Linear tetrablock quaterpolymers via triple click reactions,azide‐alkyne,diels–alder,and nitroxide radical coupling in a one‐pot fashion

Azide‐alkyne and Diels–Alder click reactions together with a click‐like nitroxide radical coupling reaction were used in a one‐pot fashion to generate tetrablock quaterpolymer. The various living polymerization generated linear polymers with orthogonal end‐functionalities, maleimide‐terminated poly(ethylene glycol) (PEG‐MI), anthracene‐ and azide‐terminated polystyrene, alkyne‐ and bromide‐terminated poly(tert‐butyl acrylate) or alkyne‐poly(n‐butyl acrylate), and tetramethylpiperidine‐1‐oxyl (TEMPO)‐terminated poly(ε‐caprolactone) (PCL‐TEMPO) were clicked together in a one‐pot fashion to generate PEG‐b‐PS‐b‐PtBA‐b‐PCL or PEG‐b‐PS‐b‐PnBA‐b‐PCL quaterpolymer using Cu(0), CuBr, and N,N,N′,N″,N″‐pentamethyldiethylenetriamine as catalyst in dimethyl formamide at 80 °C for 36 h. Linear precursors and target quaterpolymers were analyzed via ¹H NMR and gel permeation chromatography. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Copper‐Free Sonogashira Coupling for High‐Surface‐Area Conjugated Microporous Poly(aryleneethynylene) Networks

A modified one‐pot Sonogashira cross‐coupling reaction based on a copper‐free methodology has been applied for the synthesis of conjugated microporous poly(aryleneethynylene) networks (CMPs) from readily available iodoarylenes and 1,3,5‐triethynylbenzene. The polymerization reactions were carried out by using equimolar amounts of halogen and terminal alkyne moieties with extremely small loadings of palladium catalyst as low as 0.65 mol %. For the first time, CMPs with rigorously controlled structures were obtained without any indications of side reactions, as proven by FTIR and solid‐state NMR spectroscopy, while showing Brunauer–Emmett–Teller (BET) surface areas higher than any poly(aryleneethynylene) network reported before, reaching up to 2552 m² g^?1.     

Quadruple click reactions for the synthesis of cysteine‐terminated linear multiblock copolymers

Synthesis of cysteine‐terminated linear polystyrene (PS)‐b‐poly(ε‐caprolactone) (PCL)‐b‐poly(methyl methacrylate) (PMMA)/or poly(tert‐butyl acrylate)(PtBA)‐b‐poly(ethylene glycol) (PEG) copolymers was carried out using sequential quadruple click reactions including thiol‐ene, copper‐catalyzed azide–alkyne cycloaddition (CuAAC), Diels–Alder, and nitroxide radical coupling (NRC) reactions. N‐acetyl‐L ‐cysteine methyl ester was first clicked with α‐allyl‐ω‐azide‐terminated PS via thiol‐ene reaction to create α‐cysteine‐ω‐azide‐terminated PS. Subsequent CuAAC reaction with PCL, followed by the introduction of the PMMA/or PtBA and PEG blocks via Diels–Alder and NRC, respectively, yielded final cysteine‐terminated multiblock copolymers. By ¹H NMR spectroscopy, the DP_ns of the blocks in the final multiblock copolymers were found to be close to those of the related polymer precursors, indicating that highly efficient click reactions occurred for polymer–polymer coupling. Successful quadruple click reactions were also confirmed by gel permeation chromatography. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis,characterization, and investigations of antimicrobial activity of benzopyrans,benzofurans and spiro[4.5]decanes

In this study, the radical cyclization reactions of cyclic 1,3-dicarbonyl compounds (1a–c) and α,β-unsaturated alcohols (2a–d) through Mn(OAc)₃ were performed. A series of biologically interesting dihydropyrans (3–5) and dihydrofurans (6–18) were synthesized as a result of these reactions. Spiro compounds (19–20) were obtained from the reactions of 1,3-dicarbonyl compounds and (E)-2,4-diphenyl-but-3-en-2-ol (2e). The unique structure of compound 19 was also confirmed by X-ray crystallography. In addition, the antibacterial activities of synthesized compounds were screened against some bacteria. Their zone diameters showed better results than some known antibiotics.     

Facile Synthesis of Some 3-(Benzimidazol-2-yl)- and 3,6-Di(Benzimidazol-2-yl)-9-ethyl-9H-carbazoles

A simple and efficient synthesis of novel 3-(benzimidazol-2-yl)- and 3,6-di(benzimidazol-2-yl)-9-ethyl-9H-carbazoles is described. The synthetic approach for the preparation of 2-substituted benzimidazoles 4–8 and bis-benzimidazoles 9–12 was achieved by the condensation of carbazole-3-carbaldehyde 2 and carbazole-3,6-dicarbaldehyde 3 with o-phenyldiamines in dimethylformamide or dimethylsulfoxide in moderate to excellent yield. The identities of synthesized compounds were confirmed using ¹H NMR, ¹³C NMR, infrared (IR), and high-resolution mass spectrometry (HRMS).     

Outer‐Membrane Protease (OmpT) Based E. coli Sensing with Anionic Polythiophene and Unlabeled Peptide Substrate

E. coli and Salmonella are two of the most common bacterial pathogens involved in foodborne and waterborne related deaths. Hence, it is critical to develop rapid and sensitive detection strategies for near‐outbreak applications. Reported is a simple and specific assay to detect as low as 1 CFU mL^?1 of E. coli in water within 6 hours by targeting the bacteria's surface protease activity. The assay relies on polythiophene acetic acid (PTAA) as an optical reporter and a short unlabeled peptide (LL37_FRRV) previously optimized as a substrate for OmpT, an outer‐membrane protease on E. coli. LL37_FRRV interacts with PTAA to enhance its fluorescence while also inducing the formation of a helical PTAA‐LL37_FRRV construct, as confirmed by circular dichroism. However, in the presence of E. coli LL37_FRRV is cleaved and can no longer affect the conformations and optical properties of PTAA. This ability to distinguish between an intact and cleaved peptide was investigated in detail using LL37_FRRV sequence variants.     

Biopolymer-assisted synthesis of yttrium oxide nanoparticles

Yttrium oxide nanopowder was prepared by a novel technique using an alginate biopolymer as a precursor. The technique is based on thermal decomposition of an yttrium alginate gel, which is produced in the form of beads by ionic gelation between the yttrium solution and sodium alginate. The effect of post-annealing temperature on the particle size of the nanocrystals was investigated at various tempera- tures. The products were characterized using X-ray diffraction, scanning electron microscopy, and atomic force microscopy. The size of the nanocrystalline Y2O3 particles varied from 22.7 to 38.7 nm, depending on the annealing temperature and time. The grain size distribution （GSD） was also determined. The GSD became more non-symmetrical as the annealing temperature increased, and the width of the distributions for the powders produced using the alginate method was less affected by heat treatment. This alginate method was compared with the conventional glycine combustion method, on the basis of particle size. The particles obtained using the proposed technique were smaller than those obtained using the combustion method. Alginate-assisted thermal decomposition is therefore an easy and cost-effective method for preparing nanosized Y2O3 crystals.     

Investigation of nucleation and grain growth in 2-dimensional systems by using generalized Monte Carlo simulations

In this study, nucleation and grain growth was studied by using 2-dimensional generalized Monte Carlo simulations and experiments. As an attempt to improve the JMAK model, we proposed a new differential equation to be able to model nucleation and growth phenomena using nonextensive thermostatistics. One of the reasons that we would like to perform generalized Monte Carlo simulations in studying of nucleation and grain growth phenomena is that the generalized Monte Carlo algorithm was shown to be more effective than the standard Monte Carlo algorithm and also than the standard Molecular Dynamic algorithm in locating the minimum energy configuration. Therefore, for a given temperature, the fact that a configuration of the system with lower energy could be obtained by using the generalized Monte Carlo simulation means that a different textural configuration of grain growth could be also expected. In this respect, it is possible to say that the nonextensive statistics might be an appropriate tool in studying of nucleation and growth phenomena.