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Oligomers
Kinds of Oligomers Terms modified by Oligomers Selected AbstractsA Novel Fluorene-Containing Oligomer with Relative High Photoluminescence Quantum Efficiency.CHEMINFORM, Issue 42 2006Hong-Ji Jiang Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF. [source] Radical Ions from 3,3,,,,3,,,,-Tris(butylsulfanyl)-2,2,:5,,2,:5,,2,,,,5,,,,2,,,,:5,,,,,2,,,,-sexithiophene: An Experimental and Theoretical Study of the p - and n -Doped OligomerCHEMPHYSCHEM, Issue 11 2003Angelo Alberti Dr. Abstract The 3,3,,,,3,,,,-tris(butylsulfanyl)-2,2,:5,,2,:5,,2,,,,5,,,,2,,,,:5,,,,,2,,,,-sexithiophene 1 was investigated through spectroscopic (NMR, EPR, UV/Vis-NIR), electrochemical, spectroelectrochemical and theoretical (DFT) studies. The charged species obtained upon its oxidation and reduction were characterised, showing that 1 can exist in at least five different oxidation states, that is, a neutral species, a radical cation, a dication, a radical anion, and a dianion. The long term stability of the radical cation 1+. was evidenced by the 1H NMR study in the presence of small quantities of trifluoroacetic acid (TFA). This approach allowed a comparison of the relative broadening of proton signals of 1, induced by the electron exchange process with traces of radical cation 1+., and the hfc (hyperfine coupling) constants obtained from the EPR study and DFT calculations. In the radical cation, all of the heterocyclic sulphur atoms are not significantly involved in the delocalisation of the unpaired electron, whereas the opposite holds for the radical anion. Time-dependent DFT calculations reproduced well the wavelengths of the optical transitions observed in the spectroelectrochemical experiments for all the five oxidation states and support the formation of the dianion 12,. [source] A Cyclic Porphyrin Tetramer Linked by Azo and Butadiyne BridgesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 23 2010Bruno Ba Abstract A soluble cyclic porphyrin oligomer (CPO) consisting of four 5,10-diarylporphyrins linked by alternating azo and butadiyne bridges has been synthesised via an aminated dinickel(II) butadiyne dimer. This is the first cyclic tetramer that combines both azo and butadiyne bridges and extends the azoporphyrin family, which comprises only a very few examples. The electronic absorption spectrum of the tetramer is more similar to spectra of azoporphyrins than to those of butadiyne-linked dimers or tetramer, exhibiting a two-component Soret band with a splitting of 4190 cm,1 and a strongly red-shifted Q band maximum at 735 nm. [source] Metal-Assisted Hybridization of Oligonucleotides, Evaluation of Circular 2,- O -Me RNA as Ligands for the TAR RNA TargetEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 6 2003Laurence Zapata Abstract Two complementary oligonucleotides were conjugated with terpyridine ligands at their nearby 5,- and 3,-ends. Addition of a stoichiometric amount of a transition metal (Zn2+, Fe2+) resulted in a large increase in the melting temperature of the duplex. The conjugation of TPY to stem-loop oligomers provided an efficient procedure for the cyclisation of the oligomer after the addition of metal ions. Such a short stem-loop oligomer was designed to target the HIV-1 TAR RNA through loop,loop interactions. The addition of Zn2+ ions yielded a good ligand (Kd = 30 nM) for this RNA structural element. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Direct integration of cell-free-synthesized connexin-43 into liposomes and hemichannel formationFEBS JOURNAL, Issue 16 2010Yuki Moritani Proteoliposomes were directly prepared by synthesizing membrane proteins with the use of minimal protein synthesis factors isolated from Escherichia coli (the PURE system) in the presence of liposomes. Connexin-43 (Cx43), which is a water-insoluble integral membrane protein that forms a hexameric complex in membranes, was cotranslationally integrated with an essentially uniform orientation in liposomes. The addition of liposomes following protein expression (post-translational presence of liposomes) did not lead to the integration of Cx43 into the liposome membranes. The amount of integrated Cx43 increased as the liposome concentration increased. The presence of liposomes did not influence the total amount of synthesized Cx43. The Cx43 integrated into the liposome membranes formed open membrane pores. These results indicate that the liposomes act in a chaperone-like manner by preventing Cx43 from aggregating in solution, because of integration into the bilayer, and also by functionalization of the integrated Cx43 in the membrane. This is the first report that cell-free-synthesized water-insoluble membrane protein is directly integrated with a uniform orientation as a functional oligomer into liposome membranes. This simple proteoliposome preparation procedure should be a valuable approach for structural and functional studies of membrane proteins. Structured digital abstract ,,MINT-7900670: Cx-43 (uniprotkb:P08050) and Cx-43 (uniprotkb:P08050) bind (MI:0407) by cross-linking study (MI:0030) [source] Insulin is a kinetic but not a thermodynamic inhibitor of amylin aggregationFEBS JOURNAL, Issue 12 2009Wei Cui One of the most important pathological features of type 2 diabetes is the formation of islet amyloid, of which the major component is amylin peptide. However, the presence of a natural inhibitor such as insulin may keep amylin stable and physiologically functional in healthy individuals. Some previous studies demonstrated that insulin was a potent inhibitor of amylin fibril formation in vitro, but others obtained contradictory results. Hence, it is necessary to elucidate the effects of insulin on amylin aggregation. Here we report that insulin is a kinetic inhibitor of amylin aggregation, only keeping its inhibitory effect for a limited time period. Actually, insulin promotes amylin aggregation after long-term incubation. Furthermore, we found that this promotional effect could be attributed to the copolymerization of insulin and amylin. We also found that insulin copolymerized with amylin monomer or oligomer rather than preformed amylin fibrils. These results suggest that the interaction between insulin and amylin may contribute not only to the inhibition of amylin aggregation but also to the coaggregation of both peptides in type 2 diabetes. [source] R120G ,B-crystallin promotes the unfolding of reduced ,-lactalbumin and is inherently unstableFEBS JOURNAL, Issue 3 2005Teresa M. Treweek ,-Crystallin is the principal lens protein which, in addition to its structural role, also acts as a molecular chaperone, to prevent aggregation and precipitation of other lens proteins. One of its two subunits, ,B-crystallin, is also expressed in many nonlenticular tissues, and a natural missense mutation, R120G, has been associated with cataract and desmin-related myopathy, a disorder of skeletal muscles [Vicart P, Caron A, Guicheney P, Li Z, Prevost MC, Faure A, Chateau D, Chapon F, Tome F, Dupret JM, Paulin D & Fardeau M (1998) Nat Genet20, 92,95]. In the present study, real-time 1H-NMR spectroscopy showed that the ability of R120G ,B-crystallin to stabilize the partially folded, molten globule state of ,-lactalbumin was significantly reduced in comparison with wild-type ,B-crystallin. The mutant showed enhanced interaction with, and promoted unfolding of, reduced ,-lactalbumin, but showed limited chaperone activity for other target proteins. Using NMR spectroscopy, gel electrophoresis, and MS, we observed that, unlike the wild-type protein, R120G ,B-crystallin is intrinsically unstable in solution, with unfolding of the protein over time leading to aggregation and progressive truncation from the C-terminus. Light scattering, MS, and size-exclusion chromatography data indicated that R120G ,B-crystallin exists as a larger oligomer than wild-type ,B-crystallin, and its size increases with time. It is likely that removal of the positive charge from R120 of ,B-crystallin causes partial unfolding, increased exposure of hydrophobic regions, and enhances its susceptibility to proteolysis, thus reducing its solubility and promoting its aggregation and complexation with other proteins. These characteristics may explain the involvement of R120G ,B-crystallin with human disease states. [source] Membrane embedded location of Na+ or H+ binding sites on the rotor ring of F1F0 ATP synthasesFEBS JOURNAL, Issue 22 2002Christoph Von Ballmoos Recent crosslinking studies indicated the localization of the coupling ion binding site in the Na+ -translocating F1F0 ATP synthase of Ilyobacter tartaricus within the hydrophobic part of the bilayer. Similarly, a membrane embedded H+ -binding site is accepted for the H+ -translocating F1F0 ATP synthase of Escherichia coli. For a more definite analysis, we performed parallax analysis of fluorescence quenching with ATP synthases from both I. tartaricus and E. coli. Both ATP synthases were specifically labelled at their c subunit sites with N -cyclohexyl- N, -(1-pyrenyl)carbodiimide, a fluorescent analogue of dicyclohexylcarbodiimide and the enzymes were reconstituted into proteoliposomes. Using either soluble quenchers or spinlabelled phospholipids, we observed a deeply membrane embedded binding site, which was quantitatively determined for I. tartaricus and E. coli to be 1.3 ± 2.4 Å and 1.8 ± 2.8 Å from the bilayer center apart, respectively. These data show a conserved topology among enzymes of different species. We further demonstrated the direct accessibility for Na+ ions to the binding sites in the reconstituted I. tartaricus c11 oligomer in the absence of any other subunits, pointing to intrinsic rotor channels. The common membrane embedded location of the binding site of ATP synthases suggest a common mechanism for ion transfer across the membrane. [source] Physical characterization of plakophilin 1 reconstituted with and without zincFEBS JOURNAL, Issue 14 2000Ilse Hofmann Plakophilin 1 (PKP1) belongs to the arm -repeat protein family which is characterized by the presence of a conserved 42-amino-acid motif. Despite individual members of the family containing a similar type of structural domain, they exhibit diverse cellular functions. PKP1 is ubiquitously expressed in human tissues and, depending on the type of cell, found prominently in the karyoplasm and/or in desmosomes. In surface plasmon resonance detection experiments, we noticed that PKP1 specifically bound zinc but not calcium or magnesium. Therefore we have used circular dichroism spectroscopy, limited proteolysis, analytical ultracentrifugation, electron microscopy and dynamic light scattering to establish the physical properties of recombinant PKP1 depending on the presence or absence of zinc. The , helix content of PKP1 was considerably higher when reconstituted with zinc than without. By atomic absorption spectroscopy 7.3 atoms zinc were shown to be tightly associated with one molecule of wild-type PKP1. The zinc-reconstituted protein formed globular particles of 21.9 ± 8.4 nm diameter, as measured by electron microscopy after glycerol spraying/rotary metal shadowing. In parallel, the average sedimentation coefficient (s20,w) for zinc-containing PKP1 was 41S and its diffusion coefficient, as obtained by dynamic light scattering, 1.48 × 10,7 cm2·s,1. The molecular mass of 2.44 × 106 obtained from s and D yields an average stoichiometry of 30 for the PKP1 oligomer. In contrast, PKP1, reconstituted without zinc, contained no significant amount of zinc, sedimented with 4.6S, and was present in monomeric form as determined by sedimentation equilibrium centrifugation. [source] Flame-retardant finishing of cotton fleece fabric: part I. The use of a hydroxy-functional organophosphorus oligomer and dimethyloldihydroxylethyleneureaFIRE AND MATERIALS, Issue 1 2007Charles Q. Yang Abstract Cotton fleece has become a popular fashion in recent years. However, most of the 100% cotton fleece fabric is not able to meet the federal flammability standard (,16 CFR Part 1610: Standard for the Flammability of Clothing Textiles') without chemical treatment. In this research, we investigated the use of the combination of a hydroxy-functional organophosphorus oligomer (HFPO) as the flame-retarding agent and dimethyloldihydroxylethyleneurea (DMDHEU) as the binder to reduce the flammability of cotton fleece. We found that HFPO is effective in reducing the flammability of the cotton fleece whereas DMDHEU enhances the effectiveness of HFPO due to phosphorus,nitrogen synergism. The flammability as well as other properties of the treated cotton fleece is affected by both the concentration of HFPO and that of DMDHEU. The cotton fleece treated with HFPO/DMDHEU passes the federal flammability standard and shows high strength retention with little change in fabric whiteness and hand. We also found that the flame-retardant finishing system is durable to multiple home launderings. The combination of HFPO and DMDHEU has the potential to become a practical flame-retardant finishing system to reduce the flammability of cotton fleeces. Copyright © 2006 John Wiley & Sons, Ltd. [source] The combination of a hydroxy-functional organophosphorus oligomer and melamine-formaldehyde as a flame retarding finishing system for cottonFIRE AND MATERIALS, Issue 2 2005Charles Q. Yang Abstract In previous research, it was found that melamine-formaldehyde resin can be used as a binder for a hydroxy-functional organophosphorus flame retarding agent (FR) on cotton. The role that trimethylol melamine (TMM) plays in this flame retarding system was studied. When TMM is applied to cotton, it forms crosslinks between cellulose molecules. When TMM is applied to cotton in the presence of FR, it reacts with FR to form a crosslinked polymeric network in addition to reacting with cotton. The formation of the crosslinked network improves the laundering durability of FR and also increases the fabric stiffness. The number of crosslinks among cotton cellulose formed by TMM decreases as the FR concentration in the system is increased. TMM also functions as a nitrogen provider to enhance the flame retarding performance of FR due to phosphorus,nitrogen synergism. Therefore, the amount of TMM used in a FR/TMM formula plays the most critical role in determining the effectiveness of this flame retarding system. The finish bath pH also plays a significant role in influencing the performance of the flame retarding system on cotton. The optimum pH was found to be around 4. Copyright © 2004 John Wiley & Sons, Ltd. [source] Combination of a hydroxy-functional organophosphorus oligomer and a multifunctional carboxylic acid as a flame retardant finishing system for cotton: Part II.FIRE AND MATERIALS, Issue 5 2003Formation of calcium salt during laundering Abstract Multifunctional carboxylic acids, such as 1,2,3,4-butanetetracarboxylic acid (BTCA), were used to bond a hydroxy-functional organophosphorus oligomer (FR) to cotton fabric in the presence of a catalyst, such as sodium hypophosphite (NaH2PO2). Previously, it was found that the cotton fabric treated with FR and BTCA showed a high level of phosphorus retention after one home laundering cycle. However, the flame retardant properties quickly deteriorated as the number of home laundering cycles was increased. In this research, it was found that the free carboxylic acid groups bound to the cotton fabric form an insoluble calcium salt during home laundering, thus diminishing the flame retardant properties of the treated cotton fabric. It was also found that the free carboxylic acid groups on the treated cotton fabric were esterified by triethanolamine (TEA), and that the formation of calcium salt on the fabric was suppressed by the esterification of the free carboxylic acid groups by TEA. The cotton fabric treated with BTCA and the hydroxy-functional organophosphorus oligomer significantly improved its flame retardance when a new catalyst system consisting of hypophosphorous acid (H3PO2) and TEA was used in the system. Copyright © 2003 John Wiley & Sons, Ltd. [source] Dynamics of yeast prion aggregates in single living cellsGENES TO CELLS, Issue 9 2006Shigeko Kawai-Noma Prions are propagating proteins that are ordered protein aggregates, in which the phenotypic trait is retained in the altered protein conformers. To understand the dynamics of the prion aggregates in living cells, we directly monitored the fate of the aggregates using an on-chip single-cell cultivation system as well as fluorescence correlation spectroscopy (FCS). Single-cell imaging revealed that the visible foci of yeast prion Sup35 fused with GFP are dispersed throughout the cytoplasm during cell growth, but retain the prion phenotype. FCS showed that [PSI+] cells, irrespective of the presence of foci, contain diffuse oligomers, which are transmitted to their daughter cells. Single-cell observations of the oligomer-based transmission provide a link between previous in vivo and in vitro analyses of the prion and shed light on the relationship between the protein conformation and the phenotype. [source] Organic Thin-Film Photovoltaic Cells Based on Oligothiophenes with Reduced Bandgap,ADVANCED FUNCTIONAL MATERIALS, Issue 15 2007C. Uhrich Abstract The best polymeric solar cells reported so far are based on a so-called bulk heterojunction of a polythiophene as donor and a soluble fullerene derivative as acceptor. However, these cells still suffer from an unsatisfying photovoltage, typically below 0.7,V. Here, we show that we can achieve higher photovoltages using a new terthiophene end-capped with electron withdrawing dicyanovinyl groups (DCV3T) that increase both the ionization energy and even more strongly the electron affinity of the compound. The new material is tested in cells using a photoactive heterojunction to separate the excitons generated in the oligomer and a p-doped wide-gap transport layer. The solar cells show an open circuit voltage of up to 1.04,V and a broad spectral sensitivity band ranging from 420,nm to 650,nm. Solar cells based on such oligothiophenes are promising candidates for stacked organic solar cells tailored to the sun-spectrum. Moreover, we present first examples of a new concept for organic solar cells: By blending DCV3T with fullerene C60, an enhanced generation of triplet excitons on the oligomer can be achieved via a back and forth transfer of excitons (ping-pong-effect). [source] Cycloaddition approach to the curing of polyimides via precursor containing thiophene- S,S -dioxideHETEROATOM CHEMISTRY, Issue 7 2006Andrew Magyarosy A new method for linear polymerization of maleimides via the Diels,Alder reaction has been developed. This method involves use of a new cross-linking agent, benzene-3,4-dimethylenesuccinimide, which can be generated in situ from its thiophene precursor, benzene-2,5-dihydrothiophene-3,4-dicarboximide- S,S -dioxide. This new cross-linking agent is reasonably reactive, readily prepared, and stable at room temperature. A controlled molecular weight oligomer has been synthesized and applied to the polymerization to yield a highly thermal stable polyimide. © 2006 Wiley Periodicals, Inc. Heteroatom Chem 17:648,652, 2006; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20249 [source] Bicolor Pixels from a Single Active Molecular Material by Surface-Tension-Driven Deposition,ADVANCED MATERIALS, Issue 12 2007I. Viola The fabrication of a green- and red-emitting pixel structure (see figure, scale bar 10,,m) by the single-step, surface-tension-driven assembly of a single luminescent thiophene-based molecular material is reported. The solid-state organization of the selected thiophene-based oligomer is controlled by exploiting the molecular structural arrangement, induced during a dewetting process and facilitated by the great conformational flexibility of the oligomer, typical of several substituted oligothiophenes. [source] Oligomeric alpha-synuclein and its role in neuronal deathIUBMB LIFE, Issue 5 2010David R. Brown Abstract Alpha-synuclein is a natively unfolded protein associated with a number of neurodegenerative disorders that include Parkinson's disease. In the past, research has focused on the fibrillar form of the protein. Current research now indicates that oligomeric alpha-synuclein is the form of the protein most likely to causes neuronal death. Recent research has suggested that a unique oligomer associated with the copper binding capacity of the protein is the neurotoxic form of the protein. This review looks at the evidence for this possibility. © 2010 IUBMB IUBMB Life, 62(5): 334,339, 2010 [source] Chaperone-like activity and hydrophobicity of ,-crystallinIUBMB LIFE, Issue 11 2006G. Bhanuprakash Reddy Abstract ,-Crystallin, a prominent member of small heat shock protein (sHsp) family and a major structural protein of the eye lens is a large polydisperse oligomer of two isoforms, ,A- and ,B-crystallins. Numerous studies have demonstrated that ,-crystallin functions like a molecular chaperone in preventing the aggregation of various proteins under a wide range of stress conditions. The molecular chaperone function of ,-crystallin is thus considered to be vital in the maintenance of lens transparency and in cataract prevention. ,-Crystallin selectively interacts with non-native proteins thereby preventing them from aggregation and helps maintain them in a folding competent state. It has been proposed and generally accepted that ,-crystallin suppresses the aggregation of other proteins through the interaction between hydrophobic patches on its surface and exposed hydrophobic sites of partially unfolded substrate protein. However, a quantifiable relationship between hydrophobicity and chaperone-like activity remains a matter to be concerned about. On an attentive review of studies on ,-crystallin chaperone-like activity, particularly the studies that have direct or indirect implications to hydrophobicity and chaperone-like activity, we found several instances wherein the correlation between hydrophobicity and its chaperone-like activity is paradoxical. We thus attempted to provide an overview on the role of hydrophobicity in chaperone-like activity of ,-crystallin, the kind of evaluation done for the first time. iubmb Life, 58: 632 - 641, 2006 [source] Property enhancement of epoxy resins by using a combination of polyamide and montmorilloniteADVANCES IN POLYMER TECHNOLOGY, Issue 4 2007M. Bakar Abstract A bisphenol-A epoxy resin cured with triethylenetetramine was modified with the addition of a polyamide oligomer and a small amount of montmorillonite. Compositions with different amounts of modifiers were obtained and tested for their impact strength, flexural strength, and resistance to crack propagation. The latter was assessed by measuring the critical stress intensity factor in a three-point bending mode. Scanning electron microscopy was used to examine the sample fracture surfaces. It was found that the addition of 2% montmorillonite or 5% polyamide resulted in the best improvement of the impact strength and the critical stress intensity factor relative to the unmodified epoxy resin. However, the flexural strength and toughness measured under three-point bending mode was found to increase to a lesser extent. Hybrid compositions containing specific combinations of both modifier and nanofiller not only exhibited a higher impact strength and resistance to crack propagation but also displayed a synergistic effect in relation to the fracture energy. The results indicate that the improvement in mechanical properties of the epoxy resin was due to the formation of a heterogeneous morphology resulting from phase separation of the polymeric modifier. From the scanning electron microscopy and thermal analysis, it appears that the toughening may arise from chemical reactions that have taken place between the epoxy resin and the polymeric modifier, which was partially solubilized in the resin matrix. © 2008 Wiley Periodicals, Inc. Adv Polym Techn 26:223,231, 2007; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/adv.20103 [source] Effect of boron-containing materials on the flammability and thermal degradation of polyamide 6 composites containing melamineJOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2010Mehmet Do Abstract Three different boron-containing substances,zinc borate (ZnB), borophosphate (BPO4), and a boron- and silicon-containing oligomer (BSi),were used to improve the flame retardancy of melamine in a polyamide 6 (PA-6) matrix. The combustion and thermal degradation characteristics of PA-6 composites were investigated with the limiting oxygen index (LOI), the UL-94 standard, thermogravimetric analysis (TGA)/Fourier transform infrared (FTIR) spectroscopy, and differential scanning calorimetry (DSC). A slight increase was seen in the LOI values of a sample containing BSi (1 wt %). BPO4 at high loadings showed a V0 rating (indicating the best flame retardancy) and slightly lower LOI values in comparison with samples with only melamine. For ZnB and BSi, glassy film and char formation decreased the dripping rate and sublimation of melamine, and this led to low LOIs. According to the TGA,FTIR results, the addition of boron compounds did not change the decomposition product distribution of melamine and PA-6. The addition of boron compounds affected the flame retardancy by physical means. The TGA data showed that boron compounds and melamine reduced the decomposition temperature of PA-6. According to the DSC data, the inclusion of boron compounds increased the onset temperature of sublimation of melamine and also affected the flame retardancy negatively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] Studies on synthesis and characterization of a novel acrylic aromatic amide oligomer of aminolysed endproducts generated from pet waste with hydrazine monohydrate and its photocuring with acrylate monomersJOURNAL OF APPLIED POLYMER SCIENCE, Issue 2 2010R. K. Soni Abstract A novel acrylic aromatic amide oligomer was synthesized by using depolymerized end product of PET waste with hydrazine monohydrate. The end product of aminolysed PET waste was synthesized under ambient conditions and was used in the preparation of novel acrylic oligomer with the reaction of acryloyl chloride prepared from acrylic acid. The acrylic oligomer was characterized by spectroscopic techniques, such as FTIR, 1H-NMR, UV, Mass spectrometry, and by other analytical techniques such as, Iodine value, TGA, and DSC. The proposed structure of the oligomer is supported by its spectral analysis and the same is inferred from other techniques. The acrylic oligomer mixed with other acrylate monomers such as methylmethacrylate, ethylhexylacrylate, acrylic acid, and photoinitiator, can be cured by UV radiation and can thus be used as an adhesion promoter on metal/glass surface. This article presents the possibility of using a difunctional aromatic amide oligomer with excellent hydrogen bonding capacity as an alternative to urethane acrylates in radiation curable formulations. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] Preparation and properties of organic,inorganic hybrid composites based on polystyrene and an incompletely condensed polyvinylsilsesquioxane oligomerJOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2010Zhen Dai Abstract An incompletely condensed polyvinylsilsesquioxane (PVSQ) oligomer containing abundant silanol groups was synthesized and characterized by FTIR, 1H-NMR, 29Si-NMR, and MALDI-TOF-MS. Polystyrene/polyvinylsilsesquioxane (PS/PVSQ) hybrid composites were prepared by an in situ bulk polymerization. The hybrid composites showed higher Tg, Td, and char yield than PS homopolymer and without mechanical loss. The improvements in the properties of PS/PVSQ hybrid composites can be ascribed to the crosslinking function of PVSQ by silanol condensation in later processing. The hybrids showed different morphology from discrete microstructure to continuous network depending on the concentration of PVSQ. Because of the surface enrichment, a PVSQ protection layer was formed, which made the hybrid surface more hydrophobic. The structure and the reaction mechanism of PS/PVSQ hybrid composites were also investigated. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] Modification of cellulose acetate with oligomeric polycaprolactone by reactive processing: Efficiency, compatibility, and propertiesJOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2009Szilvia Klébert Abstract Oligomeric polycaprolactone (oPCL) was used for the modification of cellulose acetate by reactive processing in an internal mixer at 180°C, 50 rpm, 60 min reaction time, and 45 wt % caprolactone (CL) content. The product of the reaction was characterized by several analytical techniques and its mechanical properties were determined by dynamic mechanical thermal analysis and tensile testing. The synthesized oPCL contained small and large molecular weight components. The small molecular weight fraction plasticized cellulose acetate externally and helped fusion. Although composition and structure did not differ considerably from each other when CL monomer or polycaprolactone oligomer was used for modification, the grafting of a few long chains had considerable effect on some properties of the product. The large molecular weight chains attached to CA increased the viscosity of the melt considerably and resulted in larger deformability. oPCL homopolymer is not miscible with cellulose acetate and migrates to the surface of the polymer. Exuded polycaprolactone oligomers crystallize on the surface but can be removed very easily. More intense conditions may favor the grafting of long chains leading to polymers with advantageous properties. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] Synthesis and characterization of low relative molecular weight trans -1,4-poly(isoprene)JOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2008Huafeng Shao Abstract Low relative molecular weight trans-1,4-polyisoprene oligomers were synthesized successfully by bulk precipitation and solution polymerization with supported titanium catalyst using hydrogen as relative molecular weight modifier. The effects of polymerization conditions on intrinsic viscosity ([,]), catalyst efficiency (CE) and structure of polymer were studied. Increasing the hydrogen pressure resulted in the decrease of [,] of the polymer. With the increasing of hydrogen pressure and reaction temperature, CE decreased but still maintained above 2500 g polymer/g Ti. The percentage composition of (trans-1, 4-unit) in the polymer was over 90% in all results. The crystallinity of polymer was about 50,60% with Tm being about 60°C. The relative molecular weight distribution index (MWD) was quite difference according to the polymerization method. While number average molecular weight (Mn) exceeded 860, polymer turned from viscous materials to fragile wax materials, and then to toughness materials at 1800. Dynamic property testing showed that the additional of this oligomer could increase the wet-skid resistance of the rubber. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] A heterogeneous kinetic model of the oxidative polymerization of 2,6-dimethylphenol with a copper-EDTA complex in waterAICHE JOURNAL, Issue 10 2009Qun Liu Abstract The heterogeneous oxidative polymerization kinetics of 2,6-dimethylphenol (DMP) catalyzed by a copper(II)-EDTA complex in water was studied. During the oxidative polymerization of DMP in water the oxygen uptake rate increases with an increase in DMP concentration and an increase in temperature. The Michaelis,Menten kinetic model as applied to the polymerization of DMP in organic solvents is not appropriate for the description of the full course of DMP polymerization in water. A new heterogeneous kinetic model is proposed to describe the catalyst deactivation during the oxidative polymerization as well as the difference in reactivity between the monomer, water-soluble oligomer and water-insoluble oligomer. The polymerization rate estimated by the new model is consistent with the measured data. © 2009 American Institute of Chemical Engineers AIChE J, 2009 [source] The influence of cytosine methylation on the chemoselectivity of benzo[a]pyrene diol epoxide-oligonucleotide adducts determined using nanoLC/MS/MSJOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 8 2009James Glick Abstract Benzo[a]pyrene is a major carcinogen implicated in human lung cancer. Almost 60% of human lung cancers have a mutation in the p53 tumor suppressor gene at several specific codons. An on-line nanoLC/MS/MS method using a monolithic nanocolumn was applied to investigate the chemoselectivity of the carcinogenic diol epoxide metabolite, ( ± )-(7R,8S,9S,10R)-benzo[a]pyrene 7,8-diol 9,10-epoxide [( ± )- anti -benzo[a]pyrene diol epoxide (BPDE)], which was reacted in vitro with a synthesized 14-mer double stranded oligonucleotide (5,-ACCCG5CG7TCCG11CG13C-3,/5,-GCGCGGGCGCGGGT-3,) derived from the p53 gene. This sequence contained codons 157 and 158, which are considered mutational ,hot spots' and have also been reported as chemical ,hot spots' for the formation of BPDE-DNA adducts. In evaluating the effect of cytosine methylation on BPDE-DNA adduct binding, it was found that codon 156, containing the nucleobase G5 instead of the mutational hot spot codons 157 (G7) and 158 (G11), was the preferential chemoselective binding site for BPDE. In all permethylated cases studied, the relative ratio for adduction was found to be G5, G11 > G13 > G7. Permethylation of CpG dinucleotide sites on either the nontranscribed or complementary strand did not change the order of sequence preference but did enhance the relative adduction level of the G11 CpG site (codon 158) approximately two-fold versus the unmethylated oligomer. Permethylation of all CpG dinucleotide sites on the duplex changed the order of relative adduction to G5, G7 > G11 > G13. The three- to four-fold increase in adduction at the mutational hot spot codon 157 (G7) relative to the unmethylated or single-stranded permethylated cases suggests a possible relationship between the state of methylation and adduct formation for a particular mutation site in the p53 gene. Using this method, only 125 ng (30 pmol) of adducted oligonucleotide was analyzed with minimal sample cleanup and high chromatographic resolution of positional isomers in a single chromatographic run. Copyright © 2009 John Wiley & Sons, Ltd. [source] Metabotropic glutamate type 5, dopamine D2 and adenosine A2a receptors form higher-order oligomers in living cellsJOURNAL OF NEUROCHEMISTRY, Issue 5 2009Nuria Cabello Abstract G protein-coupled receptors are known to form homo- and heteromers at the plasma membrane, but the stoichiometry of these receptor oligomers are relatively unknown. Here, by using bimolecular fluorescence complementation, we visualized for the first time the occurrence of heterodimers of metabotropic glutamate mGlu5 receptors (mGlu5R) and dopamine D2 receptors (D2R) in living cells. Furthermore, the combination of bimolecular fluorescence complementation and bioluminescence resonance energy transfer techniques, as well as the sequential resonance energy transfer technique, allowed us to detect the occurrence receptor oligomers containing more than two protomers, mGlu5R, D2R and adenosine A2A receptor (A2AR). Interestingly, by using high-resolution immunoelectron microscopy we could confirm that the three receptors co-distribute within the extrasynaptic plasma membrane of the same dendritic spines of asymmetrical, putative glutamatergic, striatal synapses. Also, co-immunoprecipitation experiments in native tissue demonstrated the existence of an association of mGlu5R, D2R and A2AR in rat striatum homogenates. Overall, these results provide new insights into the molecular composition of G protein-coupled receptor oligomers in general and the mGlu5R/D2R/A2AR oligomer in particular, a receptor oligomer that might constitute an important target for the treatment of some neuropsychiatric disorders. [source] Intrastrand foldamer crosslinking by reductive aminationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 4 2010Ronald A. Smaldone Abstract A series of m -phenylene ethynylene (mPE) foldamers were crosslinked in their helical conformation using a reductive amination-based strategy. This was accomplished by placing aldehyde moieties in the backbone of the oligomer at specific residues, which allowed a diamine crosslinker to covalently link the helical loops together. Three different foldamers with crosslinks placed at different locations in the backbone were synthesized and characterized by mass spectrometry, 1H NMR, and gel permeation chromatography. The effect of the crosslinking on the stability of the folded state was evaluated through solvent denaturation studies. These studies show a reduction in the oligomer's ability to unfold of up to 30% relative to an unmodified mPE oligomer of the same length in solvents that promote unfolding. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 927,935, 2010 [source] Synthesis of fluoro-substituted silole-containing conjugated materialsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 19 2009Sven Horst Abstract 2,5-Dihydroxyboryl-1,1-dimethyl-3,4-bis(3-fluorophenyl)-silole (2a) was prepared in 40% overall yield by reaction between 3-fluorophenyl-acetylene and dichlorodimethylsilane to yield bis[2(3-fluorophenyl)ethynyl]dimethylsilane (1a), which subsequently undergoes a reductive cyclization reaction using an excess of lithium naphthalenide. The fluoro substituted silole was applied as a co-monomer in the Suzuki polycondensation reaction with 2,7-dibromo-9,9-dioctyl-fluorene. An oligomer (3a) with a degree of polymerization of 6 was prepared and compared with an oligomer without fluoro substitution on the silole (3b), with a degree of polymerization of 4. The new oligomers were spin coated onto glass slides and showed weak green photoluminescence (PL) in the solid state. Cyclic voltammetry, visible absorption spectroscopy, and density functional theory calculations showed that the fluoro substituents were sufficiently electron withdrawing to lower both the highest occupied molecular orbital and the lowest unoccupied molecular orbital in the oligomer. Two further alternating co-oligomers were prepared from 2,5-dihydroxyboryl-1,1-dimethyl-3,4-bis(phenyl)-silole (2b) and 1,3-dibromo-5-fluoro-benzene (4a) or 1,3-dibromobenzene (4b). These oligomers both had degrees of polymerization of 8 and showed green PL in the solid state. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5116,5125, 2009 [source] Synthesis and characterization of postsulfonated poly(arylene ether sulfone) diblock copolymers for proton exchange membranesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 3 2009Shogo Takamuku Abstract Sulfonated poly(arylene ether sulfone) diblock copolymers were studied through the postsulfonation process. Two kinds of hydrophobic oligomers with a molecular weight of 20 kDa were prepared in advance as block sequences and then coupled together to obtain diblock copolymers. One oligomer was synthesized from bis(4-hydroxyphenyl) sulfone (BHPS) and 4,4,-difluorodiphenyl sulfone (DFDPS), which was thought to be incapable of postsulfonation. The other oligomer was synthesized from hydroquinone (HQ) and 4,4,-dichlorodiphenyl sulfone (DCDPS), which successfully proceeded to a hydrophilic sequence as a result of sulfonation onto the HQ moiety after the coupling reaction. Consequently, a diblock copolymer with high molecular weight was obtained; although its intrinsic viscosity was too low to form a tough membrane because of its high rigidity and high crystallinity. Therefore, the use of decafluorobiphenyl (10F) as a termination reagent was investigated with the aim of achieving higher coupling reactivity and a kinky property. As a result, a sulfonated diblock copolymer was successfully obtained with sufficient molecular weight and intrinsic viscosity to form the membrane, as well as with adequate thermal properties. It was observed that proton conductivity, water uptake, and the water diffusion coefficient increased with higher ion exchange capacity. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 700,712, 2009 [source] | |||||||||||||||||||||||||||||||||||||||||||||||||