.1 M LiClO₄ dissolved in acetonitrile. The electronic band gaps (E_g) of the polymers P5 and P6 were found to be 2.02 eV and 2.16 eV, respectively. On the other hand, the corresponding polymers are electroactive and exhibited electrochromic features.

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