Surface modification of UV‐cured epoxy resins by click chemistry

A novel method for surface modification of UV‐cured epoxy network was described. Photoinitiated cationic copolymerization of a bisepoxide, namely 3,4‐epoxy cyclohexylmethyl 3,4‐epoxycyclohexanecarboxylate (EEC) with epibromohydrine (EBH) by using a cationic photoinitiator, [4‐(2‐methylpropyl)phenyl]4‐methylphenyl‐iodonium hexafluorophosphate, in propylene carbonate solution was studied. The real‐time Fourier transform infrared spectroscopic, gel content determination and thermal characterization studies revealed that both EEC and EBH monomers take part in the polymerization and epoxy network possessing bromomethyl functional groups was obtained. The bromine functions of the cured product formed on the glass surface were converted to azide functionalities with sodium azide. Independently prepared alkyne functional poly(ethylene glycol) (PEG) was subsequently anchored to azide‐modified epoxy surface by a “click” reaction. Surface modification of the network through incorporation of hydrophilic PEG chain was evidenced by contact angle measurements. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2862–2868, 2010     

Gold nanoparticles produced in a microalga

An efficient biological route to production of gold nanoparticles which allows the nanoparticles to be easily recovered remains elusive. Live cells of the green microalga Chlorella vulgaris were incubated with a solution of gold chloride and harvested by centrifugation. Nanoparticles inside intact cells were identified by transmission electron microscopy and confirmed to be metallic gold by synchrotron based X-ray powder diffraction and X-ray absorption spectroscopy. These intracellular gold nanoparticles were 40–60 nm in diameter. At a concentration of 1.4% Au in the alga, a better than 97% recovery of the gold from solution was achieved. A maximum of 4.2% Au in the alga was obtained. Exposure of C. vulgaris to solutions containing dissolved salts of palladium, ruthenium, and rhodium also resulted in the production of the corresponding nanoparticles within the cells. These were surmised to be also metallic, but were produced at a much lower intracellular concentration than achieved with gold. Iridium was apparently toxic to the alga. No nanoparticles were observed using platinum solutions. C. vulgaris provides a possible route to large scale production of gold nanoparticles.     

Characterization,slab-pair modeling and phase analysis of circular fishnet metamaterials

Planar metamaterials, which have incident to normal plane excitation unlike SRR-type structures and that are easily fabricated in multilayer form, have received great interest in recent years. In this paper, one-dimensional and polarization independent circular fishnet metamaterials and their equivalent discontinuous slab-pair modeling for tuning resonance frequencies are introduced. After the numerical and experimental demonstration of the inclusions, the standard retrieval characterization methods and the correspondent/related backward-wave propagation observation are realized in order to check the physical explanation mentioned in the paper. In addition, a detailed phase analysis is performed in order to demonstrate the application of the suggested structure as a phase compensator.     

Quantitative measurement of different ceramide species from crude cellular extracts by normal-phase high-performance liquid chromatography coupled to atmospheric pressure ionization mass spectrometry

Normal-phase high-performance liquid chromatography (NP-HPLC) coupled to atmospheric pressure ionization mass spectrometry (APCI-MS) allows quantitative analysis of endogenous ceramide and dihydroceramide species from crude lipid extracts. Qualitative information for the species comes from observation of differences in chromatographic and mass spectrometric behavior between species (Pettus et al. Rapid Commun. Mass Spectrom. 2003; 17: 1017-1026). Quantitative analysis is achieved by (1) use of a synthetic internal standard as an extraction and injection control, (2) lack of salt adduction, ion suppression, or other matrix effects in APCI mode, and (3) consistent fragmentation and ionization of external standards across the physiologically relevant concentration range found in endogenous lipid samples. Application to the analysis and quantitation of ceramide and dihydroceramide from various cell lines is demonstrated. The results from APCI-MS analysis corroborate and enhance information acquired from use of the diacylglycerol kinase assay for total ceramide measurement. This technique readily allows simultaneous quantitation of ceramide and dihydroceramide species.     

Structure and characterization of N-(2-hydroxy-1-naphthylidene)threonine

Threonine Schiff base derived 2-hydroxy-1-naphthaldehyde and threonine has been isolated and investigated. The stoichiometry of this compound was derived from the results of elemental analyses, IR, ¹H-NMR and UV spectroscopic techniques. X-ray diffraction method was also used to obtain the single-crystal structure. The compound crystallizes in the space group P2₁ with cell dimensions a=5.109(2), b=11.334(2), and β=91(3)° with Z=2. The molecule has phenol-imine tautomeric form in the crystal structure. Some of bond lengths and angles found in the molecular structure are distorted due to π-electron delocalization and steric effect of naphthylidene and threonine groups.     

Synthesis of H‐shaped complex macromolecular structures by combination of atom transfer radical polymerization,photoinduced radical coupling,ring‐opening polymerization,and iniferter processes

Three controlled/living polymerization processes, namely atom transfer radical polymerization (ATRP), ring‐opening polymerization (ROP) and iniferter polymerization, and photoinduced radical coupling reaction were combined for the preparation of ABCBD‐type H‐shaped complex copolymer. First, α‐benzophenone functional polystyrene (BP‐PS) and poly(methyl methacrylate) (BP‐PMMA) were prepared independently by ATRP. The resulting polymers were irradiated to form ketyl radicals by hydrogen abstraction of the excited benzophenone moieties present at each chain end. Coupling of these radicals resulted in the formation of polystyrene‐b‐poly(methyl methacrylate) (PS‐b‐PMMA) with benzpinacole structure at the junction point possessing both hydroxyl and iniferter functionalities. ROP of ε‐caprolactone (CL) by using PS‐b‐PMMA as bifunctional initiator, in the presence of stannous octoate yielded the corresponding tetrablock copolymer, PCL‐PS‐PMMA‐PCL. Finally, the polymerization of tert‐butyl acrylate (tBA) via iniferter process gave the targeted H‐shaped block copolymer. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4601–4607     

Structure and magnetic properties of the Al1−xGaxFeO3 family of oxides: A combined experimental and theoretical study

Magnetic properties of the Al_1−xGa_xFeO₃ family of oxides crystallizing in a non-centrosymmetric space group have been investigated in detail along with structural aspects by employing X-ray and neutron diffraction, Mössbauer spectroscopy and other techniques. The study has revealed the occurrence of several interesting features related to unit cell parameters, site disorder and ionic size. Using first-principles density functional theory based calculations, we have attempted to understand how magnetic ordering and related properties in these oxides depend sensitively on disorder at the cation site. The origin and tendency of cations to disorder and the associated properties are traced to the local structure and ionic sizes.     

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     

Synthesis and characterization of sulfone containing main chain oligobenzoxazine precursors

The preparation of soluble and processable polybenzoxazine precursors capable of forming high performance networks is an important field of research with a broad spectrum of application. This study demonstrates an approach that utilizes aromatic sulfonediamine, bisphenol‐A, and formaldehyde in Mannich‐type polycondesation to prepare polybenzoxazine precursor. The structure of the oligomeric precursor (M_n = 2600) was confirmed by FTIR and ¹H NMR spectral analysis. The precursor contained both sulfone and benzoxazine ring structures in the backbone. It was shown that small amount of ring‐opened phenolic groups were also present. Thermally activated self‐curing behavior of precursor in the absence of catalyst was studied by differential scanning calorimetry. Thermal properties of the cured polymers were also investigated by thermo gravimetric analysis. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011