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Sample records for charged pyrrole oligomers

  1. Charge transfer in conjugated oligomers encapsulated into carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Almadori, Y.; Alvarez, L.; Michel, T.; Le Parc, R.; Bantignies, J.L.; Hermet, P.; Sauvajol, J.L. [Laboratoire Charles Coulomb UMR 5521, Universite Montpellier 2, 34095 Montpellier (France); Laboratoire Charles Coulomb UMR 5521, CNRS, 34095 Montpellier (France); Arenal, R. [Laboratoire d' Etude des Microstructures, CNRS-ONERA, 92322 Chatillon (France); Laboratorio de Microscopias Avanzadas, Instituto de Nanociencia de Aragon, U. Zaragoza, 50018 Zaragoza (Spain); Babaa, R. [Laboratoire de Chimie des Surfaces et Interfaces, CEA, IRAMIS, SPCSI, 91191 Gif-sur-Yvette Cedex (France); Chemical Engineering Department, University of Technology PETRONAS, UTP, Ipoh-Perak (Malaysia); Jouselme, B.; Palacin, S. [Laboratoire de Chimie des Surfaces et Interfaces, CEA, IRAMIS, SPCSI, 91191 Gif-sur-Yvette Cedex (France)

    2011-11-15

    This study deals with a hybrid system consisting in quaterthiophene derivative encapsulated inside single-walled and multi-walled carbon nanotubes. Investigations of the encapsulation step are performed by transmission electron microscopy. Raman spectroscopy data point out different behaviors depending on the laser excitation energy with respect to the optical absorption of quaterthiophene. At low excitation energy (far from the oligomer resonance window) there is no significant modification of the Raman spectra before and after encapsulation. By contrast, at high excitation energy (close to the oligomer resonance window), Raman spectra exhibit a G-band shift together with an important RBM intensity loss, suggesting a significant charge transfer between the inserted molecule and the host nanotubes. Those results suggest a photo induced process leading to a significant charge transfer. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  2. Site-selective nanoscale-polymerization of pyrrole on gold nanoparticles via plasmon induced charge separation.

    Science.gov (United States)

    Takahashi, Y; Furukawa, Y; Ishida, T; Yamada, S

    2016-04-28

    We proposed a nanoscale oxidative polymerization method which enables site-selective deposition on the surface of gold nanoparticles (AuNPs) combined with TiO2 by using plasmon induced charge separation (PICS) under visible-to-near infrared (IR) light irradiation. The method also revealed that the anodic site of PICS was located at the surface of AuNPs.

  3. Effects of Molecular Structure on Intramolecular Charge Carrier Transport in Dithieno [3,2-b: 2,3-d] Pyrrole-Based Conjugated Copolymers

    Directory of Open Access Journals (Sweden)

    Yoshihito Honsho

    2012-01-01

    Full Text Available Intramolecular mobility of positive charge carriers in conjugated polymer films based on dithieno [2,3-b: 2,3-d] pyrrole (DTP is studied by time-resolved microwave conductivity (TRMC. A series of DTP homopolymer and copolymers combined with phenyl, 2,2-biphenyl, thiophene, 2,2-bithiophene, and 9,9-dioctylfluorene were synthesized by Suzuki-Miyaura and Yamamoto coupling reactions. Polymers containing DTP unit are reported to show high value of hole mobility measured by FET method, and this type of polymers is expected to have stable HOMO orbitals which are important for hole transportation. Among these copolymers, DTP coupled with 9,9-dioctylfluorene copolymer showed the highest charge carrier mobility as high as 1.7 cm2/Vs, demonstrating an excellent electrical property on rigid copolymer backbones.

  4. Designing thiophene-based azomethine oligomers with tailored properties: Self-assembly and charge carrier mobility

    DEFF Research Database (Denmark)

    Kiriy, N.; Bocharova, V.; Kiriy, A.;

    2004-01-01

    addition of hexane to the solution in THF, the addition of hexane to QT-amide solution induces a red shift of lambda(max) and appearance of fine structure believed to be vibronic in nature. The concentration dependence of the solvatochromism gives strong support for the intermolecular origin of this effect...... and clearly indicates that the planarization of the oligomer backbone is forced by the aggregation. Although, no clear signs of the molecular order for various QT-aniline films are observed by AFM, UV-vis, and XRD measurements, the QT-amide film after the annealing at 180 degreesC displays important molecular...

  5. Transverse charge transport through DNA oligomers in large-area molecular junctions

    Science.gov (United States)

    Katsouras, Ilias; Piliego, Claudia; Blom, Paul W. M.; de Leeuw, Dago M.

    2013-09-01

    We investigate the nature of charge transport in deoxyribonucleic acid (DNA) using self-assembled layers of DNA in large-area molecular junctions. A protocol was developed that yields dense monolayers where the DNA molecules are not standing upright, but are lying flat on the substrate. As a result the charge transport is measured not along the DNA molecules but in the transverse direction, across their diameter. The electrical transport data are consistent with the derived morphology. We demonstrate that the charge transport mechanism through DNA is identical to non-resonant tunneling through alkanethiols with identical length, classifying DNA as a dielectric.

  6. Transverse charge transport through DNA oligomers in large-area molecular junctions

    NARCIS (Netherlands)

    Katsouras, I.; Piliego, C.; Blom, P.W.M.; Leeuw, D.M. de

    2013-01-01

    We investigate the nature of charge transport in deoxyribonucleic acid (DNA) using self-assembled layers of DNA in large-area molecular junctions. A protocol was developed that yields dense monolayers where the DNA molecules are not standing upright, but are lying flat on the substrate. As a result

  7. Cis- and trans-isomerization-induced transition of charge transport property in PPV oligomers

    International Nuclear Information System (INIS)

    Graphical abstract: Cis→trans isomerization of 2,5-diphenyl-1,4-distyrylbenzene (DPDSB, model compound of PPV) induces significant changes in charge transport properties. Cis-DPDSB demonstrates hole-majority transport while trans-DPDSB exhibits balanced transport. Highlights: → 2,5-diphenyl-1,4-distyrylbenzene (DPDSB) is a model compound of PPV derivatives. → Cis→trans isomerization induces significant changes in charge transport property. → Cis-DPDSB displays hole-majority transport while trans-DPDSB shows balanced one. → This finding helps to understand structure/property relationship in PPV derivatives. - Abstract: Photoisomerization of vinylenes is well known to cause remarkable changes in the photophysical properties of poly (p-phenylene vinylene) (PPV) derivatives. Cis-/trans- isomerization is also expected to induce significant changes in their charge transport properties. In this study, the charge transport properties of cis- and trans-isomers of 2,5-diphenyl-1,4-distyrylbenzene (DPDSB, model compound of PPV) were investigated using a Marcus hopping model. As expected, this conformational transition from cis- to trans-isomer gives rise to a significant difference between hole and electron transport properties. Cis-DPDSB demonstrates an overwhelmingly superior hole transport (μh/μe = 51), which is even higher than that of trans-DPDSB. By contrast, trans-DPDSB exhibits approximately balanced carrier transport property (μh/μe = 1.79). These results are understood on a molecular level by considering the structure-transport relationship through two key parameters: transfer integral and reorganization energy. This finding may be helpful in understanding and extrapolating the structure-property relationship and charge transport property of the corresponding PPV polymers derivatives.

  8. Aqueous dispersions of oligomer-grafted carbon nanomaterials with controlled surface charge and minimal framework damage

    Science.gov (United States)

    Hu, Sheng; Chen, Shu; Menzel, Robert; Goode, Angela D.; Ryan, Mary P.; Porter, Alexandra E.; Shaffer, Milo S. P.

    2015-01-01

    Functionalised carbon nanomaterials (CNMs), with an undamaged carbon framework and controlled physiochemical properties, are desirable for a wide range of scientific studies and commercial applications. The use of a thermochemical grafting approach provides a versatile means to functionalise both multi-walled carbon nanotubes (MWCNTs) and carbon black (CB) nanoparticles without altering their inherent structure. The functionalisation process was investigated by employing various types of grafting monomers; to improve water solubility, reagents were chosen that introduced ionic character either intrinsically or after further chemical reaction. The degree of grafting for both MWCNTs and CB ranged from 3 to 27 wt%, as established by thermal gravimetric analysis (TGA). Raman spectroscopy confirmed that the structural framework of the MWNTs was unaffected by the thermochemical treatment. The effectiveness of the surface modification was demonstrated by significantly improved dispersibility and stability in water, and further quantified by zeta-potential analysis. The concentration of stable, individualised, grafted MWNTs in water ranged from 30 to 80 µg mL−1, whereas functionalised CB (CB) in water showed improved dispersibility up to ~460 µg mL−1 after centrifugation at 10, 000 g for 15 minutes. The successful preparation of structurally identical but differently functionalised nanoparticles panels, with high water compatibility and minimal framework damage, are useful for controlled experiments. For example, they can be used to explore the relationship between toxicological effects and specific physiochemical properties, such as surface charge and geometry. PMID:25254653

  9. Charge Delocalization in Oligomers of Poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene), PBTTT

    KAUST Repository

    Zhang, Yuexing

    2016-04-25

    We investigate theoretically charge delocalization in radical-cations, i.e., positive polarons, formed on oligomer chains of poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene), PBTTT. We use non-empirically tuned range-separated density functionals (TRS-DFT), including LC-ωPBE, LC-BLYP, and ωB97XD. We consider the evolution with oligomer length of the molecular geometric and electronic structures, optical absorption features, and spin densities. The TRS-DFT results indicate that a positive polaron can delocalize ideally over some 10 thiophene rings when the backbone is non-planar and up to 14 rings for a backbone forced to be completely planar. Interestingly, up to six polarons can co-exist side-by-side in a hexamer (which contains 24 thiophene rings), which is consistent with the highest degrees of doping (oxidation) experimentally achievable in polythiophene derivatives.

  10. Flexible supercapacitor based on electrochemically synthesized pyrrole formyl pyrrole copolymer coated on carbon microfibers

    Science.gov (United States)

    Gholami, Mehrdad; Moozarm Nia, Pooria; Narimani, Leila; Sokhakian, Mehran; Alias, Yatimah

    2016-08-01

    The main objective of this work is to prepare a flexible supercapacitor using electrochemically synthesized pyrrole formyl pyrrole copolymer P(Py-co-FPy) coated on the carbon microfibers. Due to difficulties of working with carbon microfibers, glassy carbon was used to find out optimized conditions by varying mole ratio of pyrrole and formyl pyrrole monomers on the capacitance value. The prepared electrodes were characterized using Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscope (FESEM), Brunauer-Emmett-Teller (BET) analysis, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Then the X-ray photoelectron spectroscopy (XPS) was used to characterize the optimized electrode. The specific capacitance is calculated using cyclic voltammetry, charge/discharge method, and impedance spectroscopy. The charge/discharge study reveals that the best specific capacitance is estimated to be 220.3 mF cm-2 for equal mole fraction of pyrrole and formyl pyrrole Py (0.1)-FP (0.1) at discharge current of 3 × 10-4 A. This optimized electrode keeps about 92% of its capacitance value in high current of discharging. The specific capacitances calculated by all the mentioned methods are in agreement with each other. Finally, the found optimized conditions were successfully applied to produce a flexible supercapacitor on the surface of carbon microfibers.

  11. The Oxidation of Pyrrole.

    Science.gov (United States)

    Howard, James K; Rihak, Kieran J; Bissember, Alex C; Smith, Jason A

    2016-01-01

    The dearomatization of heterocycles has been a powerful means for producing functional molecules in synthesis. In the case of pyrroles, reductive methods (such as the Birch reduction) have been most widely exploited, while oxidative methods are generally dismissed as too difficult or unpredictable to be useful. However, since the early twentieth century considerable research has been carried out on the controlled oxidation of pyrroles to give highly functionalized products, using a variety of oxidants. This review presents a summary of all work up until the present day in the area of pyrrole oxidation, looking at the use of peroxide, singlet oxygen, hypervalent iodine reagents, a range or organic and inorganic oxidants, and electrochemical approaches. It also offers some perspective on the potential future role of pyrrole oxidation in synthesis. PMID:26294175

  12. Valence Band Dependent Charge Transport in Bulk Molecular Electronic Devices Incorporating Highly Conjugated Multi-[(Porphinato)Metal] Oligomers.

    Science.gov (United States)

    Bruce, Robert C; Wang, Ruobing; Rawson, Jeff; Therien, Michael J; You, Wei

    2016-02-24

    Molecular electronics offers the potential to control device functions through the fundamental electronic properties of individual molecules, but realization of such possibilities is typically frustrated when such specialized molecules are integrated into a larger area device. Here we utilize highly conjugated (porphinato)metal-based oligomers (PM(n) structures) as molecular wire components of nanotransfer printed (nTP) molecular junctions; electrical characterization of these "bulk" nTP devices highlights device resistances that depend on PM(n) wire length. Device resistance measurements, determined as a function of PM(n) molecular length, were utilized to evaluate the magnitude of a phenomenological β corresponding to the resistance decay parameter across the barrier; these data show that the magnitude of this β value is modulated via porphyrin macrocycle central metal atom substitution [β(PZn(n); 0.065 Å(-1)) < β(PCu(n); 0.132 Å(-1)) < β(PNi(n); 0.176 Å(-1))]. Cyclic voltammetric data, and ultraviolet photoelectron spectroscopic studies carried out at gold surfaces, demonstrate that these nTP device resistances track with the valence band energy levels of the PM(n) wire, which were modulated via porphyrin macrocycle central metal atom substitution. This study demonstrates the ability to fabricate "bulk" and scalable electronic devices in which function derives from the electronic properties of discrete single molecules, and underscores how a critical device function--wire resistance--may be straightforwardly engineered by PM(n) molecular composition. PMID:26829704

  13. Morphology and electrical properties of electrochemically synthesized pyrrole-formyl pyrrole copolymer

    Science.gov (United States)

    Gholami, Mehrdad; Nia, Pooria Moozarm; Alias, Yatimah

    2015-12-01

    A direct electrochemical copolymerization of pyrrole-formyl pyrrole (Py-co-FPy) was carried out by oxidative copolymerization of formyl pyrrole and pyrrole in LiClO4 aqueous solution through galvanostatic method. The (Py-co-FPy) copolymer was characterized using Fourier-transform infrared spectroscopy (FT-IR), field emission scanning electron microscope (FESEM), energy-filtering transmission electron microscope (EFTEM), thermal gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The FESEM images showed that the synthesized copolymer had a hollow whelk-like helixes structure, which justifies the enhancement of charge transportation through the copolymer film. Cyclic voltammetry studies revealed that the electrocatalytic activity of synthesized copolymer has improved and the surface coverage in copolymer enhanced 1.6 times compared to polypyrrole alone. Besides, (Py-co-FPy) copolymer showed 2.5 times lower electrochemical charge transfer resistance (Rct) value in impedance spectroscopy. Therefore, this copolymer has a strong potential to be used in several applications such as sensor applications.

  14. Synthesis and electrochemical properties of novel, donor–acceptor pyrrole derivatives with 1,8-naphthalimide units and their polymers

    International Nuclear Information System (INIS)

    A new class of bipolar monomers with pyrrole or thiophene–pyrrole–thiophene as electron donor and 1,8-naphthalimide as electron acceptor unit is reported. Donor–acceptor conjugated polymers were generated electrochemically. The synthesis of monomers, optical, electrochemical and spectroelectrochemical properties supported by theoretical calculations are presented. 1,8-naphthalimide units were attached directly to pyrrole in compounds 1a and 2a or by different bridges in the case of 1b and 2b. Intra-molecular donor–acceptor interactions of the monomers and its polymers were investigated using cyclic voltammetry, in-situ UV–Vis-NIR, electron spin resonance (ESR) spectroelectrochemistry and fluorescence spectroscopy. Studied compounds present large discrepancy (up to 1.31 eV for 2a) between energy gap values determined through electrochemical and optical measurements. The Time-dependent density functional theory (TDDFT) calculations help to explain this discrepancy. This is caused by weak HOMO to LUMO transition, 2000 times weaker than HOMO−2 to LUMO or HOMO to LUMO+1 transition. Altering the structure of monomers yields different stability and properties of obtained polymers. The p- and n-doping processes are separated. Anions are localized mainly on 1,8-naphthalimide units. Cations are localized mainly on pyrrole or thiophene–pyrrole–thiophene moiety and their polymer chains. Attachment of the additional thiophene units decreases the oxidation potential of the monomer and reduces the influence of the steric hindrance between 1,8-naphthalimide moiety and polymer/oligomers chain. This new class of model compounds is promising for use as a material with enhanced charge separation for wide range of optoelectronic, electrochromic and photovoltaic applications

  15. Electrogenerated poly(pyrrole-lactosyl) and poly(pyrrole-3'-sialyllactosyl) interfaces: towards the impedimetric detection of lectins

    Science.gov (United States)

    Gondran, Chantal; Dubois, Marie-Pierre; Fort, Sebastien; Cosnier, Serge

    2013-07-01

    This paper reports on the impedimetric transduction of binding reaction between polymerized saccharides and target lectins. The controlled potential electro-oxidation of pyrrole-lactosyl and pyrrole-3’-sialyllactosyl at 0.95 V vs Ag/AgCl, provides thin and reproducible poly(pyrrole-saccharide) films. The affinity binding of two lectins: Arachis hypogaea, (PNA) and Maackia amurensis (MAA) onto poly(pyrrole-lactosyl) and poly(pyrrole-3’-sialyllactosyl) electrodes, was demonstrated by cyclic voltammetry in presence of ruthenium hexamine and hydroquinone. In addition, rotating disk experiments were carried out to determine the permeability of both polypyrrole films and its evolution after incubating with lectin target. Finally, the possibility of using the poly(pyrrole-lactosyl) or poly(pyrrole-3’-siallyllactosyl) films for the impedimetric transduction of the lectin binding reaction, was investigated with hydroquinone (2×10-3 mol L-1) as a redox probe in phosphate buffer. The resuting impedance spectra were interpreted and modeled as an equivalent circuit indicating that charge transfer resistance (Rct) and relaxation frequency (f°) parameters are sensitive to the lectin binding. Rct increases from 77 to 97 Ω cm2 for PNA binding and from 93 to 131 Ω cm2 for MAA binding. In parallel, f° decreases from 276 to 222 Hz for PNA binding and from 223 to 131 Hz for MAA binding. This evolution of both parameters reflects the steric hindrances generated by the immobilised lectins towards the permeation of the redox probe.

  16. Electrogenerated poly(pyrrole-lactosyl and poly(pyrrole-3’-sialyllactosyl interfaces: towards the impedimetric detection of lectins

    Directory of Open Access Journals (Sweden)

    Chantal eGondran

    2013-07-01

    Full Text Available This paper reports on the impedimetric transduction of binding reaction between polymerized saccharides and target lectins. The controlled potential electro-oxidation of pyrrole-lactosyl and pyrrole-3’-sialyllactosyl at 0.95 V vs Ag/AgCl, provides thin and reproducible poly(pyrrole-saccharide films. The affinity binding of two lectins: Arachis hypogaea, (PNA and Maackia amurensis (MAA onto poly(pyrrole-lactosyl and poly(pyrrole-3’-sialyllactosyl electrodes, was demonstrated by cyclic voltammetry in presence of ruthenium hexamine and hydroquinone. In addition, rotating disk experiments were carried out to determine the permeability of both polypyrrole films and its evolution after incubating with lectin target. Finally, the possibility of using the poly(pyrrole-lactosyl or poly(pyrrole-3’-siallyllactosyl films for the impedimetric transduction of the lectin binding reaction, was investigated with hydroquinone (2×10-3 mol L-1 as a redox probe in phosphate buffer. The resuting impedance spectra were interpreted and modeled as an equivalent circuit indicating that charge transfer resistance (Rct and relaxation frequency (f° parameters are sensitive to the lectin binding. Rct increases from 77 to 97 Ω cm2 for PNA binding and from 93 to 131 Ω cm2 for MAA binding. In parallel, f° decreases from 276 to 222 Hz for PNA binding and from 223 to 131 Hz for MAA binding. This evolution of both parameters reflects the steric hindrances generated by the immobilised lectins towards the permeation of the redox probe.

  17. Study on the nature of interaction of pyrrole with various hydrides

    International Nuclear Information System (INIS)

    Graphical abstract: The equilibrium geometries of the pyrrole-HnX (X=F, O, N, Cl, S and P) complexes are shown in above figure. These geometries are classified as N-H...X type and H-π-type (also referred to in this paper as geometry types I and II, respectively). The N-H...X type geometry features a hydrogen bond formed between the hydrogen atom of pyrrole and X atom of HnX, and has C1 symmetry. The π-type geometry is characterized by an H-π bond formed between a hydrogen atom of HnX and the π-electron system of the aromatic ring, and has C1 symmetry. For the pyrrole-HF, H2O, NH3, H2S and -PH3 complexes have N-H...X type and π-type. For the pyrrole-HCl complexes have only H-π-type. Display Omitted Highlights: → We investigated the intermolecular interaction of pyrrole with the various hydrides. → There are N-H...X and H-π-type hydrogen-bonding complexes. → With the exception of pyrrole-H2O and pyrrole-NH3 complexes, all of the other pyrrole-HnX complexes favors π-type H-bonding. → The electrostatic and dispersion interactions dominate the H-π-type complexes. - Abstract: Equilibrium geometries, interaction energies, atomic charge, and charge transfer for the N-H...X and H-π-type hydrogen-bonding complexes between pyrrole and various hydrides HnX (X=F, O, N, Cl, S, and P) were studied at the MP2/aug-cc-pVDZ level. With the exception of pyrrole-H2O and pyrrole-NH3 complexes, all of the other pyrrole-HnX complexes favors π-type H-bonding. To further study the nature of the π-type H-bonding, an SAPT (the symmetry adapted perturbation theory) energy decomposition analysis was carried out and the results indicate that the electrostatic and dispersion interactions dominate the H-π-type complexes.

  18. Calix[4]pyrrole-based ion pair receptors.

    Science.gov (United States)

    Kim, Sung Kuk; Sessler, Jonathan L

    2014-08-19

    Ion pair receptors, which are able to bind concurrently both a cation and an anion, often display higher selectivity and affinity for specific ion pairs than simple ion receptors capable of recognizing primarily either a cation or an anion. This enhancement in recognition function is attributable to direct or indirect cooperative interactions between cobound ions via electrostatic attractions between oppositely charged ions, as well as to positive allosteric effects. In addition, by virtue of binding the counterions of the targeted ion, ion pair receptors can minimize the solvation of the counterions, which can otherwise have a negative effect on the interactions between the receptors and the targeted ions. As a result of their more favorable interactions, ion pair receptors are attractive for use in applications, such as extraction and sensing, where control of the binding interactions is advantageous. In this Account, we illustrate this potential in the context of ion pair receptors based on the calix[4]pyrrole scaffold. Both simple ditopic ion pair receptors, containing sites for the recognition of a single anion and single cation, and so-called multitopic ion pair receptors will be discussed. The latter systems differ from conventional, so-called ditopic ion pair receptors in that they contain more than one binding site for a given targeted ion (e.g., a cation). This permits a level of selectivity and control over binding function not normally seen for simple ion or ion pair receptors containing one or two binding sites, respectively. Calix[4]pyrroles are macrocyclic compounds consisting of four pyrrole units linked via fully substituted sp(3) hybridized meso carbon atoms. They are effective receptors for Lewis basic anions (e.g., halides) in typical organic media and under certain conditions will recognize ion pairs containing charge diffuse cations, such as a small alkylammonium, imidazolium, or cesium cations. The calix[4]pyrrole framework is further

  19. Radiation curable oligomers

    International Nuclear Information System (INIS)

    A process is described for the high energy radiation curing of oligomers for use as coatings. The method is particularly applicable to the reaction products of certain low molecular weight epoxy compounds and certain low molecular weight mono-hydroxy vinyl compounds having at least one vinylic unsaturation. The curable mixture is applied as a thin film and cured very quickly

  20. Multiphoton ionization of pyrrole-water mixed clusters

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Multiphoton ionization of the hydrogen-bonded pyrrole-water clusters ( C4H5 N)n H2O)m is studied with a reflectron—time of flight mass spectrometer at 355 nm. With increasing partial concentration of pyrrole in a gas mixture source, a series of poly-pyrrole-water binary-mixed cluster ions can be observed, including unprotonated cluster ions [(C4H5N)x (H2O)y]* , protonated cluster ions [(C4H5N)x (H2O)yH]* and dehydrogenated cluster ions [ ( C4 H4 N) ( C4 H5 N) x ( H2O) y ] + . Ab initio calculations of their structures, bond strengths, charge distributions and re action energies are carried out. Stable structures of these clusters are obtained from the calculations. A probable forma tion mechanism of the cluster ions [(C4H5N)x(H2O)y] + , [(C4H5N)x (H2O)y]H+ and [(C4H4N) (C4H5N)x (H2O)y]-is supposed to be the ionization of clusters followed by dissociation.

  1. Electrophilic surface sites as precondition for the chemisorption of pyrrole on GaAs(001) surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Bruhn, Thomas [Institut für Festkörperphysik, Technische Universität Berlin, Hardenbergstr.36, D-10623 Berlin (Germany); Leibniz-Institut für Analytische Wissenschaften - ISAS - e.V., Albert-Einstein-Str.9, 12489 Berlin (Germany); Fimland, Bjørn-Ove [Department of Electronics and Telecommunications, Norwegian University of Science and Technology, NO-7491 Trondheim (Norway); Vogt, Patrick, E-mail: patrick.vogt@tu-berlin.de [Institut für Festkörperphysik, Technische Universität Berlin, Hardenbergstr.36, D-10623 Berlin (Germany)

    2015-03-14

    We report how the presence of electrophilic surface sites influences the adsorption mechanism of pyrrole on GaAs(001) surfaces. For this purpose, we have investigated the adsorption behavior of pyrrole on different GaAs(001) reconstructions with different stoichiometries and thus different surface chemistries. The interfaces were characterized by x-ray photoelectron spectroscopy, scanning tunneling microscopy, and by reflectance anisotropy spectroscopy in a spectral range between 1.5 and 5 eV. On the As-rich c(4 × 4) reconstruction that exhibits only nucleophilic surface sites, pyrrole was found to physisorb on the surface without any significant modification of the structural and electronic properties of the surface. On the Ga-rich GaAs(001)-(4 × 2)/(6 × 6) reconstructions which exhibit nucleophilic as well as electrophilic surface sites, pyrrole was found to form stable covalent bonds mainly to the electrophilic (charge deficient) Ga atoms of the surface. These results clearly demonstrate that the existence of electrophilic surface sites is a crucial precondition for the chemisorption of pyrrole on GaAs(001) surfaces.

  2. Electrophilic surface sites as precondition for the chemisorption of pyrrole on GaAs(001) surfaces

    International Nuclear Information System (INIS)

    We report how the presence of electrophilic surface sites influences the adsorption mechanism of pyrrole on GaAs(001) surfaces. For this purpose, we have investigated the adsorption behavior of pyrrole on different GaAs(001) reconstructions with different stoichiometries and thus different surface chemistries. The interfaces were characterized by x-ray photoelectron spectroscopy, scanning tunneling microscopy, and by reflectance anisotropy spectroscopy in a spectral range between 1.5 and 5 eV. On the As-rich c(4 × 4) reconstruction that exhibits only nucleophilic surface sites, pyrrole was found to physisorb on the surface without any significant modification of the structural and electronic properties of the surface. On the Ga-rich GaAs(001)-(4 × 2)/(6 × 6) reconstructions which exhibit nucleophilic as well as electrophilic surface sites, pyrrole was found to form stable covalent bonds mainly to the electrophilic (charge deficient) Ga atoms of the surface. These results clearly demonstrate that the existence of electrophilic surface sites is a crucial precondition for the chemisorption of pyrrole on GaAs(001) surfaces

  3. A new pyrrole alkaloid from seeds of Castanea sativa.

    Science.gov (United States)

    Hiermann, Alois; Kedwani, Samir; Schramm, Hans Wolfgang; Seger, Christoph

    2002-02-01

    A new pyrrole alkaloid, methyl-(5-formyl-1H-pyrrole-2-yl)-4-hydroxybutyrate (1), was isolated from sweet chestnut seeds and its structure elucidated on the basis of data from NMR spectroscopy and by comparison with synthetic analogues.

  4. Tris[2-(pyrrol-2-ylmethyleneaminoethyl]amine

    Directory of Open Access Journals (Sweden)

    Hongbing Fu

    2008-03-01

    Full Text Available The title compound, C21H27N7, was synthesized by reaction of tris(2-aminoethylamine and pyrrole-2-carbaldehyde in ethanol at room temperature. The structure is stabilized by intra- and intermolecular C—H...N and N—H...N hydrogen-bonding interactions.

  5. Identification of a new electron-transfer relaxation pathway in photoexcited pyrrole dimers.

    Science.gov (United States)

    Neville, Simon P; Kirkby, Oliver M; Kaltsoyannis, Nikolas; Worth, Graham A; Fielding, Helen H

    2016-04-21

    Photoinduced electron transfer is central to many biological processes and technological applications, such as the harvesting of solar energy and molecular electronics. The electron donor and acceptor units involved in electron transfer are often held in place by covalent bonds, π-π interactions or hydrogen bonds. Here, using time-resolved photoelectron spectroscopy and ab initio calculations, we reveal the existence of a new, low-energy, photoinduced electron-transfer mechanism in molecules held together by an NH⋯π bond. Specifically, we capture the electron-transfer process in a pyrrole dimer, from the excited π-system of the donor pyrrole to a Rydberg orbital localized on the N-atom of the acceptor pyrrole, mediated by an N-H stretch on the acceptor molecule. The resulting charge-transfer state is surprisingly long lived and leads to efficient electronic relaxation. We propose that this relaxation pathway plays an important role in biological and technological systems containing the pyrrole building block.

  6. Identification of a new electron-transfer relaxation pathway in photoexcited pyrrole dimers

    Science.gov (United States)

    Neville, Simon P.; Kirkby, Oliver M.; Kaltsoyannis, Nikolas; Worth, Graham A.; Fielding, Helen H.

    2016-04-01

    Photoinduced electron transfer is central to many biological processes and technological applications, such as the harvesting of solar energy and molecular electronics. The electron donor and acceptor units involved in electron transfer are often held in place by covalent bonds, π-π interactions or hydrogen bonds. Here, using time-resolved photoelectron spectroscopy and ab initio calculations, we reveal the existence of a new, low-energy, photoinduced electron-transfer mechanism in molecules held together by an NH⋯π bond. Specifically, we capture the electron-transfer process in a pyrrole dimer, from the excited π-system of the donor pyrrole to a Rydberg orbital localized on the N-atom of the acceptor pyrrole, mediated by an N-H stretch on the acceptor molecule. The resulting charge-transfer state is surprisingly long lived and leads to efficient electronic relaxation. We propose that this relaxation pathway plays an important role in biological and technological systems containing the pyrrole building block.

  7. Marked Consequences of Systematic Oligothiophene Catenation in Thieno[3,4-c]pyrrole-4,6-dione and Bithiopheneimide Photovoltaic Copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Nanjia; Guo, Xugang; Ponce Ortiz, Rocio; Harschneck, Tobias; Manley, Eric F.; Lou, Sylvia J.; Hartnett, Patrick E.; Yu, Xinge; Horwitz, Noah E.; Mayorga Burrezo, Paula; Aldrich, Thomas J.; Lopez Navarrete, Juan T.; Wasielewski, Michael R.; Chen, Lin X.; Chang, Robert P. H.; Facchetti, Antonio; Marks, Tobin J.

    2015-10-07

    As effective building blocks for high-mobility transistor polymers, oligothiophenes are receiving attention for polymer solar cells (PSCs) because the resulting polymers can effectively suppress charge recombination. Here we investigate two series of in-chain donor-acceptor copolymers, PTPDnT and PBTInT, based on thieno[3,4-c]pyrrole-4,6-dione (TPD) or bithiopheneimide (BTI) as electron acceptor units, respectively, and oligothiophenes (nTs) as donor counits, for high-performance PSCs. Intramolecular S···O interaction leads to more planar TPD polymer backbones, however backbone torsion yields greater open-circuit voltages for BTI polymers. Thiophene addition progressively raises polymer HOMOs but marginally affects their band gaps. FT-Raman spectra indicate that PTPDnT and PBTInT conjugation lengths scale with nT catenation up to n = 3 and then saturate for longer oligomer. Furthermore, the effects of oligothiophene alkylation position are explored, revealing that the alkylation pattern greatly affects film morphology and PSC performance. The 3T with “outward” alkylation in PTPD3T and PBTI3T affords optimal π-conjugation, close stacking, long-range order, and high hole mobilities (0.1 cm2/(V s)). These characteristics contribute to the exceptional ~80% fill factors for PTPD3T-based PSCs with PCE = 7.7%. The results demonstrate that 3T is the optimal donor unit among nTs (n = 1-4) for photovoltaic polymers. Grazing incidence wide-angle X-ray scattering, transmission electron microscopy, and time-resolved microwave conductivity measurements reveal that the terthiophene-based PTPD3T blend maintains high crystallinity with appreciable local mobility and long charge carrier lifetime. These results provide fundamental materials structure-device performance correlations and suggest guidelines for designing oligothiophene-based polymers with optimal thiophene catenation and appropriate alkylation pattern to maximize PSC performance.

  8. The electrochemical synthesis of poly(pyrrole-co-o-anisidine) on 3102 aluminum alloy and its corrosion protection properties

    Energy Technology Data Exchange (ETDEWEB)

    Mert, B. Dogru, E-mail: bdogru@cu.edu.tr [Cukurova University, Science and Letters Faculty, Chemistry Department, 01330 Balcali, Adana (Turkey); Yazici, B. [Cukurova University, Science and Letters Faculty, Chemistry Department, 01330 Balcali, Adana (Turkey)

    2011-02-15

    Research highlights: {yields} The electrochemical synthesis of strongly adherent, uniform polypyrrole (PPy) and poly(pyrrole-co-o-anisidine) coatings were successfully achieved on 3102 aluminum alloy from 0.1 M monomer (pyrrole and pyrrole:o-anisidine, 8:2) containing oxalic acid by means of the cyclic voltammetry technique. {yields} The results were showed that the water permeation of copolymer coating is lower than PPy. {yields} This study was showed that copolymer is suitable coating for protection of 3102 Al alloy against corrosion. - Abstract: The electrochemical syntheses of polypyrrole (PPy) and poly(pyrrole-co-o-anisidine) were achieved on 3102 aluminum alloy (Al) from 0.1 M monomer (pyrrole:o-anisidine, 8:2) containing 0.4 M oxalic acid solution using the cyclic voltammetry technique. The synthesized films were characterized by FT-IR spectroscopy. The thermal stability of films was determined by thermogravimetric analysis (TGA) technique. Surface morphologies were characterized by scanning electron microscope (SEM) images. The potential of zero charge (pzc) of Al was determined using electrochemical impedance spectroscopy (EIS). The corrosion behavior of samples was investigated with open circuit potential (E{sub ocp})-time, EIS, and anodic polarization techniques. It was found that copolymer coated Al provides better barrier property against of corrosion in 3.5% NaCl solution.

  9. Modelling the size-dependence effects on the electronic properties of conjugated oligomers

    OpenAIRE

    Correia, Helena M. G.; Ramos, Marta M. D.

    2011-01-01

    Comunicação oral. Conjugated oligomers are materials that have the potential to be used in organic and hybrid electronic and optoelectronic devices as an active component. However, the electronic properties responsible for their electrical and optical behaviour are size-dependent. Here we use a self-consistent quantum molecular dynamics method to study the effect of the oligomers length at nanosize regime on the ionization potential, electron affinity, charge (electrons and holes) mobility...

  10. Preparation of conductive membranes using poly pyrrole

    International Nuclear Information System (INIS)

    Conductive membranes show many benefits including fouling reduction for feeds containing ionic species. These membranes may be prepared either by conductive polymers or coating of the surfaces of non-conductive membranes with conductive polymer. In this research, the commercial micro filtration GVHP membrane manufactured from PVDF was coated with poly pyrrole using two different techniques. The conductivity of the prepared membranes was measured. In this paper, effects of various factors including concentration of the solutions, oxidizing agents, time for leaving the support in the solutions, support type and temperature on membrane conductivity were investigated

  11. Revisiting the relaxation dynamics of isolated pyrrole

    Energy Technology Data Exchange (ETDEWEB)

    Montero, Raúl; Ovejas, Virginia; Fernández-Fernández, Marta; Longarte, Asier, E-mail: asier.longarte@ehu.es [Departamento de Química Física, Universidad del País Vasco (UPV/EHU), Apart. 644, 48080 Bilbao (Spain); Peralta Conde, Álvaro [Centro de Láseres Pulsados (CLPU), Edificio M3, Parque Científico, 37185 Villamayor (Spain)

    2014-07-07

    Herein, the interpretation of the femtosecond-scale temporal evolution of the pyrrole ion signal, after excitation in the 267–217 nm interval, recently published by our group [R. Montero, A. Peralta Conde, V. Ovejas, M. Fernández-Fernández, F. Castaño, J. R. Vázquez de Aldana, and A. Longarte, J. Chem. Phys.137, 064317 (2012)] is re-visited. The observation of a shift in the pyrrole{sup +} transient respect to zero delay reference, initially attributed to ultrafast dynamics on the πσ{sup *} type state (3s a{sub 1} ← π 1a{sub 2}), is demonstrated to be caused by the existence of pump + probe populated states, along the ionization process. The influence of these resonances in pump-prone ionization experiments, when multi-photon probes are used, and the significance of a proper zero-time reference, is discussed. The possibility of preparing the πσ{sup *} state by direct excitation is investigated by collecting 1 + 1 photoelectron spectra, at excitation wavelengths ranging from 255 to 219 nm. No conclusive evidences of ionization through this state are found.

  12. Living on pyrrolic foundations - Advances in natural and artificial bioactive pyrrole derivatives.

    Science.gov (United States)

    Domagala, Anna; Jarosz, Tomasz; Lapkowski, Mieczyslaw

    2015-07-15

    Pyrrole, a simple heterocyclic system, is an important building block for numerous biologically active compounds both natural and synthetic in origin, which boast an immense array of qualities, baleful and beneficial alike. The latter have given rise to a bountiful variety of pyrrole-based drugs, with many more being designed, developed and applied each year, as evidenced by the amount of entries in the Cambridge Structural Database skyrocketing from about six hundred in 2004 to more than a thousand over the course of the last decade. Particularly important in light of the ever-encroaching menace of drug-resistant bacteria, the vast progress in the field necessitates a sound organisational framework and summary - a task, to which we contribute this summary and checklist of the most recent developments, indicating the classes of compounds, which have attracted the most significant research attention. PMID:26087028

  13. Pyrrole-Pyridine and Pyrrole-Naphthyridine Hosts for Anion Recognition

    Directory of Open Access Journals (Sweden)

    M. Angeles García

    2015-05-01

    Full Text Available The association constants of the complexes formed by two hosts containing pyrrole, amide and azine (pyridine and 1,8-naphthyridine groups and six guests, all monoanions (Cl−, CH3CO2−, NO3−, H2PO4−, BF4−, PF6−, have been determined using NMR titrations. The X-ray crystal structure of the host N2,N5-bis(6-methylpyridin-2-yl-3,4-diphenyl-1H-pyrrole- 2,5-dicarboxamide (1 has been solved (P21/c monoclinic space group. B3LYP/6-31G(d,p and calculations were carried out in an attempt to rationalize the trends observed in the experimental association constants.

  14. Bandgap Engineering in π-Extended Pyrroles. A Modular Approach to Electron-Deficient Chromophores with Multi-Redox Activity.

    Science.gov (United States)

    Zhylitskaya, Halina; Cybińska, Joanna; Chmielewski, Piotr; Lis, Tadeusz; Stępień, Marcin

    2016-09-01

    A family of bandgap-tunable pyrroles structurally related to rylene dyes was computationally designed and prepared using robust, easily scalable chemistry. These pyrroles show highly variable fluorescence properties and can be used as building blocks for the synthesis of electron-deficient oligopyrroles. The latter application is demonstrated through the development of π-extended porphyrins containing naphthalenediamide or naphthalenediimide units. These new macrocycles exhibit simultaneously tunable visible and near-IR absorptions, an ability to accept up to 8 electrons via electrochemical reduction, and high internal molecular free volumes. When chemically reduced under inert conditions, the most electron-deficient of these macrocycles revealed reversible formation of eight charged states, characterized by remarkably red-shifted optical absorptions, extending beyond 2200 nm. Such features make these oligopyrroles of interest as functional chromophores, charge-storage materials, and tectons for crystal engineering. PMID:27533895

  15. Low frequency ac conduction and dielectric relaxation in poly(N-methyl pyrrole)

    Indian Academy of Sciences (India)

    Amarjeet K Narula; Ramadhar Singh; Subhas Chandra

    2000-06-01

    The ac conductivity and dielectric constant of poly(N-methyl pyrrole) thin films have been investigated in the temperature range 77–350 K and in the frequency range 102–106 Hz. The well defined loss peaks have been observed in the temperature region where measured ac conductivity approaches dc conductivity. These loss peaks are associated with the hopping of the charge carriers. The frequency and temperature dependence of ac conductivity have been qualitatively explained by considering the contribution from two mechanisms; one giving a linear dependence of conductivity on frequency and other having distribution of relaxation times giving rise to broad dielectric loss peak.

  16. Polymerization of Pyrrole and Thiophene on Polyethylene Adipate Electrodes

    OpenAIRE

    Erturan, Seyfettin; TORAMAN, Burcu YALVAÇ and Sena

    1998-01-01

    Polymerizations of pyrrole and thiophene on a platinum foil coated by polyethylene adipate (PEA) were carried out in acetonitrile by electrochemical methods. Different compositions of semi-conducting composite films of PEA/Polypyrrole(PPy), PEA/Polythiophene(PT) were prepared by the electrochemical polymerization of pyrrole and thiophene on PEA electrode. The polymerization was possible only for a certain thickness of the polyethylene adipate(PEA) on the platinum. Conductivities of PEA/PPy, P...

  17. An Electrochemical Investigation into a Series of Tricyanovinylated Pyrrole Moieties

    NARCIS (Netherlands)

    McCormac, Timothy; Farrell, David; Browne, Wesley; Vos, Johannes G.

    2004-01-01

    The electrochemical behavior of three tri-cyanovinylated pyrrole species namely, 2-tricyanovinyl-pyrrole (C4H4N-C5N3), 2-tricyanovinyl-N-methylpyrrole (C5H6N-C5N3) and 2-tricyanovinyl-N-phenylpyrrole (C10H8N-C5N3), has been studied. All compounds were found to exhibit both an irreversible oxidation

  18. Simple two-step synthesis of 2,4-disubstituted pyrroles and 3,5-disubstituted pyrrole-2-carbonitriles from enones

    Directory of Open Access Journals (Sweden)

    Murat Kucukdisli

    2014-02-01

    Full Text Available The cyclocondensation of enones with aminoacetonitrile furnishes 3,4-dihydro-2H-pyrrole-2-carbonitriles which can be readily converted to 2,4-disubstituted pyrroles by microwave-induced dehydrocyanation. Alternatively, oxidation of the intermediates produces 3,5-disubstituted pyrrole-2-carbonitriles.

  19. Prion protein oligomer and its neurotoxicity

    Institute of Scientific and Technical Information of China (English)

    Pei Huang; Fulin Lian; Yi Wen; Chenyun Guo; Donghai Lin

    2013-01-01

    The prion diseases,also known as transmissible spongiform encephalopathies,are fatal neurodegenerative disorders.According to the 'protein only' hypothesis,the key molecular event in the pathogenesis of prion disease is the conformational conversion of the host-derived cellular prion protein (PrPC) into a misfolded form (scrapie PrP,prpSc).Increasing evidence has shown that the most infectious factor is the smaller subfibrillar oligomers formed by prion proteins.Both the prion oligomer and PrPSc are rich in β-sheet structure and resistant to the proteolysis of proteinase K.The prion oligomer is soluble in physiologic environments whereas PrPSc is insoluble.Various prion oligomers are formed in different conditions.Prion oligomers exhibited more neurotoxicity both in vitro and in vivo than the fibrillar forms of PrPSc,implying that prion oligomers could be potential drug targets for attacking prion diseases.In this article,we describe recent experimental evidence regarding prion oligomers,with a special focus on prion oligomer formation and its neurotoxicity.

  20. Absorption enhancing effects of chitosan oligomers on the intestinal absorption of low molecular weight heparin in rats.

    Science.gov (United States)

    Zhang, Hailong; Mi, Jie; Huo, Yayu; Huang, Xiaoyan; Xing, Jianfeng; Yamamoto, Akira; Gao, Yang

    2014-05-15

    Absorption enhancing effects of chitosan oligomers with different type and varying concentration on the intestinal absorption of low molecular weight heparin (LMWH) were examined by an in situ closed loop method in different intestinal sections of rats. Chitosan hexamer with the optimal concentration of 0.5% (w/v) showed the highest absorption enhancing ability both in the small intestine and large intestine. The membrane toxicities of chitosan oligomers were evaluated by morphological observation and determining the biological markers including amount of protein and activity of lactate dehydrogenase (LDH) released from intestinal epithelium cells. There was no obvious change both in levels of protein and LDH and morphology in the intestinal membrane between control and various chitosan oligomers groups, suggesting that chitosan oligomers did not induce any significant membrane damage to the intestinal epithelium. In addition, zeta potentials became less negative and amount of free LMWH gradually decreased when various chitosan oligomers were added to LMWH solution, revealing that electrostatic interaction between positively charged chitosan oligomers and negative LMWH was included in the absorption enhancing mechanism of chitosan oligomers. In conclusion, chitosan oligomers, especially chitosan hexamer, are safe and efficient absorption enhancers and can be used promisingly to improve oral absorption of LMWH.

  1. Ultrafast Photoinduced Electron Transfer in a π-Conjugated Oligomer/Porphyrin Complex

    KAUST Repository

    Aly, Shawkat Mohammede

    2014-10-02

    Controlling charge transfer (CT), charge separation (CS), and charge recombination (CR) at the donor-acceptor interface is extremely important to optimize the conversion efficiency in solar cell devices. In general, ultrafast CT and slow CR are desirable for optimal device performance. In this Letter, the ultrafast excited-state CT between platinum oligomer (DPP-Pt(acac)) as a new electron donor and porphyrin as an electron acceptor is monitored for the first time using femtosecond (fs) transient absorption (TA) spectroscopy with broad-band capability and 120 fs temporal resolution. Turning the CT on/off has been shown to be possible either by switching from an organometallic oligomer to a metal-free oligomer or by controlling the charge density on the nitrogen atom of the porphyrin meso unit. Our time-resolved data show that the CT and CS between DPP-Pt(acac) and cationic porphyrin are ultrafast (approximately 1.5 ps), and the CR is slow (ns time scale), as inferred from the formation and the decay of the cationic and anionic species. We also found that the metallic center in the DPP-Pt(acac) oligomer and the positive charge on the porphyrin are the keys to switching on/off the ultrafast CT process.

  2. α-Synuclein oligomers induced by docosahexaenoic acid affect membrane integrity.

    Directory of Open Access Journals (Sweden)

    Chiara Fecchio

    Full Text Available A key feature of Parkinson disease is the aggregation of α-synuclein and its intracellular deposition in fibrillar form. Increasing evidence suggests that the pathogenicity of α-synuclein is correlated with the activity of oligomers formed in the early stages of its aggregation process. Oligomers toxicity seems to be associated with both their ability to bind and affect the integrity of lipid membranes. Previously, we demonstrated that α-synuclein forms oligomeric species in the presence of docosahexaenoic acid and that these species are toxic to cells. Here we studied how interaction of these oligomers with membranes results in cell toxicity, using cellular membrane-mimetic and cell model systems. We found that α-synuclein oligomers are able to interact with large and small unilamellar negatively charged vesicles acquiring an increased amount of α-helical structure, which induces small molecules release. We explored the possibility that oligomers effects on membranes could be due to pore formation, to a detergent-like effect or to fibril growth on the membrane. Our biophysical and cellular findings are consistent with a model where α-synuclein oligomers are embedded into the lipid bilayer causing transient alteration of membrane permeability.

  3. Synthesis, autoxidation and photooxidation of hindered pyrrole derivatives. Hindered pyrrolic nitroxide radicals; Synthese, autoxydation et photoxidation de pyrroles encombres radicaux nitroxydes pyrroliques encombres

    Energy Technology Data Exchange (ETDEWEB)

    Ramasseul, R. [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1969-07-01

    2,5-di-t-butyl and 2,3,5-tri-t-butyl pyrrole are prepared from pinacoline and their structure is confirmed by comparison with 2,5-di-t-butyl furan and thiophene (I.R., U.V. and N.M.R. {sup 13}C satellites observation giving J{sub 13{sub C-H}} and J{sub H{sub 3}-H{sub 4}}). The sensitized photooxidation of these hindered pyrroles gives corresponding hydroperoxides which most likely structure is determined using physical and chemical methods. Oxidation of 2,5-di-t-butyl and 2,3,5-tri-t-butyl pyrrole by hydrogen peroxide in presence of inorganic per-acid of by p-nitro-perbenzoic acid does not give the pyrrolic nitroxides in contrast with secondary amines. Some N-hydroxypyrroles are then prepared from pinacoline and ethyl pivaloyl-acetate. Their oxidation by lead dioxide gives the corresponding pyrrolic nitroxides. 2,5-di-t-butyl 3,4-di-ethoxycarbonyl pyrryl 1-oxy is isolated and studied spectroscopically (visible and U.V., E.P.R.). In marked contrast with ordinary nitroxides it does not show solvent effect. It can be compared with 2,4-di-t-butyl cyclopentadienone, a carbon analog. For both, the long wave length transition does not show the usual n - {pi}* behaviour; that is confirmed by E.P.R. Using Huckel method for pyrrolic nitroxide skeleton, it is possible to have a good interpretation of experimental data. (author) [French] Les di-t-butyl 2,5 et tri-t-butyl-2,3,5 pyrrole sont synthetises a partir de la pinacoline et leur structure confirmee par comparaison avec les di-t-butyl-2,5 furanne et thiophene (I.R., U.V. et R.M.N.: observation des satellites {sup 13}C conduisant a la mesure des J{sub 13{sub C-H}} et J{sub H{sub 3}{sub -H{sub 4}}). La photoxydation sensibilisee de ces pyrroles encombres conduit aux hydroperoxydes correspondants dont la structure la plus probable est determinee par les methodes physicochimiques. L'oxydation des di-t-butyl-2,5 et tri-t-butyl-2,3,5 pyrrole par l'eau oxygenee en presence de peracide mineral ou par l'acide p

  4. CHANGES OF STRUCTURE AND PROPERTIES OF POLY (ETHYLENE TEREPHTHALATE)CAUSED BY IN-SITU POLYMERIZATION OF PYRROLE

    Institute of Scientific and Technical Information of China (English)

    HE Jiasong; FENG Zhihai

    1991-01-01

    Conductive polymer composites based on crystalline polymer matrix have been prepared by using an in-situ polymerization process of pyrrole in amorphous poly (ethylene terephthalate) (PET) film.The DSC and WAXD measurement and SEM observation show that liquid-induced crystallization of PET matrix has occurred during the preparation of composite films. Depending upon the equilibrium degree of swelling and crystallinity, the limited depth of penetration of pyrrole molecules results in a skin-core structure of the composite film. The skin layer containing charge transfer intercalated polypyrrole has a surface resistance of 3.5 × 104 Ω. Rigid and heat-resistant polypyrrole molecules formed in PET film increase the tensile modulus and, especially, the rigidity of PET at elevated temperatures. However, they decrease the tensile strength and elongation at break, and impair the thermal ductility of PET.

  5. Polycondensation of pyrrole and benzaldehyde catalyzed by Maghnite–H+

    Directory of Open Access Journals (Sweden)

    2007-07-01

    Full Text Available Rapid synthesis of poly[(pyrrole-2,5-diyl-co-(benzylidene] was achieved under microwave irradiation via the condensation of pyrrole and benzaldehyde in 1,2-dichloroethane using acid exchanged montmorillonite clay called Maghnite–H+ (Mag–H+ as an efficient catalyst. The effect of the amount of catalyst and of time on the polymerization yield and on the viscosity of the polymers was studied. Compared with conventional static interfacial polymerization, the microwave-radiation polymerization reaction proceeded rapidly and was completed within 35 s. The conjugated polymer was characterized by means of 1H-NMR, X-ray diffraction, FT-IR spectroscopy and AFM. The X-ray data showed the presence of a backbone form of the [(pyrrole-2,5-diyl-co-(benzylidene] formed.

  6. Hydrazonoyl Chlorides as Precursors for Synthesis of Novel Bis-Pyrrole Derivatives

    OpenAIRE

    Nabila Abdelshafy Kheder

    2016-01-01

    A convenient synthesis of some novel bis-pyrrole derivatives via hydrazonoyl halides is described. Antimicrobial evaluation of some selected examples of the synthesized products was carried out. The bis-pyrrole derivative having chloro substituents showed good activity against all of the used microbes. The molecular docking of the bis-pyrrole derivatives was performed by the Molecular Operating Environment (MOE) program.

  7. The first direct synthesis of β-unsubstituted meso-decamethylcalix[5]pyrrole

    OpenAIRE

    Chacón-García, Luis; Chávez, Lizbeth; Cacho, Denisse R; Altamirano-Hernández, Josue

    2009-01-01

    The first direct synthesis of β-unsubstituted meso-decamethylcalix[5]pyrrole from pyrrole and acetone, with moderate yield, is described. The results showed that a bismuth salt was necessary to obtain calix[5]pyrrole, with the best results obtained using Bi(NO3)3.

  8. The first direct synthesis of β-unsubstituted meso-decamethylcalix[5]pyrrole

    OpenAIRE

    Luis Chacón-García; Lizbeth Chávez; Cacho, Denisse R; Josue Altamirano-Hernández

    2009-01-01

    The first direct synthesis of β-unsubstituted meso-decamethylcalix[5]pyrrole from pyrrole and acetone, with moderate yield, is described. The results showed that a bismuth salt was necessary to obtain calix[5]pyrrole, with the best results obtained using Bi(NO3)3.

  9. A colorimetric tetrathiafulvalene-calix 4 pyrrole anion sensor

    DEFF Research Database (Denmark)

    Nielsen, K. A.

    2012-01-01

    The interaction and colorimetric sensing properties of a tetrathiafulvalene substituted calix[4]pyrrole sensor with anions were investigated using H-1 NMR and absorption spectroscopic techniques. Visual color changes were observed upon addition of different anions (Cl-, Br-, CN-, and AcO-) to a s......The interaction and colorimetric sensing properties of a tetrathiafulvalene substituted calix[4]pyrrole sensor with anions were investigated using H-1 NMR and absorption spectroscopic techniques. Visual color changes were observed upon addition of different anions (Cl-, Br-, CN-, and Ac......O-) to a solution of the sensor. (C) 2012 Elsevier Ltd. All rights reserved....

  10. Polymers and copolymers of pyrrole and thiophene as electrodes in lithium cells

    Energy Technology Data Exchange (ETDEWEB)

    Pinto, M.I.S. de; Mishima, H.T.; Mishima, B.A.L. de [Universidad Nacional de Santiago del Estero (Argentina). Inst. de Cs. Quimicas

    1997-07-01

    The performance of pyrrole and thiophene polymer electrodes in lithium cells has been examined in the lithium perchlorate-propylene carbonate electrolyte by cyclic voltammetry. Polypyrrole films were synthesized in `wet` and `dry` conditions; pyrrole and thiophene copolymers were prepared at different potentials and bilayers were prepared by sequential deposition of polythiophene (PTh) and polypyrrole (PPy) films. The polymers were cycled between 2.0V and 4.0V in the lithium cells. The effects of disconnecting the electrodes from the cell on the behaviour of the polymers regarding doping and coulombic efficiency were also studied. The cycling performance of the `wet` PPy is better than `dry` PPy, bilayer PTg/PPy and copolymers. No mixed behaviour was observed for a bilayer where the inner layer was polythiophene and the outer layer was polypyrrole with a thickness PP6/Pth ratio equal to ten. The copolymer prepared at 3.9V vs Li/Li{sup +} showed the higher energy capacity in Wh kg{sup -1} calculated from the anodic charge. (Author)

  11. High-capacity conductive nanocellulose paper sheets for electrochemically controlled extraction of DNA oligomers.

    Directory of Open Access Journals (Sweden)

    Aamir Razaq

    Full Text Available Highly porous polypyrrole (PPy-nanocellulose paper sheets have been evaluated as inexpensive and disposable electrochemically controlled three-dimensional solid phase extraction materials. The composites, which had a total anion exchange capacity of about 1.1 mol kg(-1, were used for extraction and subsequent release of negatively charged fluorophore tagged DNA oligomers via galvanostatic oxidation and reduction of a 30-50 nm conformal PPy layer on the cellulose substrate. The ion exchange capacity, which was, at least, two orders of magnitude higher than those previously reached in electrochemically controlled extraction, originated from the high surface area (i.e. 80 m(2 g(-1 of the porous composites and the thin PPy layer which ensured excellent access to the ion exchange material. This enabled the extractions to be carried out faster and with better control of the PPy charge than with previously employed approaches. Experiments in equimolar mixtures of (dT(6, (dT(20, and (dT(40 DNA oligomers showed that all oligomers could be extracted, and that the smallest oligomer was preferentially released with an efficiency of up to 40% during the reduction of the PPy layer. These results indicate that the present material is very promising for the development of inexpensive and efficient electrochemically controlled ion-exchange membranes for batch-wise extraction of biomolecules.

  12. Electrografting of conductive oligomers and polymers using diazonium electroreduction

    International Nuclear Information System (INIS)

    This paper describes the attachment of conjugated oligomers onto electrode surface through the reduction of diazonium compounds. In this connection some properties of conjugated oligomers and of layers grafted through diazonium electroreduction will first be briefly presented. The electrochemical behavior of conjugated oligomers grafted on a surface using diazonium electroreduction will then be discussed. (paper)

  13. The Toxicity of Amyloid ß Oligomers

    Directory of Open Access Journals (Sweden)

    Lock Yue Chew

    2012-06-01

    Full Text Available Abstract: In this review, we elucidate the mechanisms of Aβ oligomer toxicity which may contribute to Alzheimer’s disease (AD. In particular, we discuss on the interaction of Aβ oligomers with the membrane through the process of adsorption and insertion. Such interaction gives rises to phase transitions  in the sub-structures of the Aβ peptide from α-helical to β-sheet  structure. By means of a coarse-grained model, we exhibit the tendency of β-sheet structures to aggregate, thus providing further insights to the process of membrane induced aggregation. We show that the aggregated oligomer causes membrane invagination, which is a precursor to the formation of pore structures and ion channels. Other pathological progressions to AD due to Aβ oligomers  are also covered,  such as their interaction with the membrane receptors, and their direct versus indirect effects on oxidative  stress and intraneuronal accumulation.  We further illustrate that the molecule curcumin is a potential Aβ toxicity inhibitor as a β-sheet breaker by having  a high propensity to interact with certain Aβ residues without  binding to them. The comprehensive understanding gained from these current  researches on the various toxicity mechanisms show promises in the provision of better therapeutics and treatment strategies in the near future.

  14. Opposite translocation of long and short oligomers through a nanopore

    Science.gov (United States)

    Getfert, Sebastian; Töws, Thomas; Reimann, Peter

    2013-06-01

    We consider elongated cylindrical particles, modeling, e.g., DNA fragments or nanorods, while they translocate under the action of an externally applied voltage through a solid state nanopore. Particular emphasis is put on the concomitant potential energy landscape encountered by the particle on its passage through the pore due to the complex interplay of various electrohydrodynamic effects beyond the realm of small Debye lengths. We find that the net potential energy difference across the membrane may be of opposite sign for short and long particles of equal diameters and charge densities (e.g., oligomers). Thermal noise thus leads to biased diffusion through the pore in opposite directions. By means of an additional membrane gate electrode it is even possible to control the specific particle length at which this transport inversion occurs.

  15. Numerical Analysis Of Hooke Jeeves-Runge Kutta To Determine Reaction Rate Equation In Pyrrole Polymerization

    International Nuclear Information System (INIS)

    The numerical analysis of Hooke Jeeves Methods combined with Runge Kutta Methods is used to determine the exact model of reaction rate equation of pyrrole polymerization. Chemical polymerization of pyrrole was conducted with FeCI3 / pyrrole solution at concentration ratio of 1.62 mole / mole and 2.18 mole / mole with varrying temperature of 28, 40, 50, and 60 oC. FeCl3 acts as an oxidation agent to form pyrrole cation that will polymerize. The numerical analysis was done to examine the exact model of reaction rate equation which is derived from reaction equation of initiation, propagation, and termination. From its numerical analysis, it is found that the pyrrole polymerization follows third order of pyrrole cation concentration

  16. High-Capacity Conductive Nanocellulose Paper Sheets for Electrochemically Controlled Extraction of DNA Oligomers

    OpenAIRE

    Aamir Razaq; Gustav Nyström; Maria Strømme; Albert Mihranyan; Leif Nyholm

    2011-01-01

    Highly porous polypyrrole (PPy)-nanocellulose paper sheets have been evaluated as inexpensive and disposable electrochemically controlled three-dimensional solid phase extraction materials. The composites, which had a total anion exchange capacity of about 1.1 mol kg(-1), were used for extraction and subsequent release of negatively charged fluorophore tagged DNA oligomers via galvanostatic oxidation and reduction of a 30-50 nm conformal PPy layer on the cellulose substrate. The ion exchange ...

  17. Hydrazonoyl Chlorides as Precursors for Synthesis of Novel Bis-Pyrrole Derivatives

    Directory of Open Access Journals (Sweden)

    Nabila Abdelshafy Kheder

    2016-03-01

    Full Text Available A convenient synthesis of some novel bis-pyrrole derivatives via hydrazonoyl halides is described. Antimicrobial evaluation of some selected examples of the synthesized products was carried out. The bis-pyrrole derivative having chloro substituents showed good activity against all of the used microbes. The molecular docking of the bis-pyrrole derivatives was performed by the Molecular Operating Environment (MOE program.

  18. Poly(pyrrole-co-pyrrole propylic acid) film and its application in label-free surface plasmon resonance immunosensors.

    Science.gov (United States)

    Hu, Weihua; Li, Chang Ming; Dong, Hua

    2008-12-01

    In this work, surface plasmon resonance (SPR) was used to study protein immobilization on poly(pyrrole-co-pyrrole propylic acid) (PPy/PPa) for immunosensing applications. SPR was employed to in situ monitor the electropolymerization process and to control thickness of the PPy/PPa copolymer film. Goat IgG as a model protein was covalently immobilized on the carboxyl-containing film through EDC/NHS as the coupling reagents. The effect of pyrrole propylic acid (Pa) proportion in the deposition solution on the protein immobilization capability was systemically investigated. The immobilization efficiency was demonstrated by a label-free SPR immunosensor. The heterogeneous kinetics of the immune reaction was discussed. This work could provide a facile method to immobilize proteins on an electrode surface by electropolymerized copolymer, and renders a universal approach to in situ study the protein immobilization process and sensing kinetics for scientific insights of the heteroimmunosensing scheme particularly in surface chemistry and molecular biology for further improvement of immunosensors. PMID:19068327

  19. Solid state properties of oligomers containing dithienothiophene or fluorene residues suitable for field effect transistor devices

    Energy Technology Data Exchange (ETDEWEB)

    Porzio, William [Istituto per lo Studio delle Macromolecole del C.N.R. via E. Bassini 15, 20133 Milan (Italy)]. E-mail: w.porzio@ismac.cnr.it; Destri, Silvia [Istituto per lo Studio delle Macromolecole del C.N.R. via E. Bassini 15, 20133 Milan (Italy); Giovanella, Umberto [Istituto per lo Studio delle Macromolecole del C.N.R. via E. Bassini 15, 20133 Milan (Italy); Pasini, Mariacecilia; Marin, Luminita [Istituto per lo Studio delle Macromolecole del C.N.R. via E. Bassini 15, 20133 Milan (Italy); Institute of Macromolecular Chemistry 41A Grigore Ghica Voda Alley, 708487 Iasi (Romania); Iosip, Mariana Dana [Istituto per lo Studio delle Macromolecole del C.N.R. via E. Bassini 15, 20133 Milan (Italy); Institute of Macromolecular Chemistry 41A Grigore Ghica Voda Alley, 708487 Iasi (Romania); Campione, Marcello [Dipartimento di Scienza dei Materiali, Universita di Milano Bicocca, via E. Cozzi 53, Milan (Italy)

    2007-06-25

    A series of three thiophene based oligomers has been extensively characterized. The chemical design has been addressed to obtain ionization potential (IP) and electronic affinity (EA) values matching the work function of commonly used electrode materials. Such IP and EA values were tested by cyclovoltammetry. In order to tune electron-donation and drawing strength the sequence of the molecule subunits in the oligomer has been varied. The thermal properties with particular reference to their stability during preparation and operation were checked by using differential scanning calorimetry, polarised light microscopy and thermogravimetric analysis techniques. Prototypes of thin film field effect transistor, based on this series of oligomers have been electrically and structurally characterized. The long axes of the molecules are oriented nearly perpendicular to the gate insulator, in agreement with both highly sensitive X-ray diffraction and atomic force microscopy. From powder diffraction data the structure of oligomer I was solved. A general relation is envisaged between charge mobility and packing closeness in the series. For the most promising molecule a study of mobility/temperature behaviour was performed yielding interesting results.

  20. Asymmetric Wave Propagation Through Saturable Nonlinear Oligomers

    Directory of Open Access Journals (Sweden)

    Daniel Law

    2014-10-01

    Full Text Available In the present paper we consider nonlinear dimers and trimers (more generally, oligomers embedded within a linear Schrödinger lattice where the nonlinear sites are of saturable type. We examine the stationary states of such chains in the form of plane waves, and analytically compute their reflection and transmission coefficients through the nonlinear oligomer, as well as the corresponding rectification factors which clearly illustrate the asymmetry between left and right propagation in such systems. We examine not only the existence but also the dynamical stability of the plane wave states. Lastly, we generalize our numerical considerations to the more physically relevant case of Gaussian initial wavepackets and confirm that the asymmetry in the transmission properties also persists in the case of such wavepackets.

  1. Oligomer functionalized nanotubes and composites formed therewith

    Energy Technology Data Exchange (ETDEWEB)

    Zettl, Alexander K; Sainsbury, Toby; Frechet, Jean M.J.

    2014-03-18

    Disclosed herein is a sequential functionalization methodology for the covalent modification of nanotubes with between one and four repeat units of a polymer. Covalent attachment of oligomer units to the surface of nanotubes results in oligomer units forming an organic sheath around the nanotubes, polymer-functionalized-nanotubes (P-NTs). P-NTs possess chemical functionality identical to that of the functionalizing polymer, and thus provide nanoscale scaffolds which may be readily dispersed within a monomer solution and participate in the polymerization reaction to form a polymer-nanotube/polymer composite. Formation of polymer in the presence of P-NTs leads to a uniform dispersion of nanotubes within the polymer matrix, in contrast to aggregated masses of nanotubes in the case of pristine-NTs. The covalent attachment of oligomeric units to the surface of nanotubes represents the formation of a functional nanoscale building block which can be readily dispersed and integrated within the polymer to form a novel composite material.

  2. Risk of oligomers in the textile industry

    Energy Technology Data Exchange (ETDEWEB)

    Giachino, G.M.; Perrelli, G.; Passarino, G.; Comino, E.; Pira, E.; Scansetti, G.; Rubino, G.F.

    1982-11-01

    An experimental research was carried out at the Institute of Occupational Health of Turin University on the risks following exposure to oligomers with particular reference to the textile industry. A group of 36 Sprague-Dawley rats were injected endotracheally with a suspension of dust collected from various sections of twisting and spinning departments while 6 rats used as controls were treated with normal solution. Five rats had pneumonia and 1 rat showed the presence of aspecific granuloma; the histological patterns for the other rats were found to be similar to those of the control group. In the Authors' opinion it is impossible at the moment to give a definite conclusion as to the role of oligomers in lung damage.

  3. Non-Traditional Aromatic Topologies and Biomimetic Assembly Motifs as Components of Functional Pi-Conjugated Oligomers

    Directory of Open Access Journals (Sweden)

    Stephen R. Diegelmann

    2010-02-01

    Full Text Available This article will highlight our recent work using conjugated oligomers as precursors to electroactive polymer films and self-assembling nanomaterials. One area of investigation has focused on nonbenzenoid aromaticity in the context of charge delocalization in conjugated polymers. In these studies, polymerizable pi-conjugated units were coupled onto unusual aromatic cores such as methano[10]annulene. This article will also show how biologically-inspired assembly of molecularly well-defined oligopeptides that flank pi-conjugated oligomers has resulted in the aqueous construction of 1-dimensional nanomaterials that encourage electronic delocalization among the pi-electron systems.

  4. Enzymatic hydrolysis of PTT polymers and oligomers

    OpenAIRE

    Eberl, A.; Heumann, Sonja; Kotek, R.; Kaufmann, F; Mitscher, S.; Paulo, Artur Cavaco; Gübitz, Georg M.

    2008-01-01

    Oligomers and polymers (film, fabrics) of the linear aromatic polyester poly(trimethylene terephthalate) (PTT) were treated with polyesterases from Thermomyces lanuginosus, Penicillium citrinum, Thermobifida fusca and Fusarium solani pisi. The cutinase from T. fusca was found to release the highest amounts of hydrolysis products from PTT materials and was able to open and hydrolyse a cyclic PTT dimer according to RP-HPLC–UV detection. In contrast, the lipase from T. lanuginosus also showed ac...

  5. Peptide oligomers for holographic data storage

    DEFF Research Database (Denmark)

    Berg, Rolf Henrik; Hvilsted, Søren; Ramanujam, P.S.

    1996-01-01

    SEVERAL classes of organic materials (such as photoanisotropic liquid-crystalline polymers(1-4) and photorefractive polymers(5-7)) are being investigated for the development of media for optical data storage. Here we describe a new family of organic materials-peptide oligomers containing azobenze....... Straightforward extension of this peptide-based strategy to other molecular structures should allow the rational design of a wide range of organic materials with potentially useful optical properties....

  6. Interesting reactivity of diketones with pyrrole under acidic condition

    Indian Academy of Sciences (India)

    Sanjeev Pran Mahanta; Pradeepta Kumar Panda

    2011-09-01

    The acid catalysed condensation of diketones with pyrrole did not result in the formation of expected divergent bisdipyrromethane always; instead the product depends on the chain length of the diketones, in particular the distance between the two carbonyl functional groups.When the two carbonyl groups are linked via one or two methylene groups, unusual ring annulation occurs resulting in the formation of various bridged bipyrroles. However, on further increase in the length of the spacer, between the two carbonyl groups, synthesis of the expected bisdipyrromethanes could be achieved.

  7. A Novel TetraTTF-calix[4]pyrrole Ouroborand for Explosive Detection

    DEFF Research Database (Denmark)

    Bähring, Steffen; Nielsen, Kent

    We have synthesized the first example of an asymmetric tetraTTF-calix[4]pyrrole. This system features Ouroborand qualities due to selfcomplexation with the pyridine substituent. This forces the usually highly flexible calix[4]pyrrole into a preorganized conformation with improved explosive...

  8. Novel and efficient supramolecular synthesis of pyrroles in the presence of β-cyclodextrin in water

    Institute of Scientific and Technical Information of China (English)

    K. Ramesh; K. Karnakar; G. Satish; Y.V.D. Nageswar

    2012-01-01

    A simple and efficient synthesis of highly substituted pyrroles was achieved in water medium via multi-component strategy,using amine,DMAD/DEAD as well as phenacyl bromide catalyzed by β-CD.Utilizing this protocol various pyrrole derivatives were synthesized in good to excellent yields.

  9. A Novel TetraTTF-calix[4]pyrrole Ouroborand for Explosive Detection

    DEFF Research Database (Denmark)

    Bähring, Steffen; Nielsen, Kent

    2010-01-01

    We have synthesized the first example of an asymmetric tetraTTF-calix[4]pyrrole. This system features Ouroborand qualities due to selfcomplexation with the pyridine substituent. This forces the usually highly flexible calix[4]pyrrole into a preorganized conformation with improved explosive...

  10. Multifunctional oligomer incorporation: a potent strategy to enhance the transfection activity of poly(l-lysine).

    Science.gov (United States)

    Liu, Shuai; Yang, Jixiang; Ren, Hongqi; O'Keeffe-Ahern, Jonathan; Zhou, Dezhong; Zhou, Hao; Chen, Jiatong; Guo, Tianying

    2016-03-01

    Natural polycations, such as poly(l-lysine) (PLL) and chitosan (CS), have inherent superiority as non-viral vectors due to their unparalleled biocompatibility and biodegradability. However, the application was constrained by poor transfection efficiency and safety concerns. Since previous modification strategies greatly weakened the inherent advantages of natural polycations, developing a strategy for functional group introduction with broad applicability to enhance the transfection efficiency of natural polycations without compromising their cationic properties is imperative. Herein, two uncharged functional diblock oligomers P(DMAEL-b-NIPAM) and P(DMAEL-b-Vlm) were prepared from a lactose derivative, N-iso-propyl acrylamide (NIPAM) as well as 1-vinylimidazole (Vlm) and further functionalized with four small ligands folate, glutathione, cysteine and arginine, respectively, aiming to enhance the interactions of complexes with cells, which were quantified utilizing a quartz crystal microbalance (QCM) biosensor, circumventing the tedious material screening process of cell transfection. Upon incorporation with PLL and DNA, the multifunctional oligomers endow the formulated ternary complexes with great properties suitable for transfection, such as anti-aggregation in serum, destabilized endosome membrane, numerous functional sites for promoted endocytosis and therefore robust transfection activity. Furthermore, different from the conventional strategy of decreasing cytotoxicity by reducing the charge density, the multifunctional oligomer incorporation strategy maintains the highly positive charge density, which is essential for efficient cellular uptake. This system develops a new platform to modify natural polycations towards clinical gene therapy. PMID:26797493

  11. Pyrrolic Amide: A New Hydrogen Bond Building Block for Self-assembly

    Institute of Scientific and Technical Information of China (English)

    YIN Zhen-Ming; LI Jian-Feng; HE Jia-Qi; ZHU Xiao-Qing; CHENG Jin-Pei

    2003-01-01

    @@ Molecular self-assembly has emerged as a powerful technology for the synthesis of nanostructured materials. In design of various molecular assemblies, hydrogen bonding is a preferably selected intra- or inter-molecular weak interaction in recent research by virtue of the directionality and specificity. The research for novel hydrogen bond building blocks that self-assembly into well defined structures is great important not only for gaining an understanding of the concepts of self-assembly but also for the design of new molecular materials. Pyrrolic amide moiety has one hydrogen bond acceptor (C =O) and two hydrogen bond donors (pyrrole NH and amide NH). By deliberately design, pyrrolic amide compounds would be new kinds hydrogen bond building blocks. So, pyrrolic amide compounds 1 ~ 6, which bear one, two or three pyrrolic amide moieties respectively, were designed and synthesized.

  12. Vibronic Lineshapes of PTCDA Oligomers in Helium Nanodroplets

    OpenAIRE

    Roden, Jan; Eisfeld, Alexander; Dvorak, Matthieu; Buenermann, Oliver; Stienkemeier, Frank

    2010-01-01

    Oligomers of the organic semiconductor PTCDA are studied by means of helium nanodroplet isolation (HENDI) spectroscopy. In contrast to the monomer absorption spectrum, which exhibits clearly separated, very sharp absorption lines, it is found that the oligomer spectrum consists of three main peaks having an apparent width orders of magnitude larger than the width of the monomer lines. Using a simple theoretical model for the oligomer, in which a Frenkel exciton couples to internal vibrational...

  13. High-affinity triplex targeting of double stranded DNA using chemically modified peptide nucleic acid oligomers

    DEFF Research Database (Denmark)

    Hansen, Mads E; Bentin, Thomas; Nielsen, Peter E

    2009-01-01

    While sequence-selective dsDNA targeting by triplex forming oligonucleotides has been studied extensively, only very little is known about the properties of PNA-dsDNA triplexes-mainly due to the competing invasion process. Here we show that when appropriately modified using pseudoisocytosine...... substitution, in combination with (oligo)lysine or 9-aminoacridine conjugation, homopyrimidine PNA oligomers bind complementary dsDNA targets via triplex formation with (sub)nanomolar affinities (at pH 7.2, 150 mM Na(+)). Binding affinity can be modulated more than 1000-fold by changes in pH, PNA oligomer...... length, PNA net charge and/or by substitution of pseudoisocytosine for cytosine, and conjugation of the DNA intercalator 9-aminoacridine. Furthermore, 9-aminoacridine conjugation also strongly enhanced triplex invasion. Specificity for the fully matched target versus one containing single centrally...

  14. Pigments and oligomers for inks - moving towards the best combination

    International Nuclear Information System (INIS)

    The formulation of UV curable printing inks depends on several complex factors. If the individual components of the ink are not complementary, then performance problems can arise. One critical combination is that between the pigment and the oligomer. In a new approach to improve understanding of pigment/oligomer interactions, the resources of a pigment manufacturer and an oligomer manufacturer have been combined to investigate the problem. Initial screening of process yellow pigments and several oligomer types highlighted performance variations which were then examined in more detail

  15. Mx oligomer: a novel capsid pattern sensor?

    Science.gov (United States)

    Kong, Jia; Ma, Min; He, Shuangyi; Qin, Xiaohong

    2016-08-01

    Myxovirus resistance proteins represent a family of interferon-induced restriction factors of the innate and adaptive immune system. Human MxB acts as a novel restriction factor with antiviral activity against a range of HIV-1 and other retroviruses mainly by inhibiting the uncoating process after reverse transcription but prior to integration. Based on published data and conservation analysis, we propose a novel hypothesis, in which MxB dimers form higher order oligomers that restrict retroviral replication by binding to the viral capsid. Insights into the mechanistic basis of structural and functional characteristics of MxB will greatly advance our understanding of MxB. PMID:27492442

  16. Macrocyclic 2,7-Anthrylene Oligomers.

    Science.gov (United States)

    Yamamoto, Yuta; Wakamatsu, Kan; Iwanaga, Tetsuo; Sato, Hiroyasu; Toyota, Shinji

    2016-05-01

    A macrocyclic compound consisting of six 2,7-anthrylene units was successfully synthesized by Ni-mediated coupling of the corresponding dibromo precursor as a novel π-conjugated compound. This compound was sufficiently stable and soluble in organic solvents due to the presence of mesityl groups. X-ray analysis showed that the molecule had a nonplanar and hexagonal wheel-shaped framework of approximately S6 symmetry. The dynamic process between two S6 structures was observed by using the dynamic NMR technique, the barrier being 58 kJ mol(-1) . The spectroscopic properties of the hexamer were compared with those of analogous linear oligomers.

  17. Anharmonic Vibrational Dynamics of DNA Oligomers

    CERN Document Server

    Kühn, O; Krishnan, G M; Fidder, H; Heyne, K

    2008-01-01

    Combining two-color infared pump-probe spectroscopy and anharmonic force field calculations we characterize the anharmonic coupling patterns between fingerprint modes and the hydrogen-bonded symmetric NH$_2$ stretching vibration in adenine-thymine dA$_{20}$-dT$_{20}$ DNA oligomers. Specifically, it is shown that the anharmonic coupling between the NH$_2$ bending and the CO stretching vibration, both absorbing around 1665 cm-1, can be used to assign the NH$_2$ fundamental transition at 3215 cm-1 despite the broad background absorption of water.

  18. Biocatalytic Synthesis of Fluorescent Conjugated Indole Oligomers

    Directory of Open Access Journals (Sweden)

    Ryan M. Bouldin

    2014-12-01

    Full Text Available Fluorescent conjugated materials exhibiting reasonable biocompatibility that are capable of interacting with biological molecules are of interest for bio-sensing and imaging applications. Traditional approaches do not allow for the synthesis of conjugated materials in the presence of biologically relevant substrates. Further conjugated polymers synthesized using conventional methods are doped and not fluorescent. Here we explore the possibility of synthesizing fluorescent oligomers of indole using enzymes as catalyst under mild conditions. The peroxidase catalyzed coupling reaction presented here creates a photoluminescent material that allows for direct utilization (without purification and separation of the dopant in biosensing applications. The polymerization reaction proceeds smoothly in just deionized water and ethanol. Monitoring of the absorption and fluorescence spectra over one hour shows that the concentration of both absorbing and emitting species grows steadily over time. The presence of anionic buffers and templates is shown to effectively retard the development of light emitting species and instead leads to the formation of an electrically doped conjugated polymer. Structural characterization through FTIR and 1H-NMR analysis suggests that the oligomer is coupled through the 2 and 3 positions on the indole ring.

  19. Cooperative Switching in Nanofibers of Azobenzene Oligomers

    Science.gov (United States)

    Weber, Christopher; Liebig, Tobias; Gensler, Manuel; Zykov, Anton; Pithan, Linus; Rabe, Jürgen P.; Hecht, Stefan; Bléger, David; Kowarik, Stefan

    2016-05-01

    Next-generation molecular devices and machines demand the integration of molecular switches into hierarchical assemblies to amplify the response of the system from the molecular level to the meso- or macro-scale. Here, we demonstrate that multi-azobenzene oligomers can assemble to form robust supramolecular nanofibers in which they can be switched repeatedly between the E- and Z-configuration. While in isolated oligomers the azobenzene units undergo reversible photoisomerization independently, in the nanofibers they are coupled via intermolecular interactions and switch cooperatively as evidenced by unusual thermal and kinetic behavior. We find that the photoisomerization rate from the Z-isomer to the E-isomer depends on the fraction of Z-azobenzene in the nanofibers, and is increased by more than a factor of 4 in Z-rich fibers when compared to E-rich fibers. This demonstrates the great potential of coupling individual photochromic units for increasing their quantum efficiency in the solid state with potential relevance for actuation and sensing.

  20. Solvent induced track sensitization. Extraction of oligomers

    Science.gov (United States)

    Apel, P.; Angert, N.; Brüchle, W.; Hermann, H.; Kampschulte, U.; Klein, P.; Kravets, L. I.; Oganessian, Yu. Ts.; Remmert, G.; Spohr, R.; Steckenreiter, T.; Trautmann, C.; Vetter, J.

    1994-04-01

    Oligomer extraction from polyethylene terephthalate (PET) irradiated by xenon ions of 11.4 MeV/u is investigated using UV spectrophotometry and gel permeation chromatography (GPC). The cyclic trimer is identified as the predominant diffusing species removed during extraction by dimethyl formamide (DMF). Extraction dynamics is modeled by a rapid (time constant ≈ 2 min) and a slow (time constant ≈ 100 min) diffusion process attributed to the latent ion tracks and to the virgin material, respectively. Thereby latent tracks act simultaneously as irrigation and drainage pipes for the transfer of the solvent into and the extraction of oligomers from the polymer matrix. Thus tracks help to release osmotic pressure differences and to avoid blistering of the unirradiated polymer during solvent exchange. The total extracted mass per track shows a characteristic decrease with increasing ion fluence interpreted as oxygen effect, due to the decreasing supply of oxygen in the sample during irradiation. The extractable mass corresponds to an equivalent track diameter of initially around 10 nm contracting with increasing ion fluence to an asymptotic value around 3 nm.

  1. Highly Stable Foams from Block Oligomers Synthesized by Enzymatic Reactions

    NARCIS (Netherlands)

    Sagis, L.M.C.; Boeriu, C.G.; Frissen, A.E.; Schols, H.A.; Wierenga, P.A.

    2008-01-01

    We have synthesized a new amphiphilic block oligomer by the enzymatic linking of a fatty acid (lauric acid) to a fructan oligomer (inulin) and tested the functionality of this carbohydrate derivative in foam stabilization. The structure of the modified oligosaccharide was found to be (Fruc)n(Glc)1CO

  2. Ru-catalyzed site-selective direct arylation polycondensation via ortho-metalation of pyrrole derivative

    International Nuclear Information System (INIS)

    A Ti-conjugated polymer consisting of pyrrole and fluorene units was synthesized via Ru-catalyzed direct arylation polycondensation. The introduction of a 2-pyrimidinyl substituent into the N -position of the pyrrole monomer as a directing group induced ortho-metalation, with effective site-selective polycondensation at the α-position of the pyrrole monomer, without the need for protection of the β-position. Subsequent removal of the 2-pyrimidinyl substituent led to the elongation of π-conjugation along the main chain of the polymer via elimination of the steric hindrance due to the bulky substituent

  3. 2-Ethyl 4-methyl 5-ethyl-3-methyl-1H-pyrrole-2,4-dicarboxylate

    Directory of Open Access Journals (Sweden)

    Gui-Fen Lu

    2012-02-01

    Full Text Available The title pyrrole derivative compound, C12H17NO4, was synthesized from methyl 3-oxopentanoate by a Knorr-type reaction and contains a pyrrole ring to which two diagonal alkoxycarbonyl groups and two diagonal alkyl substituents are attached. The methylcarbonyl and ethylcarbonyl substituents are approximately co-planar with the pyrrole ring, making dihedral angles of 5.64 (2 and 3.44 (1°, respectively. In the crystal, adjacent molecules are assembled by pairs of N—H...O hydrogen bonds into dimers in a head-to-head mode.

  4. Vibronic line shapes of PTCDA oligomers in helium nanodroplets.

    Science.gov (United States)

    Roden, Jan; Eisfeld, Alexander; Dvořák, Matthieu; Bünermann, Oliver; Stienkemeier, Frank

    2011-02-01

    Oligomers of the organic semiconductor 3,4,9,10-perylene-tetracarboxylic-dianhydride, C(24)H(8)O(6) (PTCDA) are studied by means of helium nanodroplet isolation spectroscopy. In contrast to the monomer absorption spectrum, which exhibits clearly separated, very sharp absorption lines, it is found that the oligomer spectrum consists of three main peaks having an apparent width orders of magnitude larger than the width of the monomer lines. Using a simple theoretical model for the oligomer, in which a Frenkel exciton couples to internal vibrational modes of the monomers, these experimental findings are nicely reproduced. The three peaks present in the oligomer spectrum can already be obtained taking only one effective vibrational mode of the PTCDA molecule into account. The inclusion of more vibrational modes leads to quasicontinuous spectra, resembling the broad oligomer spectra. PMID:21303160

  5. Statistical mechanics of thermal denaturation of DNA oligomers

    Indian Academy of Sciences (India)

    Navin Singh; Yashwant Singh

    2003-08-01

    Double stranded DNA chain is known to have non-trivial elasticity. We study the effect of this elasticity on the denaturation profile of DNA oligomer by constraining one base pair at one end of the oligomer to remain in unstretched (or intact) state. The effect of this constraint on the denaturation profile of the oligomer has been calculated using the Peyrard–Bishop Hamiltonian. The denaturation profile is found to be very different from the free (i.e. without the constraint) oligomer. We have also examined how this constraint affects the denaturation profile of the oligomer having a segment of defect sites located at different parts of the chain.

  6. Properties of Surface Cyclic Oligomers Present on Polyester Fiber

    Institute of Scientific and Technical Information of China (English)

    郑敏; 宋心远

    2003-01-01

    The effects of different treatments, such as dry heat,wet heat, solvent vapor and ultrasonic, on properties of the cyclic oligomers on the surface of polyester fiber are studied. The components of surface oligomers are analyzed through Thin-Layer Chromatograph. The result shows that: all of the treatments, especially solvent vapor treatment, can significantly increase the content of surface cyclic oligomers. The content of cyclic trimer is increased more considerably than other oligomers. Moreover, the morphology and the distribution of surface cyclic oligomers are also different from different treatments: Dry heat and wet heat cause larger polygonal solids distributed evenly on the surface of fiber; solvent vapor makes fiber surface exhibit irregular rodlike crystal shapes randomly; ultrasonic treatment induces some obscure and smaller deposits on the surface of fiber.

  7. Atomic View of a Toxic Amyloid Small Oligomer

    Energy Technology Data Exchange (ETDEWEB)

    Laganowsky, Arthur; Liu, Cong; Sawaya, Michael R.; Whitelegge, Julian P.; Park, Jiyong; Zhao, Minglei; Pensalfini, Anna; Soriaga, Angela B.; Landau, Meytal; Teng, Poh K.; Cascio, Duilio; Glabe, Charles; Eisenberg, David (UCI); (UCLA)

    2012-04-30

    Amyloid diseases, including Alzheimer's, Parkinson's, and the prion conditions, are each associated with a particular protein in fibrillar form. These amyloid fibrils were long suspected to be the disease agents, but evidence suggests that smaller, often transient and polymorphic oligomers are the toxic entities. Here, we identify a segment of the amyloid-forming protein {alpha}{beta} crystallin, which forms an oligomeric complex exhibiting properties of other amyloid oligomers: {beta}-sheet-rich structure, cytotoxicity, and recognition by an oligomer-specific antibody. The x-ray-derived atomic structure of the oligomer reveals a cylindrical barrel, formed from six antiparallel protein strands, that we term a cylindrin. The cylindrin structure is compatible with a sequence segment from the {beta}-amyloid protein of Alzheimer's disease. Cylindrins offer models for the hitherto elusive structures of amyloid oligomers.

  8. A Submarine Journey: The Pyrrole-Imidazole Alkaloids

    Directory of Open Access Journals (Sweden)

    Alessandra Scolaro

    2009-11-01

    Full Text Available In his most celebrated tale “The Picture of Dorian Gray”, Oscar Wilde stated that “those who go beneath the surface do so at their peril”. This sentence could be a prophetical warning for the practitioner who voluntarily challenges himself with trying to synthesize marine sponge-deriving pyrrole-imidazole alkaloids. This now nearly triple-digit membered community has been growing exponentially in the last 20 years, both in terms of new representatives and topological complexity − from simple, achiral oroidin to the breathtaking 12-ring stylissadines A and B, each possessing 16 stereocenters. While the biosynthesis and the role in the sponge economy of most of these alkaloids still lies in the realm of speculations, significant biological activities for some of them have clearly emerged. This review will account for the progress in achieving the total synthesis of the more biologically enticing members of this class of natural products.

  9. A submarine journey: the pyrrole-imidazole alkaloids.

    Science.gov (United States)

    Forte, Barbara; Malgesini, Beatrice; Piutti, Claudia; Quartieri, Francesca; Scolaro, Alessandra; Papeo, Gianluca

    2009-11-27

    In his most celebrated tale "The Picture of Dorian Gray", Oscar Wilde stated that "those who go beneath the surface do so at their peril". This sentence could be a prophetical warning for the practitioner who voluntarily challenges himself with trying to synthesize marine sponge-deriving pyrrole-imidazole alkaloids. This now nearly triple-digit membered community has been growing exponentially in the last 20 years, both in terms of new representatives and topological complexity--from simple, achiral oroidin to the breathtaking 12-ring stylissadines A and B, each possessing 16 stereocenters. While the biosynthesis and the role in the sponge economy of most of these alkaloids still lies in the realm of speculations, significant biological activities for some of them have clearly emerged. This review will account for the progress in achieving the total synthesis of the more biologically enticing members of this class of natural products.

  10. A Submarine Journey: The Pyrrole-Imidazole Alkaloids †

    Science.gov (United States)

    Forte, Barbara; Malgesini, Beatrice; Piutti, Claudia; Quartieri, Francesca; Scolaro, Alessandra; Papeo, Gianluca

    2009-01-01

    In his most celebrated tale “The Picture of Dorian Gray”, Oscar Wilde stated that “those who go beneath the surface do so at their peril”. This sentence could be a prophetical warning for the practitioner who voluntarily challenges himself with trying to synthesize marine sponge-deriving pyrrole-imidazole alkaloids. This now nearly triple-digit membered community has been growing exponentially in the last 20 years, both in terms of new representatives and topological complexity – from simple, achiral oroidin to the breathtaking 12-ring stylissadines A and B, each possessing 16 stereocenters. While the biosynthesis and the role in the sponge economy of most of these alkaloids still lies in the realm of speculations, significant biological activities for some of them have clearly emerged. This review will account for the progress in achieving the total synthesis of the more biologically enticing members of this class of natural products. PMID:20098608

  11. Synthesis, Characterization and Biological Study of Novel Pyrrole Derivatives

    Directory of Open Access Journals (Sweden)

    Rakesh R. Mishra

    2012-07-01

    Full Text Available A facile condensation of aromatic aldehydes with 2-(5-(phenoxymethyl-2-thioxo-1,3,4-oxadiazol-3(2H-ylaceto hydrazide (1 was give the corresponding N’-aryl-2-(5-(phenoxymethyl-2-thioxo-1,3,4-oxadiazol-3(2H-ylacetohydrazide (2a-e in good yield. Cyclo condensation of compounds (2a-e with maleic anhydride yields 2-aryl-5-oxo-1-(2-(5-(phenoxymethyl-2-thioxo-1,3,4-oxadiazol-3(2H-ylacetamido-2,5-dihydro-1H-pyrrole-3-carboxylic acid (3a-e. The structures of these compounds were established on the basis of analytical and spectral data. All the newly synthesized compounds were evaluated for their antibacterial and antifungal activities.

  12. Characterization of multi-walled carbon nanotube electrodes functionalized by electropolymerized tris(pyrrole-ether bipyridine) ruthenium (II)

    Energy Technology Data Exchange (ETDEWEB)

    Le Goff, Alan; Holzinger, Michael [Departement de Chimie Moleculaire UMR-5250, ICMG FR-2607, CNRS Universite Joseph Fourier, BP-53, 38041 Grenoble (France); Cosnier, Serge, E-mail: Serge.Cosnier@ujf-grenoble.f [Departement de Chimie Moleculaire UMR-5250, ICMG FR-2607, CNRS Universite Joseph Fourier, BP-53, 38041 Grenoble (France)

    2011-04-01

    We synthesized new electropolymerizable [Ru(bpy){sub n}L{sub m}](PF{sub 6}){sub 2} (L = 4,4 bis(3-pyrrol-1-ylpropyloxy)bipyridyl) derivatives. The introduction of electron donating ether groups in the bipyridine ligand induced a negative shift of the Ru(III)/(II) redox couple. The electrochemical behavior of complex Ru1 (n = 2, m = 1) and complex Ru2 (n = 0, m = 3) were compared using platinum and Multi-Walled Carbon Nanotube (MWCNT) electrode. Higher polymerization yields and surface concentrations were obtained at MWCNT electrodes. Furthermore, MWCNT electrodes increase polymer permeability and decrease the charge trapping phenomenon involved in the oxidation and reduction of the polypyrrolic skeleton of the Ru(II) functionalized polymers.

  13. The Synthesis of Novel 3-Substituted Poly(pyrroles) Bearing Crown-ether Moieties and a Study of their Electrochemical Properties

    DEFF Research Database (Denmark)

    Guernion, Nicolas J.L.; Blencowe, A.; Hayes, Wayne;

    2006-01-01

    polypyrrole derivatives was characterised by Scanning Electron Microscopy (SEM). These polymers exhibited an open porous structure and half the charge was required when compared to polypyrrole to afford films of equal thickness. The mass change during polymerisation was followed by Electrochemical Quartz......A series of fourteen novel pyrrole monomers substituted at the 3-position with aliphatic and aromatic crown-ether moieties have been synthesised in good yield and characterised extensively. Several of those compounds were electropolymerised successfully in acetonitrile, using both potentiostatic...... Crystal Microbalance measurement (EQCM), and the rate of polymer growth was found to be non-linear when compared to polypyrrole....

  14. HAMLET forms annular oligomers when deposited with phospholipid monolayers.

    Science.gov (United States)

    Baumann, Anne; Gjerde, Anja Underhaug; Ying, Ming; Svanborg, Catharina; Holmsen, Holm; Glomm, Wilhelm R; Martinez, Aurora; Halskau, Oyvind

    2012-04-20

    Recently, the anticancer activity of human α-lactalbumin made lethal to tumor cells (HAMLET) has been linked to its increased membrane affinity in vitro, at neutral pH, and ability to cause leakage relative to the inactive native bovine α-lactalbumin (BLA) protein. In this study, atomic force microscopy resolved membrane distortions and annular oligomers (AOs) produced by HAMLET when deposited at neutral pH on mica together with a negatively charged lipid monolayer. BLA, BAMLET (HAMLET's bovine counterpart) and membrane-binding Peptide C, corresponding to BLA residues 75-100, also form AO-like structures under these conditions but at higher subphase concentrations than HAMLET. The N-terminal Peptide A, which binds to membranes at acidic but not at neutral pH, did not form AOs. This suggests a correlation between the capacity of the proteins/peptides to integrate into the membrane at neutral pH-as observed by liposome content leakage and circular dichroism experiments-and the formation of AOs, albeit at higher concentrations. Formation of AOs, which might be important to HAMLET's tumor toxic action, appears related to the increased tendency of the protein to populate intermediately folded states compared to the native protein, the formation of which is promoted by, but not uniquely dependent on, the oleic acid molecules associated with HAMLET.

  15. Enzymatic hydrolysis of PTT polymers and oligomers.

    Science.gov (United States)

    Eberl, A; Heumann, S; Kotek, R; Kaufmann, F; Mitsche, S; Cavaco-Paulo, A; Gübitz, G M

    2008-05-20

    Oligomers and polymers (film, fabrics) of the linear aromatic polyester poly(trimethylene terephthalate) (PTT) were treated with polyesterases from Thermomyces lanuginosus, Penicillium citrinum, Thermobifida fusca and Fusarium solani pisi. The cutinase from T. fusca was found to release the highest amounts of hydrolysis products from PTT materials and was able to open and hydrolyse a cyclic PTT dimer according to RP-HPLC-UV detection. In contrast, the lipase from T. lanuginosus also showed activity on the PTT fibres and on bis(3-hydroxypropyl) terephthalate (BHPT) but was not able to hydrolyse the polymer film, mono(3-hydroxypropyl) terephthalate (MHPT) nor the cyclic dimer of PTT. As control enzymes inhibited with mercury chloride were used. Surface hydrophilicity changes were investigated with contact angle measurements and the degree of crystallinity changes were determined with DSC. PMID:18405994

  16. Design, synthesis, and characterization of biomimetic oligomers

    DEFF Research Database (Denmark)

    Laursen, Jonas Striegler

    . Using NMR spectroscopy, X-ray crystallographic analysis, and density functional theory (DFT) calculations, we found evidence for the presence of thioamide–aromatic interactions through Csp2-H···Samide hydrogen bonding. Based on these studies we designed a ß-peptoid oligomer from residues prone to fit......Peptides and proteins made from the 20 canonical amino acids are responsible for many processes necessary for organisms to function. Beside their composition, proteins obtain their activity and unique selectivity through an ability to display functionalities accurately in the three......, for their ability to mimic the structural elements seen in proteins. Two prominent peptidomimetics are ß-peptides and a-peptoids (N-alkylglycines), which have been shown to fold into helical and sheet-like arrangements. To expand the chemical space available for mimicking protein structure their features have been...

  17. Poly [(pyrrole-2, 5-diyl) co(4-Nitro benzylidene)]: A new synthetic approach and electronic properties

    Science.gov (United States)

    Gherras, H.; Hachemaoui, A.; Yahiaoui, A.; Belbachir, M.; Belfedal, A.

    2012-02-01

    A new poly (heteroarylene methylene) containing one to four α-pyrrole rings alternating with an sp3-carbon atom in the main chain were synthesized and characterized. The synthesized poly [(pyrrole-2, 5-diyl)-co-(4-nitrobenzylidene)] was found to be highly dehydrogenated, thus resulting in black materials with conjugated segments larger than a single pyrrole ring. The conjugated polymers containing alternating aromatic and quinoid heteroarylene moieties in the main chain were prepared by polycondensation of 4-nitrobenzaldehyde and pyrrole catalysed by Maghnite-H+. The new polymer is useful precursors to small-bandgap polymers based on poly (heteroarylene methines) and is also useful model system for the investigation of the effects of π-conjugation length on the electronic and optical properties of conjugated polymers.

  18. Auto-oligomerization and hydration of pyrrole revealed by x-ray absorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Advanced Light Source; Schwartz, Craig P.; Uejio, Janel S.; Duffin, Andrew M.; England, Alice H.; Prendergast, David; Saykally, Richard J

    2009-05-29

    Near edge x-ray absorption fine structure (NEXAFS) spectra have been measured at the carbon and nitrogen K-edges of the prototypical aromatic molecule, pyrrole, both in the gas phase and when solvated in water, and compared with spectra simulated using a combination of classical molecular dynamics and first principles density functional theory in the excited state core hole approximation. The excellent agreement enabled detailed assignments. Pyrrole is highly reactive, particularly in water, and reaction products formed by the auto-oligomerization of pyrrole are identified. The solvated spectra have been measured at two different temperatures, indicating that the final states remain largely unaffected by both hydration and temperature. This is somewhat unexpected, since the nitrogen in pyrrole can donate a hydrogen bond to water.

  19. Synthesis and biological activity of pyrrole analogues of combretastatin A-4.

    Science.gov (United States)

    Jung, Eun-Kyung; Leung, Euphemia; Barker, David

    2016-07-01

    A series of pyrrole analogues of combretastatin (CA-4) were synthesized and tested for their anti-proliferative activity. The highly diastereoselective acyl-Claisen rearrangement was used to provide 2,3-syn disubstituted morpholine amides which were used as precursors for the various analogues. This synthesis allows for the preparation of 1,2- and 2,3-diaryl-1H-pyrroles which are both geometrically similar to CA-4. These pyrrolic analogues were tested for their anti-proliferative activity against two human cell lines, K562 and MDA-MB-231 with 2,3-diaryl-1H-pyrrole 35 exhibiting the most potent activity with IC50 value of 0.07μM against MDA-MB-231 cell line.

  20. One-Pot Conversion of Carbohydrates into Pyrrole-2-carbaldehydes as Sustainable Platform Chemicals.

    Science.gov (United States)

    Adhikary, Nirmal Das; Kwon, Sunjeong; Chung, Wook-Jin; Koo, Sangho

    2015-08-01

    A practical conversion method of carbohydrates into N-substituted 5-(hydroxymethyl)pyrrole-2-carbaldehydes (pyrralines) was developed by the reaction with primary amines and oxalic acid in DMSO at 90 °C. Further cyclization of the highly functionalized pyrralines afforded the pyrrole-fused poly-heterocyclic compounds as potential intermediates for drugs, food flavors, and functional materials. The mild Maillard variant of carbohydrates and amino esters in heated DMSO with oxalic acid expeditiously produced the pyrrole-2-carbaldehyde skeleton, which can be concisely transformed into the pyrrole alkaloid natural products, 2-benzyl- and 2-methylpyrrolo[1,4]oxazin-3-ones 8 and 9, lobechine 10, and (-)-hanishin 11 in 23-32% overall yields from each carbohydrate.

  1. Development of Novel Bioanalytical Methods to Determine the Effective Concentrations of Phosphorodiamidate Morpholino Oligomers in Tissues and Cells

    OpenAIRE

    Schnell, Frederick J.; Crumley, Stacy L.; Mourich, Dan V.; Iversen, Patrick L.

    2013-01-01

    Abstract Phosphorodiamidate morpholino oligomers (PMO) are neutrally charged, sequence-specific antisense agents that interfere with targeted gene expression. PMO have been shown to be highly specific and potent therapies after cellular uptake, yet methods to detect PMO in tissue and inside the cell are limited. We offer in this report novel methods for the detection of cellular resident PMO using flow cytometry-fluorescence in situ hybridization (flow FISH) and a sandwich hybridization techn...

  2. Synthesis of new 2,5-dimethyl pyrrole derivatives from acetonylacetone

    Institute of Scientific and Technical Information of China (English)

    Xiao Ming Ji; Ye Lu; Ming Qin Zhao; Xiao Yun Zhang; Yun Liu; Le Liu

    2010-01-01

    Acetonylacetone 1 was treated with thiourea, aniline, glycine and glutamic acid to give pyrrole derivatives 2, 3, 5, and 9 by Paal-Knorr reaction, respectively. Then 3 was successfully transformed into the related pyrrole derivative 4 by Mannich reaction.Compounds 6, 7 and 8 were obtained by reacting 5 with phenethyl alcohol, phenylallylic alcohol and leaf alcohol by esterification reactions, respectively. The structures of all new products were elucidated by IR, NMR and HRMS spectra.

  3. Energetics of 1-(aminophenyl)pyrroles: A joint calorimetric and computational study

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Ana Filipa L.O.M. [Centro de Investigacao em Quimica, Department of Chemistry and Biochemistry, Faculty of Science, University of Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal); Ribeiro da Silva, Manuel A.V., E-mail: risilva@fc.up.pt [Centro de Investigacao em Quimica, Department of Chemistry and Biochemistry, Faculty of Science, University of Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal)

    2011-10-15

    Highlights: > Enthalpy of formation of crystalline 1-(2-aminophenyl)pyrrole was determined by combustion calorimetry. > Vapor pressures of 1-(aminophenyl)pyrrole were measured as function of temperature by the Knudsen effusion technique. > Enthalpies of formation of the three gaseous isomers of 1-(aminophenyl)pyrrole were obtained by G3(MP2)//B3LYP calculations. - Abstract: Static bomb calorimetry and the Knudsen effusion mass-loss technique were used to derive, respectively, the standard (p{sup o} = 0.1 MPa) molar enthalpy of formation, in the crystalline phase, {Delta}{sub f}H{sub m}{sup 0}(cr), and the standard molar enthalpy of sublimation, at T = 298.15 K, {Delta}{sub cr}{sup g}H{sub m}{sup 0}, of 1-(2-aminophenyl)pyrrole. These experiments allowed the determination of its standard (p{sup o} = 0.1 MPa) molar enthalpy of formation, in the gaseous phase, {Delta}{sub f}H{sub m}{sup 0}(g), at T = 298.15 K, as (224.1 {+-} 2.4) kJ . mol{sup -1}. The gas-phase enthalpy of formation of 1-(2-aminophenyl)pyrrole was also estimated by G3(MP2)//B3LYP calculations, which were further extended to the (aminophenyl)pyrroles that were not studied experimentally. Experimental and theoretical results are in very good agreement.

  4. Metalloporphyrins with all the pyrrole nitrogens replaced with phosphorus atoms, MP(P)4 (M = Sc, Ti, Fe, Ni, Cu, Zn)

    International Nuclear Information System (INIS)

    Highlights: • First systematic DFT study of the MP(P)4 compounds with increasing number of d-electrons. • Complete substitution of pyrrole nitrogens by P-atoms does not change the ground spin state. • Complete substitution of pyrrole nitrogens by P-atoms results in a bowl-like shape. • Significant stabilization of the MP(P)4 LUMOs compared to the MP counterparts. • MP(P)4 HOMO/LUMO gaps are smaller than the MP HOMO/LUMO gaps. - Abstract: We performed first systematic DFT study of the structures and electronic features (frontier orbitals energies, HOMO/LUMO and optical gaps, IPs and EAs) of the MP(P)4 compounds, with increasing number of d-electrons: 3d14s2 (Sc) → 3d24s2 (Ti) → 3d64s2 (Fe) → 3d84s2 (Ni) → 3d104s1 (Cu) → 3d104s2 (Zn). We performed systematic comparison with the tetrapyrrole MP counterparts. Complete substitution of the pyrrole nitrogens by P-atoms does not change the calculated ground spin state of the compound. All the MP(P)4 species adopt a bowl-like shape, compared to generally planar or slightly distorted shapes of their MP counterparts. Significant positive charge accumulates on P-atoms in MP(P)4. Positive charges on the metals in MP(P)4 are noticeably lower than in the MP counterparts. The calculated MP(P)4 HOMO/LUMO gaps and optical gaps are noticeably smaller than the corresponding gaps in their MP counterparts, which is explained by stabilization of the MP(P)4 LUMOs

  5. Metalloporphyrins with all the pyrrole nitrogens replaced with phosphorus atoms, MP(P){sub 4} (M = Sc, Ti, Fe, Ni, Cu, Zn)

    Energy Technology Data Exchange (ETDEWEB)

    Kuznetsov, Aleksey E., E-mail: aleksey73kuznets@gmail.com

    2015-02-02

    Highlights: • First systematic DFT study of the MP(P){sub 4} compounds with increasing number of d-electrons. • Complete substitution of pyrrole nitrogens by P-atoms does not change the ground spin state. • Complete substitution of pyrrole nitrogens by P-atoms results in a bowl-like shape. • Significant stabilization of the MP(P){sub 4} LUMOs compared to the MP counterparts. • MP(P){sub 4} HOMO/LUMO gaps are smaller than the MP HOMO/LUMO gaps. - Abstract: We performed first systematic DFT study of the structures and electronic features (frontier orbitals energies, HOMO/LUMO and optical gaps, IPs and EAs) of the MP(P){sub 4} compounds, with increasing number of d-electrons: 3d{sup 1}4s{sup 2} (Sc) → 3d{sup 2}4s{sup 2} (Ti) → 3d{sup 6}4s{sup 2} (Fe) → 3d{sup 8}4s{sup 2} (Ni) → 3d{sup 10}4s{sup 1} (Cu) → 3d{sup 10}4s{sup 2} (Zn). We performed systematic comparison with the tetrapyrrole MP counterparts. Complete substitution of the pyrrole nitrogens by P-atoms does not change the calculated ground spin state of the compound. All the MP(P){sub 4} species adopt a bowl-like shape, compared to generally planar or slightly distorted shapes of their MP counterparts. Significant positive charge accumulates on P-atoms in MP(P){sub 4}. Positive charges on the metals in MP(P){sub 4} are noticeably lower than in the MP counterparts. The calculated MP(P){sub 4} HOMO/LUMO gaps and optical gaps are noticeably smaller than the corresponding gaps in their MP counterparts, which is explained by stabilization of the MP(P){sub 4} LUMOs.

  6. Interaction of derived polymers from pyrrole with biocompatible solutions

    International Nuclear Information System (INIS)

    This work presents a study about the synthesis by plasma, the electric properties and superficial interaction of polymers derived from pyrrole doped with Iodine with potential use as bio material. Poly-pyrrole is a semiconductor and biocompatible polymer with potential application in the development of artificial muscles and implants where the electric interaction between cells and material is an important variable. The syntheses were made at 13.5 MHz in a glass tubular reactor of 1500 cm3 with electrodes of 6.5 cm diameter and stainless steel flanges. An electrode was connected to the RF terminal of the power supply that is combined with a matching coupling resistance. The monomer and dopant used in this work were pyrrole and Iodine respectively, in closed containers. They were vaporized and injected separately into the reactor at room temperature and 0.1 mbar. The vapors of the reagents mixed freely in the reactor. The synthesis time was 240 min at 40, 60, 80 and 100 W. The polymers were obtained as thin films adhered to the reactor walls. The films were washed and swollen with distilled water and removed from the reactor walls with a small spatula. The polymers were irradiated with gamma rays at 18 and 22 KGy. Due to the fact that the doses are cumulative, the final dose applied was 40 KGy. The polymers characterization was carried out by Fourier Transform Infrared Spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy, contact angle, electrical conductivity and X-ray diffraction. The analyses indicates that the polymers have very similar structure in almost the entire power range, showing C-O, C=C, C-H, O-H, N-H bonds with a predominantly amorphous structure. The TGA analyses showed that the material has 4 or 5 loses of material. The first one starts after that 115 C except for the material irradiated at 40 KGy, this one begins in 87 C, the second one is in the interval of 196 and 295 C, the third one between 311 and 500 C, and the last

  7. Synthesis of π-conjugated systems bearing thiophene and pyrrole heterocycles through palladium-catalyzed decarboxylative cross-coupling reaction

    OpenAIRE

    Castro, M. Cidália R.; Fonseca, A. Maurício C.; Raposo, M. Manuela M.

    2012-01-01

    Thiophene and pyrrole moieties play important roles in synthetic and medicinal chemistry, as they are present in a large number of natural products and biologically active compounds. For this reason, amongst all five-membered aromatic heterocycles, molecules containing the pyrrole nucleus have attracted the greatest attention of researchers and have been studied in most detail. Especially, 2-aryl- and 2-heteroaryl-substituted pyrroles are of great interest to the pharmaceutical industry, for ...

  8. The Challenge of Synthesizing Oligomers for Molecular Wires

    Directory of Open Access Journals (Sweden)

    Frederik C. Krebs

    2011-02-01

    Full Text Available Controlling the size of the oligomer and introducing functional groups at the ends of the oligomer that allow it to react with separate electrodes are critical issues when preparing materials for molecular wires. We demonstrate a general synthetic approach to oligophenylenevinylene (OPV derivative molecules with a molecular length up to 9–10 nm which allow for the introduction of aromatic thioacetate functionality in fully conjugated oligomer systems. Oligomers containing 3–15 phenyl units were synthesized by step wise Horner-Wadsworth-Emmons (HWE reactions of a bifunctional OPV-monomer, which demonstrated good control of the size of the OPVs. Workup after each reaction step ensures a high purity of the final products. End group functionalization was introduced as a last step.

  9. Revisting the physics of Fano resonances for nanoparticle oligomers

    CERN Document Server

    Hopkins, Ben; Miroshnichenko, Andrey E; Kivshar, Yuri S

    2013-01-01

    We present a new and robust approach for interpreting the physics of Fano resonances in both metallic and dielectric oligomer nanostructures. A key mechanism for Fano resonances is revealed by demonstrating that Fano resonances can be generated purely from the interference of non-orthogonal collective eigenmodes, which are clearly identified based on the coupled-dipole approximation. We prove analytically a general theorem to identify the number of collective eigenmodes that can be excited in ring-type nanoparticle oligomers and further demonstrate that no dark mode excitation is necessary for existence of Fano resonances in symmetric oligomers. As a consequence, we unify the understanding of Fano resonances for both plasmonic and all-dielectric oligomers.

  10. Length dependence of rectification in organic co-oligomer spin rectifiers

    Science.gov (United States)

    Gui-Chao, Hu; Zhao, Zhang; Ying, Li; Jun-Feng, Ren; Chuan-Kui, Wang

    2016-05-01

    The rectification ratio of organic magnetic co-oligomer diodes is investigated theoretically by changing the molecular length. The results reveal two distinct length dependences of the rectification ratio: for a short molecular diode, the charge-current rectification changes little with the increase of molecular length, while the spin-current rectification is weakened sharply by the length; for a long molecular diode, both the charge-current and spin-current rectification ratios increase quickly with the length. The two kinds of dependence switch at a specific length accompanied with an inversion of the rectifying direction. The molecular ortibals and spin-resolved transmission analysis indicate that the dominant mechanism of rectification suffers a change at this specific length, that is, from asymmetric shift of molecular eigenlevels to asymmetric spatial localization of wave functions upon the reversal of bias. This work demonstrates a feasible way to control the rectification in organic co-oligomer spin diodes by adjusting the molecular length. Project supported by the National Natural Science Foundation of China (Grant No. 11374195), the Natural Science Foundation of Shandong Province, China (Grant No. ZR2014AM017), the Taishan Scholar Project of Shandong Province, China, and the Excellent Young Scholars Research Fund of Shandong Normal University, China.

  11. Subdiffusion of proteins and oligomers on membranes

    Science.gov (United States)

    Lepzelter, David; Zaman, Muhammad

    2012-11-01

    Diffusion of proteins on lipid membranes plays a central role in cell signaling processes. From a mathematical perspective, most membrane diffusion processes are explained by the Saffman-Delbrück theory. However, recent studies have suggested a major limitation in the theoretical framework, the lack of complexity in the modeled lipid membrane. Lipid domains (sometimes termed membrane rafts) are known to slow protein diffusion, but there have been no quantitative theoretical examinations of how much diffusion is slowed in a general case. We provide an overall theoretical framework for confined-domain ("corralled") diffusion. Further, there have been multiple apparent contradictions of the basic conclusions of Saffman and Delbrück, each involving cases in which a single protein or an oligomer has multiple transmembrane regions passing through a lipid phase barrier. We present a set of corrections to the Saffman-Delbrück theory to account for these experimental observations. Our corrections are able to provide a quantitative explanation of numerous cellular signaling processes that have been considered beyond the scope of the Saffman-Delbrück theory, and may be extendable to other forms of subdiffusion.

  12. Optimizing antisense oligonucleotides using phosphorodiamidate morpholino oligomers.

    Science.gov (United States)

    Popplewell, Linda J; Malerba, Alberto; Dickson, George

    2012-01-01

    Duchenne muscular dystrophy (DMD) is caused by mutations that disrupt the reading frame of the human DMD gene. Selective removal of exons flanking an out-of-frame DMD mutation can result in an in-frame mRNA transcript that may be translated into an internally deleted Becker muscular dystrophy-like functionally active dystrophin protein with therapeutic activity. Antisense oligonucleotides (AOs) can be designed to bind to complementary sequences in the targeted mRNA and modify pre-mRNA splicing to correct the reading frame of a mutated transcript. AO-induced exon skipping resulting in functional truncated dystrophin has been demonstrated in animal models of DMD both in vitro and in vivo, in DMD patient cells in vitro in culture, and in DMD muscle explants. The recent advances made in this field suggest that it is likely that AO-induced exon skipping will be the first gene therapy for DMD to reach the clinic. However, it should be noted that personalized molecular medicine may be necessary, since the various reading frame-disrupting mutations are spread across the DMD gene. The different deletions that cause DMD would require skipping of different exons, which would require the optimization and clinical trial workup of many specific AOs. This chapter describes the methodologies available for the optimization of AOs, in particular phosphorodiamidate morpholino oligomers, for the targeted skipping of specific exons on the DMD gene. PMID:22454060

  13. Opto-electronic properties of charged conjugated molecules

    NARCIS (Netherlands)

    Fratiloiu, S.

    2007-01-01

    The aim of this thesis is to provide fundamental insight into the nature and opto-electronic properties of charge carriers on conjugated oligomers and polymers. Electronic structure, optical absorption properties and distribution of charge carriers along the chains of different conjugated materials

  14. Ultrasound promoted N-alkylation of pyrrole using potassium superoxide as base in crown ether.

    Science.gov (United States)

    Yim, E S; Park, M K; Han, B H

    1997-04-01

    Ultrasound accelerates the N-alkylation of pyrrole by alkylating reagents using potassium superoxide as base in the presence of 18-crown-6. A much lower yield of N-alkylated pyrrole was realized in the absence of ultrasound. N-alkylating reagents employed for pyrrole are methyl iodide, ethyl bromide, benzyl bromide, as well as acrylonitrile allyl cyanide and methyl acrylate. In an extension of this work, we have found that ultrasound was not necessary for the N-alkylation of indole and alkyl amine, such as diphenyl amine and piperidine with alkyl halides using our reagents. In all cases we observed that the 18-crown-6 catalyzed N-alkylation reaction gives higher yields of N-alkylated products than that without crown ether, when potassium superoxide was used as base. These observations are probably due to the potassium-crown complex which can be released when the reaction goes to completion. PMID:11237050

  15. A novel and facile approach for synthesis of 5-amino-7-aryl-6-cyano-4-pyrano[3,2-]pyrroles

    Indian Academy of Sciences (India)

    Reza Sandaroos; Saman Damavandi

    2012-07-01

    An efficient and iron-catalysed synthesis of 4-pyrano[3,2-]pyrrole is reported. The reactions proceed through a one-pot, three component cyclocondensation of 3-hydroxypyrrole, malononitrile and various aldehydes to afford 4-pyrano[3,2-]pyrrole derivatives in moderate to good yield using ferric hydrogensulphate, Fe(HSO4)3, as the catalyst.

  16. Synthesis of poly[(pyrrole-2,5-diyl)-co-(4-hydroxylbenzylidene)] catalysed by Maghnite– H+

    OpenAIRE

    Bouhadjar Larbi; Aïcha Hachemaoui; Yahiaoui Ahmed; Bouchama Abdelghani; Chikh Karime; Belbachir Mohamed

    2014-01-01

    Rapid synthesis of poly[(pyrrole-2,5-diyl)-co-(4-hydroxylbenzylidene)] was achieve via the condensation of pyrrole and 4-hydroxylbenzylidene in dichloromethane using acid exchanged montmorillonite clay called Maghnite– H+ (Mag–H+) as an efficient catalyst The conjugated polymer was characterized by means of 1H-NMR, UV-visible, FT-IR spectroscopy and TGA.

  17. Synthesis of 2,2'-Dipyrryl Ketones from Pyrrole-2-carboxylic Acids with Trifluoroacetic Anhydride

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Se Hee; Lim, Jin Woo; Yu, Jin; Kim, Jae Nyoung [Chonnam National Univ., Gwangju (Korea, Republic of)

    2013-09-15

    An efficient synthesis of 2,2'-dipyrryl ketones has been carried out from pyrrole-2-carboxylic acids using trifluoroacetic anhydride (TFAA). Simultaneous generation of both mixed anhydride and 2-unsubstituted pyrrole, via facile decarboxylation with in-situ generated TFA, made their cross reaction (intermolecular Friedel-Crafts acylation) possible and efficient.

  18. Observation of Fano resonances in all-dielectric nanoparticle oligomers.

    Science.gov (United States)

    Chong, Katie E; Hopkins, Ben; Staude, Isabelle; Miroshnichenko, Andrey E; Dominguez, Jason; Decker, Manuel; Neshev, Dragomir N; Brener, Igal; Kivshar, Yuri S

    2014-05-28

    It is well-known that oligomers made of metallic nanoparticles are able to support sharp Fano resonances originating from the interference of two plasmonic resonant modes with different spectral width. While such plasmonic oligomers suffer from high dissipative losses, a new route for achieving Fano resonances in nanoparticle oligomers has opened up after the recent experimental observations of electric and magnetic resonances in low-loss dielectric nanoparticles. Here, light scattering by all-dielectric oligomers composed of silicon nanoparticles is studied experimentally for the first time. Pronounced Fano resonances are observed for a variety of lithographically-fabricated heptamer nanostructures consisting of a central particle of varying size, encircled by six nanoparticles of constant size. Based on a full collective mode analysis, the origin of the observed Fano resonances is revealed as a result of interference of the optically-induced magnetic dipole mode of the central particle with the collective mode of the nanoparticle structure. This allows for effective tuning of the Fano resonance to a desired spectral position by a controlled size variation of the central particle. Such optically-induced magnetic Fano resonances in all-dielectric oligomers offer new opportunities for sensing and nonlinear applications. PMID:24616191

  19. Pyrrole-added Fe2O3 films by ultrasonic spray pyrolisis

    OpenAIRE

    Carlos Torres Frausto; Alejandro Avila Garcia

    2009-01-01

    Fe2O3 thin films were grown by Ultrasonic Spray Pyrolisis from a 0.05 aqueous solution of FeCl3 added with a small amount of pyrrole monomer. Films at different substrate temperature and pyrrole content were grown. They were characterized by using x-ray diffraction (XRD), infrared spectroscopy (FTIR) and atomic force microscopy (AFM). Results indicated that at low substrate temperature (approximately 200ºC) the films mainly resemble the polypyrrole structure. At higher temperatures up to 400...

  20. 2-[(E-(1H-Pyrrol-2-ylmethylidenehydrazinyl]pyridine monohydrate

    Directory of Open Access Journals (Sweden)

    James L. Wardell

    2009-12-01

    Full Text Available The title hydrate, C10H10N4·H2O, shows a small twist in the hydrozone derivative, the dihedral angle between the pyridine and pyrrole rings being 11.08 (12°. The pyridine and pyrrole N atoms lie to the same side of the molecule being sustained in place by hydrogen-bonding interactions with the water molecule. Further intermolecular O—H...N and N—H...O hydrogen bonding leads to the formation of supramolecular arrays in the ab plane.

  1. Synthesis and recognition properties of higher order tetrathiafulvalene (TTF) calix n pyrroles (n=4-6)

    DEFF Research Database (Denmark)

    Park, J. S.; Bejger, C.; Larsen, K. R.;

    2012-01-01

    (Cl-, Br-, I-, CH3COO-, H2PO4-, and HSO4-) and neutral (1,3,5-trinitrobenzene (TNB) and 2,4,6-trinitrotoluene (TNT)) substrates revealed that as a general rule the calix[6]pyrrole derivative proved to be the most efficient molecular receptor for anions, while the calix[4]pyrrole congener proves most...... effective for the recognition of TNB and TNT. These findings are rationalized in terms of the number of electron rich TTF subunits and NH hydrogen bond donor groups within the series, as well as an ability to adopt conformations suitable for substrate recognition, and are supported by solid state structural...

  2. A Brief Review of Chelators for Radiolabeling Oligomers

    Directory of Open Access Journals (Sweden)

    Yuxia Liu

    2010-05-01

    Full Text Available The chemical modification of oligomers such as DNA, PNA, MORF, LNA to attach radionuclides for nuclear imaging and radiotherapy applications has become a field rich in innovation as older methods are improved and new methods are introduced. This review intends to provide a brief overview of several chelators currently in use for the labeling of oligomers with metallic radionuclides such as 99mTc, 111In and 188Re. While DNA and its analogs have been radiolabeled with important radionuclides of nonmetals such as 32P, 35S, 14C, 18F and 125I, the labeling methods for these isotopes involve covalent chemistry that is quite distinct from the coordinate-covalent chelation chemistry described herein. In this review, we provide a summary of the several chelators that have been covalently conjugated to oligomers for the purpose of radiolabeling with metallic radionuclides by chelation and including details on the conjugation, the choice of radionuclides and labeling methods.

  3. Hydrolytic study of the copolymer Poly pyrrole/ Polyethyleneglycol and Poly pyrrole synthesized by plasma; Estudio hidrolitico del copolimero polipirrol/polietilenglicol y polipirrol sintetizado por plasma

    Energy Technology Data Exchange (ETDEWEB)

    Colin, E.; Enriquez, M.A.; Olayo, M.G.; Cruz, G.J.; Carapia, L.; Romero, M. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico); Morales, J.; Olayo, R. [UAM-I, A.P. 55-534 Iztapalapa, Mexico D.F. (Mexico)

    2006-07-01

    In this work the study about the hydrolytic compatibility of semiconductor polymers, copolymer Poly pyrrole/ Polyethyleneglycol (PPy/PEG) and Poly pyrrole (PPy) for their possible use as biomaterials. The polymers were synthesized by plasma between 10 and 100 W, with discharges of splendor RF to 13.5 MHz with resistive coupling. The hydrolytic affinity was evaluated calculating the contact angle with solutions of NaCl, NaCl-MgSO{sub 4} and Krebs-Ringer. The results show a hydrophilicity increment due to the increase of the surface ruggedness with the synthesis energy. On the contrary, the crystallinity diminishes when increasing the power in PPy and it stays approximately constant in PPy/PEG. The electric conductivity presents a growth from 2 to 4 magnitude orders in function of the water content in the polymers. (Author)

  4. Gas chromatographic retention characteristics of different polysiloxane oligomers

    Energy Technology Data Exchange (ETDEWEB)

    Van Lenten, F. J.; Conaway, J. E.; Rogers, L. B.

    1975-01-01

    The effects on the Kovats and McReynolds indices for a modified set of Rohrschneider solutes have been examined using two different batches of a commercial polysiloxane stationary phase, Dow-Corning DC-710, and five pure oligomers isolated from the mixture. The significant differences that were found between batches appear to be due primarily to changes in the percentage of one oligomer, the cyclic pentamer. This finding emphasizes the desirability of using a pure stationary phase as well as carefully specifying the column temperature in order to improve intra- and inter- laboratory comparisons of retention indices.

  5. Photogeneration of Polarons in Sexithiophene Oligomers

    Science.gov (United States)

    Ehrenfreund, Eitan

    1996-03-01

    We present photoexcitation studies of vacuum deposited neutral films of sexithiophene (6T) using photoinduced absorption spectroscopy and photoinduced absorption detected magnetic resonance (PADMR) techniques. We find evidence for photoinduced polarons (photoexcited ``radical ions'') having spin 1/2, with two absorption bands at 0.80 and 1.54 eV, respectively, and with negative PADMR signal at g~=2. Similar absorption bands are observed in lightly p-doped sexithiophene, and are interpreted as due to 6T^ -- + radical cations. In addition, a photoinduced absorption band is found at ~=1.1 eV, which is shorter lived and decreases faster with increasing temperature than the polaron bands. We identify this band as due to spinless bipolarons (photoexcited ``di-ions''). A similar di-cation (6T^++) band has been identified in heavily p-doped sexithiophene. Each of the polaron and bipolaron peaks, observed here, is accompanied by a secondary shoulder on its low energy side. This observation may indicate a possible breaking of charge conjugation symmetry, with negatively charged polarons (bipolarons) having lower energy transitions than positively charged polarons (bipolarons). Finally, we have identified triplet excitons (S=1) with triplet-triplet transition energy at ~=1.45 eV. Work done in collaboration with J. Poplawski (Technion), X. Wei, P. Lane and Z.V. Vardeny (University of Utah, Salt Lake City, UT), M. Ibrahim and A.J. Frank (NREL, Golden, CO). Supported by the US--Israel Binational Science Foundation (BSF 94--256).

  6. Oligomer Molecules for Efficient Organic Photovoltaics.

    Science.gov (United States)

    Lin, Yuze; Zhan, Xiaowei

    2016-02-16

    Solar cells, a renewable, clean energy technology that efficiently converts sunlight into electricity, are a promising long-term solution for energy and environmental problems caused by a mass of production and the use of fossil fuels. Solution-processed organic solar cells (OSCs) have attracted much attention in the past few years because of several advantages, including easy fabrication, low cost, lightweight, and flexibility. Now, OSCs exhibit power conversion efficiencies (PCEs) of over 10%. In the early stage of OSCs, vapor-deposited organic dye materials were first used in bilayer heterojunction devices in the 1980s, and then, solution-processed polymers were introduced in bulk heterojunction (BHJ) devices. Relative to polymers, vapor-deposited small molecules offer potential advantages, such as a defined molecular structure, definite molecular weight, easy purification, mass-scale production, and good batch-to-batch reproducibility. However, the limited solubility and high crystallinity of vapor-deposited small molecules are unfavorable for use in solution-processed BHJ OSCs. Conversely, polymers have good solution-processing and film-forming properties and are easily processed into flexible devices, whereas their polydispersity of molecular weights and difficulty in purification results in batch to batch variation, which may hamper performance reproducibility and commercialization. Oligomer molecules (OMs) are monodisperse big molecules with intermediate molecular weights (generally in the thousands), and their sizes are between those of small molecules (generally with molecular weights 10000). OMs not only overcome shortcomings of both vapor-deposited small molecules and solution-processed polymers, but also combine their advantages, such as defined molecular structure, definite molecular weight, easy purification, mass-scale production, good batch-to-batch reproducibility, good solution processability, and film-forming properties. Therefore, OMs are a

  7. Determination of solvation and binding site profile within electropolymerised poly(pyrrole-N-propionic acid)

    DEFF Research Database (Denmark)

    Glidle, A.; Swann, M.J.; Gadegaard, Nikolaj;

    2000-01-01

    Specular neutron reflectivity measurements were performed on electropolymerised films of poly(pyrrole-N-propionic acid) to determine the degree to which the solvents are capable of supporting biological macromolecules can penetrate the polymer film. The permeation profile of Ni2+ ions which chelate...

  8. Synthesis of Iso-condensed Heteroaromatic Pyrroles and Their Application in the Preparation of Conducting Polymers

    Institute of Scientific and Technical Information of China (English)

    Chin-Kang Sha; Su-Ya Cheng; Yuan-Liang Kuo; Liu Chia-Lin; V. Raghukumar

    2004-01-01

    Iso-condensed heteroaromatic pyrroles 1 are 10 -electron aromatic compounds. They are of interest from both theoretical and synthetic points of view. They are the cyclic analogues of heteroaromatic ortho-quinodimethanes 2, and can react with dienophiles in a Diels-Alder reaction to give the synthetically useful cycloadducts 3. Many of them are also of potential pharmaceutical importance because they are isosteric with indoles. Iso-condensed heteroaromatic pyrroles 1 can be used also as the monomers for the synthesis of new conducting polymers 5 with special properties and characteristics. However, the methods for the efficient preparation of the iso-condensed heteroaromatic pyrroles are quite limited. Iso-condensed heteroaromatic pyrroles are generally unstable in acidic conditions and are easily oxidized by air. In our laboratories, we developed three methods for the preparation of this labile heterocyclic ring system under acidic, neutral, and basic conditions.1 Synthesis of the conjugated systems such as 6 for OLED applications will also be discussed.

  9. A Facile Synthesis of Polysubstituted Pyrroles by One-Pot Three-Component Reaction

    OpenAIRE

    Anaraki-Ardakani, Hossein; Noei, Maziar; Karbalaei-Harofteh, Mina; Zomorodbakhsh, Shahab

    2012-01-01

    A new and efficient one-pot synthesis of polysubstituted pyrrole derivatives by three-component reaction between dialkyl acetylenedicarboxylates, triphenylphosphine, 2-aminopyridin derivatives in the presence of arylglyoxals is described. The reactions were performed in dichloromethane at room temperature and neutral conditions and afforded high yields of products.

  10. Synthesis of Dihydropyrrolizine and Tetrahydroindolizine Scaffolds from Pyrroles by Titanocene(III) Catalysis.

    Science.gov (United States)

    Hildebrandt, Sven; Gansäuer, Andreas

    2016-08-01

    A synthetic approach to dihydropyrrolizine and tetrahydroindolizine scaffolds from pyrroles has been developed. The key step, a titanocene(III)-catalyzed radical arylation that proceeds by C-H functionalization is atom-economical and tolerates a large variety of functional groups. The reaction is therefore attractive for the swift assembly of functional and structural diversity. PMID:27383638

  11. VIS/NIR absorption spectra of positively charged oligo(phenylenevinylene)s and comparison with time-dependent density functional theory calculations

    NARCIS (Netherlands)

    Fratiloiu, S; Candeias, LP; Grozema, FC; Wildeman, J; Siebbeles, LDA

    2004-01-01

    A combined experimental and theoretical study of the optical properties of positively charged unsubstituted and dialkoxy-substituted phenylenevinylene (PV) oligomers in solution is presented. Cations of PV oligomers were produced by irradiation of a solution with high-energy electron pulses. The opt

  12. Nanoaggregates from Thiophene/Phenylene Co-oligomers

    DEFF Research Database (Denmark)

    Schiek, Manuela; Balzer, F.; Al-Shamery, Katharina;

    2009-01-01

    The growth of thiophene/phenylene cooligomers is investigated on the basal surface of muscovite mica. Both the phenyl end-capped 5,5′-di-4-biphenylyl-2,2′-bithiophene (PPTTPP) and the thienyl end-capped 4,4′-di-2,2′-bithienylbiphenyl (TTPPTT) co-oligomers form fiberlike nanostructures from...

  13. Plasma amyloid beta peptides and oligomers antibodies in Alzheimer's disease

    OpenAIRE

    Zhou, L.; Chu, LW; Kwan, JSC; Ho, JWM; Lam, KSL; Ho, PWL; Chan, KH

    2011-01-01

    INTRODUCTION: Various forms of amyloid beta (Aβ) including Aβ peptides, oligomers, protofibrils and fibrils are thought to be pathogenic in Alzheimer’s disease (AD). The exact pathophysiological role of endogenous Aβ autoantibodies (Ab) in healthy subjects and AD patients are uncertain. Potential protective role ...

  14. Oligomer Formation of Toxic and Functional Amyloid Peptides Studied with Atomistic Simulations.

    Science.gov (United States)

    Carballo-Pacheco, Martín; Ismail, Ahmed E; Strodel, Birgit

    2015-07-30

    Amyloids are associated with diseases, including Alzheimer's, as well as functional roles such as storage of peptide hormones. It is still unclear what differences exist between aberrant and functional amyloids. However, it is known that soluble oligomers formed during amyloid aggregation are more toxic than the final fibrils. Here, we perform molecular dynamics simulations to study the aggregation of the amyloid-β peptide Aβ25-35, associated with Alzheimer's disease, and two functional amyloid-forming tachykinin peptides: kassinin and neuromedin K. Although the three peptides have similar primary sequences, tachykinin peptides, in contrast to Aβ25-35, form nontoxic amyloids. Our simulations reveal that the charge of the C-terminus is essential to controlling the aggregation process. In particular, when the kassinin C-terminus is not amidated, the aggregation kinetics decreases considerably. In addition, we observe that the monomeric peptides in extended conformations aggregate faster than those in collapsed hairpin-like conformations. PMID:26130191

  15. Pyrrolo[3,2-b]pyrrole-Based Copolymers as Donor Materials for Organic Photovoltaics

    International Nuclear Information System (INIS)

    A new accepter unit, pyrrolo[3,2-b]pyrrole-2,5-dione, was prepared and utilized for the synthesis of the conjugated polymers containing electron donor-acceptor pair for OPVs. Pyrrolo[3,2-b]pyrrole-2,5-dione unit, regioisomer of the known pyrrolo[3,4-c]pyrrole-1,4-dione, is originated from the structure of stable synthetic pigment. The new conjugated polymers with 1,4-diphenylpyrrolo[3,2-b]pyrrole-2,5-dione, thiophene and carbazole were synthesized using Suzuki polymerization to generate P1 and P2. The solid films of P1 and P2 show absorption bands with maximum peaks at about 377, 554 and 374, 542 nm and the absorption onsets at 670 and 674 nm, corresponding to band gaps of 1.85 and 1.84 eV, respectively. To improve the hole mobility of the polymer with 1,4-bis(4-butylphenyl)-pyrrolo[3,2-b]-pyrrole-2,5-dione unit, which was previously reported by us, the butyl group at the 4-positions of the N-substituted phenyl group was substituted with hydrogen and methyl group. The field-effect hole mobility of P2 is 9.6 Χ 10-5 cm2/Vs. The device with P2:PC71BM (1:2) showed VOC value of 0.84 V, JSC value of 5.10 mA/cm2, and FF of 0.33, giving PCE of 1.42%

  16. Ferroelectric and dielectric properties of electroactive oligomers and nanocomposites

    Science.gov (United States)

    Kraemer, Kristin L.

    Polyvinylidene fluoride (PVDF) and its copolymers have been well established as ferroelectric polymers. The dielectric and ferroelectric properties for vinylidene fluoride (VDF) oligomer thin films were investigated. By synthesizing oligomers instead of long polymer chains, films with higher crystalinity can be formed and the locations of oligomers can be controlled for applications such as molecular electronics. Evidence of ferroelectricity was observed in oligomer thin films evaporated onto room temperature substrates and by Langmuir-Blodgett (LB) deposition. Voltage and frequency dependence of the capacitance was measured. Oligomers functionalized with phosphonic acid formed self-assembled monolayers (SAM) on aluminum and mica substrates. Film thickness was measured by ellipsometry and atomic force microscopy (AFM). The time dependence on film growth was measured for SAMs on mica substrates by AFM. The islands had already formed by 1 minute, and by 1 hour film was continuous. Additionally, studies were performed on composite dielectric systems with the goal of fabricating high energy density dielectrics containing nanoparticles with an organic shell. The first two types of samples had barium titante nanoparticles coated with functionalized alkanes or VDF oligomers. The first sample type consisted of coated nanoparticles embedded in a PVDF copolymer or terpolymer spin-coated film. At low particle concentrations, the matrix properties dominated the electrical measurements while at high concentrations, the samples were electrically fragile. The second sample type consisted of alternating layers of LB terpolymer and LB nanoparticles. These samples allowed for high particle concentrations while maintaining the high breakdown strength of the polymer layers. The final type of sample was titanium dioxide nanoparticles formed by cluster deposition and coated with an evaporated paraffin or VDF oligomer. These samples tended to have low breakdown strengths and poor

  17. Self-assembly of 33-mer gliadin peptide oligomers.

    Science.gov (United States)

    Herrera, M G; Benedini, L A; Lonez, C; Schilardi, P L; Hellweg, T; Ruysschaert, J-M; Dodero, V I

    2015-11-28

    The 33-mer gliadin peptide, LQLQPF(PQPQLPY)3PQPQPF, is a highly immunogenic peptide involved in celiac disease and probably in other immunopathologies associated with gliadin. Herein, dynamic light scattering measurements showed that 33-mer, in the micromolar concentration range, forms polydisperse nano- and micrometer range particles in aqueous media. This behaviour is reminiscent of classical association of colloids and we hypothesized that the 33-mer peptide self-assembles into micelles that could be the precursors of 33-mer oligomers in water. Deposition of 33-mer peptide aqueous solution on bare mica generated nano- and microstructures with different morphologies as revealed by atomic force microscopy. At 6 μM, the 33-mer is organised in isolated and clusters of spherical nanostructures. In the 60 to 250 μM concentration range, the spherical oligomers associated mainly in linear and annular arrangements and structures adopting a "sheet" type morphology appeared. At higher concentrations (610 μM), mainly filaments and plaques immersed in a background of nanospherical structures were detected. The occurrence of different morphologies of oligomers and finally the filaments suggests that the unique specific geometry of the 33-mer oligomers has a crucial role in the subsequent condensation and organization of their fractal structures into the final filaments. The self-assembly process on mica is described qualitatively and quantitatively by a fractal diffusion limited aggregation (DLA) behaviour with the fractal dimension in the range of 1.62 ± 0.02 to 1.73 ± 0.03. Secondary structure evaluation of the oligomers by Attenuated Total Reflection FTIR spectroscopy (ATR-FTIR) revealed the existence of a conformational equilibrium of self-assembled structures, from an extended conformation to a more folded parallel beta elongated structures. Altogether, these findings provide structural and morphological information about supramolecular organization of the 33-mer

  18. Induction of volatile organic compound in the leaves of Lycopersicon esculentum by chitosan oligomer

    Institute of Scientific and Technical Information of China (English)

    He Peiqing; Lin Xuezheng; Shen Jihong; Huang Xiaohang; Chen Kaoshan; Li Guangyou

    2005-01-01

    Induction of VOCs (volatile organic compounds) in the leaves of Lycopersicon esculentum by chitosan oligomer elictor was studied. The results demonstrated that VOCs in chitosan oligomer-treated leaves showed stronger inhibitory activity against Botrytis cinerea than that in water-treated leaves, and the spore germination was reduced by 22.1% in 144h after elicitor treatment at a concentration of 1.0%. A total of 16 constituents were detected in water-treated leaves, and chitosan oligomer treatment increased the amount of VOCs production. Chitosan oligomer at different concentration and different time courses of induction treatment could induce different amount of VOCs. Chitosan oligomer resulted in an optimal production of VOCs in 144h after elicitation at concentration of 0.6%. Chitosan oligomer also enhanced activtity of PAL and LOX. The results showed that the enhancement of VOCs production after chitosan oligomer treatment might be an important agent for L.esculentum acquiring resistance against pathogen.

  19. An electric nose based on arylenevinylene polymers and oligomers

    Science.gov (United States)

    de Wit, Michael

    An electronic nose is an instrument, which comprises an array of electronic chemical sensors with partial specificity and an appropriate pattern-recognition system, capable of recognising simple or complex odours. Our efforts are centred around the sensors part of the nose. In fact, we applied a number of polymeric and oligomeric members of the arylenevinylene group of molecules as the active layer for conductimetric sensors (chemiresistors). The electric resistance of the active layer changes when it is exposed to vapors. The response of the sensor on a vapour is defined as the fractional, percentual change of the resistance compared to that in clean air. We made the sensors by depositing the organic layers on a substrate containing pre-printed gold contacts. At first we tested poly(2,5-thienylene vinylene) (PTV). A synthetic method was employed in which a soluble methoxy-precursor polymer of PTV was isolated, which was then spin-coated onto the substrate, and after being converted thermally to PTV, subsequently doped by iodine. The values of the responses of the PTV sensors are comparable to those sensors based on other conducting polymers, but the (partial) selectivity for the vapors is different. The responses of the PTV sensor are linearly related to the concentration. Incomplete conversion of the precursor polymer to the final PTV leads to copolymers of methoxy-PTV and PTV itself varying inter alia in the degree of conjugation. Chemiresistors based on these new materials show an affinity to vapors differing from that of PTV. We discovered that the arylenevinylenes need not to be of polymeric nature for this application. In fact, the arylenevinylene oligomers perform better. The oligomers are easier to modify and to process than polymers. We tested 2,5-dimethoxy-1,4-bis(3,4,5-trimethoxystyrylbenzene) (OMT) in its pure form and in blends with polycarbonate. The responses of these oligomeric sensors are on the average five times higher than those of the

  20. Use of Graphite Oxide and Graphene Oxide as Catalysts in the Synthesis of Dipyrromethane and Calix[4]pyrrole

    Directory of Open Access Journals (Sweden)

    Sweta Mishra

    2011-08-01

    Full Text Available Graphite oxide and graphene oxides have been used as solid catalysts for the synthesis of 5,5-dialkyldipyrromethanes and calix[4]pyrroles in organic and aqueous solutions at room temperature.

  1. Alzheimer's therapeutics targeting amyloid beta 1-42 oligomers II: Sigma-2/PGRMC1 receptors mediate Abeta 42 oligomer binding and synaptotoxicity.

    Science.gov (United States)

    Izzo, Nicholas J; Xu, Jinbin; Zeng, Chenbo; Kirk, Molly J; Mozzoni, Kelsie; Silky, Colleen; Rehak, Courtney; Yurko, Raymond; Look, Gary; Rishton, Gilbert; Safferstein, Hank; Cruchaga, Carlos; Goate, Alison; Cahill, Michael A; Arancio, Ottavio; Mach, Robert H; Craven, Rolf; Head, Elizabeth; LeVine, Harry; Spires-Jones, Tara L; Catalano, Susan M

    2014-01-01

    Amyloid beta (Abeta) 1-42 oligomers accumulate in brains of patients with Mild Cognitive Impairment (MCI) and disrupt synaptic plasticity processes that underlie memory formation. Synaptic binding of Abeta oligomers to several putative receptor proteins is reported to inhibit long-term potentiation, affect membrane trafficking and induce reversible spine loss in neurons, leading to impaired cognitive performance and ultimately to anterograde amnesia in the early stages of Alzheimer's disease (AD). We have identified a receptor not previously associated with AD that mediates the binding of Abeta oligomers to neurons, and describe novel therapeutic antagonists of this receptor capable of blocking Abeta toxic effects on synapses in vitro and cognitive deficits in vivo. Knockdown of sigma-2/PGRMC1 (progesterone receptor membrane component 1) protein expression in vitro using siRNA results in a highly correlated reduction in binding of exogenous Abeta oligomers to neurons of more than 90%. Expression of sigma-2/PGRMC1 is upregulated in vitro by treatment with Abeta oligomers, and is dysregulated in Alzheimer's disease patients' brain compared to age-matched, normal individuals. Specific, high affinity small molecule receptor antagonists and antibodies raised against specific regions on this receptor can displace synthetic Abeta oligomer binding to synaptic puncta in vitro and displace endogenous human AD patient oligomers from brain tissue sections in a dose-dependent manner. These receptor antagonists prevent and reverse the effects of Abeta oligomers on membrane trafficking and synapse loss in vitro and cognitive deficits in AD mouse models. These findings suggest sigma-2/PGRMC1 receptors mediate saturable oligomer binding to synaptic puncta on neurons and that brain penetrant, small molecules can displace endogenous and synthetic oligomers and improve cognitive deficits in AD models. We propose that sigma-2/PGRMC1 is a key mediator of the pathological effects of

  2. Alzheimer's therapeutics targeting amyloid beta 1-42 oligomers II: Sigma-2/PGRMC1 receptors mediate Abeta 42 oligomer binding and synaptotoxicity.

    Directory of Open Access Journals (Sweden)

    Nicholas J Izzo

    Full Text Available Amyloid beta (Abeta 1-42 oligomers accumulate in brains of patients with Mild Cognitive Impairment (MCI and disrupt synaptic plasticity processes that underlie memory formation. Synaptic binding of Abeta oligomers to several putative receptor proteins is reported to inhibit long-term potentiation, affect membrane trafficking and induce reversible spine loss in neurons, leading to impaired cognitive performance and ultimately to anterograde amnesia in the early stages of Alzheimer's disease (AD. We have identified a receptor not previously associated with AD that mediates the binding of Abeta oligomers to neurons, and describe novel therapeutic antagonists of this receptor capable of blocking Abeta toxic effects on synapses in vitro and cognitive deficits in vivo. Knockdown of sigma-2/PGRMC1 (progesterone receptor membrane component 1 protein expression in vitro using siRNA results in a highly correlated reduction in binding of exogenous Abeta oligomers to neurons of more than 90%. Expression of sigma-2/PGRMC1 is upregulated in vitro by treatment with Abeta oligomers, and is dysregulated in Alzheimer's disease patients' brain compared to age-matched, normal individuals. Specific, high affinity small molecule receptor antagonists and antibodies raised against specific regions on this receptor can displace synthetic Abeta oligomer binding to synaptic puncta in vitro and displace endogenous human AD patient oligomers from brain tissue sections in a dose-dependent manner. These receptor antagonists prevent and reverse the effects of Abeta oligomers on membrane trafficking and synapse loss in vitro and cognitive deficits in AD mouse models. These findings suggest sigma-2/PGRMC1 receptors mediate saturable oligomer binding to synaptic puncta on neurons and that brain penetrant, small molecules can displace endogenous and synthetic oligomers and improve cognitive deficits in AD models. We propose that sigma-2/PGRMC1 is a key mediator of the pathological

  3. Synthesis of hollow poly(aniline-co-pyrrole)-Fe3O4 composite nanospheres and their microwave absorption behavior

    OpenAIRE

    Zhu, Yao-Feng; Zhang, Li; Natsuki, Toshiaki; Fu, Ya-Qin; Ni, Qing-Qing

    2012-01-01

    Hollow poly(aniline-co-pyrrole)-Fe3O4 (HPAP-Fe3O4) nanospheres with significant electromagnetic properties were successfully prepared via the oxidative polymerization of a mixture of aniline and pyrrole in the presence of a magnetic fluid, using a non-ionic surfactant as a template. The products were characterized by field emission scanning electron microscopy, transmission electron microscopy. Fourier transform infrared spectroscopy, X-ray powder diffraction, thermogravimetric analysis and X...

  4. Synthesis of poly[(pyrrole-2,5-diyl-co-(4-hydroxylbenzylidene] catalysed by Maghnite– H+

    Directory of Open Access Journals (Sweden)

    Bouhadjar Larbi

    2014-01-01

    Full Text Available Rapid synthesis of poly[(pyrrole-2,5-diyl-co-(4-hydroxylbenzylidene] was achieve via the condensation of pyrrole and 4-hydroxylbenzylidene in dichloromethane using acid exchanged montmorillonite clay called Maghnite– H+ (Mag–H+ as an efficient catalyst The conjugated polymer was characterized by means of 1H-NMR, UV-visible, FT-IR spectroscopy and TGA.

  5. Dichloridobis(4-pyridylmethyl 1H-pyrrole-2-carboxylate-κNzinc

    Directory of Open Access Journals (Sweden)

    Guilong Zhang

    2012-03-01

    Full Text Available In the title molecule, [ZnCl2(C11H10N2O22], the ZnII ion, situated on a twofold axis, is in a distorted tetrahedral coordination environment formed by two chloride anions and two pyridine N atoms of the two organic ligands. In the pyrrole-2-carboxylate unit, the pyrrole N—H group and the carbonyl group point approximately in the same direction. The dihedral angle between the two pyridine rings is 54.8 (3°. The complex molecules are connected into chains extending along [101] by N—H...Cl hydrogen bonds. The chains are further assembled into (-101 layers by C—H...O and C—H...Cl interactions.

  6. Ab initio multiple cloning simulations of pyrrole photodissociation: TKER spectra and velocity map imaging.

    Science.gov (United States)

    Makhov, Dmitry V; Saita, Kenichiro; Martinez, Todd J; Shalashilin, Dmitrii V

    2015-02-01

    We report a detailed computational simulation of the photodissociation of pyrrole using the ab initio Multiple Cloning (AIMC) method implemented within MOLPRO. The efficiency of the AIMC implementation, employing train basis sets, linear approximation for matrix elements, and Ehrenfest configuration cloning, allows us to accumulate significant statistics. We calculate and analyze the total kinetic energy release (TKER) spectrum and Velocity Map Imaging (VMI) of pyrrole and compare the results directly with experimental measurements. Both the TKER spectrum and the structure of the velocity map image (VMI) are well reproduced. Previously, it has been assumed that the isotropic component of the VMI arises from long time statistical dissociation. Instead, our simulations suggest that ultrafast dynamics contributes significantly to both low and high energy portions of the TKER spectrum. PMID:25523235

  7. The electropolymerization of pyrrole at a CuNi electrode: corrosion protection properties

    Energy Technology Data Exchange (ETDEWEB)

    Fenelon, Anna M.; Breslin, Carmel B

    2003-12-01

    Pyrrole was successfully electropolymerized at a copper-nickel electrode in a near-neutral sodium oxalate solution containing Cu{sup 2+} cations to generate a homogenous and adherent polypyrrole film. The presence of the Cu{sup 2+} ions increased both the rate of the electropolymerization reaction and the adherence of the polymer at the CuNi interface. In the absence of these cations, oxidation of the electrode occurred generating a nickel-rich layer that was not sufficiently conducting, under the electropolymerization conditions employed, to facilitate the electron-transfer reaction and the electropolymerization of pyrrole. These films remained stable and exhibited significant corrosion protection properties in acidified and neutral 0.1 mol dm{sup -3} NaCl solutions even on polarization of the electrodes to high anodic potentials.

  8. 3-/3,5-Pyrrole-substituted BODIPY derivatives and their photophysical and electrochemical studies

    Indian Academy of Sciences (India)

    KARTHIKA J KADASSERY; AKANKSHA NIMESH; SANOJ RAJ; NEERAJ AGARWAL

    2016-09-01

    Nucleophilic substitution on 3-bromo/3,5-dibromo-4,4'-difluoro-8-(aryl)-4-bora-3a,4a-diaza-sindacene (BODIPY), substituted with anisyl or thienyl at meso positions, with neat pyrrole afforded the mono and di-pyrrole substituted BODIPYs 1–4 in good yields. Large bathochromic shifts, upto ∼180 nm in absorption maxima (581–682 nm), and fluorescence maxima (606–695 nm) were observed for these BODIPYs. Absorption and fluorescence properties were studied in different solvents to compare the effect of mono and di substitution on BODIPY. The Lippert-Mataga equations were used which predict strong polarization of monosubstituted BODIPYs. Electrochemical studies were carried out to find the oxidation potential and HOMO energy levels were calculated. Theoretical studies of 1–4 provide the insight on the electron density distribution in 1–4. Theoretical and experimental photo-physical studies in different solvents were correlated to findthe substituent effects on BODIPY.

  9. Effect of Pyrrole and N-Methylpyrrole Coatings on Corrosion Resistance of Mild Steel

    Institute of Scientific and Technical Information of China (English)

    AliAshrafi; M.A.Golozarl; S.Mallakpour; AliGhasemi

    2004-01-01

    Electrochemical polymerizations of various ratios of pyrrole and methylpyrrole monomers were performed in aqueous toluene-4-sulfinic acid sodium salt (T4SNa) electrolyte, using galvanostatic method, pH of electrolyte was adjusted by p-toluene sulfonic acid (PTSA). In order to prevent corrosion of mild steel substrates during coating deposition, specimens were pretreated in 0.5M oxalic acid solution, employing galvanostatic method. This would passivate the steel substrate and facilitate the coating process as well. Corrosion resistance of coated substrates was investigated in 1M NaCl solution using Tafel polarization technique. In addition, using scanning electron microscopy (SEM), morphological characterization of coatings produced, was investigated. Regarding the corrosion characteristics, results obtained revealed that the ratio of 1 to 1(Pyrrole/Methylpyrrole) could play an important role.

  10. Conjugated polymers with pyrrole as the conjugated bridge: synthesis, characterization, and two-photon absorption properties.

    Science.gov (United States)

    Li, Qianqian; Zhong, Cheng; Huang, Jing; Huang, Zhenli; Pei, Zhiguo; Liu, Jun; Qin, Jingui; Li, Zhen

    2011-07-14

    The synthesis, one- and two-photon absorption (2PA) and emission properties of two novel pyrrole-based conjugated polymers (P1 and P2) are reported. They emitted strong yellow-green and orange fluorescence with fluorescent quantum yields (Φ) of 46 and 33%, respectively. Their maximal 2PA cross sections (δ) measured by the two-photon-induced fluorescence method using femtosecond laser pulses in THF were 2392 and 1938 GM per repeating unit, respectively, indicating that the 2PA chromophores consisting of the triphenylamine with nonplanar structure as the donor and electron-rich pyrrole as the conjugated bridge could be the effective repeating units to enhance the δ values.

  11. Circular dichroism from Fano resonances in planar chiral oligomers

    Science.gov (United States)

    Hopkins, Ben; Poddubny, Alexander N.; Miroshnichenko, Andrey E.; Kivshar, Yuri S.

    2015-05-01

    Here we present a general approach for describing the physics of Fano resonances in nanoparticle oligomers. It is shown that the interference of nonorthogonal collective eigenmodes is a sufficient condition to produce Fano resonances. We then show that such nonorthogonality between eigenmodes also permits the existence of a new form circular dichroism in the absorption and scattering cross-sections, even when circular dichroism is forbidden in the extinction cross-section.

  12. Oligomers, organosulfates, and nitroxy organosulfates identified in rainwater

    Science.gov (United States)

    Altieri, K. E.; Turpin, B. J.; Seitzinger, S. P.

    2008-12-01

    Wet deposition is an important removal mechanism for atmospheric organic matter, and a potentially important input for receiving ecosystems, yet less than 50 percent of rainwater organic matter is considered chemically characterized. Precipitation samples collected in New Jersey, USA, were analyzed by negative ion ultra-high resolution electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). We document the presence of 552 unique compounds in the rainwater over a mass range of 50-500 Da, in four compound classes (i.e., CHO, CHOS, CHON, and CHONS). The presence of oligomers, organosulfates, nitroxy organosulfates, organic acids, and linear alkylbenzene sulfonates is reported. Some compounds detected have distinct primary sources; however, the composition of the bulk of this material suggests it is formed in the atmosphere and composed of known contributors to secondary organic aerosol. For example, eight oligomer series known to form through aqueous photooxidation of methylglyoxal and organosulfate compounds known to form from 4 precursors in smog chamber experiments were identified in the rainwater samples. The oligomers, organosulfates, and nitroxy organosulfates detected in the rainwater could all contribute to the HULIS fraction of atmospheric organic matter.

  13. The Viscoelastic Behavior of Polymer/Oligomer Blends

    Science.gov (United States)

    Zheng, Wei; McKenna, Gregory; Simon, Sindee

    2009-03-01

    The dynamics in athermal blends of poly(α-methyl styrene) (PaMS) and its short chain oligomer are investigated using rheometry and differential scanning calorimetry (DSC). Master curves for the dynamic shear responses, G' and G", are successfully constructed for both the pure materials and the blends, indicating the validity of the time-temperature superposition principle. The temperature dependence of the shift factor follows the WLF (Williams-Landel-Ferry) behavior over the temperature range studied, and for the blends, the dependence is dominated by the high mobility oligomer. The discrete relaxation spectra of the materials are calculated and are found to be broader for the blends than for the pure materials. A similar domination of the dynamics by the oligomer is observed in DSC enthalpy recovery studies and in the broadened glass transition from DSC. The ability to predict the dynamic responses of the blends from the responses of the neat materials is examined, and whether this prediction needs to incorporate the self-concentration idea as described in Colmenero's model will be discussed.

  14. Molecular simulation of oligomer inhibitors for calcite scale

    Institute of Scientific and Technical Information of China (English)

    Qiuyu Zhang; Hua Ren; Wenwen Wang; Junping Zhang; Hepeng Zhang

    2012-01-01

    Molecular simulation was performed to study the interaction between CaCO3 crystal and several oligomer inhibitors,by using the equilibrium morphology method to calculate the growth morphology of CaCO3 without inhibitors.The calculated morphology agreed well with SEM photographs.Then,a double-layer model was built to investigate the interaction between calcite crystal and oligomer inhibitors containing maleic anhydride (MA) and acrylic acid (AA).Interaction energy per gram of an oligomer inhibitor was introduced as a scale of inhibition efficiency of different monomers.The results indicated that,for calcite scale inhibition,acrylamide (AM) and vinyl phosphonic acid (VPA) were the most efficient monomers,while allylsulfonic acid (AS) was the poorest.Increasing proportion of AM in dimer inhibitor molecule would improve the inhibition efficiency of MA,though,for a trimer,such as MA-AA-AM,certain sequence of monomers in the inhibitor molecule was necessary besides higher proportion of AM.

  15. tert-Butyl 2-borono-1H-pyrrole-1-carboxylate

    Directory of Open Access Journals (Sweden)

    Zheng Zhong

    2009-04-01

    Full Text Available In the crystal structure of the title compound, C9H14BNO4, the boronic acid group and carbamate groups are nearly co-planar with the pyrrole ring, making dihedral angles of 0.1 (2 and 2.2 (2°, respectively. Intramolecular and intermolecular O—H...O hydrogen bonds help to stabilize the structure, the latter interaction leading to inversion dimers..

  16. A joint experimental and computational investigation on the thermochemistry of (nitrophenyl)pyrroles

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Ana Filipa L.O.M. [Centro de Investigacao em Quimica, Department of Chemistry, Faculty of Science, University of Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal); Ribeiro da Silva, Manuel A.V., E-mail: risilva@fc.up.p [Centro de Investigacao em Quimica, Department of Chemistry, Faculty of Science, University of Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal)

    2010-08-15

    This paper reports the standard (p{sup o} = 0.1 MPa) molar enthalpies of formation, in the gaseous phase, {Delta}{sub f}H{sub m}{sup 0}(g), at T = 298.15 K, of 1-(2-nitrophenyl)pyrrole and of 1-(4-nitrophenyl)pyrrole as (235.7 {+-} 2.7) kJ . mol{sup -1} and (205.5 {+-} 2.5) kJ . mol{sup -1}, respectively. These values were derived from experimental thermodynamic parameters, namely from the standard (p{sup o} = 0.1 MPa) molar enthalpies of formation, in the crystalline phase, {Delta}{sub f}H{sub m}{sup 0}(cr), at T = 298.15 K, obtained from the standard molar enthalpies of combustion, {Delta}{sub c}H{sub m}{sup 0}, measured by static-bomb combustion calorimetry, and from the standard molar enthalpies of sublimation, at T = 298.15 K, determined from the temperature-vapour pressure dependence, obtained by the Knudsen mass loss effusion method. Additionally, the gas-phase enthalpies of formation were estimated by G3(MP2)//B3LYP calculations, using several gas-phase working reactions, and were compared with the experimental determined ones. Experimental and theoretical results are in very good agreement and show that 1-(4-nitrophenyl)pyrrole is thermodynamically more stable than the 2-isomer. This composite approach was also used to estimate the gas-phase enthalpy of formation of the 1-(3-nitrophenyl)pyrrole.

  17. Pyrrole Azocrown Ethers. Synthesis, Complexation, Selective Lead Transport and Ion-Selective Membrane Electrode Studies

    OpenAIRE

    Luboch, Elzbieta; Wagner-Wysiecka, Ewa; Fainerman-Melnikova, Marina; Lindoy, Leonard F.; Biernat, Jan F.

    2006-01-01

    Abstract New 21-membered lipophilic crown ethers, each incorporating a pyrrole unit and two azo groups as macrocyclic ring components, have been synthesized. The complexation behavior of these and two further macrocycles has been investigated in acetonitrile. These ligand systems have been employed as ionophores in transport experiments involving the competitive transport behavior of an equimolar mixture of Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Ag+ and Pb2+ across a water (pH 4.9)/chlorof...

  18. FABRICATION OF HIGHLY HYDROPHOBIC FILMS OF POLY(3-HEXADECYL PYRROLE) NANOPARTICLES BY LANGMUIR-BLODGETT TECHNIQUE

    Institute of Scientific and Technical Information of China (English)

    Zhen-min Hong; Gao-quan Shi; Xu-feng Wu; Liang-ti Qu

    2006-01-01

    Thin films of poly(3-hexadecyl pyrrole) (P3HDP) nanoparticles have been fabricated by using Langmuir-Blodgett film deposition technique. The structures and morphology of the films were studied by using infrared spectroscopy, scanning and transmission microscopes. The experimental results demonstrated that the nanoparticles were formed by self-assembling P3HDP at air-water surface. The water contact angles of these films with different deposition layers were measured to be as high as 110°.

  19. Electrochemical impedance of poly(9-tosyl-9H-carbazole-co-pyrrole) electrocoated carbon fiber

    Energy Technology Data Exchange (ETDEWEB)

    Ates, Murat; Uludag, Nesimi [Department of Chemistry, Faculty of Arts and Sciences, Namik Kemal University, Degirmenalti Campus, 59030, Tekirdag (Turkey); Sarac, A. Sezai, E-mail: sarac@itu.edu.tr [Department of Chemistry, Polymer Science and Technology, Istanbul Technical University, Maslak, 34469, Istanbul (Turkey)

    2011-05-16

    Research highlights: {yields} Impedance study of poly(9-tosyl-9H-carbazole-co-pyrrole) electrocoated carbon fiber. {yields} Copolymer of 9-tosyl-9H-carbazole and pyrrole were electrocoated on carbon fiber. {yields} Impedance spectroscopy and circuit models of poly(9-tosyl-9H-carbazole-co-pyrrole). - Abstract: In this paper, copolymer of 9-tosyl-9H-carbazole (TCz) and pyrrole (Py) comonomers were electrochemically deposited onto carbon fiber micro electrode (CFME) as an active electrode material. An electrochemical impedance study on the prepared electrodes is reported. Poly(TCz-co-Py)/CFME is characterized by cyclic voltammetry (CV), Fourier transform infrared reflectance-attenuated total reflection spectroscopy (FTIR-ATR), scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX), and electrochemical impedance spectroscopy (EIS). Capacitive behaviors of modified CFMEs were defined via Nyquist, Bode-magnitude and Bode-phase plots. An examination is made of which equivalent circuits of R(C(R(Q(RW)))) and R(C(R(Q(RW))))(CR) used for modeling the system. The effect of monomer ratio (mole fraction, X{sub TCz} = n{sub TCz}/n{sub TCz} + n{sub Py}) on the formation of copolymer is reported in 0.1 M sodium perchlorate (NaClO{sub 4})/acetonitrile (ACN) solution. The inclusion of TCz in the copolymer structure was also confirmed by FTIR-ATR, SEM, and CV measurements. The highest low frequency capacitance (C{sub LF} = 22.7 for R(C(R(Q(RW)))) and C{sub LF} = 22.6 mF cm{sup -2} for R(C(R(Q(RW))))(CR)) were obtained for X{sub TCz} = 0.91.

  20. Preparation and characterization of new poly-pyrrole having side chain liquid crystalline moieties

    Energy Technology Data Exchange (ETDEWEB)

    Hosseini, S. Hossein, E-mail: hosseini_sh44@yahoo.com [Department of Chemistry, Faculty of Science and Engineering, Imam Hossein University, Babaee Express Way, Tehran (Iran, Islamic Republic of); Mohammadi, M. [Department of Chemistry, Faculty of Science and Engineering, Imam Hossein University, Babaee Express Way, Tehran (Iran, Islamic Republic of)

    2009-06-01

    We have synthesized a novel liquid-crystalline (LC)-conducting polymer by introducing LC group into pyrrole monomer and polymerizing it with FeCl{sub 3}. The N-substituted pyrrole with LC group (Py-RedII) was prepared by direct reaction of potassium pyrrole salt with 2-[N-ethyl-N-[4-[(4-nitrophenyl)azo]-phenyl]amino]ethyl-3-chloropropionate (RedII). The polymerization of this monomer was successful, giving a conjugated polymer system with liquid crystalline moieties in moderate yield. The polymer obtained was soluble in organic solvents and had a thermotropic liquid crystallinity with mosaic texture characterized by polarizing optical microscopy. Phase transitions, thermal analysis and rheological studies were also evaluated by means of differential scanning calorimetry (DSC), thermogravimetry analysis (TGA) and scanning electron microscopy (SEM), respectively. Spectral properties of poly (2-[N-ethyl-N-[4-[(nitrophenyl)azo]phenyl]amino]ethyl-N-pyrrolyl propionate) (PPy-RedII) were characterized by UV, IR, {sup 1}H NMR, and {sup 13}C NMR spectroscopies. The photoluminescence spectrum of the film showed that maximum photoluminescence peak emission is located at 437 nm, corresponding to the photon energy of 2.5 eV. Electrical conductivity of PPy-RedII was studied by the four-probe method and produced a conductivity of 7.5 x 10{sup -4} S cm{sup -1}.

  1. Series of Multifluorine Substituted Oligomers for Organic Solar Cells with Efficiency over 9% and Fill Factor of 0.77 by Combination Thermal and Solvent Vapor Annealing.

    Science.gov (United States)

    Wang, Jin-Liang; Liu, Kai-Kai; Yan, Jun; Wu, Zhuo; Liu, Feng; Xiao, Fei; Chang, Zheng-Feng; Wu, Hong-Bin; Cao, Yong; Russell, Thomas P

    2016-06-22

    We report the synthesis of a family of multifluorine substituted oligomers and the corresponding polymer that have the same backbones but different conjugation lengths and amounts of fluorine atoms on the backbone. The physical properties and photovoltaic performances of these materials were systematically investigated using optical absorption, charge mobility, atomic force microscopy, transmission electron microscopy, grazing incidence X-ray diffraction, resonant soft X-ray scattering methods, and photovoltaic devices. The power conversion efficiencies (PCEs) based on oligomers were much higher than that in the polymer. Moreover, the devices based on BIT6F and BIT10F, which have an axisymmetric electron-deficient difluorobenzothiadiazole as the central unit, gave slightly higher PCEs than those with centrosymmetric electron-rich indacenodithiophene (IDT) as the central unit (BIT4F or BIT8F). Using proper solvent vapor annealing (SVA), particularly using thermal annealing (TA) followed by SVA, the device performance could be significantly improved. Notably, the best PCE of 9.1% with a very high FF of 0.76 was achieved using the medium-sized oligomer BIT6F with the optimized film morphology. This efficiency is the highest value reported for organic solar cells from small-molecules without rhodanine terminal group. More excitingly, devices from the shortest oligomer BIT4F showed an impressively high FF of 0.77 (the highest FF value reported for solution-processed small-molecule organic solar cells). These results indicate that photovoltaic performances of oligomers can be modulated through successive change in chain-length and fluorine atoms, alternating spatial symmetric core, and combined post-treatments. PMID:27225322

  2. Reactions of a Ruthenium Complex with Substituted N-Propargyl Pyrroles.

    Science.gov (United States)

    Chia, Pi-Yeh; Huang, Shou-Ling; Liu, Yi-Hong; Lin, Ying-Chih

    2016-04-01

    In an investigation into the chemical reactions of N-propargyl pyrroles 1 a-c, containing aldehyde, keto, and ester groups on the pyrrole ring, with [Ru]-Cl ([Ru]=Cp(PPh3 )2 Ru; Cp=C5 H5 ), an aldehyde group in the pyrrole ring is found to play a crucial role in stimulating the cyclization reaction. The reaction of 1 a, containing an aldehyde group, with [Ru]-Cl in the presence of NH4 PF6 yields the vinylidene complex 2 a, which further reacts with allyl amine to give the carbene complex 6 a with a pyrrolizine group. However, if 1 a is first reacted with allyl amine to yield the iminenyne 8 a, then the reaction of 8 a with [Ru]-Cl in the presence of NH4 PF6 yields the ruthenium complex 9 a, containing a cationic pyrrolopyrazinium group, which has been fully characterized by XRD analysis. These results can be adequately explained by coordination of the triple bond of the propargyl group to the ruthenium metal center first, followed by two processes, that is, formation of a vinylidene intermediate or direct nucleophilic attack. Additionally, the deprotonation of 2 a by R4 NOH yields the neutral acetylide complex 3 a. In the presence of NH4 PF6 , the attempted alkylation of 3 a resulted in the formation the Fischer-type amino-carbene complex 5 a as a result of the presence of NH3 , which served as a nucleophile. With KPF6 , the alkylation of 3 a with ethyl and benzyl bromoacetates afforded the disubstituted vinylidene complexes 10 a and 11 a, containing ester groups, which underwent deprotonation reactions to give the furyl complexes 12 a and 13 a, respectively. For 13 a, containing an O-benzyl group, subsequent 1,3-migration of the benzyl group was observed to yield product 14 a with a lactone unit. Similar reactivity was not observed for the corresponding N-propargyl pyrroles 1 b and 1 c, which contained keto and ester groups, respectively, on the pyrrole ring. PMID:26865008

  3. Chitosan polymer sizes effective in inducing phytoalexin accumulation and fungal suppression are verified with synthesized oligomers.

    Science.gov (United States)

    Hadwiger, L A; Ogawa, T; Kuyama, H

    1994-01-01

    Biologically derived chitosan has been reported to induce pisatin and disease resistance response proteins in pea tissue and also to inhibit the germination and growth of some fungal pathogens. Stereo-controlled synthesis of chitosan tetramer, hexamer, and octamer allowed the precise verification of oligomer size required for biological activity. The octameric oligomer optimally induced pisatin accumulation and inhibited fungal growth, verifying previous results obtained with column-purified oligomers derived from crab shells.

  4. Tight-binding modeling of charge migration in DNA devices

    OpenAIRE

    Cuniberti, G.; Macia, E.; Rodriguez, A.; R.A. Römer

    2007-01-01

    Long range charge transfer experiments in DNA oligomers and the subsequently measured -- and very diverse -- transport response of DNA wires in solid state experiments exemplifies the need for a thorough theoretical understanding of charge migration in DNA-based natural and artificial materials. Here we present a review of tight-binding models for DNA conduction which have the intrinsic merit of containing more structural information than plain rate-equation models while still retaining suffi...

  5. Adsorption behavior of conjugated {C}3-oligomers on Si(100) and HOPG surfaces

    CERN Document Server

    Mahieu, G; Stiévenard, Didier; Krzeminski, Christophe; Delerue, Christophe; Roncali, Jean; Martineau, C; 10.1021/la026907n

    2012-01-01

    A pi-conjugated {C}3h-oligomer involving three dithienylethylene branches bridged at the meta positions of a central benzenic core has been synthesized and deposited either on the Si(100) surface or on the HOPG surface. On the silicon surface, scanning tunneling microscopy allows the observation of isolated molecules. Conversely, by substituting the thiophene rings of the oligomers with alkyl chains, a spontaneous ordered film is observed on the HOPG surface. As the interaction of the oligomers is different with both surfaces, the utility of the Si(100) surface to characterize individual oligomers prior to their use into a 2D layer is discussed.

  6. Oligomer Formation Reactions of Criegee Intermediates in the Ozonolysis of Small Unsaturated Hydrocarbons

    Science.gov (United States)

    Sakamoto, Y.; Inomata, S.; Hirokawa, J.

    2013-12-01

    Secondary organic aerosol (SOA) constitutes a substantial fraction of atmospheric fine particulate matters and has an effect on visibility, climate and human health. One of the major oxidizing processes leading to SOA formation is an ozonolysis of unsaturated hydrocarbons (UHCs).[1] Despite of its importance, the contribution of the ozonolysis of UHCs to the SOA formation in the troposphere is not sufficiently understood due to a lack of information on reaction pathways to produce low volatile compounds. While many studies have previously been focused on SOA formation from the ozonolysis of large UHCs, SOA formation from the ozonolysis of UHCs with less than six carbon atoms have been rarely investigated because their products are expected to be too volatile to contribute to the SOA formation. Very recently, a few studies have reported the SOA formation from the ozonolysis of such small UHCs but chemical mechanisms are still unclear. [2-4] In order to understand SOA formation from the ozonolysis of the small UHCs, this study investigated gas- and particle-phase products in laboratory experiments with a Teflon bag using a negative ion chemical ionization mass spectrometry (NI-CIMS) with chloride ion transfer for chemical ionization. This technique is suitable for analysis of compounds such as carboxylic acids and hydroperoxides expected to be produced in the ozonolysis of UHCs with less fragmentation, high selectivity, and high sensitivity. In the particle-phase analysis, SOAs collected on a PTFE filter were heated, and thermally desorbed compounds were analyzed. In the gas-phase analysis, series of peaks with an interval of a mass-to-charge ratio equal to the molecular weight of a Criegee intermediate formed in their ozonolysis were observed. These peaks were attributed to oligomeric hydroperoxides composed of Criegee intermediates as a chain unit. These oligomeric hydroperoxides were also observed in the particle-phase analysis, indicating that the oligomeric

  7. Molecular determinants of S100B oligomer formation.

    Directory of Open Access Journals (Sweden)

    Eva Thulin

    Full Text Available BACKGROUND: S100B is a dimeric protein that can form tetramers, hexamers and higher order oligomers. These forms have been suggested to play a role in RAGE activation. METHODOLOGY/PRINCIPAL FINDINGS: Oligomerization was found to require a low molecular weight trigger/cofactor and could not be detected for highly pure dimer, irrespective of handling. Imidazol was identified as a substance that can serve this role. Oligomerization is dependent on both the imidazol concentration and pH, with optima around 90 mM imidazol and pH 7, respectively. No oligomerization was observed above pH 8, thus the protonated form of imidazol is the active species in promoting assembly of dimers to higher species. However, disulfide bonds are not involved and the process is independent of redox potential. The process was also found to be independent of whether Ca(2+ is bound to the protein or not. Tetramers that are purified from dimers and imidazol by gel filtration are kinetically stable, but dissociate into dimers upon heating. Dimers do not revert to tetramer and higher oligomer unless imidazol is again added. Both tetramers and hexamers bind the target peptide from p53 with retained stoichiometry of one peptide per S100B monomer, and with high affinity (lgK = 7.3±0.2 and 7.2±0.2, respectively in 10 mM BisTris, 5 mM CaCl(2, pH 7.0, which is less than one order of magnitude reduced compared to dimer under the same buffer conditions. CONCLUSION/SIGNIFICANCE: S100B oligomerization requires protonated imidazol as a trigger/cofactor. Oligomers are kinetically stable after imidazol is removed but revert back to dimer if heated. The results underscore the importance of kinetic versus thermodynamic control of S100B protein aggregation.

  8. Biological activity of two new pyrrole derivatives against stored-product species: influence of temperature and relative humidity.

    Science.gov (United States)

    Boukouvala, M C; Kavallieratos, N G; Athanassiou, C G; Hadjiarapoglou, L P

    2016-08-01

    Members of the pyrrole group are likely to have interesting properties that merit additional investigation as insecticides at the post-harvest stages of agricultural commodities. In the present work, the insecticidal effect of two new pyrrole derivatives, ethyl 3-(benzylthio)-4,6-dioxo-5-phenyl-2,4,5,6-tetrahydropyrrolo[3,4-c]pyrrole-carboxylate (3i) and isopropyl 3-(benzylthio)-4,6-dioxo-5-phenyl-2,4,5,6-tetrahydropyrrolo[3,4-c]pyrrole-carboxylate (3k) were studied as stored-wheat protectants against two major stored-product insect species, the confused flour beetle, Tribolium confusum Jaquelin du Val adults and larvae and the Mediterranean flour moth, Ephestia kuehniella Zeller larvae at different doses (0.1, 1 and 10 ppm), exposure intervals (7, 14 and 21 days), temperatures (20, 25 and 30°C) and relative humidity (55 and 75%) levels. For T. confusum adults, in the case of the pyrrole derivative 3i, mortality was low and it did not exceed 32.2% in wheat treated with 10 ppm 3i at 30°C and 55% relative humidity. Progeny production was very low (insecticidal effect, but this effect is moderated by the exposure, the target species, the temperature and the relative humidity. PMID:27087458

  9. A synthetic analogue of melittin aggregates in large oligomers.

    OpenAIRE

    John, E.; Jähnig, F

    1992-01-01

    An analogue of melittin synthesized in the group of E. T. Kaiser (DeGrado, W. F., F. J. Keźdy, and E. T. Kaiser. 1981. J. Am. Chem. Soc. 103:679-681) was investigated by Raman spectroscopy and fluorescence anisotropy decay. In water, the analogue is completely alpha-helical and aggregates in large oligomers of about 50 monomers. In vesicle membranes, it undergoes orientational fluctuations similar to melittin. The most significant difference from melittin, therefore, is the formation of strai...

  10. Structural Transitions of Solvent-Free Oligomer-Grafted Nanoparticles

    KAUST Repository

    Chremos, Alexandros

    2011-09-01

    Novel structural transitions of solvent-free oligomer-grafted nanoparticles are investigated by using molecular dynamics simulations of a coarse-grained bead-spring model. Variations in core size and grafting density lead to self-assembly of the nanoparticles into a variety of distinct structures. At the boundaries between different structures, the nanoparticle systems undergo thermoreversible transitions. This structural behavior, which has not been previously reported, deviates significantly from that of simple liquids. The reversible nature of these transitions in solvent-free conditions offers new ways to control self-assembly of nanoparticles at experimentally accessible conditions. © 2011 American Physical Society.

  11. Electrochemical polymerization of pyrrole over AZ31 Mg alloy for biomedical applications

    International Nuclear Information System (INIS)

    Highlights: ► Polymerization of pyrrole over AZ31 Mg was carried out using cyclic voltammetry. ► Pyrrole concentration was optimized to accomplish the adherent and uniform coating. ► Effect of monomer concentration on the surface morphology was discussed. ► Corrosion resistance of AZ31 Mg in SBF was studied as a function of Py concentration. ► PPy coated AZ31 Mg alloy exhibited enhanced corrosion resistance at 0.25 M of Py. -- Abstract: Electrochemical polymerization of pyrrole (Py) from aqueous salicylate solution over AZ31 Mg alloy was carried out using cyclic voltammetry (CV). The effect of monomer concentration on the surface and electrochemical corrosion in simulated body fluid (SBF) were analysed. Attenuated total reflection-infrared (ATR-IR) spectra showed the characteristic ring stretching peaks for polypyrrole (PPy). Scanning electron microscopy (SEM) and atomic force microscopy (AFM) studies exhibited typical cauliflower morphology with rough surface for PPy coated AZ31 Mg alloy. Open circuit potential measurement and potentiodynamic polarization studies revealed that the coating prepared using 0.25 M of Py had positive shift of about 120 mV in corrosion potential and lower corrosion current density (0.03 mA/cm2) compared to other concentrations and uncoated AZ31 Mg alloy (0.25 mA/cm2). Electrochemical impedance spectroscopic (EIS) studies of uncoated and PPy coated Mg alloy in SBF revealed three-time constants behaviour with about one order of increment in impedance value for 0.25 M of Py

  12. Quantification of CH-π Interactions Using Calix[4]pyrrole Receptors as Model Systems

    Directory of Open Access Journals (Sweden)

    Gemma Aragay

    2015-09-01

    Full Text Available We describe the use of two series of aryl-extended calix[4]pyrrole receptors bearing two and four electronically tunable phenyl groups, respectively, in their meso-positions as model systems for the quantification of CH-π interactions in solution. The “four-wall” and the “two-wall” receptors formed thermodynamically stable 1:1 complexes in acetonitrile solution with both trimethylamine N-oxide and trimethylphosphine P-oxide as guests. The complexes were mainly stabilized by the formation of four convergent hydrogen bonds between the oxygen atom of the guests and the pyrrole NHs of the host. In general, the N-oxide produced thermodynamically more stable hydrogen bonding interactions than the P-oxide. Upon guest binding, the receptors adopted the cone conformation and the methyl groups of the included guests engaged in CH-π interactions with the aromatic walls. We show that the modification of the electronic properties of the aromatic surfaces, in any of the receptor series, did not have a significant impact in the measured binding affinities for a given guest. However, the larger binding affinities determined for the “four-wall” receptors in comparison to the “two-wall” counterparts supported the importance of CH-π interactions on guest complexation. The strength of the CH-π interactions present in the inclusion complexes was quantified employing the octamethyl calix[4]pyrrole as reference. We determined an average magnitude of ~1 kcal·mol−1 for each CH-π interaction. The CH-π interactions featured a reduced electrostatic nature and thus dispersion forces were assigned as main contributors of their strength.

  13. EGFP oligomers as natural fluorescence and hydrodynamic standards.

    Science.gov (United States)

    Vámosi, György; Mücke, Norbert; Müller, Gabriele; Krieger, Jan Wolfgang; Curth, Ute; Langowski, Jörg; Tóth, Katalin

    2016-01-01

    EGFP oligomers are convenient standards for experiments on fluorescent protein-tagged biomolecules. In this study, we characterized their hydrodynamic and fluorescence properties. Diffusion coefficients D of EGFP1-4 were determined by analytical ultracentrifugation with fluorescence detection and by fluorescence correlation spectroscopy (FCS), yielding 83.4…48.2 μm(2)/s and 97.3…54.8 μm(2)/s from monomer to tetramer. A "barrels standing in a row" model agreed best with the sedimentation data. Oligomerization red-shifted EGFP emission spectra without any shift in absorption. Fluorescence anisotropy decreased, indicating homoFRET between the subunits. Fluorescence lifetime decreased only slightly (4%) indicating insignificant quenching by FRET to subunits in non-emitting states. FCS-measured D, particle number and molecular brightness depended on dark states and light-induced processes in distinct subunits, resulting in a dependence on illumination power different for monomers and oligomers. Since subunits may be in "on" (bright) or "off" (dark) states, FCS-determined apparent brightness is not proportional to that of the monomer. From its dependence on the number of subunits, the probability of the "on" state for a subunit was determined to be 96% at pH 8 and 77% at pH 6.38, i.e., protonation increases the dark state. These fluorescence properties of EGFP oligomeric standards can assist interpreting results from oligomerized EGFP fusion proteins of biological interest. PMID:27622431

  14. Amyloid oligomer structure characterization from simulations: A general method

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Phuong H., E-mail: phuong.nguyen@ibpc.fr [Laboratoire de Biochimie Théorique, UPR 9080, CNRS Université Denis Diderot, Sorbonne Paris Cité IBPC, 13 rue Pierre et Marie Curie, 75005 Paris (France); Li, Mai Suan [Institute of Physics, Polish Academy of Sciences, Al. Lotnikow 32/46, 02-668 Warsaw (Poland); Derreumaux, Philippe, E-mail: philippe.derreumaux@ibpc.fr [Laboratoire de Biochimie Théorique, UPR 9080, CNRS Université Denis Diderot, Sorbonne Paris Cité IBPC, 13 rue Pierre et Marie Curie, 75005 Paris (France); Institut Universitaire de France, 103 Bvd Saint-Germain, 75005 Paris (France)

    2014-03-07

    Amyloid oligomers and plaques are composed of multiple chemically identical proteins. Therefore, one of the first fundamental problems in the characterization of structures from simulations is the treatment of the degeneracy, i.e., the permutation of the molecules. Second, the intramolecular and intermolecular degrees of freedom of the various molecules must be taken into account. Currently, the well-known dihedral principal component analysis method only considers the intramolecular degrees of freedom, and other methods employing collective variables can only describe intermolecular degrees of freedom at the global level. With this in mind, we propose a general method that identifies all the structures accurately. The basis idea is that the intramolecular and intermolecular states are described in terms of combinations of single-molecule and double-molecule states, respectively, and the overall structures of oligomers are the product basis of the intramolecular and intermolecular states. This way, the degeneracy is automatically avoided. The method is illustrated on the conformational ensemble of the tetramer of the Alzheimer's peptide Aβ{sub 9−40}, resulting from two atomistic molecular dynamics simulations in explicit solvent, each of 200 ns, starting from two distinct structures.

  15. Access to pyrrolo-pyridines by gold-catalyzed hydroarylation of pyrroles tethered to terminal alkynes

    Directory of Open Access Journals (Sweden)

    Elena Borsini

    2011-10-01

    Full Text Available In a simple procedure, the intramolecular hydroarylation of N-propargyl-pyrrole-2-carboxamides was accomplished with the aid of gold(III catalysis. The reaction led to differently substituted pyrrolo[2,3-c]pyridine and pyrrolo[3,2-c]pyridine derivatives arising either from direct cyclization or from a formal rearrangement of the carboxamide group. Terminal alkynes are essential to achieve bicyclic pyrrolo-fused pyridinones by a 6-exo-dig process, while the presence of a phenyl group at the C–C triple bond promotes the 7-endo-dig cyclization giving pyrrolo-azepines.

  16. Thermal Diffusivity Measurement of Poly pyrrole-Chitosan Composite by Photoacoustic Technique

    International Nuclear Information System (INIS)

    Thermal diffusivity is a physical quantity that represents an intrinsic property for a material and indicates how fast heat propagates through a sample. The photoacoustic (PA) technique has recently been recognized as a powerful and reliable experimental technique in measuring thermal diffusivity. This effect is described as the periodic heating generated in the sample by a nonradiative deexcitation process due to the absorption of a modulated light source [1]. In present work, the conducting polymer composite films of poly pyrrole-chitosan (PPy- CHI) were synthesized by electrochemical polymerization method. The electrical conductivity and thermal diffusivity of composite film were studied as a function of electro polymerization conditions. (author)

  17. Synthesis and Physical Characterization of Carbon Nano tubes Coated by Conducting Poly pyrrole

    International Nuclear Information System (INIS)

    This study describes the preparation of poly pyrrole multi walled carbon nano tube (PPy/ MWNT) composites by in situ chemical oxidative polymerization. Various ratios of functionalized MWNTs are dispersed in the water, and PPy are then synthesized via in-situ chemical oxidative polymerization on the surface of the carbon nano tubes. The morphology of the resulting complex nano tubes (MWNT-PPY) was characterized by scanning electron microscopy (SEM). The conductivity of each composite showed a maximum in the temperature scale of 120- 160 degree Celsius and then decreased dramatically with the increase of temperature. (author)

  18. Organocatalytic Enantioselective Aza-Friedel-Crafts Reaction of Cyclic Ketimines with Pyrroles using Imidazolinephosphoric Acid Catalysts.

    Science.gov (United States)

    Nakamura, Shuichi; Matsuda, Nazumi; Ohara, Mutsuyo

    2016-07-01

    Organocatalytic enantioselective aza-Friedel-Crafts reactions of cyclic ketimines with pyrroles or indoles were catalyzed by imidazoline/phosphoric acid catalysts. The reaction was applied to various 3H-indol-3-ones to afford products in excellent yields and enantioselectivities. The chiral catalysts can be recovered by a single separation step using column chromatography and are reusable without further purification. Based on the experimental investigations, a possible transition state has been proposed to explain the origin of the asymmetric induction. PMID:27124556

  19. Sustainable Pathways to Pyrroles through Iron-Catalyzed N-Heterocyclization from Unsaturated Diols and Primary Amines.

    Science.gov (United States)

    Yan, Tao; Barta, Katalin

    2016-09-01

    Pyrroles are prominent scaffolds in pharmaceutically active compounds and play an important role in medicinal chemistry. Therefore, the development of new, atom-economic, and sustainable catalytic strategies to obtain these moieties is highly desired. Direct catalytic pathways that utilize readily available alcohol substrates have been recently established; however, these approaches rely on the use of noble metals such as ruthenium or iridium. Here, we report on the direct synthesis of pyrroles using a catalyst based on the earth-abundant and inexpensive iron. The method uses 2-butyne-1,4-diol or 2-butene-1,4-diol that can be directly coupled with anilines, benzyl amines, and aliphatic amines to obtain a variety of N-substituted pyrroles in moderate-to-excellent isolated yields.

  20. Sustainable Pathways to Pyrroles through Iron-Catalyzed N-Heterocyclization from Unsaturated Diols and Primary Amines.

    Science.gov (United States)

    Yan, Tao; Barta, Katalin

    2016-09-01

    Pyrroles are prominent scaffolds in pharmaceutically active compounds and play an important role in medicinal chemistry. Therefore, the development of new, atom-economic, and sustainable catalytic strategies to obtain these moieties is highly desired. Direct catalytic pathways that utilize readily available alcohol substrates have been recently established; however, these approaches rely on the use of noble metals such as ruthenium or iridium. Here, we report on the direct synthesis of pyrroles using a catalyst based on the earth-abundant and inexpensive iron. The method uses 2-butyne-1,4-diol or 2-butene-1,4-diol that can be directly coupled with anilines, benzyl amines, and aliphatic amines to obtain a variety of N-substituted pyrroles in moderate-to-excellent isolated yields. PMID:27493031

  1. CHEMISTRY OF SULFONYLMETHYL ISOCYANIDES .37. SYNTHESIS OF 3,4-DISUBSTITUTED PYRROLES BEARING SUBSTITUENTS OF ELECTRON-WITHDRAWING AND/OR ELECTRON-DONATING NATURE

    NARCIS (Netherlands)

    VANLEUSEN, D; VANECHTEN, E; van Leusen, A.M.

    1992-01-01

    The synthesis is described of a series of 3,4-disubstituted pyrroles 8 from 1-isocyano-1-tosyl-1-alkenes and a variety of Michael donors. It is possible to use this method for the synthesis of pyrroles that bear no electron-withdrawing substitutents.

  2. Electronic structure of thienylene vinylene oligomers : Singlet excited states, triplet excited states, cations, and dications

    NARCIS (Netherlands)

    Grozema, FC; van Duijnen, PT; Siebbeles, LDA; Goossens, A

    2004-01-01

    This paper describes a quantum chemical study of the electronic structure of thienylene vinylene oligomers ranging in size from two thienylene rings (2TV) to 12TV. The geometries of the TV oligomers in the ground state, the lowest triplet state, and the singly and doubly oxidized states were optimiz

  3. Tau oligomers impair memory and induce synaptic and mitochondrial dysfunction in wild-type mice

    Directory of Open Access Journals (Sweden)

    Jackson George R

    2011-06-01

    Full Text Available Abstract Background The correlation between neurofibrillary tangles of tau and disease progression in the brains of Alzheimer's disease (AD patients remains an area of contention. Innovative data are emerging from biochemical, cell-based and transgenic mouse studies that suggest that tau oligomers, a pre-filament form of tau, may be the most toxic and pathologically significant tau aggregate. Results Here we report that oligomers of recombinant full-length human tau protein are neurotoxic in vivo after subcortical stereotaxic injection into mice. Tau oligomers impaired memory consolidation, whereas tau fibrils and monomers did not. Additionally, tau oligomers induced synaptic dysfunction by reducing the levels of synaptic vesicle-associated proteins synaptophysin and septin-11. Tau oligomers produced mitochondrial dysfunction by decreasing the levels of NADH-ubiquinone oxidoreductase (electron transport chain complex I, and activated caspase-9, which is related to the apoptotic mitochondrial pathway. Conclusions This study identifies tau oligomers as an acutely toxic tau species in vivo, and suggests that tau oligomers induce neurodegeneration by affecting mitochondrial and synaptic function, both of which are early hallmarks in AD and other tauopathies. These results open new avenues for neuroprotective intervention strategies of tauopathies by targeting tau oligomers.

  4. Alzheimer's therapeutics targeting amyloid beta 1-42 oligomers I: Abeta 42 oligomer binding to specific neuronal receptors is displaced by drug candidates that improve cognitive deficits.

    Directory of Open Access Journals (Sweden)

    Nicholas J Izzo

    Full Text Available Synaptic dysfunction and loss caused by age-dependent accumulation of synaptotoxic beta amyloid (Abeta 1-42 oligomers is proposed to underlie cognitive decline in Alzheimer's disease (AD. Alterations in membrane trafficking induced by Abeta oligomers mediates reduction in neuronal surface receptor expression that is the basis for inhibition of electrophysiological measures of synaptic plasticity and thus learning and memory. We have utilized phenotypic screens in mature, in vitro cultures of rat brain cells to identify small molecules which block or prevent the binding and effects of Abeta oligomers. Synthetic Abeta oligomers bind saturably to a single site on neuronal synapses and induce deficits in membrane trafficking in neuronal cultures with an EC50 that corresponds to its binding affinity. The therapeutic lead compounds we have found are pharmacological antagonists of Abeta oligomers, reducing the binding of Abeta oligomers to neurons in vitro, preventing spine loss in neurons and preventing and treating oligomer-induced deficits in membrane trafficking. These molecules are highly brain penetrant and prevent and restore cognitive deficits in mouse models of Alzheimer's disease. Counter-screening these compounds against a broad panel of potential CNS targets revealed they are highly potent and specific ligands of the sigma-2/PGRMC1 receptor. Brain concentrations of the compounds corresponding to greater than 80% receptor occupancy at the sigma-2/PGRMC1 receptor restore cognitive function in transgenic hAPP Swe/Ldn mice. These studies demonstrate that synthetic and human-derived Abeta oligomers act as pharmacologically-behaved ligands at neuronal receptors--i.e. they exhibit saturable binding to a target, they exert a functional effect related to their binding and their displacement by small molecule antagonists blocks their functional effect. The first-in-class small molecule receptor antagonists described here restore memory to normal in

  5. Alzheimer's therapeutics targeting amyloid beta 1-42 oligomers I: Abeta 42 oligomer binding to specific neuronal receptors is displaced by drug candidates that improve cognitive deficits.

    Science.gov (United States)

    Izzo, Nicholas J; Staniszewski, Agnes; To, Lillian; Fa, Mauro; Teich, Andrew F; Saeed, Faisal; Wostein, Harrison; Walko, Thomas; Vaswani, Anisha; Wardius, Meghan; Syed, Zanobia; Ravenscroft, Jessica; Mozzoni, Kelsie; Silky, Colleen; Rehak, Courtney; Yurko, Raymond; Finn, Patricia; Look, Gary; Rishton, Gilbert; Safferstein, Hank; Miller, Miles; Johanson, Conrad; Stopa, Edward; Windisch, Manfred; Hutter-Paier, Birgit; Shamloo, Mehrdad; Arancio, Ottavio; LeVine, Harry; Catalano, Susan M

    2014-01-01

    Synaptic dysfunction and loss caused by age-dependent accumulation of synaptotoxic beta amyloid (Abeta) 1-42 oligomers is proposed to underlie cognitive decline in Alzheimer's disease (AD). Alterations in membrane trafficking induced by Abeta oligomers mediates reduction in neuronal surface receptor expression that is the basis for inhibition of electrophysiological measures of synaptic plasticity and thus learning and memory. We have utilized phenotypic screens in mature, in vitro cultures of rat brain cells to identify small molecules which block or prevent the binding and effects of Abeta oligomers. Synthetic Abeta oligomers bind saturably to a single site on neuronal synapses and induce deficits in membrane trafficking in neuronal cultures with an EC50 that corresponds to its binding affinity. The therapeutic lead compounds we have found are pharmacological antagonists of Abeta oligomers, reducing the binding of Abeta oligomers to neurons in vitro, preventing spine loss in neurons and preventing and treating oligomer-induced deficits in membrane trafficking. These molecules are highly brain penetrant and prevent and restore cognitive deficits in mouse models of Alzheimer's disease. Counter-screening these compounds against a broad panel of potential CNS targets revealed they are highly potent and specific ligands of the sigma-2/PGRMC1 receptor. Brain concentrations of the compounds corresponding to greater than 80% receptor occupancy at the sigma-2/PGRMC1 receptor restore cognitive function in transgenic hAPP Swe/Ldn mice. These studies demonstrate that synthetic and human-derived Abeta oligomers act as pharmacologically-behaved ligands at neuronal receptors--i.e. they exhibit saturable binding to a target, they exert a functional effect related to their binding and their displacement by small molecule antagonists blocks their functional effect. The first-in-class small molecule receptor antagonists described here restore memory to normal in multiple AD models

  6. Alzheimer's therapeutics targeting amyloid beta 1-42 oligomers I: Abeta 42 oligomer binding to specific neuronal receptors is displaced by drug candidates that improve cognitive deficits.

    Science.gov (United States)

    Izzo, Nicholas J; Staniszewski, Agnes; To, Lillian; Fa, Mauro; Teich, Andrew F; Saeed, Faisal; Wostein, Harrison; Walko, Thomas; Vaswani, Anisha; Wardius, Meghan; Syed, Zanobia; Ravenscroft, Jessica; Mozzoni, Kelsie; Silky, Colleen; Rehak, Courtney; Yurko, Raymond; Finn, Patricia; Look, Gary; Rishton, Gilbert; Safferstein, Hank; Miller, Miles; Johanson, Conrad; Stopa, Edward; Windisch, Manfred; Hutter-Paier, Birgit; Shamloo, Mehrdad; Arancio, Ottavio; LeVine, Harry; Catalano, Susan M

    2014-01-01

    Synaptic dysfunction and loss caused by age-dependent accumulation of synaptotoxic beta amyloid (Abeta) 1-42 oligomers is proposed to underlie cognitive decline in Alzheimer's disease (AD). Alterations in membrane trafficking induced by Abeta oligomers mediates reduction in neuronal surface receptor expression that is the basis for inhibition of electrophysiological measures of synaptic plasticity and thus learning and memory. We have utilized phenotypic screens in mature, in vitro cultures of rat brain cells to identify small molecules which block or prevent the binding and effects of Abeta oligomers. Synthetic Abeta oligomers bind saturably to a single site on neuronal synapses and induce deficits in membrane trafficking in neuronal cultures with an EC50 that corresponds to its binding affinity. The therapeutic lead compounds we have found are pharmacological antagonists of Abeta oligomers, reducing the binding of Abeta oligomers to neurons in vitro, preventing spine loss in neurons and preventing and treating oligomer-induced deficits in membrane trafficking. These molecules are highly brain penetrant and prevent and restore cognitive deficits in mouse models of Alzheimer's disease. Counter-screening these compounds against a broad panel of potential CNS targets revealed they are highly potent and specific ligands of the sigma-2/PGRMC1 receptor. Brain concentrations of the compounds corresponding to greater than 80% receptor occupancy at the sigma-2/PGRMC1 receptor restore cognitive function in transgenic hAPP Swe/Ldn mice. These studies demonstrate that synthetic and human-derived Abeta oligomers act as pharmacologically-behaved ligands at neuronal receptors--i.e. they exhibit saturable binding to a target, they exert a functional effect related to their binding and their displacement by small molecule antagonists blocks their functional effect. The first-in-class small molecule receptor antagonists described here restore memory to normal in multiple AD models

  7. Diethyl 2-amino-5-[(E-(1-methyl-1H-pyrrol-2-ylmethylideneamino]thiophene-3,4-dicarboxylate

    Directory of Open Access Journals (Sweden)

    Stéphane Dufresne

    2010-12-01

    Full Text Available The structure of the title compound, C16H19N3O4S, shows the planes described by the thiophene and the pyrroles are twisted by 17.06 (4°. Additionally, the structure shows the azomethine bond adopts the E configuration, while the pyrrole is disordered as a heterocycle flip [occupancy ratio 0.729 (5:0.271 (5]. The three-dimensional network is well packed and involves N–H...O hydrogen bonding and π–π stacking [centroid–centroid distance = 4.294 (8 Å].

  8. Synthesis of furans and pyrroles via migratory and double migratory cycloisomerization reactions of homopropargylic aldehydes and imines

    Science.gov (United States)

    Shiroodi, Roohollah Kazem; Vera, Claudia I. Rivera; Dudnik, Alexander S.; Gevorgyan, Vladimir

    2015-01-01

    A novel gold-catalyzed divergent sysnthesis of furans and pyrroles employing readily available homopropargylic aldehydes and imines have been developed. The regiochemical outcome of this reaction is dependent on the substituent on the terminal alkyne of substrate. Thus, substrates possessing alkyl and aryl substituent at the alkyne moiety produce 2,3,5-substituted furans and pyrroles via a migratory cycloisomerizaton reaction. Whereas, their silicon analogues are capable to undergo a double migratory process leading to 2,3,4-substituted heterocycles. PMID:26185336

  9. Ethyl (2E-2-cyano-3-(1-methyl-1H-pyrrol-2-ylprop-2-enoate

    Directory of Open Access Journals (Sweden)

    Abdullah M. Asiri

    2011-09-01

    Full Text Available The 15 non-H atoms of the title compound, C11H12N2O2, are approximately coplanar, the r.m.s. deviation being 0.145 Å. The major deviation from coplanarity is seen in a twist between the ethene (E configuration and pyrrole rings [C—C—N—C torsion angle = −8.26 (18°]. The carbonyl O and cyano N atoms are syn to each other. In the crystal, supramolecular linear tapes linked by C—H...O and C—H...N interactions are further connected by C—H...π(pyrrole interactions.

  10. Preparation of Chito-Oligomers by Hydrolysis of Chitosan in the Presence of Zeolite as Adsorbent.

    Science.gov (United States)

    Ibrahim, Khalid A; El-Eswed, Bassam I; Abu-Sbeih, Khaleel A; Arafat, Tawfeeq A; Al Omari, Mahmoud M H; Darras, Fouad H; Badwan, Adnan A

    2016-01-01

    An increasing interest has recently been shown to use chitin/chitosan oligomers (chito-oligomers) in medicine and food fields because they are not only water-soluble, nontoxic, and biocompatible materials, but they also exhibit numerous biological properties, including antibacterial, antifungal, and antitumor activities, as well as immuno-enhancing effects on animals. Conventional depolymerization methods of chitosan to chito-oligomers are either chemical by acid-hydrolysis under harsh conditions or by enzymatic degradation. In this work, hydrolysis of chitosan to chito-oligomers has been achieved by applying adsorption-separation technique using diluted HCl in the presence of different types of zeolite as adsorbents. The chito-oligomers were retrieved from adsorbents and characterized by differential scanning calorimetry (DSC), liquid chromatography/mass spectroscopy (LC/MS), and ninhydrin test. PMID:27455287

  11. Preparation of Chito-Oligomers by Hydrolysis of Chitosan in the Presence of Zeolite as Adsorbent

    Directory of Open Access Journals (Sweden)

    Khalid A. Ibrahim

    2016-07-01

    Full Text Available An increasing interest has recently been shown to use chitin/chitosan oligomers (chito-oligomers in medicine and food fields because they are not only water-soluble, nontoxic, and biocompatible materials, but they also exhibit numerous biological properties, including antibacterial, antifungal, and antitumor activities, as well as immuno-enhancing effects on animals. Conventional depolymerization methods of chitosan to chito-oligomers are either chemical by acid-hydrolysis under harsh conditions or by enzymatic degradation. In this work, hydrolysis of chitosan to chito-oligomers has been achieved by applying adsorption-separation technique using diluted HCl in the presence of different types of zeolite as adsorbents. The chito-oligomers were retrieved from adsorbents and characterized by differential scanning calorimetry (DSC, liquid chromatography/mass spectroscopy (LC/MS, and ninhydrin test.

  12. Preparation of Chito-Oligomers by Hydrolysis of Chitosan in the Presence of Zeolite as Adsorbent

    Science.gov (United States)

    Ibrahim, Khalid A.; El-Eswed, Bassam I.; Abu-Sbeih, Khaleel A.; Arafat, Tawfeeq A.; Al Omari, Mahmoud M. H.; Darras, Fouad H.; Badwan, Adnan A.

    2016-01-01

    An increasing interest has recently been shown to use chitin/chitosan oligomers (chito-oligomers) in medicine and food fields because they are not only water-soluble, nontoxic, and biocompatible materials, but they also exhibit numerous biological properties, including antibacterial, antifungal, and antitumor activities, as well as immuno-enhancing effects on animals. Conventional depolymerization methods of chitosan to chito-oligomers are either chemical by acid-hydrolysis under harsh conditions or by enzymatic degradation. In this work, hydrolysis of chitosan to chito-oligomers has been achieved by applying adsorption-separation technique using diluted HCl in the presence of different types of zeolite as adsorbents. The chito-oligomers were retrieved from adsorbents and characterized by differential scanning calorimetry (DSC), liquid chromatography/mass spectroscopy (LC/MS), and ninhydrin test. PMID:27455287

  13. Tenfibgen ligand nanoencapsulation delivers bi-functional anti-CK2 RNAi oligomer to key sites for prostate cancer targeting using human xenograft tumors in mice.

    Directory of Open Access Journals (Sweden)

    Janeen H Trembley

    Full Text Available Protected and specific delivery of nucleic acids to malignant cells remains a highly desirable approach for cancer therapy. Here we present data on the physical and chemical characteristics, mechanism of action, and pilot therapeutic efficacy of a tenfibgen (TBG-shell nanocapsule technology for tumor-directed delivery of single stranded DNA/RNA chimeric oligomers targeting CK2αα' to xenograft tumors in mice. The sub-50 nm size TBG nanocapsule (s50-TBG is a slightly negatively charged, uniform particle of 15 - 20 nm size which confers protection to the nucleic acid cargo. The DNA/RNA chimeric oligomer (RNAi-CK2 functions to decrease CK2αα' expression levels via both siRNA and antisense mechanisms. Systemic delivery of s50-TBG-RNAi-CK2 specifically targets malignant cells, including tumor cells in bone, and at low doses reduces size and CK2-related signals in orthotopic primary and metastatic xenograft prostate cancer tumors. In conclusion, the s50-TBG nanoencapsulation technology together with the chimeric oligomer targeting CK2αα' offer significant promise for systemic treatment of prostate malignancy.

  14. Cholesterol facilitates interactions between α-synuclein oligomers and charge-neutral membranes

    DEFF Research Database (Denmark)

    van Maarschalkerweerd, Andreas; Vetri, Valeria; Vestergaard, Bente

    2015-01-01

    membranes are either unperturbed, disrupt, or undergo dramatic morphological changes and segregate into structurally different components, which we visualize by 2-photon fluorescence microscopy and generalized polarization analysis using the fluorescent probe Laurdan. Our results highlight the crucial role...

  15. Wire-like charge transport at near constant bridge energy through fluorene oligomers

    OpenAIRE

    Goldsmith, Randall H.; Sinks, Louise E.; Kelley, Richard F.; Betzen, Laura J.; Liu, Wenhao; Weiss, Emily A.; Ratner, Mark A.; Wasielewski, Michael R.

    2005-01-01

    The study of photoinitiated electron transfer in donor–bridge–acceptor molecules has helped elucidate the distance dependence of electron transfer rates and behavior of various electron transfer mechanisms. In all reported cases, the energies of the bridge electronic states involved in the electron transfer change dramatically as the length of the bridge is varied. We report here, in contrast, an instance in which the length of the bridge, and therefore the distance over which the electron is...

  16. Superhalogens beget superhalogens: a case study of (BO2)n oligomers.

    Science.gov (United States)

    Kandalam, Anil K; Kiran, Boggavarapu; Jena, P; Pietsch, S; Ganteför, G

    2015-10-28

    Superhalogens belong to a class of molecules that not only mimic the chemistry of halogen atoms but also possess electron affinities that are much larger than that of chlorine, the element with the highest electron affinity in the periodic table. Using BO2 as an example and the synergy between density functional theory-based calculations and photoelectron spectroscopy experiments we demonstrate another unusual property of superhalogens. Unlike halogens, whose ability to accept an electron falls upon dimerization, B2O4, the dimer of BO2, has an electron affinity larger than that of the BO2 building block. This ability of (BO2)2 and subsequent, higher oligomers (BO2)n (n = 3 and 4), to retain their superhalogen characteristics can be traced to the enhanced bonding interactions between oxygen and boron atoms and due to the delocalization of the charge of the extra-electron over the terminal oxygen atoms. These results open the door to the design and synthesis of a new class of metal-free highly negative ions with potential for novel applications. PMID:26394536

  17. Synthesis of Conductive PPy/SiO2 Aerogels Nanocomposites by In Situ Polymerization of Pyrrole

    Directory of Open Access Journals (Sweden)

    Daliana Muller

    2015-01-01

    Full Text Available Electrical conductive nanocomposite aerogels were synthesized through in situ oxidative polymerization of pyrrole (Py using ammonium persulfate (APS as an oxidizing agent in SiO2 gels. The effect of Py concentration on the electrical conductivity and physical and morphological properties of aerogels SiO2/PPy was evaluated. B.E.T. analysis indicated that the surface area of the composite SiO2/PPy decreases with increasing concentration of Py. CHN analysis showed an increase in the amount of PPy, from 13 wt.% to 23 wt.%, with increasing concentration of pyrrole synthesis. FTIR-ATR analysis of the composites revealed bands in the region of 1500–1400 cm−1, indicating the presence of the conductive polymer in the silica aerogel as well as the characteristic bands of Si-O-Si and Si-OH covalent bonds. TEM micrographs revealed the presence of particles of PPy with the increased size of the nanoparticles. The composites were successfully applied as passive components, in RC circuits, for low-pass frequency filters. The filters exhibited a cutoff frequency at approximately 435 Hz. The aerogels obtained in this work exhibited suitable electrical conductivity for use in various other applications in electronics.

  18. Poly(1-(2-carboxyethyl)pyrrole)/polypyrrole composite nanowires for glucose biosensor

    International Nuclear Information System (INIS)

    A novel glucose biosensor based on poly(1-(2-carboxyethyl)pyrrole) (PPyCOOH)/polypyrrole (PPy) composite nanowires was developed by immobilizing glucose oxidase (GOD) on the nanowires via covalent linkages. The PPyCOOH/PPy composite nanowires were fabricated by a facile two-step electrochemical synthesis route. First, PPy nanowires were synthesized in phosphate buffer solution using organic sulfonic acid, p-toluenesulfonate acid, as soft-template. Then, PPyCOOH/PPy composite nanowires were obtained by polymerizing 1-(2-carboxyethyl)pyrrole onto PPy nanowires via electrochemical method. Scanning electron microscopic, FT-IR spectra, X-ray photoelectron spectroscopy and cyclic voltammograms were used to characterize the structural and electrical behaviors of the composite nanowires. The PPyCOOH/PPy composite nanowires exhibited uniform diameter, high reactive site (-COOH), large specific surface, excellent electroactivity and good adhesion to electrode. The glucose biosensor was constructed by covalently coupling GOD to the composite nanowires. The biosensor response was rapid (5 s), highly sensitive (33.6 μA mM−1 cm−2) with a wide linear range (up to 10.0 mM) and low detection limit (0.63 μM); it also exhibited high stability and specificity to glucose. The attractive electrochemical and structural properties of PPyCOOH/PPy composite nanowires suggested potential application for electrocatalysis and biosensor.

  19. Amyloid β oligomers in Alzheimer's disease pathogenesis, treatment, and diagnosis.

    Science.gov (United States)

    Viola, Kirsten L; Klein, William L

    2015-02-01

    Protein aggregation is common to dozens of diseases including prionoses, diabetes, Parkinson's and Alzheimer's. Over the past 15 years, there has been a paradigm shift in understanding the structural basis for these proteinopathies. Precedent for this shift has come from investigation of soluble Aβ oligomers (AβOs), toxins now widely regarded as instigating neuron damage leading to Alzheimer's dementia. Toxic AβOs accumulate in AD brain and constitute long-lived alternatives to the disease-defining Aβ fibrils deposited in amyloid plaques. Key experiments using fibril-free AβO solutions demonstrated that while Aβ is essential for memory loss, the fibrillar Aβ in amyloid deposits is not the agent. The AD-like cellular pathologies induced by AβOs suggest their impact provides a unifying mechanism for AD pathogenesis, explaining why early stage disease is specific for memory and accounting for major facets of AD neuropathology. Alternative ideas for triggering mechanisms are being actively investigated. Some research favors insertion of AβOs into membrane, while other evidence supports ligand-like accumulation at particular synapses. Over a dozen candidate toxin receptors have been proposed. AβO binding triggers a redistribution of critical synaptic proteins and induces hyperactivity in metabotropic and ionotropic glutamate receptors. This leads to Ca(2+) overload and instigates major facets of AD neuropathology, including tau hyperphosphorylation, insulin resistance, oxidative stress, and synapse loss. Because different species of AβOs have been identified, a remaining question is which oligomer is the major pathogenic culprit. The possibility has been raised that more than one species plays a role. Despite some key unknowns, the clinical relevance of AβOs has been established, and new studies are beginning to point to co-morbidities such as diabetes and hypercholesterolemia as etiological factors. Because pathogenic AβOs appear early in the disease, they

  20. One-Step Synthesis of Precursor Oligomers for Organic Photovoltaics: A Comparative Study between Polymers and Small Molecules.

    Science.gov (United States)

    Li, Wei; Wang, Daojuan; Wang, Suhao; Ma, Wei; Hedström, Svante; James, David Ian; Xu, Xiaofeng; Persson, Petter; Fabiano, Simone; Berggren, Magnus; Inganäs, Olle; Huang, Fei; Wang, Ergang

    2015-12-16

    Two series of oligomers TQ and rhodanine end-capped TQ-DR were synthesized using a facile one-step method. Their optical, electrical, and thermal properties and photovoltaic performances were systematically investigated and compared. The TQ series of oligomers were found to be amorphous, whereas the TQ-DR series are semicrystalline. For the TQ oligomers, the results obtained in solar cells show that as the chain length of the oligomers increases, an increase in power conversion efficiency (PCE) is obtained. However, when introducing 3-ethylrhodanine into the TQ oligomers as end groups, the PCE of the TQ-DR series of oligomers decreases as the chain length increases. Moreover, the TQ-DR series of oligomers give much higher performances compared to the original amorphous TQ series of oligomers owing to the improved extinction coefficient (ε) and crystallinity afforded by the rhodanine. In particular, the highly crystalline oligomer TQ5-DR, which has the shortest conjugation length shows a high hole mobility of 0.034 cm(2) V(-1) s(-1) and a high PCE of 3.14%, which is the highest efficiency out of all of the six oligomers. The structure-property correlations for all of the oligomers and the TQ1 polymer demonstrate that structural control of enhanced intermolecular interactions and crystallinity is a key for small molecules/oligomers to achieve high mobilities, which is an essential requirement for use in OPVs.

  1. Diffusivities and Viscosities of Poly(ethylene oxide) Oligomers

    KAUST Repository

    Hong, Bingbing

    2010-10-14

    Diffusivities and viscosities of poly(ethylene oxide) (PEO) oligomer melts with 1 to 12 repeat units have been obtained from equilibrium molecular dynamics simulations using the TraPPE-UA force field. The simulations generated diffusion coefficients with high accuracy for all of the molar masses studied, but the statistical uncertainties in the viscosity calculations were significantly larger for longer chains. There is good agreement of the calculated viscosities and densities with available experimental data, and thus, the simulations can be used to bridge gaps in the data and for extrapolations with respect to chain length, temperature, and pressure. We explored the convergence characteristics of the Green-Kubo formulas for different chain lengths and propose minimal production times required for convergence of the transport properties. The chain-length dependence of the transport properties suggests that neither Rouse nor reptation models are applicable in the short-chain regime investigated. © 2010 American Chemical Society.

  2. Electrochemical Detection of Clenbuterol in Pig Liver at Pyrrole-DNA Modified Boron-doped Diamond Electrode

    Institute of Scientific and Technical Information of China (English)

    WU Jing; LI Xiao-li; WU Xu-mei; HUAN Shuang-yan; SHEN Guo-li; YU Ru-qin

    2005-01-01

    The direct detection of clenbuterol(CL) in pig liver without any extraction separation at a pyrrole-DNA modified boron-doped diamond(BDD) electrode is reported. The pyrrole-DNA modified BDD electrode has a strong electrocatalytic effect on the redox reaction of CL. One oxidization and two reduction peaks of CL appear at 340.2, 299.8 and 166.6 mV(versus SCE), respectively. The pyrrole polymer alone cannot electrocatalyze the above reaction at a BDD electrode; the electrocatalytic effect of a BDD electrode modified with DNA membrane is unsufficient for the analytical detection of CL; the replacement of boron-doped diamond by glass carbon makes the electrocatalytic reaction impossible; the redox process is pH dependent. The influences of various experimental parameters on the pyrrole-DNA modified BDD electrode were investigated. A sensitive cyclic voltammetric response for CL was obtained in a linear range from 3.4×10-6 to 5×10-4 mol/L with a detection limit of 8.5×10-7 mol/L. A mean recovery of 102.7% of CL in the pig liver sample solution and a reproducibility of 3.2% were obtained.

  3. Tetraaryl-, Pentaaryl-, and Hexaaryl-1,4-dihydropyrrolo 3,2-b pyrroles: Synthesis and Optical Properties

    DEFF Research Database (Denmark)

    Krzeszewski, M.; Thorsted, B.; Brewer, J.;

    2014-01-01

    Efficient conditions for the synthesis of tetra-, penta-, and hexasubstituted derivatives of 1,4-dihydropyrrolo[3,2-b]pyrrole were developed. The tetraaryl derivatives were obtained in a novel one-pot reaction among aromatic aldehydes, aromatic amines, and butane-2,3-dione. After a thorough exami...

  4. Pseudocapacitive Electrodes Produced by Oxidant-Free Polymerization of Pyrrole between the Layers of 2D Titanium Carbide (MXene).

    Science.gov (United States)

    Boota, Muhammad; Anasori, Babak; Voigt, Cooper; Zhao, Meng-Qiang; Barsoum, Michel W; Gogotsi, Yury

    2016-02-17

    Heterocyclic pyrrole molecules are in situ aligned and polymerized in the -absence of an oxidant between layers of the 2D Ti3C2Tx (MXene), resulting in high volumetric and gravimetric capacitances with capacitance retention of 92% after 25,000 cycles at a 100 mV s(-1) scan rate.

  5. Characteristics of Amyloid-Related Oligomers Revealed by Crystal Structures of Macrocyclic [beta]-Sheet Mimics

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Cong; Sawaya, Michael R.; Cheng, Pin-Nan; Zheng, Jing; Nowick, James S.; Eisenberg, David (UCI); (UCLA)

    2011-09-20

    Protein amyloid oligomers have been strongly linked to amyloid diseases and can be intermediates to amyloid fibers. {beta}-Sheets have been identified in amyloid oligomers. However, because of their transient and highly polymorphic properties, the details of their self-association remain elusive. Here we explore oligomer structure using a model system: macrocyclic peptides. Key amyloidogenic sequences from A{beta} and tau were incorporated into macrocycles, thereby restraining them to {beta}-strands, but limiting the growth of the oligomers so they may crystallize and cannot fibrillate. We determined the atomic structures for four such oligomers, and all four reveal tetrameric interfaces in which {beta}-sheet dimers pair together by highly complementary, dry interfaces, analogous to steric zippers found in fibers, suggesting a common structure for amyloid oligomers and fibers. In amyloid fibers, the axes of the paired sheets are either parallel or antiparallel, whereas the oligomeric interfaces display a variety of sheet-to-sheet pairing angles, offering a structural explanation for the heterogeneity of amyloid oligomers.

  6. SYNTHESIS, CHARACTERIZATION AND RING-OPENING POLYMERIZATION OF CYCLIC (ARYLENE PHOSPHONATE) OLIGOMERS

    Institute of Scientific and Technical Information of China (English)

    Hong-ming Zhang; Qing-zhong Guo; Tian-lu Chen

    2004-01-01

    A series of cyclic (arylene phosphonate) oligomers were prepared by reaction of phenylphosphonic dichloride (PPD) with various bisphenols under pseudo-high dilution conditions via interfacial polycondensation. The yield of cyclic (arylenc phosphonate) oligomers is over 85% by using hexadecyltrimethylammonium bromide as phase transfer catalyst (PTC) at 0 ℃. The structures of the cyclic oligomers were confirmed by a combination of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and IR analysis. These cyclic oligomers undergo facile ring-opening polymerization in the melt by using potassium 4,4'-biphenoxide as the initiator to give linear polyphosphonate. Free-radical ring-opening polymerization of cyclic(arylene phosphonate) oligomers containing sulfur linkages was also performed in the melt using 2,2'-dithiobis(benzothiazole) (DTB) as the initiator at 270℃ and the resulting polymer had a Mw of 8 × 103 with a molecular weight distribution of 4. Ring-opening copolymerization of these cyclic oligomers with cyclic carbonate oligomers was also achieved. The average molecular weight of the resulting copolymer is higher than the corresponding homopolymer and the thermal stability of the copolymer is better than the corresponding homopolymer.

  7. Conformational stability of fibrillar amyloid-beta oligomers via protofilament pair formation - a systematic computational study.

    Directory of Open Access Journals (Sweden)

    Anna Kahler

    Full Text Available Amyloid-[Formula: see text] (A[Formula: see text] oligomers play a crucial role in Alzheimer's disease due to their neurotoxic aggregation properties. Fibrillar A[Formula: see text] oligomerization can lead to protofilaments and protofilament pairs via oligomer elongation and oligomer association, respectively. Small fibrillar oligomers adopt the protofilament topology, whereas fibrils contain at least protofilament pairs. To date, the underlying growth mechanism from oligomers to the mature fibril still remains to be elucidated. Here, we performed all-atom molecular dynamics simulations in explicit solvent on single layer-like protofilaments and fibril-like protofilament pairs of different size ranging from the tetramer to the 48-mer. We found that the initial U-shaped topology per monomer is maintained over time in all oligomers. The observed deviations of protofilaments from the starting structure increase significantly with size due to the twisting of the in-register parallel [Formula: see text]-sheets. This twist causes long protofilaments to be unstable and leads to a breakage. Protofilament pairs, which are stabilized by a hydrophobic interface, exhibit more fibril-like properties such as the overall structure and the twist angle. Thus, they can act as stable conformational templates for further fibril growth. Key properties like the twist angle, shape complementarity, and energetics show a size-dependent behavior so that small oligomers favor the protofilament topology, whereas large oligomers favor the protofilament pair topology. The region for this conformational transition is at the size of approximately twelve A[Formula: see text] monomers. From that, we propose the following growth mechanism from A[Formula: see text] oligomers to fibrils: (1 elongation of short protofilaments; (2 breakage of large protofilaments; (3 formation of short protofilament pairs; and (4 elongation of protofilament pairs.

  8. Conformational stability of fibrillar amyloid-beta oligomers via protofilament pair formation - a systematic computational study.

    Science.gov (United States)

    Kahler, Anna; Sticht, Heinrich; Horn, Anselm H C

    2013-01-01

    Amyloid-[Formula: see text] (A[Formula: see text]) oligomers play a crucial role in Alzheimer's disease due to their neurotoxic aggregation properties. Fibrillar A[Formula: see text] oligomerization can lead to protofilaments and protofilament pairs via oligomer elongation and oligomer association, respectively. Small fibrillar oligomers adopt the protofilament topology, whereas fibrils contain at least protofilament pairs. To date, the underlying growth mechanism from oligomers to the mature fibril still remains to be elucidated. Here, we performed all-atom molecular dynamics simulations in explicit solvent on single layer-like protofilaments and fibril-like protofilament pairs of different size ranging from the tetramer to the 48-mer. We found that the initial U-shaped topology per monomer is maintained over time in all oligomers. The observed deviations of protofilaments from the starting structure increase significantly with size due to the twisting of the in-register parallel [Formula: see text]-sheets. This twist causes long protofilaments to be unstable and leads to a breakage. Protofilament pairs, which are stabilized by a hydrophobic interface, exhibit more fibril-like properties such as the overall structure and the twist angle. Thus, they can act as stable conformational templates for further fibril growth. Key properties like the twist angle, shape complementarity, and energetics show a size-dependent behavior so that small oligomers favor the protofilament topology, whereas large oligomers favor the protofilament pair topology. The region for this conformational transition is at the size of approximately twelve A[Formula: see text] monomers. From that, we propose the following growth mechanism from A[Formula: see text] oligomers to fibrils: (1) elongation of short protofilaments; (2) breakage of large protofilaments; (3) formation of short protofilament pairs; and (4) elongation of protofilament pairs.

  9. Modelling Ser129 phosphorylation inhibits membrane binding of pore-forming alpha-synuclein oligomers.

    Directory of Open Access Journals (Sweden)

    Georg Sebastian Nübling

    Full Text Available BACKGROUND: In several neurodegenerative diseases, hyperphosphorylation at position Ser129 is found in fibrillar deposits of alpha-synuclein (asyn, implying a pathophysiological role of asyn phosphorylation in neurodegeneration. However, recent animal models applying asyn phosphorylation mimics demonstrated a protective effect of phosphorylation. Since metal-ion induced asyn oligomers were identified as a potential neurotoxic aggregate species with membrane pore-forming abilities, the current study was undertaken to determine effects of asyn phosphorylation on oligomer membrane binding. METHODS: We investigated the influence of S129 phosphorylation on interactions of metal-ion induced asyn oligomers with small unilamellar lipid vesicles (SUV composed of POPC and DPPC applying the phosphorylation mimic asyn129E. Confocal single-particle fluorescence techniques were used to monitor membrane binding at the single-particle level. RESULTS: Binding of asyn129E monomers to gel-state membranes (DPPC-SUV is slightly reduced compared to wild-type asyn, while no interactions with membranes in the liquid-crystalline state (POPC-SUV are seen for both asyn and asyn129E. Conversely, metal-ion induced oligomer formation is markedly increased in asyn129E. Surprisingly, membrane binding to POPC-SUV is nearly absent in Fe(3+ induced asyn129E oligomers and markedly reduced in Al(3+ induced oligomers. CONCLUSION: The protective effect of pseudophosphorylation seen in animal models may be due to impeded oligomer membrane binding. Phosphorylation at Ser129 may thus have a protective effect against neurotoxic asyn oligomers by preventing oligomer membrane binding and disruption of the cellular electrophysiological equilibrium. Importantly, these findings put a new complexion on experimental pharmaceutical interventions against POLO-2 kinase.

  10. Electrochemical and optical properties of biphenyl bridged-dicarbazole oligomer films: Electropolymerization and electrochromism

    Energy Technology Data Exchange (ETDEWEB)

    Koyuncu, Sermet [Department of Chemistry, Faculty of Sciences and Arts, Canakkale Onsekiz Mart University, 17020 Canakkale (Turkey); Can Vocational School, Canakkale Onsekiz Mart University, 17400 Canakkale (Turkey)], E-mail: sermetkoyuncu@hotmail.com; Gultekin, Burak [Solar Energy Institute, Ege University, 35100 Bornova, Izmir (Turkey); Zafer, Ceylan [Solar Energy Institute, Ege University, 35100 Bornova, Izmir (Turkey)], E-mail: ceylan.zafer@ege.edu.tr; Bilgili, Hakan; Can, Mustafa; Demic, Serafettin [Solar Energy Institute, Ege University, 35100 Bornova, Izmir (Turkey); Kaya, Ismet [Department of Chemistry, Faculty of Sciences and Arts, Canakkale Onsekiz Mart University, 17020 Canakkale (Turkey); Icli, Siddik [Solar Energy Institute, Ege University, 35100 Bornova, Izmir (Turkey)

    2009-10-01

    4,4'-Di(N-carbazoyl)biphenyl monomer (CBP) was synthesized and coated onto ITO-glass surface by electrochemical oxidative polymerization. Its CV shows two distinct one-electron and stepwise oxidation processes occurred at 1.29 and 1.61 V. By using this property, the monomer was electrochemically polymerized separately at these oxidation states and thus, two different oligomer films were obtained afterwards. Their spectro-electrochemical and electrochromic properties were also investigated. Switching ability of the oligomers was evaluated by kinetic studies upon measuring the percent transmittance (%T) at their maximum contrast point, indicating that these oligomers were found to be suitable material for electrochromic devices.

  11. Ruthenium(II)-catalyzed synthesis of pyrrole- and indole-fused isocoumarins by C-H bond activation in DMF and water

    Digital Repository Service at National Institute of Oceanography (India)

    Singh, K.S.; Sawant, S.G.; Dixneuf, P.H.

    : ChemCatChem, vol.8(6); 2016; 1046-1050 Ruthenium(II) catalysed synthesis of pyrrole and indole fused isocoumarins via C-H bond activation in DMF and water† Keisham S. Singh*,a Sneha G. Sawanta, Pierre H. Dixneuf*,b Abstract: Pyrrole and indole... isocoumarins from simple 1-methyl pyrrole-2- carboxylic acid and 1-methylindole-3-carboxylic acid via annulation with alkyne in the presence ruthenium(II) catalyst based on [RuCl2(p-cymene)]2 and Cu(OAc)2.H2O as oxidant in DMF. This ruthenium(II) catalysed...

  12. Outer-Sphere Mechanism in the Oxidation of Pyrrole-2- Carboxaldehyde by Hexacyanoferrate (III Complex.

    Directory of Open Access Journals (Sweden)

    Abd-Alhakeem H. Abu-Nawwas

    2014-01-01

    Full Text Available The kinetics and mechanism of base-catalyzed oxidation of pyrrole-2-carboxaldehyde with hexacyanoferrate (III is reported. The reaction showed first order with respect to aldahyde , alkali and hexaeyanoferrate(III. The kinetic data suggest that the oxidation involves the formation of an anion of the substrate undergoes oxidation with hexaeyanoferrate(III via outer sphere mechanism process. The free radical thus produced is further oxidized to form the final products. A suitable mechanism was proposed and rate law was derived as − d[Fe CN 6 ] 3− = 2k1k2 RC(OH2 [Fe CN 6 ] 3−[OH−] k−1 H2O

  13. -pyrrole substituted porphyrin-pyrene dyads using vinylene spacer: Synthesis, characterization and photophysical properties

    Indian Academy of Sciences (India)

    P Silviya Reeta; Ravi Kumar Kanaparthi; L Giribabu

    2013-03-01

    We have designed and synthesized donor-acceptor conjugates having donor pyrene at the pyrrole- position of either free-base porphyrin or Zn(II) porphyrin using vinylene spacer. Both the dyads have been completely characterized by elemental analysis,MALDI-MS, UV-Vis., and fluorescence (steady state and timeresolved) spectroscopies as well as cyclic voltammetry. The absorption maxima of both dyads are red-shifted by 8-12 nm. The ground state properties showed that there exist minimum - interaction between the aromatic subunits of these D-A systems. Quenched emission was observed in both the dyads when excited at 290 nm. The quenched emission explained in terms of intramolecular excitation energy transfer competes with the photo-induced electron transfer reaction in these D-A system.

  14. ELECTRICALLY CONDUCTIVE COMPOSITE PREPARED BY ELECTROCHEMICAL POLYMERIZATION OF PYRROLE IN POLY- (p- PHENYLENE TEREPHTHALAMIDE ) MATRIX

    Institute of Scientific and Technical Information of China (English)

    BI Xiantong; PEI Qibing; HAN Baozhen; BAO Jingshen

    1991-01-01

    The preparation of PPy/PPTA conductive composite films by electrochemical method is presented.The first step is to cast a thin layer of poly (p-phenylene-terephthalamide)(PPTA)on a slice of Pt working electrode. The second step is to electrochemically polymerize pyrrole on the PPTA/Pt working electrode. Both of the electrical conductivity and the mechanical properties of the PPy/PPTA composite film are better than those of the pure PPy film, and the film has excellent flexibility at low temperature, even in liquid nitrogen.The SEM picture of the cross-section of PPy/PPTA composite film showed that the two components were well mixed.Cyclic voltammograms of PPy/PPTA film in aqueous solution showed that the conductive films could be reduced and reoxidized.

  15. A novel quinoxaline bearing electroactive monomer: Pyrrole as the donor moiety

    Energy Technology Data Exchange (ETDEWEB)

    Taskin, Asli Tuba; Balan, Abidin; Epik, Bugra; Yildiz, Ersin [Middle East Technical University, Department of Chemistry, 06531, Ankara (Turkey); Udum, Yasemin Arslan [Gazi University, Institute of Science and Technology, Department of Advanced Technologies, 06570, Ankara (Turkey); Toppare, Levent [Middle East Technical University, Department of Chemistry, 06531, Ankara (Turkey)], E-mail: toppare@metu.edu.tr

    2009-09-30

    A novel electroactive monomer 5,8-di(1H-pyrrol-2-yl)-2,3-di(thiophen-2-yl)quinoxaline (PTQ) was successfully synthesized and its electrochromic properties were reported. Nuclear magnetic resonance ({sup 1}H NMR-{sup 13}C NMR) and mass spectroscopy were used to characterize the monomer. The monomer was electrochemically polymerized in the presence of tetrabutylammonium perchlorate (TBAP) as supporting electrolyte in dichloromethane. Monomer reveals relatively low oxidation potential at +0.70 V. Spectroelectrochemical behaviors and switching ability of homopolymer were investigated by UV-vis spectroscopy and cyclic voltammetry. Two {pi}-{pi}* transitions were observed at 400 and 815 nm with a low band gap, 1.0 eV. Polymer possesses 66% optical contrast in the Near IR region, which may be promising in NIR electrochromic device applications.

  16. Theoretical Study on Measure of Hydrogen Bonding Strength: R-C≡N…pyrrole Complexes

    Institute of Scientific and Technical Information of China (English)

    史福强; 安静仪; 俞稼镛

    2005-01-01

    The R-C≡N…pyrrole (R=H, CH3, CH2F, CHF2, CF3, NH2, BH2, OH, F, CH2Cl, CHCl2, CCl3, Li, Na) complexes were considered as the simple sample for measure of hydrogen bonding strength. Density functional theory B3LYP/6-311 + + G** level was applied to the optimization of geometries of complexes and monomers. Measure of hydrogen bonding strength based on geometrical and topological parameters, which were derived from the AIM theory, was analyzed. Additionally, natural bond orbital (NBO) analysis and frequency calculations were performed.From the computation results it was found that the electronic density at N-H bond critical points was also strictly correlated with the hydrogen bonding strength.

  17. Crystal structure of 1-benzyl-4-formyl-1H-pyrrole-3-carb-oxamide.

    Science.gov (United States)

    Zhong, Qi-Di; Hu, Sheng-Quan; Yan, Hong

    2016-02-01

    In the title compound, C13H12N2O2 (I), the mean planes of the pyrrole and benzyl rings are approximately perpendicular, forming a dihedral angle of 87.07 (4) °. There is an intra-molecular N-H⋯O hydrogen bond forming an S(7) ring motif. In the crystal, mol-ecules are linked via a pair of N-H⋯O hydrogen bonds forming inversion dimers. C-H⋯O hydrogen bonds link the dimers into chains along direction [10-1]. The chains are further linked by weak C-H⋯π inter-actions forming layers parallel to the ac plane. PMID:26958371

  18. Tumor Repression of VCaP Xenografts by a Pyrrole-Imidazole Polyamide.

    Directory of Open Access Journals (Sweden)

    Amanda E Hargrove

    Full Text Available Pyrrole-imidazole (Py-Im polyamides are high affinity DNA-binding small molecules that can inhibit protein-DNA interactions. In VCaP cells, a human prostate cancer cell line overexpressing both AR and the TMPRSS2-ERG gene fusion, an androgen response element (ARE-targeted Py-Im polyamide significantly downregulates AR driven gene expression. Polyamide exposure to VCaP cells reduced proliferation without causing DNA damage. Py-Im polyamide treatment also reduced tumor growth in a VCaP mouse xenograft model. In addition to the effects on AR regulated transcription, RNA-seq analysis revealed inhibition of topoisomerase-DNA binding as a potential mechanism that contributes to the antitumor effects of polyamides in cell culture and in xenografts. These studies support the therapeutic potential of Py-Im polyamides to target multiple aspects of transcriptional regulation in prostate cancers without genotoxic stress.

  19. A novel quinoxaline bearing electroactive monomer: Pyrrole as the donor moiety

    International Nuclear Information System (INIS)

    A novel electroactive monomer 5,8-di(1H-pyrrol-2-yl)-2,3-di(thiophen-2-yl)quinoxaline (PTQ) was successfully synthesized and its electrochromic properties were reported. Nuclear magnetic resonance (1H NMR-13C NMR) and mass spectroscopy were used to characterize the monomer. The monomer was electrochemically polymerized in the presence of tetrabutylammonium perchlorate (TBAP) as supporting electrolyte in dichloromethane. Monomer reveals relatively low oxidation potential at +0.70 V. Spectroelectrochemical behaviors and switching ability of homopolymer were investigated by UV-vis spectroscopy and cyclic voltammetry. Two π-π* transitions were observed at 400 and 815 nm with a low band gap, 1.0 eV. Polymer possesses 66% optical contrast in the Near IR region, which may be promising in NIR electrochromic device applications.

  20. State-specific tunneling lifetimes from classical trajectories: H-atom dissociation in electronically excited pyrrole

    Science.gov (United States)

    Xie, Weiwei; Domcke, Wolfgang; Farantos, Stavros C.; Grebenshchikov, Sergy Yu.

    2016-03-01

    A trajectory method of calculating tunneling probabilities from phase integrals along straight line tunneling paths, originally suggested by Makri and Miller [J. Chem. Phys. 91, 4026 (1989)] and recently implemented by Truhlar and co-workers [Chem. Sci. 5, 2091 (2014)], is tested for one- and two-dimensional ab initio based potentials describing hydrogen dissociation in the 1B1 excited electronic state of pyrrole. The primary observables are the tunneling rates in a progression of bending vibrational states lying below the dissociation barrier and their isotope dependences. Several initial ensembles of classical trajectories have been considered, corresponding to the quasiclassical and the quantum mechanical samplings of the initial conditions. It is found that the sampling based on the fixed energy Wigner density gives the best agreement with the quantum mechanical dissociation rates.

  1. Use of solvent to regulate the degree of polymerisation in weakly associated supramolecular oligomers

    DEFF Research Database (Denmark)

    Bähring, Steffen; Kim, D. S.; Duedal, T.;

    2014-01-01

    Using a tetrathiafulvalene functionalised calix[4] pyrrole (TTF-C[4]P; 1) and alkyl diester-linked bis-dinitrophenols (2-4), it was found that the solvent polarity and linker length have an effect on the molecular aggregation behaviour. 2D H-1 NOESY, DOSY NMR and UV-vis-NIR spectroscopic studies,...

  2. Gamma irradiation effect on polymers derived of pyrrole synthesized by plasma

    International Nuclear Information System (INIS)

    This work studies the effect of gamma irradiation at doses of 50, 100, 200, 400 and 800 kGy on polymers obtained from pyrrole synthesized by plasma. The evolution of the structure was studied by Fourier transform infrared spectroscopy (Ftir) and X-ray photoelectron spectroscopy (XPS). The Ftir spectra show that poly pyrroles have N-H, C-H, C=O, triple and consecutive double bonds in their structure. The irradiated polymers show the same chemical groups in their structure without significant changes. Nevertheless, a more detailed analysis by XPS allows the identification of superficial chemical states, such as: C=CH-C, C=CC-C, C-NH-C, C-NC-C, etc., and shows that most of these states are present in all polymers but with different participation. One possible mechanism indicates that as the irradiation dose increases, dehydrogenation processes are performed increasing fragmentation, crosslinking and formation of multiple bonds. The fragmentation and thermal degradation were studied by thermogravimetric analysis, indicating that the loss of moisture and light compounds formed during gamma irradiation occurs in the firsts 100 grades C. The main degradation of all polymers occurs from 150 to 700 grades C, suggesting that the thermal stability is independent of the irradiation dose in the interval studied. Morphology was studied using scanning electron microscopy techniques. Before irradiation, the polymer presented a uniform and practically smooth surface, however, after gamma irradiation, the applied energy increased roughness and macro fragmentation. The roughness and functional groups on the surface reduced the contact angle with water as the irradiation dose increased. However, the polymers are hydrophilic, because for all doses that contact angle is smaller than 90 grades C. Electrical conductivity was calculated respect to temperature in the interval from 25 to 100 grades C. Conductivity increases with temperature and is slightly greater in the irradiated polymers

  3. Aggregation behavior and electrical properties of amphiphilic pyrrole-tailed ionic liquids in water, from the viewpoint of dielectric relaxation spectroscopy.

    Science.gov (United States)

    Fan, Xiaoqing; Zhao, Kongshuang

    2014-05-14

    The self-aggregation behavior of amphiphilic pyrrole-tailed imidazolium ionic liquids (Py(CH₂)₁₂mim⁺Br⁻: Py = pyrrole, mim = methylimidazolium) in water is investigated by dielectric spectroscopy from 40 Hz to 110 MHz. Dielectric determination shows that the critical micelle concentration (CMC) is 8.5 mM, which is lower than that for traditional ionic surfactants. The thermodynamic parameter of the micellization, the Gibbs free energy ΔG, was calculated for Py(CH₂)₁₂mim⁺Br⁻ and compared to those of the corresponding C(n)mim⁺Br⁻ (n = 12, 14). It was found that the main driven forces of the Py(CH₂)₁₂mim⁺Br⁻ aggregation were hydrophobic interaction and π-π interactions among the adjacent Py groups. Further, the structure of aggregation was speculated theoretically that Py groups partially insert into the alkyl chains and the staggered arrangement in micelles is formed. When the concentration of Py(CH₂)₁₂mim⁺Br⁻ is higher than CMC, two remarkable relaxations which originated from diffusion of counterions and interfacial polarization between the micelles and solution, were observed at about 1.3 MHz and 55 MHz. The relaxation parameters representing the real properties of the whole system were obtained by fitting the experimental data with Cole-Cole equation. A dielectric model characterizing the structure and electrical properties of spherical micelles was proposed by which the conductivity, permittivity and the volume fraction of micelles as well as electrical properties of solution were calculated from the relaxation parameters. An intriguingly high permittivity of about 150 for the micelle was found to be a direct consequence of the strong orientational order of water molecules inside the core of micelle, and essentially is attributed to the special structure of the micelle. Furthermore, the calculation of the interfacial electrokinetic parameters of the micelles, i.e., the surface conductivity, surface charge density

  4. Effective models for charge transport in DNA nanowires

    OpenAIRE

    Gutierrez, Rafael; Cuniberti, Gianaurelio

    2006-01-01

    The rapid progress in the field of molecular electronics has led to an increasing interest on DNA oligomers as possible components of electronic circuits at the nanoscale. For this, however, an understanding of charge transfer and transport mechanisms in this molecule is required. Experiments show that a large number of factors may influence the electronic properties of DNA. Though full first principle approaches are the ideal tool for a theoretical characterization of the structural and elec...

  5. Transient dichroism in photoreceptor membranes indicates that stable oligomers of rhodopsin do not form during excitation.

    OpenAIRE

    Downer, N W; Cone, R A

    1985-01-01

    If a photoexcited rhodopsin molecule initiates the formation of rhodopsin oligomers during the process of visual excitation, the rate of rotational diffusion of the rhodopsin molecules involved should change markedly. Using microsecond-flash photometry, we have observed the rotational diffusion of rhodopsin throughout the time period of visual excitation and found that no detectable change occurs in its rotational diffusion rate. Partial chemical cross-linking of the retina yields oligomers o...

  6. Instability of a Class A G Protein-Coupled Receptor Oligomer Interface

    OpenAIRE

    Fonseca, Jacqueline M.; Lambert, Nevin A.

    2009-01-01

    The quaternary structure of G protein-coupled receptors (GPCRs) can influence their trafficking and ability to transduce signals. GPCR oligomers are generally portrayed as long-lived entities, although the stability of these complexes has not been studied. Here we show that D2 dopamine receptor protomers interact transiently at a specific oligomer interface. Selective immobilization of cyan fluorescent protein-D2 receptors (C-D2Rs) in the plasma membrane failed to comp...

  7. Effect of alkyl substituents on the adsorption of thienylenevinylene oligomers on the Si (100) surface

    CERN Document Server

    Grandidier, Bruno; Stiévenard, Didier; Krzeminski, Christophe; Delerue, Christophe; Frere, Pierre; Blanchard, Phillippe; Roncali, Jean; 10.1016/S0039-6028(00)00946-8

    2012-01-01

    The adsorption of thienylenevinylene oligomers on the Si(100) surface has been investigated using scanning tunneling microscopy. The mode of substitution of the thiophene ring exerts a strong influence on the adsorption configurations and the images of the oligomer based on 3,4-dihexyl thiophene are highly voltage dependent. We discuss the influence of the alkyl chains on the adsorption process and on the appearance of the molecules in the STM images.

  8. Biofunctionalized Silica Nanoparticles: Standards in Amyloid-β Oligomer-Based Diagnosis of Alzheimer's Disease.

    Science.gov (United States)

    Hülsemann, Maren; Zafiu, Christian; Kühbach, Katja; Lühmann, Nicole; Herrmann, Yvonne; Peters, Luriano; Linnartz, Christina; Willbold, Johannes; Kravchenko, Kateryna; Kulawik, Andreas; Willbold, Sabine; Bannach, Oliver; Willbold, Dieter

    2016-07-27

    Amyloid-β (Aβ) oligomers represent a promising biomarker for the early diagnosis of Alzheimer's disease (AD). However, state-of-the-art methods for immunodetection of Aβ oligomers in body fluids show a large variability and lack a reliable and stable standard that enables the reproducible quantitation of Aβ oligomers. At present, the only available standard applied in these assays is based on a random aggregation process of synthetic Aβ and has neither a defined size nor a known number of epitopes. In this report, we generated a highly stable standard in the size range of native Aβ oligomers that exposes a defined number of epitopes. The standard consists of a silica nanoparticle (SiNaP), which is functionalized with Aβ peptides on its surface (Aβ-SiNaP). The different steps of Aβ-SiNaP synthesis were followed by microscopic, spectroscopic and biochemical analyses. To investigate the performance of Aβ-SiNaPs as an appropriate standard in Aβ oligomer immunodetection, Aβ-SiNaPs were diluted in cerebrospinal fluid and quantified down to a concentration of 10 fM in the sFIDA (surface-based fluorescence intensity distribution analysis) assay. This detection limit corresponds to an Aβ concentration of 1.9 ng l-1 and lies in the sensitivity range of currently applied diagnostic tools based on Aβ oligomer quantitation. Thus, we developed a highly stable and well-characterized standard for the application in Aβ oligomer immunodetection assays that finally allows the reproducible quantitation of Aβ oligomers down to single molecule level and provides a fundamental improvement for the worldwide standardization process of diagnostic methods in AD research. PMID:27472876

  9. Cellulose oligomers production and separation for the synthesis of new fully bio-based amphiphilic compounds.

    Science.gov (United States)

    Billès, Elise; Onwukamike, Kelechukwu N; Coma, Véronique; Grelier, Stéphane; Peruch, Frédéric

    2016-12-10

    Cellulose oligomers are water-soluble, on the contrary to cellulose, which greatly increase their application range. In this study, cellulose oligomers were obtained from the acidic hydrolysis of cellulose with phosphoric acid. The global yield in water-soluble oligomers was around 23% with polymerization degree (DP) ranging from 1 to 12. The cellulose oligomers DP distribution was successfully reduced by differential solubilisation in methanol as one of the goals of this work was to avoid the use of a time-consuming full chromatographic separation. The methanol-soluble oligomers were mainly low DP (≤3). The oligomers of higher molar mass, composed of 42% of cellotetraose and 36% of cellopentaose, were then functionalized and coupled with stearic acid through azide-alkyne click chemistry to obtain amphiphilic compounds. The self-assembly of these new bio-based compounds was finally investigated by dynamic light scattering (DLS) and transmission electron microscopy (TEM) and their critical micellar concentration (CMC) was found to be in the same range as alkylmaltosides and alkylglucosides. PMID:27577903

  10. Synthesis and Characterization of Poly (Arylene Ether Benzimidazole) Oligomers

    Science.gov (United States)

    Leonard, Michael J.

    1995-01-01

    Several poly(arylene ether benzimidazole) oligomers were prepared by the nucleophilic aromatic substitution reaction of a bisphenol benzimidazole and various alkyl-substituted aromatic bisphenols with an activated aromatic dihalide in N, N-dimethylacetarnide. Moderate to high molecular weight terpolymers were obtained in all cases, as shown by their inherent viscosities, which ranged from 0.50 to 0.87 dL g(sup -1). Glass transition temperatures (T(sub g)s) of polymer powders ranged from 267-280 C. Air-dried unoriented thin film T(sub g)s were markedly lower than those of the powders, whereas T(sub g)s of films dried in a nitrogen atmosphere were identical to those of the corresponding powders. In addition, air-dried films were dark amber and brittle, whereas nitrogen-dried films were yellow and creasable. Nitrogen-dried films showed slightly higher thin-film tensile properties than the air-dried films, as well.

  11. Supercritical fluid assisted production of chitosan oligomers micrometric powders.

    Science.gov (United States)

    Du, Zhe; Shen, Yu-Bin; Tang, Chuan; Guan, Yi-Xin; Yao, Shan-Jing; Zhu, Zi-Qiang

    2014-02-15

    Chitosan oligomers (O-chitosan) micrometric particles were produced from aqueous solution using a novel process, i.e. supercritical fluid assisted atomization introduced by hydrodynamic cavitation mixer (SAA-HCM). Hydrodynamic cavitation was introduced to enhance mass transfer and facilitate the mixing between SC-CO2 and liquid solution for fine particles formation. Well defined, separated and spherical microparticles were obtained, and the particles size could be well controlled with narrow distribution ranging from 0.5 μm to 3 μm. XRD patterns showed amorphous structure of O-chitosan microparticles. FTIR, TGA and DSC analyses confirmed that no change in molecular structure and thermal stability after SAA-HCM processing, while the water content was between 5.8% and 8.4%. Finally, tap densities were determined to be below 0.45 g/cm(3) indicating hollow or porous structures of microparticles. By tuning process parameters, theoretical mass median aerodynamic sizes lied inside respirable range of 1-2 μm, which presented the potential of the O-chitosan microparticles in application as inhaled dry powders. SAA-HCM was demonstrated to be very useful in particle size engineering. PMID:24507297

  12. Mapping eGFP Oligomer Mobility in Living Cell Nuclei

    Science.gov (United States)

    Zwerger, Monika; Müller, Gabriele; Waldeck, Waldemar; Langowski, Jörg

    2009-01-01

    Movement of particles in cell nuclei can be affected by viscosity, directed flows, active transport, or the presence of obstacles such as the chromatin network. Here we investigate whether the mobility of small fluorescent proteins is affected by the chromatin density. Diffusion of inert fluorescent proteins was studied in living cell nuclei using fluorescence correlation spectroscopy (FCS) with a two-color confocal scanning detection system. We first present experiments exposing FCS-specific artifacts encountered in live cell studies as well as strategies to prevent them, in particular those arising from the choice of the fluorophore used for calibration of the focal volume, as well as temperature and acquisition conditions used for fluorescence fluctuation measurements. After defining the best acquisition conditions, we show for various human cell lines that the mobility of GFP varies significantly within the cell nucleus, but does not correlate with chromatin density. The intranuclear diffusional mobility strongly depends on protein size: in a series of GFP-oligomers, used as free inert fluorescent tracers, the diffusion coefficient decreased from the monomer to the tetramer much more than expected for molecules free in aqueous solution. Still, the entire intranuclear chromatin network is freely accessible for small proteins up to the size of eGFP-tetramers, regardless of the chromatin density or cell line. Even the densest chromatin regions do not exclude free eGFP-monomers or multimers. PMID:19347038

  13. Mapping eGFP oligomer mobility in living cell nuclei.

    Directory of Open Access Journals (Sweden)

    Nicolas Dross

    Full Text Available Movement of particles in cell nuclei can be affected by viscosity, directed flows, active transport, or the presence of obstacles such as the chromatin network. Here we investigate whether the mobility of small fluorescent proteins is affected by the chromatin density. Diffusion of inert fluorescent proteins was studied in living cell nuclei using fluorescence correlation spectroscopy (FCS with a two-color confocal scanning detection system. We first present experiments exposing FCS-specific artifacts encountered in live cell studies as well as strategies to prevent them, in particular those arising from the choice of the fluorophore used for calibration of the focal volume, as well as temperature and acquisition conditions used for fluorescence fluctuation measurements. After defining the best acquisition conditions, we show for various human cell lines that the mobility of GFP varies significantly within the cell nucleus, but does not correlate with chromatin density. The intranuclear diffusional mobility strongly depends on protein size: in a series of GFP-oligomers, used as free inert fluorescent tracers, the diffusion coefficient decreased from the monomer to the tetramer much more than expected for molecules free in aqueous solution. Still, the entire intranuclear chromatin network is freely accessible for small proteins up to the size of eGFP-tetramers, regardless of the chromatin density or cell line. Even the densest chromatin regions do not exclude free eGFP-monomers or multimers.

  14. Zur Reaktion von Pyroglutaminsäure-Derivaten mit Phosphorpentachlorid - Darstellung chlorierter Pyrrol-2-carbonsäure-Derivate (Aminosäuren ; 9)

    OpenAIRE

    Effenberger, Franz; Müller, Wolfgang; Isak, Heinz

    1987-01-01

    N-Benzyl-5-oxoprolinester 5 werden mit PCl5 über verschiedene chlorierte Zwischenstufen zu N-Benzyl-4,5-dichlor-1H-pyrrol-2-carbonsäureestern 6 chloriert, während N-Benzhydryl- L-3 und N-Acyl-5-oxoprolinester L-4 mit PCl5 unter Abspaltung des N-Substituenten L-4,4,5-Trichlor-3,4-dihydro-2H-pyrrol-2-carbon-säureester 18 bilden, die mit Base in die 4,5-Dichlor-1H-pyrrol-2-carbonsäureester 20 übergehen. Diese Umsetzungen stellen die beste Methode zur Herstellung von 4,5-Dichlor-1H-pyrrol-2-carbo...

  15. Nanoscale structure, dynamics and power conversion efficiency correlations in small molecule and oligomer-based photovoltaic devices.

    Science.gov (United States)

    Szarko, Jodi M; Guo, Jianchang; Rolczynski, Brian S; Chen, Lin X

    2011-01-01

    Photovoltaic functions in organic materials are intimately connected to interfacial morphologies of molecular packing in films on the nanometer scale and molecular levels. This review will focus on current studies on correlations of nanoscale morphologies in organic photovoltaic (OPV) materials with fundamental processes relevant to photovoltaic functions, such as light harvesting, exciton splitting, exciton diffusion, and charge separation (CS) and diffusion. Small molecule photovoltaic materials will be discussed here. The donor and acceptor materials in small molecule OPV devices can be fabricated in vacuum-deposited, multilayer, crystalline thin films, or spin-coated together to form blended bulk heterojunction (BHJ) films. These two methods result in very different morphologies of the solar cell active layers. There is still a formidable debate regarding which morphology is favored for OPV optimization. The morphology of the conducting films has been systematically altered; using variations of the techniques above, the whole spectrum of film qualities can be fabricated. It is possible to form a highly crystalline material, one which is completely amorphous, or an intermediate morphology. In this review, we will summarize the past key findings that have driven organic solar cell research and the current state-of-the-art of small molecule and conducting oligomer materials. We will also discuss the merits and drawbacks of these devices. Finally, we will highlight some works that directly compare the spectra and morphology of systematically elongated oligothiophene derivatives and compare these oligomers to their polymer counterparts. We hope this review will shed some new light on the morphology differences of these two systems.

  16. Nanoscale structure, dynamics and power conversion efficiency correlations in small molecule and oligomer-based photovoltaic devices

    Directory of Open Access Journals (Sweden)

    Lin X. Chen

    2011-08-01

    Full Text Available Photovoltaic functions in organic materials are intimately connected to interfacial morphologies of molecular packing in films on the nanometer scale and molecular levels. This review will focus on current studies on correlations of nanoscale morphologies in organic photovoltaic (OPV materials with fundamental processes relevant to photovoltaic functions, such as light harvesting, exciton splitting, exciton diffusion, and charge separation (CS and diffusion. Small molecule photovoltaic materials will be discussed here. The donor and acceptor materials in small molecule OPV devices can be fabricated in vacuum-deposited, multilayer, crystalline thin films, or spin-coated together to form blended bulk heterojunction (BHJ films. These two methods result in very different morphologies of the solar cell active layers. There is still a formidable debate regarding which morphology is favored for OPV optimization. The morphology of the conducting films has been systematically altered; using variations of the techniques above, the whole spectrum of film qualities can be fabricated. It is possible to form a highly crystalline material, one which is completely amorphous, or an intermediate morphology. In this review, we will summarize the past key findings that have driven organic solar cell research and the current state-of-the-art of small molecule and conducting oligomer materials. We will also discuss the merits and drawbacks of these devices. Finally, we will highlight some works that directly compare the spectra and morphology of systematically elongated oligothiophene derivatives and compare these oligomers to their polymer counterparts. We hope this review will shed some new light on the morphology differences of these two systems.

  17. Synthetic Antimicrobial Oligomers Induce a Composition-Dependent Topological Transition in Membranes

    Energy Technology Data Exchange (ETDEWEB)

    Yang, L.; Gordon, V.D.; Mishra, A.; Som, A.; Purdy, K.R.; Davis, M.A.; Tew, G.N.; Wong, G.C.L.

    2009-06-04

    Antimicrobial peptides (AMPs) are cationic amphiphiles that comprise a key component of innate immunity. Synthetic analogues of AMPs, such as the family of phenylene ethynylene antimicrobial oligomers (AMOs), recently demonstrated broad-spectrum antimicrobial activity, but the underlying molecular mechanism is unknown. Homologues in this family can be inactive, specifically active against bacteria, or nonspecifically active against bacteria and eukaryotic cells. Using synchrotron small-angle X-ray scattering (SAXS), we show that observed antibacterial activity correlates with an AMO-induced topological transition of small unilamellar vesicles into an inverted hexagonal phase, in which hexagonal arrays of 3.4-nm water channels defined by lipid tubes are formed. Polarized and fluorescence microscopy show that AMO-treated giant unilamellar vesicles remain intact, instead of reconstructing into a bulk 3D phase, but are selectively permeable to encapsulated macromolecules that are smaller than 3.4 nm. Moreover, AMOs with different activity profiles require different minimum threshold concentrations of phosphoethanolamine (PE) lipids to reconstruct the membrane. Using ternary membrane vesicles composed of DOPG:DOPE:DOPC with a charge density fixed at typical bacterial values, we find that the inactive AMO cannot generate the inverted hexagonal phase even when DOPE completely replaces DOPC. The specifically active AMO requires a threshold ratio of DOPE:DOPC = 4:1, and the nonspecifically active AMO requires a drastically lower threshold ratio of DOPE:DOPC = 1.5:1. Since most gram-negative bacterial membranes have more PE lipids than do eukaryotic membranes, our results imply that there is a relationship between negative-curvature lipids such as PE and antimicrobial hydrophobicity that contributes to selective antimicrobial activity.

  18. Zn(OTf)2 promoted rearrangement of 1,2-cyclopropanated sugars with amines: a convenient method for the synthesis of 3-polyhydroxyalkyl-substituted pyrrole derivatives.

    Science.gov (United States)

    Shen, Xudong; Xia, Jianhui; Liang, Peng; Ma, Xiaofeng; Jiao, Wei; Shao, Huawu

    2015-11-28

    A rearrangement reaction of 1,2-cyclopropanated sugars with alkylamines or arylamines promoted by Zn(OTf)2 is described. The method offers a series of 3-polyhydroxyalkyl-substituted pyrrole derivatives with multiple chiral centers in moderate to excellent yields. The epimerization is achieved by inverting the stereochemistry at the free hydroxyl group of the resulting pyrrole, which would give access to many more possible stereoisomers.

  19. Strikingly different luminescent properties arising from single crystals grown from solution or from the vapor phase in a diketo-pyrrolo-pyrrole analog

    OpenAIRE

    Imoda, Tomohiko; Mizuguchi, Jin

    2007-01-01

    The title compound di-cyano-pyrrolo-pyrrole (DCPP) is an analog of diketo-pyrrolo-pyrrole (DPP) known as a red pigment on the market. Brilliant orange photoluminescence has been observed in crystals of DCPP recrystallized from solution (crystal I); whereas the luminescence was quite weak in single crystals grown from the vapor phase (crystal II). To elucidate the difference in luminescent properties, a series of structural analysis together with thermal analysis has been carried out on crysta...

  20. Highly enantioselective synthesis of beta-heteroaryl-substituted dihydrochalcones through Friedel-Crafts alkylation of indoles and pyrrole.

    Science.gov (United States)

    Wang, Wentao; Liu, Xiaohua; Cao, Weidi; Wang, Jun; Lin, Lili; Feng, Xiaoming

    2010-02-01

    A highly enantioselective Friedel-Crafts (F-C) alkylation of indoles and pyrrole with chalcone derivatives catalyzed by a chiral N,N'-dioxide-Sc(OTf)(3) complex has been developed that tolerates a wide range of substrates. The reaction proceeds in moderate to excellent yields and high enantioselectivities (85-92 % enantiomeric excess) using 2 mol % (for indole) or 0.5 mol % (for pyrrole) catalyst loading, which showed the potential value of the catalyst system. Meanwhile, a strong positive nonlinear effect was observed. On the basis of the experimental results and previous reports, a possible working model is proposed to explain the origin of the activation and asymmetric induction. PMID:20013964

  1. Both visual and fluorescent sensors for Zn2 + based on bis(pyrrol-2-yl-methyleneamine) platform

    Science.gov (United States)

    Wu, Wei-Na; Mao, Pan-Dong; Jia, Lei; Wang, Yuan; Xu, Zhou-Qing

    2016-09-01

    Two bis(pyrrol-2-yl-methyleneamine) chemo-sensors, 1, 3- and 1, 4-bis[3,4-dimethyl-5-ethyloxy -carbonyl-pyrrol-2-yl-methyleneamine]benzene (H2L1 and H2L2, respectively) have been synthesized and characterized, which exhibit high selectivity as off-on fluorescence sensors toward Zn2 + in CH3CN/H2O (9:1, v/v) solution. The detection limits of both sensors are at the parts per million level. Moreover, the probes H2L1 and H2L2 could sense Zn2 + by "naked eye" with a color change from colorless to yellow, and from yellow to dark yellow, respectively. To test the practical use of the probes, the determination of Zn2 + in real water samples was also evaluated.

  2. Biofabrication Using Pyrrole Electropolymerization for the Immobilization of Glucose Oxidase and Lactate Oxidase on Implanted Microfabricated Biotransducers

    OpenAIRE

    Christian N. Kotanen; Olukayode Karunwi; Anthony Guiseppi-Elie

    2014-01-01

    The dual responsive Electrochemical Cell-on-a-Chip Microdisc Electrode Array (ECC MDEA 5037) is a recently developed electrochemical transducer for use in a wireless, implantable biosensor system for the continuous measurement of interstitial glucose and lactate. Fabrication of the biorecognition membrane via pyrrole electropolymerization and both in vitro and in vivo characterization of the resulting biotransducer is described. The influence of EDC-NHS covalent conjugation of glucose oxidas...

  3. Novel MWCNT-Support for Co-Mo Sulfide Catalyst in HDS of Thiophene and HDN of Pyrrole

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    With home-made multi-walled carbon nanotubes (MWCNTs, simplified as CNTs in later text) as support, CNT-supported Co-Mo-S catalysts, denoted as x%(mass percentage)MoiCoj/CNTs,were prepared. Their catalytic performance for thiophene hydrodesulfurization (HDS) and pyrrole hydrodenitrification (HDN) reactions was studied, and compared with the reference system supported by AC. Over the 7.24%Mo3Co1/CNTs catalyst at reaction condition of 1.5 MPa, 613 K,C4H4S/H2 =3.7/96.3(molar ratio) and GHSV≈8000 mlSTP/(g-cat.h), the specific HDS activity of thiophene the AC-based counterpart, and was 2.47 times as high as that (1.33 mmolC4H4S/(s.molMo)) of the catalysts supported by AC with the respective optimal Mo3Co1-loading amount, 16.90%Mo3Co1/AC. Analogous reaction-chemical behaviours were also observed in the case of pyrrole HDN. It was experimentally found that using the CNTs in place of AC as support of the catalyst caused little change in the apparent activation energy for the thiophene HDS or pyrrole HDN reaction, but led to a significant increase in the concentration of catalytically active Mo-species (Mo4+) at the surface of the functioning catalyst. On the other hand, H2-TPD measurements revealed that the CNT-supported catalyst could reversibly adsorb a greater amount of hydrogen under atmospheric pressure at temperatures ranging from room temperature to about 673 K. This unique feature would help to generate microenvironments with higher stationarystate concentration of active hydrogen-adspecies at the surface of the functioning catalyst. Both factors mentioned above were favorable to increasing the rate of thiophene HDS and pyrrole HDN reactions.

  4. N-Heterocyclic carbene–palladium catalysts for the direct arylation of pyrrole derivatives with aryl chlorides

    Directory of Open Access Journals (Sweden)

    Ismail Özdemir

    2013-02-01

    Full Text Available New Pd–NHC complexes have been synthesized and employed for palladium-catalyzed direct arylation of pyrrole derivatives by using electron-deficient aryl chlorides as coupling partners. The desired coupling products were obtained in moderate to good yields by using 1 mol % of these air-stable palladium complexes. This is an advantage compared to the procedures employing air-sensitive phosphines, which have been previously shown to promote the coupling of aryl chlorides with heteroarenes.

  5. Direct detection of pyridine formation by the reaction of CH (CD) with pyrrole: a ring expansion reaction

    Energy Technology Data Exchange (ETDEWEB)

    Soorkia, Satchin; Taatjes, Craig A.; Osborn, David L.; Selby, Talitha M.; Trevitt, Adam J.; Wilson, Kevin R.; Leone, Stephen R.

    2010-03-16

    The reaction of the ground state methylidyne radical CH (X2Pi) with pyrrole (C4H5N) has been studied in a slow flow tube reactor using Multiplexed Photoionization Mass Spectrometry coupled to quasi-continuous tunable VUV synchrotron radiation at room temperature (295 K) and 90 oC (363 K), at 4 Torr (533 Pa). Laser photolysis of bromoform (CHBr3) at 248 nm (KrF excimer laser) is used to produce CH radicals that are free to react with pyrrole molecules in the gaseous mixture. A signal at m/z = 79 (C5H5N) is identified as the product of the reaction and resolved from 79Br atoms, and the result is consistent with CH addition to pyrrole followed by Helimination. The Photoionization Efficiency curve unambiguously identifies m/z = 79 as pyridine. With deuterated methylidyne radicals (CD), the product mass peak is shifted by +1 mass unit, consistent with the formation of C5H4DN and identified as deuterated pyridine (dpyridine). Within detection limits, there is no evidence that the addition intermediate complex undergoes hydrogen scrambling. The results are consistent with a reaction mechanism that proceeds via the direct CH (CD) cycloaddition or insertion into the five-member pyrrole ring, giving rise to ring expansion, followed by H atom elimination from the nitrogen atom in the intermediate to form the resonance stabilized pyridine (d-pyridine) molecule. Implications to interstellar chemistry and planetary atmospheres, in particular Titan, as well as in gas-phase combustion processes, are discussed.

  6. Synthesis and spectroscopic characterization of pyrrole-2,3-diones and their following reactions with 1,2-aromatic diamines

    Directory of Open Access Journals (Sweden)

    İrfan Koca

    2012-01-01

    Full Text Available 4-aroyl-5-aryl-2,3-furandiones and N,N-dialkyl urea combine with loss of water yielding the pyrrole-2,3-dione derivatives in moderate yields (47-68%. Then, these compounds were converted into 2(1H-quinoxalinones with various 1,2-phenylenediamines. The structures and characterizations of the synthesized compounds were established by the 1H- and 13C-NMR, IR and elemental analysis.

  7. Copper-Catalyzed Coupling of 2-Siloxy-1-alkenes and Diazocarbonyl Compounds: Approach to Multisubstituted Furans, Pyrroles, and Thiophenes.

    Science.gov (United States)

    Tan, Wei Wen; Yoshikai, Naohiko

    2016-07-01

    We report herein copper(II)-catalyzed cyclization reactions of silyl enol ethers derived from methyl ketones with α-diazo-β-ketoesters or α-diazoketones to afford 2-siloxy-2,3-dihydrofuran derivatives or 2,3,5-trisubstituted furans, respectively, under mild conditions. The former cyclization products serve as versatile 1,4-diketone surrogates, allowing facile preparation of 2,3,5-trisubstituted furans, pyrroles, and thiophenes. PMID:27259097

  8. Self-propagative replication of Aβ oligomers suggests potential transmissibility in Alzheimer disease.

    Directory of Open Access Journals (Sweden)

    Amit Kumar

    Full Text Available The aggregation of amyloid-β (Aβ peptide and its deposition in parts of the brain form the central processes in the etiology of Alzheimer disease (AD. The low-molecular weight oligomers of Aβ aggregates (2 to 30 mers are known to be the primary neurotoxic agents whose mechanisms of cellular toxicity and synaptic dysfunction have received substantial attention in the recent years. However, how these toxic agents proliferate and induce widespread amyloid deposition throughout the brain, and what mechanism is involved in the amplification and propagation of toxic oligomer species, are far from clear. Emerging evidence based on transgenic mice models indicates a transmissible nature of Aβ aggregates and implicates a prion-like mechanism of oligomer propagation, which manifests as the dissemination and proliferation of Aβ toxicity. Despite accumulating evidence in support of a transmissible nature of Aβ aggregates, a clear, molecular-level understanding of this intriguing mechanism is lacking. Recently, we reported the characterization of unique replicating oligomers of Aβ42 (12-24 mers in vitro called Large Fatty Acid-derived Oligomers (LFAOs (Kumar et al., 2012, J. Biol. Chem. In the current report, we establish that LFAOs possess physiological activity by activating NF-κB in human neuroblastoma cells, and determine the experimental parameters that control the efficiency of LFAO replication by self-propagation. These findings constitute the first detailed report on monomer - oligomer lateral propagation reactions that may constitute potential mechanism governing transmissibility among Aβ oligomers. These data support the previous reports on transmissible mechanisms observed in transgenic animal models.

  9. Self-assembly of conjugated oligomers and polymers at the interface: structure and properties.

    Science.gov (United States)

    Xu, Lirong; Yang, Liu; Lei, Shengbin

    2012-08-01

    In this review, we give a brief account on the recent scanning tunneling microscopy investigation of interfacial structures and properties of π-conjugated semiconducting oligomers and polymers, either at the solid-air (including solid-vacuum) or at the solid-liquid interface. The structural aspects of the self-assembly of both oligomers and polymers are highlighted. Conjugated oligomers can form well ordered supramolecular assemblies either at the air-solid or liquid-solid interface, thanks to the relatively high mobility and structural uniformity in comparison with polymers. The backbone structure, substitution of side chains and functional groups can affect the assembling behavior significantly, which offers the opportunity to tune the supramolecular structure of these conjugated oligomers at the interface. For conjugated polymers, the large molecular weight limits the mobility on the surface and the distribution in size also prevents the formation of long range ordered supramolecular assembly. The submolecular resolution obtained on the assembling monolayers enables a detailed investigation of the chain folding at the interface, both the structural details and the effect on electronic properties. Besides the ability in studying the assembling structures at the interfaces, STM also provides a reasonable way to evaluate the distribution of the molecular weight of conjugated polymers by statistic of the contour length of the adsorbed polymer chains. Both conjugated oligomers and polymers can form composite assemblies with other materials. The ordered assembly of oligomers can act as a template to controllably disperse other molecules such as coronene or fullerene. These investigations open a new avenue to fine tune the assembling structure at the interface and in turn the properties of the composite materials. To summarize scanning tunneling microscopy has demonstrated its surprising ability in the investigation of the assembling structures and properties of

  10. Solvent free low-melt viscosity imide oligomers and thermosetting polymide composites

    Science.gov (United States)

    Chuang, Chun-Hua (Inventor)

    2012-01-01

    .[.This invention relates to the composition and a solvent-free process for preparing novel imide oligomers and polymers specifically formulated with effective amounts of a dianhydride such as 2,3,3',4-biphenyltetra carboxylic dianydride (a-BPDA), at least one aromatic diamine and an endcapped of 4-phenylethynylphthalic anhydride (PEPA) or nadic anhydride to produce imide oligomers that possess a low-melt viscosity of 1-60 poise at 260-280.degree. C. When the imide oligomer melt is cured at about 371.degree. C. in a press or autoclave under 100-500 psi, the melt resulted in a thermoset polyimide having a glass transition temperature (T.sub.g) equal to and above 310.degree. C. A novel feature of this process is that the monomers; namely the dianhydrides, diamines and the endcaps, are melt processable to form imide oligomers at temperatures ranging between 232-280.degree. C. (450-535.degree. F.) without any solvent. These low-melt imide oligomers can be easily processed by resin transfer molding (RTM), vacuum-assisted resin transfer molding (VARTM) or the resin infusion process with fiber preforms e.g. carbon, glass or quartz preforms to produce polyimide matrix composites with 288-343.degree. C. (550-650.degree. F.) high temperature performance capability..]. .Iadd.This invention relates to compositions and a solvent-free reaction process for preparing imide oligomers and polymers specifically derived from effective amounts of dianhydrides such as 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA), at least one aromatic polyamine and an end-cap such as 4-phenylethynyphthalic anhydride (PEPA) or nadic anhydride to produce imide oligomers that possess a low-melt viscosity of 1-60 poise at 260.degree. C.-280.degree. C..Iaddend.

  11. Pyrrole PMOs, incorporating new N-heterocyclic compounds on an ethene-PMO through Diels–Alder reactions

    Energy Technology Data Exchange (ETDEWEB)

    Esquivel, Dolores; De Canck, Els [Center for Ordered Materials, Organometallics and Catalysis, Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281-S3, 9000 Ghent (Belgium); Jiménez-Sanchidrián, César [Department of Organic Chemistry, Nanochemistry and Fine Chemistry Research Institute (IUIQFN), Faculty of Sciences, University of Córdoba, Campus de Rabanales, Marie Curie Building, Ctra. Nnal. IV, km 396, 14071 Córdoba (Spain); Romero-Salguero, Francisco J., E-mail: qo2rosaf@uco.es [Department of Organic Chemistry, Nanochemistry and Fine Chemistry Research Institute (IUIQFN), Faculty of Sciences, University of Córdoba, Campus de Rabanales, Marie Curie Building, Ctra. Nnal. IV, km 396, 14071 Córdoba (Spain); Van Der Voort, Pascal, E-mail: pascal.vandervoort@ugent.be [Center for Ordered Materials, Organometallics and Catalysis, Department of Inorganic and Physical Chemistry, Ghent University, Krijgslaan 281-S3, 9000 Ghent (Belgium)

    2014-11-14

    The ethenylene bridges on the walls of an ethenylene-bridged periodic mesoporous organosilica were successfully modified with a variety of pyrrole derivatives – pyrrole, methylpyrrole, dimethylpyrrole, trimethylpyrrole and 1-phenylpyrrole – through Diels–Alder reactions. X-ray diffraction measurements and N{sub 2} adsorption–desorption analysis confirmed the preservation of the ordering and mesoporosity of the parent material as well as the decoration of the pores with the surface Diels–Alder adducts. Moreover, other techniques such as DRIFT, {sup 13}C and {sup 29}Si nuclear magnetic resonances revealed the formation of the surface N-heterocyclic compounds at the parent ethenylene sites. - Highlights: • Chemical modification of the double bonds on an ethene-PMO through the Diels–Alder reaction. • A family of pyrrole derivatives act as dienes in the Diels–Alder reaction. • Well-ordering and mesoporosity are retained after the post-functionalization. • N-containing compounds on the surface of ethene-PMO are present after the Diels–Alder reaction.

  12. Synthetic, structural and biological studies of organosilicon(IV complexes of Schiff bases derived from pyrrole-2-carboxaldehyde

    Directory of Open Access Journals (Sweden)

    KIRAN SING

    2010-07-01

    Full Text Available Selected new organosilicon(IV complexes having the general formula R2SiCl[L] and R2Si[L] 2 were synthesized by the reactions of Me2SiCl2 with Schiff bases (5-mercapto-4-[(1H-pyrrol-2ylmethyleneamino]-s-triazole, 5-mercapto-3-methyl-4-[(1H-pyrrol-2ylmethyleneamino]-s-triazole and 3-ethyl-5-mercapto-4-[(1H-pyrrol-2ylmethyleneamino]-s-triazole in 1:1 and 1:2 molar ratios. All of the compounds were characterized by elemental analysis, molar conductance, and IR, UV, 1H-, 13C- and 29Si-NMR spectral studies. All the spectral data suggest an involvement with an azomethine nitrogen in coordination to the central silicon atom. With the help of above-mentioned spectral studies, penta and hexacoordinated environments around the central silicon atoms in the 1:1 and 1:2 complexes, respectively, are proposed. Finally, the free ligands and their metal complexes were tested in vitro against some pathogenic bacteria and fungi to assess their antimicrobial properties.

  13. Pyrrole PMOs, incorporating new N-heterocyclic compounds on an ethene-PMO through Diels–Alder reactions

    International Nuclear Information System (INIS)

    The ethenylene bridges on the walls of an ethenylene-bridged periodic mesoporous organosilica were successfully modified with a variety of pyrrole derivatives – pyrrole, methylpyrrole, dimethylpyrrole, trimethylpyrrole and 1-phenylpyrrole – through Diels–Alder reactions. X-ray diffraction measurements and N2 adsorption–desorption analysis confirmed the preservation of the ordering and mesoporosity of the parent material as well as the decoration of the pores with the surface Diels–Alder adducts. Moreover, other techniques such as DRIFT, 13C and 29Si nuclear magnetic resonances revealed the formation of the surface N-heterocyclic compounds at the parent ethenylene sites. - Highlights: • Chemical modification of the double bonds on an ethene-PMO through the Diels–Alder reaction. • A family of pyrrole derivatives act as dienes in the Diels–Alder reaction. • Well-ordering and mesoporosity are retained after the post-functionalization. • N-containing compounds on the surface of ethene-PMO are present after the Diels–Alder reaction

  14. Calix[4]pyrrole derivative: recognition of fluoride and mercury ions and extracting properties of the receptor-based new material.

    Science.gov (United States)

    de Namor, Angela F Danil; Khalife, Rasha

    2008-12-11

    A calix[4]pyrrole derivative, namely, meso-tetramethyl tetrakis (4-phenoxy methyl ketone) calix[4]pyrrole, 1, was synthesized and structurally (1H NMR) and thermodynamically characterized. The complexing properties of this receptor with a wide variety of anions and cations in dipolar aprotic media (acetonitrile, propylene carbonate, and dimethyl sulfoxide) were investigated through 1H NMR and conductance studies. The former technique was used to assess whether or not complexation occurs and if so to identify the active sites of interaction of 1 with ions. The composition of the complexes was established by conductance measurements. It was found that in dipolar aprotic solvents, 1 interacts only with two polluting ions (fluoride and mercury). The complexation thermodynamics of 1 and these ions in these solvents is reported. The medium effect on the binding process involving the fluoride ion is discussed taking into account the solvation properties of reactants and the product. Complexes of moderate stability are found. Given that this is an important factor to consider for the recycling of the loaded material in extraction processes, 1 was treated with formaldehyde in basic medium leading to the production of a calix[4]pyrrole based material able to extract fluoride and mercury (II) ions from water. Thus the optimum conditions for the extraction of these ions from aqueous solutions were established. The material is easily recyclable using an organic acid. Final conclusions are given. PMID:19053691

  15. Calix[4]pyrrole derivative: recognition of fluoride and mercury ions and extracting properties of the receptor-based new material.

    Science.gov (United States)

    de Namor, Angela F Danil; Khalife, Rasha

    2008-12-11

    A calix[4]pyrrole derivative, namely, meso-tetramethyl tetrakis (4-phenoxy methyl ketone) calix[4]pyrrole, 1, was synthesized and structurally (1H NMR) and thermodynamically characterized. The complexing properties of this receptor with a wide variety of anions and cations in dipolar aprotic media (acetonitrile, propylene carbonate, and dimethyl sulfoxide) were investigated through 1H NMR and conductance studies. The former technique was used to assess whether or not complexation occurs and if so to identify the active sites of interaction of 1 with ions. The composition of the complexes was established by conductance measurements. It was found that in dipolar aprotic solvents, 1 interacts only with two polluting ions (fluoride and mercury). The complexation thermodynamics of 1 and these ions in these solvents is reported. The medium effect on the binding process involving the fluoride ion is discussed taking into account the solvation properties of reactants and the product. Complexes of moderate stability are found. Given that this is an important factor to consider for the recycling of the loaded material in extraction processes, 1 was treated with formaldehyde in basic medium leading to the production of a calix[4]pyrrole based material able to extract fluoride and mercury (II) ions from water. Thus the optimum conditions for the extraction of these ions from aqueous solutions were established. The material is easily recyclable using an organic acid. Final conclusions are given.

  16. CHIRAL CONJUGATED OLIGOMER BASED ON 1,1'-BINOL WITH 3,3'-ACETYLENE-PHENYLENE-ACETYLENE SPACER

    Institute of Scientific and Technical Information of China (English)

    Tian-jun Liu; Ke-shen Zhang; Yong-jun Chen; Dong Wang; Chao-jun Li

    2001-01-01

    The 1,1'-binaphthol based oligomers 3 and 7 with 3,3'-acetylene-phenylene-acetylene spacer were prepared from BINOL 1. The high optical rotation value and CD spectra demonstrated the main chain chirality of the oligomer molecule. The UV-VIS and fluorescent spectra evidence the characteristics of conjugated structure. In comparison with oligomer 2 bearing 3,3'-acetylene spacer, the oligomers 3 and 7 have longer efficient conjugation segment, and their fluorescent quantum yields (φ) increased (0.60-0.65 versus 0.14). Extending the effective conjugation segment would improve the photophysical properties of chiral conjugated polymers.``

  17. Effect of pathogenic mutations on the structure and dynamics of Alzheimer's A beta 42-amyloid oligomers.

    Science.gov (United States)

    Kassler, Kristin; Horn, Anselm H C; Sticht, Heinrich

    2010-05-01

    Converging lines of evidence suggest that soluble A beta-amyloid oligomers play a pivotal role in the pathogenesis of Alzheimer's disease, and present direct effectors of synaptic and cognitive dysfunction. Three pathological E22-A beta-amyloid point mutants (E22G, E22K, E22Q) and the deletion mutant E22 Delta exhibit an enhanced tendency to form prefibrillar aggregates. The present study assessed the effect of these four mutations using molecular dynamics simulations and subsequent structural and energetic analyses. Our data shows that E22 plays a unique role in wild type A beta, since it has a destabilising effect on the oligomer structure due to electrostatic repulsion between adjacent E22 side chains. Mutations in which E22 is replaced by an uncharged residue result in higher oligomer stability. This effect is also observed to a lesser extent for the E22K mutation and is consistent with its lower pathogenicity compared to other mutants. Interestingly, deletion of E22 does not destroy the amyloid fold but is compensated by local changes in the backbone geometry that allow the preservation of a structurally important salt bridge. The finding that all mutant oligomers investigated exhibit higher internal stability than the wild type offers an explanation for the experimentally observed enhanced oligomer formation and stability.

  18. Mitochondrial Ca2+ overload underlies Abeta oligomers neurotoxicity providing an unexpected mechanism of neuroprotection by NSAIDs.

    Directory of Open Access Journals (Sweden)

    Sara Sanz-Blasco

    Full Text Available Dysregulation of intracellular Ca(2+ homeostasis may underlie amyloid beta peptide (Abeta toxicity in Alzheimer's Disease (AD but the mechanism is unknown. In search for this mechanism we found that Abeta(1-42 oligomers, the assembly state correlating best with cognitive decline in AD, but not Abeta fibrils, induce a massive entry of Ca(2+ in neurons and promote mitochondrial Ca(2+ overload as shown by bioluminescence imaging of targeted aequorin in individual neurons. Abeta oligomers induce also mitochondrial permeability transition, cytochrome c release, apoptosis and cell death. Mitochondrial depolarization prevents mitochondrial Ca(2+ overload, cytochrome c release and cell death. In addition, we found that a series of non-steroidal anti-inflammatory drugs (NSAIDs including salicylate, sulindac sulfide, indomethacin, ibuprofen and R-flurbiprofen depolarize mitochondria and inhibit mitochondrial Ca(2+ overload, cytochrome c release and cell death induced by Abeta oligomers. Our results indicate that i mitochondrial Ca(2+ overload underlies the neurotoxicity induced by Abeta oligomers and ii inhibition of mitochondrial Ca(2+ overload provides a novel mechanism of neuroprotection by NSAIDs against Abeta oligomers and AD.

  19. Hybrid conjugated organic oligomers consisting of oligodiacetylene and thiophene units: synthesis and optical properties.

    Science.gov (United States)

    Pilzak, Gregor S; van Gruijthuijsen, Kitty; van Doorn, Reindert H; van Lagen, Barend; Sudhölter, Ernst J R; Zuilhof, Han

    2009-09-14

    Novel and highly soluble hybrid conjugated organic oligomers consisting of oligodiacetylene and thiophene units have been synthesized in high purity through iterative and divergent approaches based on a sequence of Sonogashira reactions. The series of thiophene-containing oligodiacetylenes (ThODAs) and homocoupled ThODAs (HThODAs) show--both in solution and in the solid state--a strong optical absorption, which is progressively red shifted with increasing chain length. The linear correlation of the absorption maximum (lambda(A)(max)) with the inverse of conjugation length (CL = number of double and triple bonds) shows that the effective conjugation length of this system is extended up to at least CL = 20. Furthermore, absorption measurements of dropcast thin films display not only a bathochromic shift of the absorption maxima but also a higher wavelength absorption, which is attributed to increased pi-pi interactions. The wavelength of the maximum fluorescence emission (lambda(E)(max)) also increases with CL, and emission is maximal for oligomers with CL=7-12 (fluorescence quantum yield Phi(F) = approximately 0.2). Both longer and shorter oligomers display marginal emission. The calculated Stokes shifts of these planar materials are relatively large (0.4 eV) for all oligomers, and likely due to excitation to the S(2) state, thus suggesting that the presence of enyne moieties dominates the ordering of the lowest excited states. The fluorescence lifetimes (tau(F)) are short (tau(F,max) = line with highly rigid oligomers. PMID:19637259

  20. Parametrization of the Gay-Berne potential for conjugated oligomer with a high aspect ratio

    Science.gov (United States)

    Lee, Cheng K.; Hua, Chi C.; Chen, Show A.

    2010-08-01

    The Gay-Berne (GB) potential has been a popular semiempirical model for describing the short-range intermolecular forces for a wide variety of aspherical molecules, including liquid crystals and anisotropic colloids, with generally small molecular dimensions and low aspect ratios (<5). This study evaluates the parametrization of the GB potential for a high-aspect-ratio (=10) oligomer belonging to a model conjugated polymer. We elaborate that the semiflexibility associated with a large oligomer species demands a variant umbrella-sampling scheme in establishing the potentials of mean force (PMFs) for four pair ellipsoid arrangements typically utilized to parametrize the GB potential. The model ellipsoid so constructed is shown to capture the PMFs of essential intermediate arrangements as well, and, according to the results of simplex optimizations, recommendations are given for the minimum set of parameters to be included in the optimization of a large oligomer or particulate species. To further attest the parametrized GB potential, the coarse-grained (CG) Monte Carlo simulations employing the GB potential and the back-mapped, full-atom atomistic molecular dynamics (AMD) simulations were performed for a dense oligomer system at two representative system temperatures. The results indicated that the CG simulations can capture, with exceptional computational efficiency, the AMD predictions with good thermal transferability. In future perspectives, we remark on potential applications to construct efficient, parameter-free CG models for capturing fundamental material properties of large oligomer/particulate species as well as long-chain conjugated polymers.

  1. Thin films of arylenevinylene oligomers prepared by MAPLE for applications in non-linear optics

    Energy Technology Data Exchange (ETDEWEB)

    Stanculescu, A., E-mail: sanca@infim.ro [National Institute of Materials Physics, Optics and Spectroscopy Laboratory, 105 bis Atomistilor Street, P.O. Box MG-7, Bucharest-Magurele 077125 (Romania); Vacareanu, L.; Grigoras, M. [P. Poni' Institute of Macromolecular Chemistry, 41 A Gr. Ghica Voda Alley, 700487 Iasi (Romania); Socol, M. [National Institute of Materials Physics, Optics and Spectroscopy Laboratory, 105 bis Atomistilor Street, P.O. Box MG-7, Bucharest-Magurele 077125 (Romania); Socol, G. [National Institute for Laser, Plasma and Radiation Physics, Str. Atomistilor, Nr. 409, P.O. Box MG-36, Magurele, Bucharest 077125 (Romania); Stanculescu, F. [Faculty of Physics, University of Bucharest, Str. Atomistilor nr.405, P.O. Box MG-11, Bucharest-Magurele 077125 (Romania); Preda, N.; Matei, E. [National Institute of Materials Physics, Optics and Spectroscopy Laboratory, 105 bis Atomistilor Street, P.O. Box MG-7, Bucharest-Magurele 077125 (Romania); Ionita, I. [Faculty of Physics, University of Bucharest, Str. Atomistilor nr.405, P.O. Box MG-11, Bucharest-Magurele 077125 (Romania); Girtan, M. [Laboratoire de Photonique d' Angers, Universite d' Angers, 2, Bd. Lavoisier, 49045 Angers (France); Mihailescu, I.N. [National Institute for Laser, Plasma and Radiation Physics, Str. Atomistilor, Nr. 409, P.O. Box MG-36, Magurele, Bucharest 077125 (Romania)

    2011-04-01

    This paper discusses two arylenevinylene oligomers with optical nonlinear properties. Their trans molecular structure was confirmed by Fourier Transform Infrared Spectroscopy and Nuclear Magnetic Resonance. Second Harmonic Generation and two-photon fluorescence have been observed on Matrix Assisted Pulsed Laser Evaporation-deposited thin films. We have seen two local maxima in UV-Vis spectra and a red shift of the photoluminescence peak for carbazole-based oligomer, which can be correlated with a higher conformational flexibility and with strong polarization interactions in the solid state. Scanning Electron Microscopy and Atomic Force Microscopy images have revealed a grainy morphology of the film deposited on titanium and a higher roughness for carbazole-based oligomer. Second harmonic measurements have shown nearly equal values of the second-order nonlinear optical coefficient for the triphenylamine and carbazole-based oligomers for P{sub laser} < 100 mW. z-Scan and x-scan representations of the carbazole-based oligomer film have shown strong two-photon fluorescence intensity inside the sample confirming a volume process, and a strong second harmonic at the surface of the sample determined by the surface morphology.

  2. Determination of the critical molar mass of ovalbumin oligomers degraded by ultrasound

    Directory of Open Access Journals (Sweden)

    BRATOLJUB H. MILOSAVLJEVIC

    2000-02-01

    Full Text Available An experimental method has been developed which enables the determination of the critical molar mass (Mmc of ovalbumin oligomers degraded by ultrasound of known frequency. To test the validity of the Mmc postulate, a series of ovalbumin oligomers was prepared by the radiolytic cross-linking of 1% solutions of ovalbumin monomer dissolved in 50 mM Na/K-phosphate buffer pH 7.0 saturated with N2O. Under these conditions, irradiation with 5 kGy from a 60Co source, yielded ovalbumin dimers, trimers, tetramers, and higher order oligomers. On the basis of the results obtained with the ovalbumin oligomers, it was concluded that for ultrasound of 23 kHz frequency and 5mm amplitude, the Mmc was 274000 + 14000 g/mol. Our results confirmed that the two postulates in the chemistry of polymer degradation by ultrasound are valid when ovalbumin oligomers are used as substrates, i.e., (1 that the higher the molar mass of the original macromolecule, the faster is its degradation rate, and (2 that a lower molar mass limit (LMmL exists below which the macromolecules are resistent to further degradation.

  3. A concise synthesis of (+)-batzelladine B from simple pyrrole-based starting materials

    Science.gov (United States)

    Parr, Brendan T.; Economou, Christos; Herzon, Seth B.

    2015-09-01

    Alkaloids, secondary metabolites that contain basic nitrogen atoms, are some of the most well-known biologically active natural products in chemistry and medicine. Although efficient laboratory synthesis of alkaloids would enable the study and optimization of their biological properties, their preparation is often complicated by the basicity and nucleophilicity of nitrogen, its susceptibility to oxidation, and its ability to alter reaction outcomes in unexpected ways--for example, through stereochemical instability and neighbouring group participation. Efforts to address these issues have led to the invention of a large number of protecting groups that temper the reactivity of nitrogen; however, the use of protecting groups typically introduces additional steps and obstacles into the synthetic route. Alternatively, the use of aromatic nitrogen heterocycles as synthetic precursors can attenuate the reactivity of nitrogen and streamline synthetic strategies. Here we use such an approach to achieve a synthesis of the complex anti-HIV alkaloid (+)-batzelladine B in nine steps (longest linear sequence) from simple pyrrole-based starting materials. The route uses several key transformations that would be challenging or impossible to implement using saturated nitrogen heterocycles and highlights some of the advantages of beginning with aromatic reagents.

  4. Palladium complexes of pyrrole-2-aldehyde thiosemicarbazone: Synthesis, structure and spectral properties

    Indian Academy of Sciences (India)

    Piyali Paul; Samaresh Bhattacharya

    2014-09-01

    Reaction of pyrrole-2-aldehyde thiosemicarbazone (abbreviated as H2L, where H2 stands for the two potentially dissociable protons) with [Pd(PPh3)2Cl2] in ethanol in the presence of NEt3 afforded two complexes, [Pd(PPh3)(HLNS)Cl] and [Pd(PPh3)(LNNS)], where the thiosemicarbazone ligand is coordinated to the metal centre respectively as monoanionic N,S-donor (depicted by HLNS) and dianionic N,N,S-donor (depicted by LNNS). Similar reaction with Na2[PdCl4] afforded a bis-complex, [Pd(HLNS)2]. Crystal structures of all the three complexes have been determined.With reference to the structure of the uncoordinated thiosemicarbazone (H2L), the N,S-coordinationmode observed in [Pd(PPh3)(HLNS)Cl] and [Pd(HLNS)2] is associated with a geometrical change around the imine bond.While the N,N,S-mode of binding observed in [Pd(PPh3)(LNNS)] takes place without any such geometrical change. All three complexes display intense absorptions in the visible and ultraviolet regions, which have been analyzed by TDDFT method.

  5. Experimental and computational thermochemistry of 1-phenylpyrrole and 1-(4-methylphenyl)pyrrole

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Ana Filipa L.O.M. [Centro de Investigacao em Quimica, Department of Chemistry, Faculty of Science, University of Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal); Ribeiro da Silva, Manuel A.V., E-mail: risilva@fc.up.p [Centro de Investigacao em Quimica, Department of Chemistry, Faculty of Science, University of Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal)

    2010-06-15

    The standard (p{sup o} = 0.1 MPa) molar enthalpies of formation, in the crystalline phase, of 1-phenylpyrrole and 1-(4-methylphenyl)pyrrole, at T = 298.15 K, were derived from the standard molar energies of combustion in oxygen, measured by static-bomb combustion calorimetry. For these compounds, the standard molar enthalpies of sublimation, at T = 298.15 K, were determined from the temperature-vapour pressure dependence, obtained by the Knudsen mass-loss effusion method. Using estimated values for the heat capacity differences between the gas and the crystal phases of the studied compounds, the standard (p{sup o} = 0.1 MPa) molar enthalpies, entropies, and Gibbs energies of sublimation, at T = 298.15 K, were derived. From the experimental values, the standard molar enthalpies of formation, in the gaseous phase, at T = 298.15 K, were calculated. Additionally, the enthalpies of formation of both compounds were estimated using the composite G3(MP2)//B3LYP approach together with adequate gas-phase working reactions. There is a very good agreement between computational and experimental results.

  6. Crystal structures of unsymmetrically mixed β-pyrrole substituted nickel(II)-meso-tetraphenylporphyrins

    Indian Academy of Sciences (India)

    BHYRAPPA PUTTAIAH; VELKANNAN VEERAPANDIAN; SARANGI UJWAL KUMAR

    2016-07-01

    Crystal structures of solvated unsymmetrically substituted meso-tetraphenylporphyrins, 2,3,12,13, 17-pentachloro-5,7,8,10,15,18,20-hepta-phenylporphyrin, H₂TPP(Ph)₃(Cl)₅, 1 and its nickel(II), NiTPP(Ph)₃(Cl)₅, 2 were determined by single crystal XRD analysis. In addition, a new unsymmetricallysubstituted porphyrin, 2,3,12,13,17-pentacyano-5,7,8,10,15,18,20-heptaphenyl-porphinato nickel(II) complex, NiTPP(Ph)₃(CN)₅, 3 complex was synthesized and its solvated structure was examined by crystallography. These porphyrins exhibited dramatic nonplanar conformation of the macrocycle as evidenced from the averagedisplacement of the β-pyrrole carbon (±ΔCβ ) from the mean plane of the porphyrin ring and the trend in nonplanarity varies in the order: 2 (1.189(5) Å) > 1 (1.036(6) Å) > 3 (0.895(6) Å). The normal-coordinate structural decomposition analysis of these structures revealed mainly saddle distortion of the macrocycle combined with small degree of ruffled or domed distortions. The Hirshfeld surface analysis of structures 1-3 revealed solvate dependent intermolecular contacts with varying degree of H. . .H (43–49%), C. . .H (17–19%), H. . .Cl (25–30%) and N. . .H (~19%) contact contributions.

  7. Efficient Synthesis of Peptide and Protein Functionalized Pyrrole-Imidazole Polyamides Using Native Chemical Ligation.

    Science.gov (United States)

    Janssen, Brian M G; van Ommeren, Sven P F I; Merkx, Maarten

    2015-06-04

    The advancement of DNA-based bionanotechnology requires efficient strategies to functionalize DNA nanostructures in a specific manner with other biomolecules, most importantly peptides and proteins. Common DNA-functionalization methods rely on laborious and covalent conjugation between DNA and proteins or peptides. Pyrrole-imidazole (Py-Im) polyamides, based on natural minor groove DNA-binding small molecules, can bind to DNA in a sequence specific fashion. In this study, we explore the use of Py-Im polyamides for addressing proteins and peptides to DNA in a sequence specific and non-covalent manner. A generic synthetic approach based on native chemical ligation was established that allows efficient conjugation of both peptides and recombinant proteins to Py-Im polyamides. The effect of Py-Im polyamide conjugation on DNA binding was investigated by Surface Plasmon Resonance (SPR). Although the synthesis of different protein-Py-Im-polyamide conjugates was successful, attenuation of DNA affinity was observed, in particular for the protein-Py-Im-polyamide conjugates. The practical use of protein-Py-Im-polyamide conjugates for addressing DNA structures in an orthogonal but non-covalent manner, therefore, remains to be established.

  8. Efficient Synthesis of Peptide and Protein Functionalized Pyrrole-Imidazole Polyamides Using Native Chemical Ligation

    Directory of Open Access Journals (Sweden)

    Brian M. G. Janssen

    2015-06-01

    Full Text Available The advancement of DNA-based bionanotechnology requires efficient strategies to functionalize DNA nanostructures in a specific manner with other biomolecules, most importantly peptides and proteins. Common DNA-functionalization methods rely on laborious and covalent conjugation between DNA and proteins or peptides. Pyrrole-imidazole (Py–Im polyamides, based on natural minor groove DNA-binding small molecules, can bind to DNA in a sequence specific fashion. In this study, we explore the use of Py–Im polyamides for addressing proteins and peptides to DNA in a sequence specific and non-covalent manner. A generic synthetic approach based on native chemical ligation was established that allows efficient conjugation of both peptides and recombinant proteins to Py–Im polyamides. The effect of Py–Im polyamide conjugation on DNA binding was investigated by Surface Plasmon Resonance (SPR. Although the synthesis of different protein-Py–Im-polyamide conjugates was successful, attenuation of DNA affinity was observed, in particular for the protein-Py–Im-polyamide conjugates. The practical use of protein-Py–Im-polyamide conjugates for addressing DNA structures in an orthogonal but non-covalent manner, therefore, remains to be established.

  9. A new source of oxygenated organic aerosol and oligomers

    Directory of Open Access Journals (Sweden)

    J. Liggio

    2013-03-01

    Full Text Available A large oxygenated organic uptake to aerosols was observed when exposing ambient urban air to inorganic acidic and non-acidic sulfate seed aerosol. For non-acidic seed aerosol the uptake was attributed to the direct dissolution of primary vehicle exhaust gases into the aqueous aerosol fraction, and was correlated to the initial seed sulphate mass. The uptake of primary oxygenated organic gases to aerosols in this study represents a significant amount of organic aerosol (OA that may be considered primary when compared to that reported for primary organic aerosol (POA, but is considerably more oxygenated (O : C ~ 0.3 than traditional POA. Consequently, a fraction of measured ambient oxygenated OA, which correlates with secondary sulphate, may in fact be of a primary, rather than secondary source. These results represent a new source of oxygenated OA on neutral aerosol and imply that the uptake of primary organic gases will occur in the ambient atmosphere, under dilute conditions, and in the presence of pre-existing SO4 aerosols which contain water. Conversely, under acidic seed aerosol conditions, oligomer formation was observed with the uptake of organics being enhanced by a factor of three or more compared to neutral aerosols, and in less than 2 min, representing an additional source of SOA to the atmosphere. This resulted in a trajectory in Van Krevelen space towards higher O : C (slope ~ −1.5, despite a lack of continual gas-phase oxidation in this closed system. The results demonstrate that high molecular weight species will form on acidic aerosols at the ambient level and mixture of organic gases, but are otherwise unaffected by subsequent aerosol neutralization, and that aerosol acidity will affect the organic O : C via aerosol-phase reactions. These two processes, forming oxygenated POA under neutral conditions and SOA under acidic conditions can contribute to the total ambient OA mass and the evolution of ambient aerosol O : C ratios

  10. Biodegradable polyester-based eco-composites containing hemp fibers modified with macrocyclic oligomers

    Science.gov (United States)

    Conzatti, Lucia; Utzeri, Roberto; Hodge, Philip; Stagnaro, Paola

    2016-05-01

    An original compatibilizing pathway for hemp fibers/poly(1,4-butylene adipate-co-terephtalate) (PBAT) eco-composites was explored exploiting the capability of macrocyclic oligomers (MCOs), obtained by cyclodepolymerization (CDP) of PBAT at high dilution, of being re-converted into linear chains by entropically-driven ring-opening polymerization (ED-ROP) that occurs simply heating the MCOS in the bulk. CDP reaction of PBAT was carried out varying solvent, catalyst and reaction time. Selected MCOs were used to adjust the conditions of the ED-ROP reaction. The best experimental conditions were then adopted to modify hemp fibers. Eco-composites based on PBAT and hemp fibers as obtained or modified with PBAT macrocyclics or oligomers were prepared by different process strategies. The best fiber-PBAT compatibility was observed when the fibers were modified with PBAT oligomers before incorporation in the polyester matrix.

  11. Stress relaxation following uniaxial extension of polystyrene melt and oligomer dilutions

    DEFF Research Database (Denmark)

    Huang, Qian; Rasmussen, Henrik K.

    2016-01-01

    The filament stretching rheometer has been used to measure the stress relaxation following the startup of uniaxial extensional flow, on anarrow molar mass distribution (NMMD) polystyrene melt and styrene oligomer dilutions thereof. All samples used here were characterizedin molecular weight......, mechanical spectroscopy, and constant strain rate uniaxial extension in the work of Huang et al. [Macromolecules 46,5026–5035 (2013); ACS Macro Lett. 2, 741–744 (2013)]. The stress relaxation following the steady extensional stress was measured on a285 kg/mole NMMD polystyrene and two 1.92 kg/mole styrene...... oligomer dilutions thereof {PS-285k, PS-285k/2k-72, and PS-285k/2k-44 inthe work of Huang et al. [Macromolecules 46, 5026–5035 (2013)]}. The two dilutions contained 28 and 56 wt. % oligomer, respectively.Further, the stress relaxation on a 545 kg/mole NMMD polystyrene diluted with 48 wt. % 0.972 kg...

  12. Oligomers of heat-shock proteins: Structures that don't imply function

    CERN Document Server

    Jacobs, William M; Frenkel, Daan

    2015-01-01

    Most proteins must remain soluble in the cytosol in order to perform their biological functions. To protect against undesired protein aggregation, living cells maintain a population of molecular chaperones that ensure the solubility of the proteome. Here we report simulations of a lattice model of interacting proteins to understand how low concentrations of passive molecular chaperones, such as small heat-shock proteins, suppress thermodynamic instabilities in protein solutions. Given fixed concentrations of chaperones and client proteins, the solubility of the proteome can be increased by tuning the chaperone--client binding strength. Surprisingly, we find that the binding strength that optimizes solubility while preventing irreversible chaperone binding also promotes the formation of weakly bound chaperone oligomers, although the presence of these oligomers does not significantly affect the thermodynamic stability of the solution. Such oligomers are commonly observed in experiments on small heat-shock prote...

  13. A mechanistic model of tau amyloid aggregation based on direct observation of oligomers

    Science.gov (United States)

    Shammas, Sarah L.; Garcia, Gonzalo A.; Kumar, Satish; Kjaergaard, Magnus; Horrocks, Mathew H.; Shivji, Nadia; Mandelkow, Eva; Knowles, Tuomas P. J.; Mandelkow, Eckhard; Klenerman, David

    2015-04-01

    Protein aggregation plays a key role in neurodegenerative disease, giving rise to small oligomers that may become cytotoxic to cells. The fundamental microscopic reactions taking place during aggregation, and their rate constants, have been difficult to determine due to lack of suitable methods to identify and follow the low concentration of oligomers over time. Here we use single-molecule fluorescence to study the aggregation of the repeat domain of tau (K18), and two mutant forms linked with familial frontotemporal dementia, the deletion mutant ΔK280 and the point mutant P301L. Our kinetic analysis reveals that aggregation proceeds via monomeric assembly into small oligomers, and a subsequent slow structural conversion step before fibril formation. Using this approach, we have been able to quantitatively determine how these mutations alter the aggregation energy landscape.

  14. Linear and Nonlinear Optical Properties of Novel Multi-branched Oligomers

    Institute of Scientific and Technical Information of China (English)

    Li-jing Gong; Ying-hui Wang; Zhi-hui Kang; Tian-hao Huang; Ran Lu; Han-zhuang Zhang

    2012-01-01

    We investigate the fluorene-vinylene unit dependent photo-physical properties of multibranched truxene based oligomers (Tr-OFVn,n=1-4) employing steady-state absorption and emission spectroscopy,transient absorption spectroscopy,two-photon fluorescence,and z-scan technique.The results show that the increasing of fluorene-vinylene unit leads to a red-shift in the spectra of absorption and fluorescence,and shortens the excited state lifetime.Meanwhile,two-photon fluorescence efficiency and two-photon absorption cross section of truxene based oligomers gradually enhance in company with the extension of π-conjugated length.In addition,the values of two-photon absorption cross section modeled on the sum-over-state approach agree well with the experimental ones.The results indicate multi-branched truxene based oligomers bearing oligo(fluorene-vinylene) arms are promising organic materials for two-photon applications.

  15. Thio-urethane oligomers improve the properties of light-cured resin cements.

    Science.gov (United States)

    Bacchi, Ataís; Consani, Rafael L; Martim, Gedalias C; Pfeifer, Carmem S

    2015-05-01

    Thio-urethanes were synthesized by combining 1,6-hexanediol-diissocyante (aliphatic) with pentaerythritol tetra-3-mercaptopropionate (PETMP) or 1,3-bis(1-isocyanato-1-methylethyl)benzene (aromatic) with trimethylol-tris-3-mercaptopropionate (TMP), at 1:2 isocyanate:thiol, leaving pendant thiols. Oligomers were added at 10-30 phr to BisGMA-UDMA-TEGDMA (5:3:2, BUT). 25 wt% silanated inorganic fillers were added. Commercial cement (Relyx Veneer, 3M-ESPE) was also evaluated with 10-20 phr of aromatic oligomer. Near-IR was used to follow methacrylate conversion (DC) and rate of polymerization (Rpmax). Mechanical properties were evaluated in three-point bending (ISO 4049) for flexural strength/modulus (FS/FM, and toughness), and notched specimens (ASTM Standard E399-90) for fracture toughness (KIC). Polymerization stress (PS) was measured on the Bioman. Volumetric shrinkage (VS, %) was measured with the bonded disk technique. Results were analyzed with ANOVA/Tukey's test (α=5%). In general terms, for BUT cements, conversion and mechanical properties in flexure increased for selected groups with the addition of thio-urethane oligomers. The aromatic versions resulted in greater FS/FM than aliphatic. Fracture toughness increased by two-fold in the experimental groups (from 1.17 ± 0.36 MPam(1/2) to around 3.23 ± 0.22 MPam(1/2)). Rpmax decreased with the addition of thio-urethanes, though the vitrification point was not statistically different from the control. VS and PS decreased with both oligomers. For the commercial cement, 20 phr of oligomer increased DC, vitrification, reduced Rpmax and also significantly increased KIC, and reduced PS and FM. Thio-urethane oligomers were shown to favorably modify conventional dimethacrylate networks. Significant reductions in polymerization stress were achieved at the same time conversion and fracture toughness increased.

  16. Synthesis and incorporation of thienylene vinylene oligomers in main-chain copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Madrigal, L.G.; Elandaloussi, E.H.; Spangler, C.W.

    1998-07-01

    Poly [2,5-thienylene vinylene] (PTV) has been studied extensively over the past decade for both its metallic conductivity behavior upon chemical doping, as well as its interesting third order nonlinear optical properties. PTV oligomers have been synthesized by the group, as well as others, and the formation of polaron-like radical-cations or bipolaron-like dications by oxidative doping has been demonstrated. In this paper the authors describe a general synthetic approach to PTV oligomers functionalized for copolymer formation by step-growth reaction.

  17. Synthesis and G-Quadruplex-Binding Properties of Defined Acridine Oligomers

    Directory of Open Access Journals (Sweden)

    Rubén Ferreira

    2010-01-01

    Full Text Available The synthesis of oligomers containing two or three acridine units linked through 2-aminoethylglycine using solid-phase methodology is described. Subsequent studies on cell viability showed that these compounds are not cytotoxic. Binding to several DNA structures was studied by competitive dialysis, which showed a clear affinity for DNA sequences that form G-quadruplexes and parallel triplexes. The fluorescence spectra of acridine oligomers were affected strongly upon binding to DNA. These spectral changes were used to calculate the binding constants (K. Log K were found to be in the order of 4–6.

  18. Charge independence and charge symmetry

    CERN Document Server

    Miller, G A; Miller, Gerald A; van Oers, Willem T H

    1994-01-01

    Charge independence and charge symmetry are approximate symmetries of nature, violated by the perturbing effects of the mass difference between up and down quarks and by electromagnetic interactions. The observations of the symmetry breaking effects in nuclear and particle physics and the implications of those effects are reviewed.

  19. Considerable Enhancement of Emission Yields of [Au(CN)2(-)] Oligomers in Aqueous Solutions by Coexisting Cations.

    Science.gov (United States)

    Wakabayashi, Ryo; Maeba, Junichi; Nozaki, Koichi; Iwamura, Munetaka

    2016-08-01

    The photophysical properties of [Au(CN)2(-)] oligomers in aqueous solutions were investigated as functions of coexisting cations as well as the viscosity and temperature of solutions. A solution of [Au(CN)2(-)] in the concentration range of 0.03-0.2 mol/dm(3) exhibited emission peaks at 460-480 nm because of the presence of oligomers larger than trimers. Although the emission yields (ϕem) of K[Au(CN)2] solutions were wavelength regions were very short and independent of the viscosity of the solutions and coexisting cations (dimer, ∼25 ps; trimer, ∼2 ns). These results indicated that the deactivation of the excited-state [Au(CN)2(-)]n oligomers (n ≥ 4) was dominated by the dissociation of the oligomers to a shorter species (dimer or trimer). The hydrophobic interactions between tetraalkylammonium cations and CN ligands remarkably stabilized the larger oligomers and suppressed the dissociation of the excited-state oligomers, which enhanced the emission yield of the oligomers. This work provides a new method of "exciplex tuning" by changing the environment of excited-state [Au(CN)2(-)]n oligomers. PMID:27391559

  20. A NEW APPROACH TO ELECTROACTIVE POLYMERS VIA WELL-DEFINED OLIGOMERS WITH FURTHER POLYMERIZABLE END-GROUPS

    Institute of Scientific and Technical Information of China (English)

    Yen Wei; You-hai Yu; Wan-jin Zhang; Ce Wang; Xin-ru Jia; Susan A. Jansen

    2002-01-01

    Among the inherent drawbacks of conducting polymers are the limited processibility, uneven polydispersity in molecular weight and the existence of structure defects, which become the obstacles for many electronic, optical and biological applications that demand the materials to have well-defined structures and high chemical purity. To solve these problems, our research in the last decade or so has focused on the synthesis of electroactive oligomers of well-defined structures, controllable molecular weights, narrow or uniform polydispersity. We have developed a general strategy for the synthesis of such oligomers based on the theory of non-classical or reactivation chain polymerization. The aniline oligomers with minimum 4 nitrogen atoms and 3 phenylene rings exhibit similar characteristic redox behavior and electroactivity as polyaniline. Electronic conductivity of the oligomers of 7 or 8 aniline units approaches that of polyaniline. Solubility of the oligomers is much improved over that of conventional polyaniline. Various functional groups can be introduced into the oligomers either by proper selection of starting materials or by post-synthesis modifications via common organic reactions. The functionalized oligomers undergo further polymerizations to afford a variety of new electroactive materials, including polyamides, polyimides, polyureas, polyurethanes, polyacrylamides and epoxy polymers. Numerous potential applications, particularly as anticorrosion materials, are discussed for the oligomers and their polymeric derivatives.

  1. Enzymatic production of defined chitosan oligomers with a specific pattern of acetylation using a combination of chitin oligosaccharide deacetylases

    Science.gov (United States)

    Hamer, Stefanie Nicole; Cord-Landwehr, Stefan; Biarnés, Xevi; Planas, Antoni; Waegeman, Hendrik; Moerschbacher, Bruno Maria; Kolkenbrock, Stephan

    2015-03-01

    Chitin and chitosan oligomers have diverse biological activities with potentially valuable applications in fields like medicine, cosmetics, or agriculture. These properties may depend not only on the degrees of polymerization and acetylation, but also on a specific pattern of acetylation (PA) that cannot be controlled when the oligomers are produced by chemical hydrolysis. To determine the influence of the PA on the biological activities, defined chitosan oligomers in sufficient amounts are needed. Chitosan oligomers with specific PA can be produced by enzymatic deacetylation of chitin oligomers, but the diversity is limited by the low number of chitin deacetylases available. We have produced specific chitosan oligomers which are deacetylated at the first two units starting from the non-reducing end by the combined use of two different chitin deacetylases, namely NodB from Rhizobium sp. GRH2 that deacetylates the first unit and COD from Vibrio cholerae that deacetylates the second unit starting from the non-reducing end. Both chitin deacetylases accept the product of each other resulting in production of chitosan oligomers with a novel and defined PA. When extended to further chitin deacetylases, this approach has the potential to yield a large range of novel chitosan oligomers with a fully defined architecture.

  2. Cyclic oligomers in polyamide for food contact material: quantification by HPLC-CLND and single-substance calibration.

    Science.gov (United States)

    Heimrich, M; Bönsch, M; Nickl, H; Simat, T J

    2012-01-01

    Cyclic oligomers are the major substances migrating from polyamide (PA) food contact materials. However, no commercial standards are available for the quantification of these substances. For the first time the quantification of cyclic oligomers was carried out by HPLC coupled with a chemiluminescence nitrogen detector (CLND) and single-substance calibration. Cyclic monomer (MW = 226 Da) and dimer (MW = 452 Da) of PA66 were synthesised and equimolar N detection of CLND to synthesised oligomers, caprolactam, 6-aminohexanoic acid (monomers of PA6) and caffeine (a typical nitrogen calibrant) was proven. Relative response factors (UVD at 210 nm) referring to caprolactam were determined for cyclic PA6 oligomers from dimer to nonamer, using HPLC-CLND in combination with a UVD. A method for quantification of cyclic oligomer content in PA materials was introduced using HPLC-CLND analysis and caffeine as a single nitrogen calibrant. The method was applied to the quantification of cyclic PA oligomers in several PA granulates. For two PA6 granulates from different manufacturers markedly different oligomer contents were analysed (19.5 versus 13.4 g kg⁻¹). The elution pattern of cyclic oligomers offers the possibility of identifying the PA type and differentiating between PA copolymers and blends.

  3. Synthetic, enzyme kinetic, and protein crystallographic studies of C-β-d-glucopyranosyl pyrroles and imidazoles reveal and explain low nanomolar inhibition of human liver glycogen phosphorylase.

    Science.gov (United States)

    Kantsadi, Anastassia L; Bokor, Éva; Kun, Sándor; Stravodimos, George A; Chatzileontiadou, Demetra S M; Leonidas, Demetres D; Juhász-Tóth, Éva; Szakács, Andrea; Batta, Gyula; Docsa, Tibor; Gergely, Pál; Somsák, László

    2016-11-10

    C-β-d-Glucopyranosyl pyrrole derivatives were prepared in the reactions of pyrrole, 2-, and 3-aryl-pyrroles with O-peracetylated β-d-glucopyranosyl trichloroacetimidate, while 2-(β-d-glucopyranosyl) indole was obtained by a cross coupling of O-perbenzylated β-d-glucopyranosyl acetylene with N-tosyl-2-iodoaniline followed by spontaneous ring closure. An improved synthesis of O-perbenzoylated 2-(β-d-glucopyranosyl) imidazoles was achieved by reacting C-glucopyranosyl formimidates with α-aminoketones. The deprotected compounds were assayed with isoforms of glycogen phosphorylase (GP) to show no activity of the pyrroles against rabbit muscle GPb. The imidazoles proved to be the best known glucose derived inhibitors of not only the muscle enzymes (both a and b) but also of the pharmacologically relevant human liver GPa (Ki = 156 and 26 nM for the 4(5)-phenyl and -(2-naphthyl) derivatives, respectively). An X-ray crystallographic study of the rmGPb-imidazole complexes revealed structural features of the strong binding, and also allowed to explain the absence of inhibition for the pyrrole derivatives. PMID:27522507

  4. Zinc hexacyanoferrate film as an effective protecting layer in two-step and one-step electropolymerization of pyrrole on zinc substrate

    International Nuclear Information System (INIS)

    The two-step and one-step electrosynthesis processes of polypyrrole (PPy) films on the zinc substrate are described. The two-step process includes (i) the zinc surface pretreatment with hexacyanoferrate ion in the aqueous medium in order to form a zinc hexacyanoferrate (ZnHCF) film non-blocking passive layer on the surface and with the view to prevent its reactivity and (ii) electropolymerization of pyrrole on the ZnHCF vertical bar Zn-modified electrode in aqueous pyrrole solution. In this context, both the non-electrolytic and electrolytic procedures were adapted, and the effect of some experimental conditions such as supporting electrolyte, pH and temperature of the solution at the zinc surface pretreatment step as well as pyrrole concentration and electrochemical techniques at the polymerization step was investigated. By optimizing the experimental conditions in both steps, we have obtained a homogeneous and strongly adherent PPy films on the zinc substrate. The one-step process is based on the use of an aqueous medium containing Fe(CN)64- and pyrrole. The ferrocyanide ion passivates the substrate by formation of ZnHCF film during the electropolymerization process of pyrrole and therefore makes it possible to obtain strongly adherent PPy films, with controlled thickness, either by cyclic voltammetry or by electrolysis at constant current or constant potential without any previously treatment of the zinc electrode surface. The polypyrrole films deposited on the zinc electrode were characterized by cyclic voltammetry and scanning electron microscopic (SEM) measurement

  5. One-pot Green Synthesis of Pyrrole Derivatives Catalyzed by Nano Sulfated Zirconia as a Solid Acid Catalyst%One-pot Green Synthesis of Pyrrole Derivatives Catalyzed by Nano Sulfated Zirconia as a Solid Acid Catalyst

    Institute of Scientific and Technical Information of China (English)

    Teimouri, Abbas; Chermahini, Alireza Najafi

    2012-01-01

    A new and efficient method for the preparation of N-substituted pyrroles from one-pot Paal-Knorr condensation has been accomplished using nano-crystalline sulfated zirconia (SZ) as the catalyst in ethanol at moderate temperature. This new protocol has the advantages of easy availability, stability, reusability and eco-friendliness of the catalyst, high to excellent yields, simple experimental and work-up procedure. The synthesized compounds were confirmed through spectral characterization using IR, 1H NMR, 13C NMR and mass spectra.

  6. Construction of human Fab library and screening of a single-domain antibody of amyloid-beta 42 oligomers

    Institute of Scientific and Technical Information of China (English)

    Zuanning Yuan; Minge Du; Yiwen Chen; Fei Dou

    2013-01-01

    Screening humanized antibodies from a human Fab phage display library is an effective and quick method to obtain beta-amyloid oligomers. Thus, the present study prepared amyloid-beta 42 oli-gomers and constructed a naïve human Fab phage display library based on blood samples from six healthy people. After three rounds of biopanning in vitro, a human single-domain antibody that spe-cifical y recognized amyloid-beta 42 oligomers was identified. Western blot and enzyme-linked immunosorbent assay demonstrated this antibody bound specifical y to human amyloid-beta 42 te-tramer and nonamer, but not the monomer or high molecular weight oligomers. This study suc-cessful y constructed a human phage display library and screened a single-domain antibody that specifical y recognized amyloid-beta 42 oligomers.

  7. Crystallization and preliminary crystallographic study of oligomers of the haemolytic lectin CEL-III from the sea cucumber Cucumaria echinata.

    Science.gov (United States)

    Unno, Hideaki; Hisamatsu, Keigo; Nagao, Tomonao; Tateya, Yuki; Matsumoto, Naoki; Goda, Shuichiro; Hatakeyama, Tomomitsu

    2013-04-01

    CEL-III is a Ca(2+)-dependent haemolytic lectin isolated from the marine invertebrate Cucumaria echinata. This lectin binds to Gal/GalNAc-containing carbohydrate chains on the cell surface and, after conformational changes, oligomerizes to form ion-permeable pores in cell membranes. CEL-III also forms soluble oligomers similar to those formed in cell membranes upon binding of specific carbohydrates in high-pH and high-salt solutions. These soluble and membrane CEL-III oligomers were crystallized and X-ray diffraction data were collected. Crystals of soluble oligomers and membrane oligomers diffracted X-rays to 3.3 and 4.2 Å resolution, respectively, using synchrotron radiation and the former was found to belong to space group C2. Self-rotation functional analysis of the soluble oligomer crystal suggested that it might be composed of heptameric CEL-III. PMID:23545649

  8. Charged Leptons

    CERN Document Server

    Albrecht, J; Babu, K; Bernstein, R H; Blum, T; Brown, D N; Casey, B C K; Cheng, C -h; Cirigliano, V; Cohen, A; Deshpande, A; Dukes, E C; Echenard, B; Gaponenko, A; Glenzinski, D; Gonzalez-Alonso, M; Grancagnolo, F; Grossman, Y; Harnik, R; Hitlin, D G; Kiburg, B; Knoepfe, K; Kumar, K; Lim, G; Lu, Z -T; McKeen, D; Miller, J P; Ramsey-Musolf, M; Ray, R; Roberts, B L; Rominsky, M; Semertzidis, Y; Stoeckinger, D; Talman, R; Van De Water, R; Winter, P

    2013-01-01

    This is the report of the Intensity Frontier Charged Lepton Working Group of the 2013 Community Summer Study "Snowmass on the Mississippi", summarizing the current status and future experimental opportunities in muon and tau lepton studies and their sensitivity to new physics. These include searches for charged lepton flavor violation, measurements of magnetic and electric dipole moments, and precision measurements of the decay spectrum and parity-violating asymmetries.

  9. Electrical detection of dengue virus (DENV) DNA oligomer using silicon nanowire biosensor with novel molecular gate control.

    Science.gov (United States)

    Nuzaihan M N, M; Hashim, U; Md Arshad, M K; Kasjoo, S R; Rahman, S F A; Ruslinda, A R; Fathil, M F M; Adzhri, R; Shahimin, M M

    2016-09-15

    In this paper, a silicon nanowire biosensor with novel molecular gate control has been demonstrated for Deoxyribonucleic acid (DNA) detection related to dengue virus (DENV). The silicon nanowire was fabricated using the top-down nanolithography approach, through nanostructuring of silicon-on-insulator (SOI) layers achieved by combination of the electron-beam lithography (EBL), plasma dry etching and size reduction processes. The surface of the fabricated silicon nanowire was functionalized by means of a three-step procedure involving surface modification, DNA immobilization and hybridization. This procedure acts as a molecular gate control to establish the electrical detection for 27-mers base targets DENV DNA oligomer. The electrical detection is based on the changes in current, resistance and conductance of the sensor due to accumulation of negative charges added by the immobilized probe DNA and hybridized target DNA. The sensitivity of the silicon nanowire biosensors attained was 45.0µAM(-1), which shows a wide-range detection capability of the sensor with respect to DNA. The limit of detection (LOD) achieved was approximately 2.0fM. The demonstrated results show that the silicon nanowire has excellent properties for detection of DENV with outstanding repeatability and reproducibility performances. PMID:27107147

  10. Delayed Time-to-Treatment of an Antisense Morpholino Oligomer Is Effective against Lethal Marburg Virus Infection in Cynomolgus Macaques.

    Directory of Open Access Journals (Sweden)

    Travis K Warren

    2016-02-01

    Full Text Available Marburg virus (MARV is an Ebola-like virus in the family Filovirdae that causes sporadic outbreaks of severe hemorrhagic fever with a case fatality rate as high as 90%. AVI-7288, a positively charged antisense phosphorodiamidate morpholino oligomer (PMOplus targeting the viral nucleoprotein gene, was evaluated as a potential therapeutic intervention for MARV infection following delayed treatment of 1, 24, 48, and 96 h post-infection (PI in a nonhuman primate lethal challenge model. A total of 30 cynomolgus macaques were divided into 5 groups of 6 and infected with 1,830 plaque forming units of MARV subcutaneously. AVI-7288 was administered by bolus infusion daily for 14 days at 15 mg/kg body weight. Survival was the primary endpoint of the study. While none (0 of 6 of the saline group survived, 83-100% of infected monkeys survived when treatment was initiated 1, 24, 48, or 96 h post-infection (PI. The antisense treatment also reduced serum viremia and inflammatory cytokines in all treatment groups compared to vehicle controls. The antibody immune response to virus was preserved and tissue viral antigen was cleared in AVI-7288 treated animals. These data show that AVI-7288 protects NHPs against an otherwise lethal MARV infection when treatment is initiated up to 96 h PI.

  11. Ultrafast photoexcited dynamics probe of blends of conjugated polymerpoly{bi(dodecyl)thiophene-thieno[3,4-c]pyrrole-4,6-dione} and fullerenes for photovoltaic applications with broadband sub-10-fs visible pulse

    Science.gov (United States)

    Kao, Chih-Hsien; Yabushita, Atsushi; Su, Yu-Wei; Wei, Kung-Hwa; Lee, Yu-Hsien; Kobayashi, Takayoshi

    2016-03-01

    Conjugated polymers have been widely studied as active materials for organic solar cells, which are a promising replacement for silicon solar cells. A novel electron donor polymer of poly{bi(dodecyl)thiophene-thieno[3,4-c]pyrrole-4,6-dione} (PBTTPD) blended with an electron acceptor, [6,6]-phenyl C71 butyric acid methyl ester (PC71BM), gave a device power conversion efficiency as high as 7.3%. In the present work, we performed time-resolved absorption change spectroscopy at various mixture ratios of PC71BM in the PBTTPD/PC71BM blend. Among the obtained time constants, the shortest (60 fs) and the longest (500 fs and 15 ps) were assigned to the production and relaxation of charge-transfer (CT) states, respectively. The PC71BM blended with PBTTPD was found to suppress interchain carrier transport and increase intrachain carrier transport. The prolonged lifetime of the CT state in the equally blended PBTTPD/PC71BM film increases the probability of charge separation and thus increases the power conversion efficiency of the device.

  12. Quadrupolar, emission-tunable pi-expanded 1,4-dihydropyrrolo 3,2-b pyrroles - synthesis and optical properties

    DEFF Research Database (Denmark)

    Janiga, A.; Bednarska, D.; Thorsted, B.;

    2014-01-01

    . It was demonstrated that the increase in the molecular length of the chromophore effectively extends pi-conjugation. The effect of structural variations on photophysical properties was studied in detail for these compounds and the relationship between the structure and photophysical properties was thoroughly......The synthesis and optical characterization of six novel heteroaromatic-based chromophores is described. The new dyes present mostly an A-D-A general framework, where A is an electron-deficient aromatic ring and D is an electron-rich pyrrolo[3,2-b] pyrrole moiety, linked via triple bonds...

  13. A Hydrogen Peroxide Sensor Prepared by Electropolymerization of Pyrrole Based on Screen-Printed Carbon Paste Electrodes

    Directory of Open Access Journals (Sweden)

    Hui Xu

    2007-03-01

    Full Text Available A disposable amperometric biosensor for commercial use to detect hydrogenperoxide has been developed. The sensor is based on screen-printed carbon paste electrodesmodified by electropolymerization of pyrrole with horseradish peroxidase (HRP entrapped.The facture techniques of fabricating the enzyme electrodes are suitable for mass productionand quality control. The biosensor shows a linear amperometric response to H2O2 from 0.1to 2.0 mM, with a sensitivity of 33.24 μA mM-1 cm-2. Different operational parameters ofelectropolymerization are evaluated and optimized.

  14. Electropolymerization of pyrrole: effects of pH and anions on the conductivity and growth kinetics of polypyrrole

    Energy Technology Data Exchange (ETDEWEB)

    Kupila, E.L. (Dept. of Chemistry, Univ. of Turku (Finland)); Kankare, J. (Dept. of Chemistry, Univ. of Turku (Finland))

    1993-03-22

    Polypyrrole is one of the most studied conducting polymers. In situ AC conductimetry during electropolymerization is a method which allows the specific conductivity to be estimated for the polymer in statu nascendi. We have applied this method to the electropolymerization of pyrrole in aqueous solutions at various conditions. Polymers synthesized at lower pH range are of better quality than those synthesized at higher pH values. The use of small anions in the supporting electrolyte results in a layer of low conductivity at pH 7. The use of long-chain organic anions like sodium dodecylsulfate gives a high quality polymer even in neutral unbuffered solutions. (orig.)

  15. Ru-Catalysed C–H Arylation of Indoles and Pyrroles with Boronic Acids: Scope and Mechanistic Studies

    Science.gov (United States)

    Sollert, Carina; Devaraj, Karthik; Orthaber, Andreas; Gates, Paul J; Pilarski, Lukasz T

    2015-01-01

    The Ru-catalysed C2–H arylation of indoles and pyrroles by using boronic acids under oxidative conditions is reported. This reaction can be applied to tryptophan derivatives and tolerates a wide range of functional groups on both coupling partners, including bromides and iodides, which can be further derivatised selectively. New indole-based ruthenacyclic complexes are described and investigated as possible intermediates in the reaction. Mechanistic studies suggest the on-cycle intermediates do not possess a para-cymene ligand and that the on-cycle metalation occurs through an electrophilic attack by the Ru centre. PMID:25689052

  16. Construction of a monoanionic S,N,S-pincer ligand with a pyrrole core by sequential [1,2] phospho-Fries rearrangement. Characterization of palladium and silver coordination complexes

    NARCIS (Netherlands)

    Fraix, A.; Lutz, M.; Spek, A.L.; Klein Gebbink, R.J.M.; van Koten, G.; Salaun, J. -Y; Jaffrès, P. -A

    2010-01-01

    The synthesis of an S,NH,S-pincer ligand possessing a pyrrole core and two O,O-diethylthiophosphonyl groups to design PS lateral coordination sites is reported. The synthetic procedure to produce this ligand makes use of the nitrogen atom of the pyrrole heterocycle to successively functionalize the

  17. Oligomer formation during gas-phase ozonolysis of small alkenes and enol ethers: new evidence for the central role of the Criegee Intermediate as oligomer chain unit

    Directory of Open Access Journals (Sweden)

    A. Sadezky

    2008-05-01

    Full Text Available An important fraction of secondary organic aerosol (SOA formed by atmospheric oxidation of diverse volatile organic compounds (VOC has recently been shown to consist of high-molecular weight oligomeric species. In our previous study (Sadezky et al., 2006, we reported the identification and characterization of oligomers as main constituents of SOA from gas-phase ozonolysis of small enol ethers. These oligomers contained repeated chain units of the same chemical composition as the main Criegee Intermediates (CI formed during the ozonolysis reaction, which were CH2O2 (mass 46 for alkyl vinyl ethers (AVE and C2H4O2 (mass 60 for ethyl propenyl ether (EPE. In the present work, we extend our previous study to another enol ether (ethyl butenyl ether EBE and a variety of structurally related small alkenes (trans-3-hexene, trans-4-octene and 2,3-dimethyl-2-butene.

    Experiments have been carried out in a 570 l spherical glass reactor at atmospheric conditions in the absence of seed aerosol. SOA formation was measured by a scanning mobility particle sizer (SMPS. SOA filter samples were collected and chemically characterized off-line by ESI(+/TOF MS and ESI(+/TOF MS/MS, and elemental compositions were determined by ESI(+/FTICR MS and ESI(+/FTICR MS/MS. The results for all investigated unsaturated compounds are in excellent agreement with the observations of our previous study. Analysis of the collected SOA filter samples reveal the presence of oligomeric compounds in the mass range 200 to 800 u as major constituents. The repeated chain units of these oligomers are shown to systematically have the same chemical composition as the respective main Criegee Intermediate (CI formed during ozonolysis of the unsaturated compounds, which is C3H6O2 (mass 74 for ethyl butenyl ether (EBE, trans-3-hexene, and 2,3-dimethyl-2-butene, and C4H8

  18. Cytotoxic helix-rich oligomer formation by melittin and pancreatic polypeptide.

    Directory of Open Access Journals (Sweden)

    Pradeep K Singh

    Full Text Available Conversion of amyloid fibrils by many peptides/proteins involves cytotoxic helix-rich oligomers. However, their toxicity and biophysical studies remain largely unknown due to their highly dynamic nature. To address this, we chose two helical peptides (melittin, Mel and pancreatic polypeptide, PP and studied their aggregation and toxicity. Mel converted its random coil structure to oligomeric helical structure upon binding to heparin; however, PP remained as helix after oligomerization. Interestingly, similar to Parkinson's associated α-synuclein (AS oligomers, Mel and PP also showed tinctorial properties, higher hydrophobic surface exposure, cellular toxicity and membrane pore formation after oligomerization in the presence of heparin. We suggest that helix-rich oligomers with exposed hydrophobic surface are highly cytotoxic to cells irrespective of their disease association. Moreover as Mel and PP (in the presence of heparin instantly self-assemble into stable helix-rich amyloidogenic oligomers; they could be represented as models for understanding the biophysical and cytotoxic properties of helix-rich intermediates in detail.

  19. Manipulating Fano resonance via fs-laser melting of hybrid oligomers at nanoscale

    Science.gov (United States)

    Lepeshov, S. I.; Zuev, D. A.; Makarov, S. V.; Milichko, V. A.; Mukhin, I. S.; Krasnok, A. E.; Belov, P. A.

    2016-08-01

    Here, the novel concept of asymmetric metal-dielectric (hybrid) nanoparticles is proposed. The experimental data and the results of numerical simulation of the optical properties of hybrid nanostructures are presented. The change of their optical response after fs- laser modification is shown. The possibility of manipulating Fano resonance in hybrid oligomers by the gold nanoparticles reshaping is demonstrated.

  20. Molecular mechanisms used by chaperones to reduce the toxicity of aberrant protein oligomers

    NARCIS (Netherlands)

    Mannini, Benedetta; Cascella, Roberta; Zampagni, Mariagioia; Van Waarde-Verhagen, Maria; Meehan, Sarah; Roodveldt, Cintia; Campioni, Silvia; Boninsegna, Matilde; Penco, Amanda; Relini, Annalisa; Kampinga, Harm H.; Dobson, Christopher M.; Wilson, Mark R.; Cecchi, Cristina; Chiti, Fabrizio

    2012-01-01

    Chaperones are the primary regulators of the proteostasis network and are known to facilitate protein folding, inhibit protein aggregation, and promote disaggregation and clearance of misfolded aggregates inside cells. We have tested the effects of five chaperones on the toxicity of misfolded oligom

  1. Enhanced Volatile Organic Compounds emissions and organic aerosol mass increase the oligomer content of atmospheric aerosols

    Science.gov (United States)

    Kourtchev, Ivan; Giorio, Chiara; Manninen, Antti; Wilson, Eoin; Mahon, Brendan; Aalto, Juho; Kajos, Maija; Venables, Dean; Ruuskanen, Taina; Levula, Janne; Loponen, Matti; Connors, Sarah; Harris, Neil; Zhao, Defeng; Kiendler-Scharr, Astrid; Mentel, Thomas; Rudich, Yinon; Hallquist, Mattias; Doussin, Jean-Francois; Maenhaut, Willy; Bäck, Jaana; Petäjä, Tuukka; Wenger, John; Kulmala, Markku; Kalberer, Markus

    2016-10-01

    Secondary organic aerosol (SOA) accounts for a dominant fraction of the submicron atmospheric particle mass, but knowledge of the formation, composition and climate effects of SOA is incomplete and limits our understanding of overall aerosol effects in the atmosphere. Organic oligomers were discovered as dominant components in SOA over a decade ago in laboratory experiments and have since been proposed to play a dominant role in many aerosol processes. However, it remains unclear whether oligomers are relevant under ambient atmospheric conditions because they are often not clearly observed in field samples. Here we resolve this long-standing discrepancy by showing that elevated SOA mass is one of the key drivers of oligomer formation in the ambient atmosphere and laboratory experiments. We show for the first time that a specific organic compound class in aerosols, oligomers, is strongly correlated with cloud condensation nuclei (CCN) activities of SOA particles. These findings might have important implications for future climate scenarios where increased temperatures cause higher biogenic volatile organic compound (VOC) emissions, which in turn lead to higher SOA mass formation and significant changes in SOA composition. Such processes would need to be considered in climate models for a realistic representation of future aerosol-climate-biosphere feedbacks.

  2. Diverse metastable structures formed by small oligomers of α-synuclein probed by force spectroscopy.

    Directory of Open Access Journals (Sweden)

    Krishna Neupane

    Full Text Available Oligomeric aggregates are widely suspected as toxic agents in diseases caused by protein aggregation, yet they remain poorly characterized, partly because they are challenging to isolate from a heterogeneous mixture of species. We developed an assay for characterizing structure, stability, and kinetics of individual oligomers at high resolution and sensitivity using single-molecule force spectroscopy, and applied it to observe the formation of transient structured aggregates within single oligomers of α-synuclein, an intrinsically-disordered protein linked to Parkinson's disease. Measurements of the molecular extension as the proteins unfolded under tension in optical tweezers revealed that even small oligomers could form numerous metastable structures, with a surprisingly broad range of sizes. Comparing the structures formed in monomers, dimers and tetramers, we found that the average mechanical stability increased with oligomer size. Most structures formed within a minute, with size-dependent rates. These results provide a new window onto the complex α-synuclein aggregation landscape, characterizing the microscopic structural heterogeneity and kinetics of different pathways.

  3. Optical Properties of Oligo(fluorene-vinylene) Functionalized Anthracene Linear Oligomers: Effect of π-extension

    Institute of Scientific and Technical Information of China (English)

    Tian-hao Huang; Li-li Qu; Zhi-hui Kang; Ying-hui Wang; Ran Lu; Er-long Miao; Fei Wang

    2013-01-01

    The photo-physical properties of oligo(fluorene-vinylene) functionalized anthracene linear oligomers (An-OFVn (n=1-4)) have been systemically investigated through experimental and theoretical methods.The steady-state spectral measurement shows that the increasing of fluorene-vinylene (FV) group could lead to the red shift of absorption spectra and restrain the excimer formation between oligomers.Quantum chemical calculations exhibit that the energy levels of HOMO,LUMO,and the band gap gradually converge to a constant in accompany with the increasing of FV unit.Meanwhile,the electronic cloud which distributes on the branch arms,also gradually enhances and makes the absorption spectral shape of oligomers become similar to that of branch arms step by step.The time-resolved fluorescence tests exhibits that the lifetime of excimer emission would be ahmost invariable after the number of FV group in oligomer is >2.In nonlinear optical test,the two-photon photoluminescence efficiency and two-photon absorption cross-section will both gradually enhance and be close to an extrenum after the number of FV unit is equal to 4.These results will provide a guideline for the design of novel photo-electronic materials.

  4. Development of new fusion proteins for visualizing amyloid-β oligomers in vivo.

    Science.gov (United States)

    Ochiishi, Tomoyo; Doi, Motomichi; Yamasaki, Kazuhiko; Hirose, Keiko; Kitamura, Akira; Urabe, Takao; Hattori, Nobutaka; Kinjo, Masataka; Ebihara, Tatsuhiko; Shimura, Hideki

    2016-01-01

    The intracellular accumulation of amyloid-β (Aβ) oligomers critically contributes to disease progression in Alzheimer's disease (AD) and can be the potential target of AD therapy. Direct observation of molecular dynamics of Aβ oligomers in vivo is key for drug discovery research, however, it has been challenging because Aβ aggregation inhibits the fluorescence from fusion proteins. Here, we developed Aβ1-42-GFP fusion proteins that are oligomerized and visualize their dynamics inside cells even when aggregated. We examined the aggregation states of Aβ-GFP fusion proteins using several methods and confirmed that they did not assemble into fibrils, but instead formed oligomers in vitro and in live cells. By arranging the length of the liker between Aβ and GFP, we generated two fusion proteins with "a long-linker" and "a short-linker", and revealed that the aggregation property of fusion proteins can be evaluated by measuring fluorescence intensities using rat primary culture neurons transfected with Aβ-GFP plasmids and Aβ-GFP transgenic C. elegans. We found that Aβ-GFP fusion proteins induced cell death in COS7 cells. These results suggested that novel Aβ-GFP fusion proteins could be utilized for studying the physiological functions of Aβ oligomers in living cells and animals, and for drug screening by analyzing Aβ toxicity. PMID:26982553

  5. A cytotoxic amyloid oligomer self-triggered and NIR- enhanced amyloidosis therapeutic system

    Institute of Scientific and Technical Information of China (English)

    Can Xu[1,2; Peng Shi[1,2; Meng Li[1,2; Jinsong Ren[1; xiaogang Qu[1

    2015-01-01

    We report a new strategy for improving the efficiency of non-specific amyloidosis therapeutic drugs by coating amyloid-responsive lipid bilayers. The approach had drawn inspiration from amyloid oligomer-mediated cell membrane disruption in the pathogenesis of amyloidosis. A graphene-mesoporous silica hybrid (GMS)-supported lipid bilayer (GMS-Lip) system was used as a drug carrier, Drugs were well confined inside the nanocarrier until encountering amyloid oligomers, which could pierce the lipid bilayer coat and cause drug release. To ensure release efficiency, use of a near-infrared (NIR) laser was also introduced to facilitate drug release, taking advantage of the photothermal effect of GMS and thermal sensitivity of lipid bilayers. To facilitate tracking, fluorescent dyes were co-loaded with drugs within GMS-Lip and the NIR laser was used once the oligomer-triggered release had been signaled. Because of the spatially and temporally controllable property of light, the NIR-assisted release could be easily and selectively activated locally by tracking the fluorescence signal. Our design is based on arnyloidosis pathogenesis, the cytotoxic amyloid oligomer self-triggered release via cell membrane disruption, for the controlled release of drug molecules. The results may shed light on the development of pathogenesis- inspired drug delivery systems,

  6. Hybrid Conjugated Organic Oligomers Consisting of Oligodiacetylene and Thiophene Units: Synthesis and Optical Properties

    NARCIS (Netherlands)

    Pilzak, G.S.; Gruijthuijsen, van K.; Doorn, van R.H.; Lagen, van B.; Sudhölter, E.J.R.; Zuilhof, H.

    2009-01-01

    Novel and highly soluble hybrid conjugated organic oligomers consisting of oligodiacetylene and thiophene units have been synthesized in high purity through iterative and divergent approaches based on a sequence of Sonogashira reactions. The series of thiophene-containing oligodiacetylenes (ThODAs)

  7. Direct characterization of protein oligomers and their quaternary structures by single-molecule FRET.

    Science.gov (United States)

    Kim, Cheolhee; Kim, Jae Yeol; Kim, Seung Hyeon; Lee, Byung Il; Lee, Nam Ki

    2012-01-28

    Using a single-molecule method, we directly distinguish among oligomers from monomers to tetramers and determine their quaternary structures. Using this method, we found that RecR forms a stable dimer and its oligomeric form is modulated by its own concentration and the interaction with RecO. PMID:22159510

  8. GPCR-OKB: the G Protein Coupled Receptor Oligomer Knowledge Base.

    NARCIS (Netherlands)

    Khelashvili, G.; Dorff, K.; Shan, J.; Camacho-Artacho, M.; Skrabanek, L.; Vroling, B.; Bouvier, M.; Devi, L.A.; George, S.R.; Javitch, J.A.; Lohse, M.J.; Milligan, G.; Neubig, R.R.; Palczewski, K.; Parmentier, M.; Pin, J.P.; Vriend, G.; Campagne, F.; Filizola, M.

    2010-01-01

    SUMMARY: Rapid expansion of available data about G Protein Coupled Receptor (GPCR) dimers/oligomers over the past few years requires an effective system to organize this information electronically. Based on an ontology derived from a community dialog involving colleagues using experimental and compu

  9. Structure–property relationships of synthetic organophosphorus flame retardant oligomers by thermal analysis

    Energy Technology Data Exchange (ETDEWEB)

    Bai, Zhiman [State Key Lab of Fire Science, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui 230026 (China); USTC-CityU Joint Advanced Research Centre, Suzhou Key Laboratory of Urban Public Safety, Suzhou Institute for Advanced Study, University of Science and Technology of China, 166 Ren’ai Road Suzhou, Jiangsu 215123 (China); Wang, Xin; Tang, Gang; Song, Lei [State Key Lab of Fire Science, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui 230026 (China); Hu, Yuan, E-mail: yuanhu@ustc.edu.cn [State Key Lab of Fire Science, University of Science and Technology of China, 96 Jinzhai Road, Hefei, Anhui 230026 (China); USTC-CityU Joint Advanced Research Centre, Suzhou Key Laboratory of Urban Public Safety, Suzhou Institute for Advanced Study, University of Science and Technology of China, 166 Ren’ai Road Suzhou, Jiangsu 215123 (China); Yuen, Richard K.K., E-mail: Richard.Yuen@cityu.edu.hk [USTC-CityU Joint Advanced Research Centre, Suzhou Key Laboratory of Urban Public Safety, Suzhou Institute for Advanced Study, University of Science and Technology of China, 166 Ren’ai Road Suzhou, Jiangsu 215123 (China); Department of Building and Construction, City University of Hong Kong, Tat Chee Avenue Kowloon (Hong Kong)

    2013-08-10

    Highlights: • Oligomers with different chemical components in molecular chains were synthesized. • FP-3 containing three IFR components possessed high thermal stability. • FP-3 possessed lowest flammability. • FP-3 exhibited a synergistic interaction between gas and condensed phase. - Abstract: A series of flame retardant oligomers with different chemical components in molecular chains, designated as FP-1, FP-2 and FP-3, respectively, were successfully synthesized using solution polycondensation and well characterized. The thermal properties and flammability of these oligomers were investigated by thermogravimetric analysis (TGA) and microscale combustion calorimeter (MCC). The results demonstrated that FP-3 had the lowest flammability in terms of the lowest maximum mass loss rate, and FP-1 possessed the highest thermal stability and char yield, due to its higher stable hexatomic ring structure of piperazine compared with the linear alkane chain structure of neopentyl glycol. The gases evolved during decomposition were analyzed using Fourier transform infrared coupled with the thermogravimetric analyzer (TG–IR) technique. The char residues of the flame retardant oligomers were investigated by scanning electron microscopy (SEM) and Raman spectroscopy. The results demonstrated that FP-3 exhibited a synergistic interaction between the gas phase and condensation phase, increasing its flame retardancy.

  10. Genotoxicity of styrene oligomers extracted from polystyrene intended for use in contact with food

    Directory of Open Access Journals (Sweden)

    Makoto Nakai

    2014-01-01

    Full Text Available Here, we conducted in vitro genotoxicity tests to evaluate the genotoxicity of styrene oligomers extracted from polystyrene intended for use in contact with food. Styrene oligomers were extracted with acetone and the extract was subjected to the Ames test (OECD test guideline No. 471 and the in vitro chromosomal aberration test (OECD test guideline No. 473 under good laboratory practice conditions. The concentrations of styrene dimers and trimers in the concentrated extract were 540 and 13,431 ppm, respectively. Extraction with acetone provided markedly higher concentrations of styrene oligomers compared with extraction with 50% ethanol aqueous solution, which is the food simulant currently recommended for use in safety assessments of polystyrene by both the United States Food and Drug Administration and the European Food Safety Authority. And these high concentrations of styrene dimers and trimers were utilized for the evaluation of genotoxicity in vitro. Ames tests using five bacterial tester strains were negative both in the presence or absence of metabolic activation. The in vitro chromosomal aberration test using Chinese hamster lung cells (CHL/IU was also negative. Together, these results suggest that the risk of the genotoxicity of styrene oligomers that migrate from polystyrene food packaging into food is very low.

  11. Tracking chromosomal positions of oligomers - a case study with Illumina's BovineSNP50 beadchip

    Directory of Open Access Journals (Sweden)

    Brockmann Gudrun A

    2010-02-01

    Full Text Available Abstract Background High density genotyping arrays have become established as a valuable research tool in human genetics. Currently, more than 300 genome wide association studies were published for human reporting about 1,000 SNPs that are associated with a phenotype. Also in animal sciences high density genotyping arrays are harnessed to analyse genetic variation. To exploit the full potential of this technology single nucleotide polymorphisms (SNPs on the chips should be well characterized and their chromosomal position should be precisely known. This, however, is a challenge if the genome sequence is still subject to changes. Results We have developed a mapping strategy and a suite of software scripts to update the chromosomal positions of oligomer sequences used for SNP genotyping on high density arrays. We describe the mapping procedure in detail so that scientists with moderate bioinformatics skills can reproduce it. We furthermore present a case study in which we re-mapped 54,001 oligomer sequences from Ilumina's BovineSNP50 beadchip to the bovine genome sequence. We found in 992 cases substantial discrepancies between the manufacturer's annotations and our results. The software scripts in the Perl and R programming languages are provided as supplements. Conclusions The positions of oligomer sequences in the genome are volatile even within one build of the genome. To facilitate the analysis of data from a GWAS or from an expression study, especially with species whose genome assembly is still unstable, it is recommended to update the oligomer positions before data analysis.

  12. The role of stable α-synuclein oligomers in the molecular events underlying amyloid formation

    DEFF Research Database (Denmark)

    Lorenzen, Nikolai; Nielsen, Søren Bang; Buell, Alexander K.;

    2014-01-01

    and small-angle x-ray scattering (SAXS) data suggest that they are ellipsoidal with a high degree of flexibility at the interface with solvent. This oligomer population is unable to elongate fibrils, and indeed results in an inhibition of the kinetics of amyloid formation in a concentration-dependent manner....

  13. Quantization of the dipole moment and of the end charges in push-pull polymers

    Science.gov (United States)

    Kudin, Konstantin N.; Car, Roberto; Resta, Raffaele

    2007-11-01

    A theorem for end-charge quantization in quasi-one-dimensional stereoregular chains is formulated and proved. It is a direct analog of the well-known theorem for surface charges in physics. The theorem states the following: (1) Regardless of the end groups, in stereoregular oligomers with a centrosymmetric bulk, the end charges can only be a multiple of 1/2 and the longitudinal dipole moment per monomer p can only be a multiple of 1/2 times the unit length a in the limit of long chains. (2) In oligomers with a noncentrosymmetric bulk, the end charges can assume any value set by the nature of the bulk. Nonetheless, by modifying the end groups, one can only change the end charge by an integer and the dipole moment p by an integer multiple of the unit length a. (3) When the entire bulk part of the system is modified, the end charges may change in an arbitrary way; however, if upon such a modification the system remains centrosymmetric, the end charges can only change by multiples of 1/2 as a direct consequence of (1). The above statements imply that—in all cases—the end charges are uniquely determined, modulo an integer, by a property of the bulk alone. The theorem's origin is a robust topological phenomenon related to the Berry phase. The effects of the quantization are first demonstrated in toy LiF chains and then in a series of trans-polyacetylene oligomers with neutral and charge-transfer end groups.

  14. PrP(Sc-specific antibodies with the ability to immunodetect prion oligomers.

    Directory of Open Access Journals (Sweden)

    Mourad Tayebi

    Full Text Available The development of antibodies with binding capacity towards soluble oligomeric forms of PrPSc recognised in the aggregation process in early stage of the disease would be of paramount importance in diagnosing prion diseases before extensive neuropathology has ensued. As blood transfusion appears to be efficient in the transmission of the infectious prion agent, there is an urgent need to develop reagents that would specifically recognize oligomeric forms of the abnormally folded prion protein, PrPSc.To that end, we show that anti-PrP monoclonal antibodies (called PRIOC mAbs derived from mice immunised with native PrP-coated microbeads are able to immunodetect oligomers/multimers of PrPSc. Oligomer-specific immunoreactivity displayed by these PRIOC mAbs was demonstrated as large aggregates of immunoreactive deposits in prion-permissive neuroblastoma cell lines but not in equivalent non-infected or prn-p(0/0 cell lines. In contrast, an anti-monomer PrP antibody displayed diffuse immunoreactivity restricted to the cell membrane. Furthermore, our PRIOC mAbs did not display any binding with monomeric recombinant and cellular prion proteins but strongly detected PrPSc oligomers as shown by a newly developed sensitive and specific ELISA. Finally, PrioC antibodies were also able to bind soluble oligomers formed of Aβ and α-synuclein. These findings demonstrate the potential use of anti-prion antibodies that bind PrPSc oligomers, recognised in early stage of the disease, for the diagnosis of prion diseases in blood and other body fluids.

  15. Alzheimer's-associated Abeta oligomers show altered structure, immunoreactivity and synaptotoxicity with low doses of oleocanthal.

    Science.gov (United States)

    Pitt, Jason; Roth, William; Lacor, Pascale; Smith, Amos B; Blankenship, Matthew; Velasco, Pauline; De Felice, Fernanda; Breslin, Paul; Klein, William L

    2009-10-15

    It now appears likely that soluble oligomers of amyloid-beta1-42 peptide, rather than insoluble fibrils, act as the primary neurotoxin in Alzheimer's disease (AD). Consequently, compounds capable of altering the assembly state of these oligomers (referred to as ADDLs) may have potential for AD therapeutics. Phenolic compounds are of particular interest for their ability to disrupt Abeta oligomerization and reduce pathogenicity. This study has focused on oleocanthal (OC), a naturally-occurring phenolic compound found in extra-virgin olive oil. OC increased the immunoreactivity of soluble Abeta species, when assayed with both sequence- and conformation-specific Abeta antibodies, indicating changes in oligomer structure. Analysis of oligomers in the presence of OC showed an upward shift in MW and a ladder-like distribution of SDS-stable ADDL subspecies. In comparison with control ADDLs, oligomers formed in the presence of OC (Abeta-OC) showed equivalent colocalization at synapses but exhibited greater immunofluorescence as a result of increased antibody recognition. The enhanced signal at synapses was not due to increased synaptic binding, as direct detection of fluorescently-labeled ADDLs showed an overall reduction in ADDL signal in the presence of OC. Decreased binding to synapses was accompanied by significantly less synaptic deterioration assayed by drebrin loss. Additionally, treatment with OC improved antibody clearance of ADDLs. These results indicate oleocanthal is capable of altering the oligomerization state of ADDLs while protecting neurons from the synaptopathological effects of ADDLs and suggest OC as a lead compound for development in AD therapeutics. PMID:19631677

  16. Thermodynamically stable amyloid-β monomers have much lower membrane affinity than the small oligomers

    Directory of Open Access Journals (Sweden)

    Bidyut eSarkar

    2013-04-01

    Full Text Available Amyloid beta (Aβ is an extracellular 39-43 residue long peptide present in the mammalian cerebrospinal fluid, whose aggregation is associated with Alzheimer’s disease. Small oligomers of Aβ are currently thought to be the key to toxicity. However, it is not clear why the monomers of Aβ are non-toxic, and at what stage of aggregation toxicity emerges. Interactions of Aβ with cell membranes is thought to be the initiator of toxicity, but membrane-binding studies with different preparations of monomers and oligomers have not settled this issue. We have earlier found that thermodynamically stable Aβ monomers emerge spontaneously from oligomeric mixtures upon long term incubation in physiological solutions (Nag et al, JBC, 2011. Here we show that the membrane-affinity of these stable Aβ monomers is much lower than that of a mixture of small oligomers (containing dimers to decamers, providing a clue to the emergence of toxicity. Fluorescently labeled Aβ40 monomers show negligible binding to cell membranes of a neuronal cell line (RN46A at physiological concentrations (250 nM, while oligomers at the same concentrations show strong binding within 30 minutes of incubation. The increased affinity most likely does not require any specific neuronal receptor, since this difference in membrane-affinity was also observed in a somatic cell-line (HEK 293T. Similar results are also obtained for Aβ42 monomers and oligomers. Minimal amount of cell death is observed at these concentrations even after 36 hours of incubation. It is likely that membrane binding precedes subsequent slower toxic events induced by Aβ. Our results a provide an explanation for the non-toxic nature of Aβ monomers, b suggest that Aβ toxicity emerges at the initial oligomeric phase, and c provide a quick assay for monitoring the benign-to-toxic transformation of Aβ.

  17. Natural amyloid-β oligomers acutely impair the formation of a contextual fear memory in mice.

    Directory of Open Access Journals (Sweden)

    Kara A Kittelberger

    Full Text Available Memory loss is one of the hallmark symptoms of Alzheimer's disease (AD. It has been proposed that soluble amyloid-beta (Abeta oligomers acutely impair neuronal function and thereby memory. We here report that natural Abeta oligomers acutely impair contextual fear memory in mice. A natural Abeta oligomer solution containing Abeta monomers, dimers, trimers, and tetramers was derived from the conditioned medium of 7PA2 cells, a cell line that expresses human amyloid precursor protein containing the Val717Phe familial AD mutation. As a control we used 7PA2 conditioned medium from which Abeta oligomers were removed through immunodepletion. Separate groups of mice were injected with Abeta and control solutions through a cannula into the lateral brain ventricle, and subjected to fear conditioning using two tone-shock pairings. One day after fear conditioning, mice were tested for contextual fear memory and tone fear memory in separate retrieval trials. Three experiments were performed. For experiment 1, mice were injected three times: 1 hour before and 3 hours after fear conditioning, and 1 hour before context retrieval. For experiments 2 and 3, mice were injected a single time at 1 hour and 2 hours before fear conditioning respectively. In all three experiments there was no effect on tone fear memory. Injection of Abeta 1 hour before fear conditioning, but not 2 hours before fear conditioning, impaired the formation of a contextual fear memory. In future studies, the acute effect of natural Abeta oligomers on contextual fear memory can be used to identify potential mechanisms and treatments of AD associated memory loss.

  18. Amyloid β oligomers elicit mitochondrial transport defects and fragmentation in a time-dependent and pathway-specific manner.

    Science.gov (United States)

    Rui, Yanfang; Zheng, James Q

    2016-01-01

    Small oligomeric forms of amyloid-β (Aβ) are believed to be the culprit for declined brain functions in AD in part through their impairment of neuronal trafficking and synaptic functions. However, the precise cellular actions of Aβ oligomers and underlying mechanisms in neurons remain to be fully defined. Previous studies have identified mitochondria as a major target of Aβ toxicity contributing to early cognitive decline and memory loss in neurodegenerative diseases including Alzheimer's disease (AD). In this study, we report that Aβ oligomers acutely elicit distinct effects on the transport and integrity of mitochondria. We found that acute exposure of hippocampal neurons to Aβ oligomers from either synthetic peptides or AD brain homogenates selectively impaired fast transport of mitochondria without affecting the movement of late endosomes and lysosomes. Extended exposure of hipoocampal neurons to Aβ oligomers was found to result in mitochondrial fragmentation. While both mitochondrial effects induced by Aβ oligomers can be abolished by the inhibition of GSK3β, they appear to be independent from each other. Aβ oligomers impaired mitochondrial transport through HDAC6 activation whereas the fragmentation involved the GTPase Drp-1. These results show that Aβ oligomers can acutely disrupt mitochondrial transport and integrity in a time-dependent and pathway-specific manner. These findings thus provide new insights into Aβ-induced mitochondrial defects that may contribute to neuronal dysfunction and AD pathogenesis. PMID:27535553

  19. Protective spin-labeled fluorenes maintain amyloid beta peptide in small oligomers and limit transitions in secondary structure

    Energy Technology Data Exchange (ETDEWEB)

    Altman, Robin [Univ. of California, Davis, CA (United States). Dept. of Biochemistry and Molecular Medicine; Ly, Sonny [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Physical and Life Science Directorate; Hilt, Silvia [Univ. of California, Davis, CA (United States). Dept. of Biochemistry and Molecular Medicine; Petrlova, Jitka [Univ. of California, Davis, CA (United States). Dept. of Biochemistry and Molecular Medicine; Maezawa, Izumi [Univ. of California Davis, Sacramento, CA (United States). MIND Inst. and Dept. of Pathology and Laboratory Medicine; Kálai, Tamás [Univ. of Pecs (Hungary). Inst. of Organic and Medicinal Chemistry; Hideg, Kálmán [Univ. of Pecs (Hungary). Inst. of Organic and Medicinal Chemistry; Jin, Lee-Way [Univ. of California Davis, Sacramento, CA (United States). MIND Inst. and Dept. of Pathology and Laboratory Medicine; Laurence, Ted A. [Univ. of California, Davis, CA (United States). Dept. of Biochemistry and Molecular Medicine; Voss, John C. [Univ. of California, Davis, CA (United States). Dept. of Biochemistry and Molecular Medicine

    2015-12-01

    Alzheimer’s disease is characterized by the presence of extracellular plaques comprised of amyloid beta (Aβ) peptides. Soluble oligomers of the Aβ peptide underlie a cascade of neuronal loss and dysfunction associated with Alzheimer's disease. Single particle analyses of Aβ oligomers in solution by fluorescence correlation spectroscopy (FCS) were used to provide real-time descriptions of how spin-labeled fluorenes (SLFs; bi-functional small molecules that block the toxicity of Aβ) prevent and disrupt oligomeric assemblies of Aβ in solution. The FCS results, combined with electron paramagnetic resonance spectroscopy and circular dichroism spectroscopy, demonstrate SLFs can inhibit the growth of Aβ oligomers and disrupt existing oligomers while retaining Aβ in a largely disordered state. Furthermore, while the ability of SLF to block Aβ toxicity correlates with a reduction in oligomer size, our results suggest the conformation of Aβ within the oligomer determines the toxicity of the species. Attenuation of Aβ toxicity, which has been associated primarily with the soluble oligomeric form, can be achieved through redistribution of the peptides into smaller oligomers and arrest of the fractional increase in beta secondary structure.

  20. Tuned range separated hybrid functionals for solvated low bandgap oligomers

    Energy Technology Data Exchange (ETDEWEB)

    Queiroz, Thiago B. de, E-mail: thiago.branquinho-de-queiroz@uni-bayreuth.de; Kümmel, Stephan [Theoretical Physics IV, University of Bayreuth, D-95440 Bayreuth (Germany)

    2015-07-21

    The description of charge transfer excitations has long been a challenge to time dependent density functional theory. The recently developed concept of “optimally tuned range separated hybrid (OT-RSH) functionals” has proven to describe charge transfer excitations accurately in many cases. However, describing solvated or embedded systems is yet a challenge. This challenge is not only computational but also conceptual, because the tuning requires identifying a specific orbital, typically the highest occupied one of the molecule under study. For solvated molecules, this orbital may be delocalized over the solvent. We here demonstrate that one way of overcoming this problem is to use a locally projected self-consistent field diagonalization on an absolutely localized molecular orbital expansion. We employ this approach to determine ionization energies and the optical gap of solvated oligothiophenes, i.e., paradigm low gap systems that are of relevance in organic electronics. Dioxane solvent molecules are explicitly represented in our calculations, and the ambiguities of straightforward parameter tuning in solution are elucidated. We show that a consistent estimate of the optimal range separated parameter (ω) at the limit of bulk solvation can be obtained by gradually extending the solvated system. In particular, ω is influenced by the solvent beyond the first coordination sphere. For determining ionization energies, a considerable number of solvent molecules on the first solvation shell must be taken into account. We demonstrate that accurately calculating optical gaps of solvated systems using OT-RSH can be done in three steps: (i) including the chemical environment when determining the range-separation parameter, (ii) taking into account the screening due to the solvent, and (iii) using realistic molecular geometries.

  1. Synthesis and Crystal Structure of N-(1'-H-Pyrrol-2'-ylcarbonyl)-5-amino-1,10-phenanthroline

    Institute of Scientific and Technical Information of China (English)

    WANG Yue-Hong; LIN Hai; LIN Hua-Kuan

    2008-01-01

    The title compound,N-(1'-H-pyrrol-2'-ylcarbonyl)-5-amino-1,10-phenanthroline,was synthesized by the reaction of a-pyrrolyl carbonyl chloride and 5-amino-1,10-phenanthroline in pyridine.Determined by X-ray structure analysis,it crystallizes in triclinic system,space group P(1)with the following crystallographic data:C20H21N5O3,Mr=379.42,a=7.8559(4),b=9.1681(6),c =14.6818(9)(A),α=73.254(10),β=88.938(15),γ=68.080(10)°,V=934.66(10)(A)3,Z=2,F(000)=400.Dc=1.348 g/cm3 and μ=0.094 mm-1.The final R=0.0680 and wR=0.1419 for 2142observed reflections with I>2σ(I),and R=0.1084 and wR=0.1643 for all reflections.Two aromatic ring planes(pyrrole and phenanthroline rings)are connected by the amide plane.Two title complex molecules are connected through hydrogen bonds and weak π-π stacking interactions to generate a 3-D supramolecule.

  2. Rhodium and iridium complexes of N-(2'-hydroxyphenyl)pyrrole-2-aldimine: Synthesis, structure, and spectral and electrochemical properties

    Indian Academy of Sciences (India)

    Semanti Basu; Indrani Pal; Ray J Butcher; Georgina Rosair; Samaresh Bhattacharya

    2005-03-01

    Reaction of N-(2'-hydroxyphenyl)pyrrole-2-aldimine (H2L) with [M(PPh3)3Cl] (M = Rh, Ir) affords complexes of type [M(PPh3)2(L)Cl]. Structures of both complexes have been determined by X-ray crystallography. In both complexes, the N-(2'-hydroxyphenyl)pyrrole-2-aldimine ligand is coordinated to the metal centre, via dissociation of the acidic protons, as a dianionic tridentate N,N,O-donor. The M(L)Cl fragment constitutes an equatorial plane with the metal at the centre and the two PPh3 ligands occupying axial positions. The complexes are diamagnetic (low-spin 6, = 0) and show intense MLCT transitions in the visible region. Cyclic voltammetry of the [M(PPh3)2(L)Cl] complexes shows reversible M(III)-M(IV) oxidation near 0.5 V vs SCE and quasi-reversible ligand-centred oxidative response near 1.0 V vs SCE.

  3. Oligomer formation during gas-phase ozonolysis of small alkenes and enol ethers: new evidence for the central role of the Criegee Intermediate as oligomer chain unit

    Directory of Open Access Journals (Sweden)

    A. Sadezky

    2007-10-01

    Full Text Available An important fraction of secondary organic aerosol (SOA formed by atmospheric oxidation of diverse volatile organic compounds (VOC has recently been shown to consist of high-molecular weight oligomeric species. In our previous study (Sadezky et al., 2006, we reported the identification and characterization of oligomers as main constituents of SOA from gas-phase ozonolysis of small enol ethers. These oligomers contained repeated chain units of the same chemical composition as the main Criegee Intermediates (CI formed during the ozonolysis reaction, which were CH2O2 (mass 46 for alkyl vinyl ethers (AVE and C2H4O2 (mass 60 for ethyl propenyl ether (EPE. In the present work, we extend our previous study (Sadezky et al., 2006 to another enol ether (ethyl butenyl ether EBE and a variety of structurally related small alkenes (trans-3-hexene, trans-4-octene and 2,3-dimethyl-2-butene.

    Experiments have been carried out in a 570 l spherical glass reactor at atmospheric conditions in the absence of seed aerosol. SOA formation was measured by a scanning mobility particle sizer (SMPS. SOA filter samples were collected and chemically characterized off-line by ESI(+/MS-TOF and ESI(+/MS/MS-TOF, and elemental compositions were confirmed by ESI(+/MS/MS-FTICR. The results for all investigated unsaturated compounds are in excellent agreement with the observations of our previous study (Sadezky et al., 2006. Analysis of the collected SOA filter samples reveal the presence of oligomeric compounds in the mass range 200 to 800 u as major constituents. The repeated chain units of these oligomers are shown to systematically have the same chemical composition as the respective main Criegee Intermediate (CI formed during ozonolysis of the unsaturated compounds, which is C3H6O2 (mass 74 for ethyl butenyl ether (EBE, trans-3-hexene, and 2,3-dimethyl-2-butene

  4. Synthesis of Cycloveratrylene Macrocycles and Benzyl Oligomers Catalysed by Bentonite under Microwave/Infrared and Solvent-Free Conditions

    Directory of Open Access Journals (Sweden)

    Manuel Salmón

    2013-10-01

    Full Text Available Tonsil Actisil FF, which is a commercial bentonitic clay, promotes the formation of cycloveratrylene macrocycles and benzyl oligomers from the corresponding benzyl alcohols in good yields under microwave heating and infrared irradiation in the absence of solvent in both cases. The catalytic reaction is sensitive to the type of substituent on the aromatic ring. Thus, when benzyl alcohol was substituted with a methylenedioxy, two methoxy or three methoxy groups, a cyclooligomerisation process was induced. Unsubstituted, methyl and methoxy benzyl alcohols yielded linear oligomers. In addition, computational chemistry calculations were performed to establish a validated mechanistic pathway to explain the growth of the obtained linear oligomers.

  5. Accumulation of oligomer-prone α-synuclein exacerbates synaptic and neuronal degeneration in vivo.

    Science.gov (United States)

    Rockenstein, Edward; Nuber, Silke; Overk, Cassia R; Ubhi, Kiren; Mante, Michael; Patrick, Christina; Adame, Anthony; Trejo-Morales, Margarita; Gerez, Juan; Picotti, Paola; Jensen, Poul H; Campioni, Silvia; Riek, Roland; Winkler, Jürgen; Gage, Fred H; Winner, Beate; Masliah, Eliezer

    2014-05-01

    In Parkinson's disease and dementia with Lewy bodies, α-synuclein aggregates to form oligomers and fibrils; however, the precise nature of the toxic α-synuclein species remains unclear. A number of synthetic α-synuclein mutations were recently created (E57K and E35K) that produce species of α-synuclein that preferentially form oligomers and increase α-synuclein-mediated toxicity. We have shown that acute lentiviral expression of α-synuclein E57K leads to the degeneration of dopaminergic neurons; however, the effects of chronic expression of oligomer-prone α-synuclein in synapses throughout the brain have not been investigated. Such a study could provide insight into the possible mechanism(s) through which accumulation of α-synuclein oligomers in the synapse leads to neurodegeneration. For this purpose, we compared the patterns of neurodegeneration and synaptic damage between a newly generated mThy-1 α-synuclein E57K transgenic mouse model that is prone to forming oligomers and the mThy-1 α-synuclein wild-type mouse model (Line 61), which accumulates various forms of α-synuclein. Three lines of α-synuclein E57K (Lines 9, 16 and 54) were generated and compared with the wild-type. The α-synuclein E57K Lines 9 and 16 were higher expressings of α-synuclein, similar to α-synuclein wild-type Line 61, and Line 54 was a low expressing of α-synuclein compared to Line 61. By immunoblot analysis, the higher-expressing α-synuclein E57K transgenic mice showed abundant oligomeric, but not fibrillar, α-synuclein whereas lower-expressing mice accumulated monomeric α-synuclein. Monomers, oligomers, and fibrils were present in α-synuclein wild-type Line 61. Immunohistochemical and ultrastructural analyses demonstrated that α-synuclein accumulated in the synapses but not in the neuronal cells bodies, which was different from the α-synuclein wild-type Line 61, which accumulates α-synuclein in the soma. Compared to non-transgenic and lower-expressing mice, the

  6. Stereocomplexation in Copolymer Networks Incorporating Enantiomeric Glycerol-Based 3-Armed Lactide Oligomers and a 2-Armed ɛ-Caprolactone Oligomer

    Directory of Open Access Journals (Sweden)

    Ayaka Shibita

    2016-07-01

    Full Text Available The reactions of enantiomeric glycerol-based 3-armed lactide oligomers (H3DLAO and H3LLAO and a diethylene glycol-based 2-armed ɛ-caprolactone oligomer (H2CLO with hexamethylene diisocyanate (HDI produced polyesterurethane copolymer networks (PEU-3scLAO/2CLOs 100/0, 75/25, 50/50, 25/75 and 0/100 with different feed ratios of stereocomplex (sc lactide oligomer (H3scLAO = H3DLAO + H3LLAO, H3DLAO/H3LLAO = 1/1 and H2CLO. Thermal and mechanical properties of the copolymer networks were compared with those of a simple homochiral (hc network (PEU-3DLAO produced by the reaction of H3DLAO and HDI. X-ray diffraction and differential scanning calorimetric analyses revealed that sc crystallites are formed without any hc crystallization for PEU-3scLAO/2CLOs, and that PEU-3DLAO is amorphous. The melting temperatures of sc crystallites for PEU-3scLAO/2CLOs were much higher than that of hc crystallites of H3DLAO. The polarized optical microscopic analysis revealed that the nucleation efficiency is enhanced with increasing feed of H3scLAO fraction, whereas the spherulite growth rate is accelerated with increasing feed H2CLO fraction over 100/0-50/50 networks. PEU-3scLAO/2CLO 100/0 (i.e., PEU-3scLAO exhibited a higher tensile strength and modulus than PEU-3DLAO. The elongation at break and tensile toughness for PEU-3scLAO/2CLOs increased with an increasing feed amount of H2CLO.

  7. Amyloid β oligomers induce interleukin-1β production in primary microglia in a cathepsin B- and reactive oxygen species-dependent manner

    International Nuclear Information System (INIS)

    Amyloid β (Aβ) peptide, a causative agent of Alzheimer's disease, forms two types of aggregates: oligomers and fibrils. These aggregates induce inflammatory responses, such as interleukin-1β (IL-1β) production by microglia, which are macrophage-like cells located in the brain. In this study, we examined the effect of the two forms of Aβ aggregates on IL-1β production in mouse primary microglia. We prepared Aβ oligomer and fibril from Aβ (1–42) peptide in vitro. We analyzed the characteristics of these oligomers and fibrils by electrophoresis and atomic force microscopy. Interestingly, Aβ oligomers but not Aβ monomers or fibrils induced robust IL-1β production in the presence of lipopolysaccharide. Moreover, Aβ oligomers induced endo/phagolysosome rupture, which released cathepsin B into the cytoplasm. Aβ oligomer-induced IL-1β production was inhibited not only by the cathepsin B inhibitor CA-074-Me but also by the reactive oxygen species (ROS) inhibitor N-acetylcysteine. Random chemical crosslinking abolished the ability of the oligomers to induce IL-1β. Thus, multimerization and fibrillization causes Aβ oligomers to lose the ability to induce IL-1β. These results indicate that Aβ oligomers, but not fibrils, induce IL-1β production in primary microglia in a cathepsin B- and ROS-dependent manner. - Highlights: • We prepared amyloid β (Aβ) fibrils with minimum contamination of Aβ oligomers. • Primary microglia (MG) produced IL-1β in response to Aβ oligomers, but not fibrils. • Only Aβ oligomers induced leakage of cathepsin B from endo/phagolysosomes. • IL-1β production in response to Aβ oligomers depended on both cathepsin B and ROS. • Crosslinking reduced the ability of the Aβ oligomers to induce IL-1β from MG

  8. Amyloid β oligomers induce interleukin-1β production in primary microglia in a cathepsin B- and reactive oxygen species-dependent manner

    Energy Technology Data Exchange (ETDEWEB)

    Taneo, Jun; Adachi, Takumi [Department of Animal Development and Physiology, Kyoto University, Yoshida-Konoe, Sakyo, Kyoto 606-8501 (Japan); Yoshida, Aiko; Takayasu, Kunio [Responses to Environmental Signals and Stresses, Graduate School of Biostudies, Kyoto University, Yoshida-Konoe, Sakyo, Kyoto, Kyoto 606-8501 (Japan); Takahara, Kazuhiko, E-mail: ktakahar@zoo.zool.kyoto-u.ac.jp [Department of Animal Development and Physiology, Kyoto University, Yoshida-Konoe, Sakyo, Kyoto 606-8501 (Japan); Japan Science and Technology Agency, Core Research for Evolutional Science and Technology (CREST), Tokyo 102-0081 (Japan); Inaba, Kayo [Department of Animal Development and Physiology, Kyoto University, Yoshida-Konoe, Sakyo, Kyoto 606-8501 (Japan); Japan Science and Technology Agency, Core Research for Evolutional Science and Technology (CREST), Tokyo 102-0081 (Japan)

    2015-03-13

    Amyloid β (Aβ) peptide, a causative agent of Alzheimer's disease, forms two types of aggregates: oligomers and fibrils. These aggregates induce inflammatory responses, such as interleukin-1β (IL-1β) production by microglia, which are macrophage-like cells located in the brain. In this study, we examined the effect of the two forms of Aβ aggregates on IL-1β production in mouse primary microglia. We prepared Aβ oligomer and fibril from Aβ (1–42) peptide in vitro. We analyzed the characteristics of these oligomers and fibrils by electrophoresis and atomic force microscopy. Interestingly, Aβ oligomers but not Aβ monomers or fibrils induced robust IL-1β production in the presence of lipopolysaccharide. Moreover, Aβ oligomers induced endo/phagolysosome rupture, which released cathepsin B into the cytoplasm. Aβ oligomer-induced IL-1β production was inhibited not only by the cathepsin B inhibitor CA-074-Me but also by the reactive oxygen species (ROS) inhibitor N-acetylcysteine. Random chemical crosslinking abolished the ability of the oligomers to induce IL-1β. Thus, multimerization and fibrillization causes Aβ oligomers to lose the ability to induce IL-1β. These results indicate that Aβ oligomers, but not fibrils, induce IL-1β production in primary microglia in a cathepsin B- and ROS-dependent manner. - Highlights: • We prepared amyloid β (Aβ) fibrils with minimum contamination of Aβ oligomers. • Primary microglia (MG) produced IL-1β in response to Aβ oligomers, but not fibrils. • Only Aβ oligomers induced leakage of cathepsin B from endo/phagolysosomes. • IL-1β production in response to Aβ oligomers depended on both cathepsin B and ROS. • Crosslinking reduced the ability of the Aβ oligomers to induce IL-1β from MG.

  9. Photoinduced energy transfer in transition metal complex oligomers

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-04-01

    The work we have done over the past three years has been directed toward the preparation, characterization and photophysical examination of mono- and bimetallic diimine complexes. The work is part of a broader project directed toward the development of stable, efficient, light harvesting arrays of transition metal complex chromophores. One focus has been the synthesis of rigid bis-bidentate and bis-tridentate bridging ligands. We have managed to make the ligand bphb in multigram quantities from inexpensive starting materials. The synthetic approach used has allowed us prepare a variety of other ligands which may have unique applications (vide infra). We have prepared, characterized and examined the photophysical behavior of Ru(II) and Re(I) complexes of the ligands. Energy donor/acceptor complexes of bphb have been prepared which exhibit nearly activationless energy transfer. Complexes of Ru(II) and Re(I) have also been prepared with other polyunsaturated ligands in which two different long lived ( > 50 ns) excited states exist; results of luminescence and transient absorbance measurements suggest the two states are metal-to-ligand charge transfer and ligand localized {pi}{r_arrow}{pi}* triplets. Finally, we have developed methods to prepare polymetallic complexes which are covalently bound to various surfaces. The long term objective of this work is to make light harvesting arrays for the sensitization of large band gap semiconductors. Details of this work are provided in the body of the report.

  10. Photoinduced energy transfer in transition metal complex oligomers

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1997-06-01

    The work done over the past three years has been directed toward the preparation, characterization and photophysical examination of mono- and bimetallic diimine complexes. The work is part of a broader project directed toward the development of stable, efficient, light harvesting arrays of transition metal complex chromophores. One focus has been the synthesis of rigid bis-bidentate and bis-tridentate bridging ligands. The authors have managed to make the ligand bphb in multigram quantities from inexpensive starting materials. The synthetic approach used has allowed them to prepare a variety of other ligands which may have unique applications (vide infra). They have prepared, characterized and examined the photophysical behavior of Ru(II) and Re(I) complexes of the ligands. Energy donor/acceptor complexes of bphb have been prepared which exhibit nearly activationless energy transfer. Complexes of Ru(II) and Re(I) have also been prepared with other polyunsaturated ligands in which two different long lived (> 50 ns) excited states exist; results of luminescence and transient absorbance measurements suggest the two states are metal-to-ligand charge transfer and ligand localized {pi}{r_arrow}{pi}* triplets. Finally, the authors have developed methods to prepare polymetallic complexes which are covalently bound to various surfaces. The long term objective of this work is to make light harvesting arrays for the sensitization of large band gap semiconductors. Details of this work are provided in the body of the report.

  11. Synthesis and characterization of new electron-withdrawing moiety thieno[2,3-c]pyrrole-4,6-dione-based molecules for small molecule solar cells

    DEFF Research Database (Denmark)

    Fu, Lei; Pan, Hongbin; Larsen-Olsen, Thue Trofod;

    2013-01-01

    –π–donor–π–acceptor type end-capped with thieno[2,3-c]pyrrole-4,6-dione (TPD) units for small molecule solar cells have been prepared through coupling of dithienosilole and TPD units bridged with thienylene and bithienylene. They are soluble in common organic solvents and show an interesting absorption. These small...

  12. A Highly Efficient Synthesis of 3H-(Pyrrol-1-yl)indolin-2-ones Catalyzed by InCl3

    Institute of Scientific and Technical Information of China (English)

    SHEN,Shu-Su; JI,Shun-Jun; WANG,Shun-Yi

    2008-01-01

    A systemic and comprehensive study has been made on the formation of 3H-(pyrrol-1-yl)indolin-2-ones synthesized from various isatin derivatives and 4-hydroxyproline catalyzed by InCl3 under a refluxing condition in excellent yields (83%-99%) and purity.

  13. "Nail" and "comb" effects of cholesterol modified NIPAm oligomers on cancer targeting liposomes

    KAUST Repository

    Li, Wengang

    2014-01-01

    Thermosensitive liposomes are a promising approach to controlled release and reduced drug cytotoxicity. Low molecular weight N-isopropylacrylamide (NIPAm) oligomers (NOs) with different architectures (main chain NOs (MCNOs) and side chain NOs (SCNOs)) were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization and radical polymerization and then separately used to prepare thermosensitive liposomes. A more controlled and enhanced release was observed for both NO liposomes compared to pristine ones. Two release mechanisms depending on the oligomer architecture, namely "nail" for MCNOs and "comb" for SCNOs, are proposed. In addition to thermosensitivity, the cancer targeting property of NO liposomes was achieved by further biotinylation of the delivery system. © The Royal Society of Chemistry.

  14. Structure and Oligomers Distribution of Commercial Tara (Caesalpina spinosa Hydrolysable Tannin

    Directory of Open Access Journals (Sweden)

    Samuele GIOVANDO

    2013-03-01

    Full Text Available Solvent extracted commercial Tara tanninextract have been examined by Matrix Assisted LaserDesorption/Ionisation Time-of-Flight (MALDI-TOFmass spectrometry and by High Pressure LiquidChromatography (HPLC. The Tara extract has beenfound to be composed of a series of oligomers ofpolygallic acid attached by an ester link to one quinicacid. They constitute the oligomers in higherproportion in the extract. Other polygallic chains linkedto one only or two repeating units such as caffeic acidand methylated quinic, methylated gallic andmethylated caffeic acids are also present. Negativeion mode MALDI-TOF showed that somecarbohydrate residues appear to still be present,linked to the polyphenolic material of the extract buttheir proportion is very low as would be expected of asolvent extracted tannin.

  15. Sequence-Defined Oligomers from Hydroxyproline Building Blocks for Parallel Synthesis Applications.

    Science.gov (United States)

    Kanasty, Rosemary L; Vegas, Arturo J; Ceo, Luke M; Maier, Martin; Charisse, Klaus; Nair, Jayaprakash K; Langer, Robert; Anderson, Daniel G

    2016-08-01

    The functionality of natural biopolymers has inspired significant effort to develop sequence-defined synthetic polymers for applications including molecular recognition, self-assembly, and catalysis. Conjugation of synthetic materials to biomacromolecules has played an increasingly important role in drug delivery and biomaterials. We developed a controlled synthesis of novel oligomers from hydroxyproline-based building blocks and conjugated these materials to siRNA. Hydroxyproline-based monomers enable the incorporation of broad structural diversity into defined polymer chains. Using a perfluorocarbon purification handle, we were able to purify diverse oligomers through a single solid-phase extraction method. The efficiency of synthesis was demonstrated by building 14 unique trimers and 4 hexamers from 6 diverse building blocks. We then adapted this method to the parallel synthesis of hundreds of materials in 96-well plates. This strategy provides a platform for the screening of libraries of modified biomolecules. PMID:27365192

  16. Structural Investigations of on-pathway Oligomers of α-Synuclein

    DEFF Research Database (Denmark)

    Pedersen, Martin Nors; Horvath, Istvan; Weise, Christoph F.;

    Here we present Small Angle X-ray (SAXS) data of α-synuclein oligomers obtained by incubation with the ligand FN075. Data from complementary methods such as NMR and CD are also shown. Aggregated α-synuclein is the major constituent of the Lewy Bodies regarded as the hallmark of Parkinson’s Disease...... and Dementia with Lewy Bodies (DLB) (Spillantini et al. 1997). The role of lewy bodies in the pathology of Parkinson’s Disease and DLB is however not well understood but in vitro experiments suggest that transient oligomeric species could be involved in cell toxicity (Giehm et al. 2011). The natural function...... of α-synuclein has also not been established (Drescher et al. 2012). The monomeric species of α-synuclein is intrinsically disordered meaning it does not have just one stable conformation in solution. The solution structure of an on pathway oligomer consisting of 16 monomers has been solved...

  17. Alzheimer’s-associated Aβ oligomers show altered structure, immunoreactivity and synaptotoxicity with low doses of oleocanthal

    OpenAIRE

    Pitt, Jason; Roth, William; Lacor, Pascale; Blankenship, Matthew; Velasco, Pauline; De Felice, Fernanda; Breslin, Paul; Klein, William L.

    2009-01-01

    It now appears likely that soluble oligomers of amyloid-β1-42 peptide, rather than insoluble fibrils, act as the primary neurotoxin in Alzheimer’s disease (AD). Consequently, compounds capable of altering the assembly state of these oligomers (referred to as ADDLs) may have potential for AD therapeutics. Phenolic compounds are of particular interest for their ability to disrupt Aβ oligomerization and reduce pathogenicity. This study has focused on oleocanthal (OC), a naturally-occurring pheno...

  18. Montmorillonite catalysis of RNA oligomer formation in aqueous solution. A model for the prebiotic formation of RNA

    Science.gov (United States)

    Ferris, J. P.; Ertem, G.

    1993-01-01

    Oligomers of adenylic acid of up to the 11-mer in length are formed by the reaction of the phosphorimidazolide of adenosine (ImpA) in pH 8 aqueous solution at room temperature in the presence of Na(+)-montmorillonite. These oligomers are joined by phosphodiester bonds in which the 3',5'-linkage predominates over the 2',5'-linkage by a 2:1 ratio. Reaction of a 9:1 mixture of ImpA, A5'ppA results in the formation of oligomers with a 3:1 ratio of 3',5'- to 2',5'-linked phosphodiester bonds. A high proportion of these oligomers contain the A5'ppA grouping. A5'ppA reacts much more rapidly with ImpA than does 5'-ADP (ppA) or 5'-ATP (pppA). The exchangeable cation associated with the montmorillonite effects the observed catalysis with Li+, Na+, NH4+, and Ca2+ being the more effective while Mg2+ and Al3+ are almost ineffective catalysts. 2',5'-Linked oligomers, up to the tetramer in length, are formed using UO2(2+)-montmorillonite. The structure analysis of individual oligomer fractions was performed by selective enzymatic and KOH hydrolytic studies followed by HPLC analysis of the reaction products. It is concluded from the composition of the oligomers that the rate of addition ImpA to a 3'-terminus containing a 2',5'-linkage is slower than the addition to a nucleoside joined by a 3',5'-linked phosphodiester bond. The potential importance of mineral catalysis of the formation of RNA and other oligomers on primitive Earth is discussed.

  19. Characterization of oligomers from methylglyoxal under dark conditions: a pathway to produce secondary organic aerosol through cloud processing during nighttime

    OpenAIRE

    F. Yasmeen; N. Sauret; Gal, J.-F.; Maria, P.-C.; Massi, L.; W. Maenhaut; Claeys, M.

    2010-01-01

    Aqueous-phase oligomer formation from methylglyoxal, a major atmospheric photooxidation product, has been investigated in a simulated cloud matrix under dark conditions. The aim of this study was to explore an additional pathway producing secondary organic aerosol (SOA) through cloud processes without participation of photochemistry during nighttime. Indeed, atmospheric models still underestimate SOA formation, as field measurements have revealed more SOA than predicted. Soluble oligomers (&l...

  20. Simulation of tethered oligomers in nanochannels using multi-particle collision dynamics

    OpenAIRE

    Raghu, Riyad; Schofield, Jeremy

    2012-01-01

    The effect of a high Reynold's number, pressure-driven flow of a compressible gas on the conformation of an oligomer tethered to the wall of a square-channel is studied under both ideal solvent and poor solvent conditions using a hybrid multiparticle collision dynamics and molecular dynamics algorithm. Unlike previous studies, the flow field contains an elongational component in addition to a shear component as well as fluid slip near the walls and results in a Schmidt number for the polymer ...

  1. Self-association of TPR domains: Lessons learned from a designed, consensus-based TPR oligomer.

    Science.gov (United States)

    Krachler, Anne Marie; Sharma, Amit; Kleanthous, Colin

    2010-07-01

    The tetratricopeptide repeat (TPR) motif is a protein-protein interaction module that acts as an organizing centre for complexes regulating a multitude of biological processes. Despite accumulating evidence for the formation of TPR oligomers as an additional level of regulation there is a lack of structural and solution data explaining TPR self-association. In the present work we characterize the trimeric TPR-containing protein YbgF, which is linked to the Tol system in Gram-negative bacteria. By subtracting previously identified TPR consensus residues required for stability of the fold from residues conserved across YbgF homologs, we identified residues involved in oligomerization of the C-terminal YbgF TPR domain. Crafting these residues, which are located in loop regions between TPR motifs, onto the monomeric consensus TPR protein CTPR3 induced the formation of oligomers. The crystal structure of this engineered oligomer shows an asymmetric trimer where stacking interactions between the introduced tyrosines and displacement of the C-terminal hydrophilic capping helix, present in most TPR domains, are key to oligomerization. Asymmetric trimerization of the YbgF TPR domain and CTPR3Y3 leads to the formation of higher order oligomers both in the crystal and in solution. However, such open-ended self-association does not occur in full-length YbgF suggesting that the protein's N-terminal coiled-coil domain restricts further oligomerization. This interpretation is borne out in experiments where the coiled-coil domain of YbgF was engineered onto the N-terminus of CTPR3Y3 and shown to block self-association beyond trimerization. Our study lays the foundations for understanding the structural basis for TPR domain self-association and how such self-association can be regulated in TPR domain-containing proteins.

  2. Antiviral Effects of Antisense Morpholino Oligomers in Murine Coronavirus Infection Models▿

    OpenAIRE

    Burrer, Renaud; Neuman, Benjamin W.; Ting, Joey P.C.; Stein, David A.; Moulton, Hong M.; Iversen, Patrick L.; Kuhn, Peter; Michael J Buchmeier

    2007-01-01

    The recent emergence of novel pathogenic human and animal coronaviruses has highlighted the need for antiviral therapies that are effective against a spectrum of these viruses. We have used several strains of murine hepatitis virus (MHV) in cell culture and in vivo in mouse models to investigate the antiviral characteristics of peptide-conjugated antisense phosphorodiamidate morpholino oligomers (P-PMOs). Ten P-PMOs directed against various target sites in the viral genome were tested in cell...

  3. High-affinity triplex targeting of double stranded DNA using chemically modified peptide nucleic acid oligomers

    OpenAIRE

    Hansen, Mads E.; Bentin, Thomas; Nielsen, Peter E.

    2009-01-01

    While sequence-selective dsDNA targeting by triplex forming oligonucleotides has been studied extensively, only very little is known about the properties of PNA–dsDNA triplexes—mainly due to the competing invasion process. Here we show that when appropriately modified using pseudoisocytosine substitution, in combination with (oligo)lysine or 9-aminoacridine conjugation, homopyrimidine PNA oligomers bind complementary dsDNA targets via triplex formation with (sub)nanomolar affinities (at pH 7....

  4. Polyethylenimine-modified Pluronics (PCMs) Improve Morpholino Oligomer Delivery in Cell Culture and Dystrophic mdx Mice

    OpenAIRE

    Wang, Mingxing; Wu, Bo; Lu, Peijuan; Cloer, Caryn; Tucker, Jay D; Lu, Qilong

    2012-01-01

    We investigated a series of small-sized polyethylenimine (PEI, 0.8/1.2 k)-conjugated pluronic copolymers (PCMs) for their potential to enhance delivery of an antisense phosphorodiamidate morpholino oligomer (PMO) in vitro and in dystrophic mdx mice. PCM polymers containing pluronics of molecular weight (Mw) ranging 2–6 k, with hydrophilic-lipophilic balance (HLB) 7–23, significantly enhanced PMO-induced exon-skipping in a green fluorescent protein (GFP) reporter-based myoblast culture system....

  5. PFO-BPy Solubilizers for SWNTs: Modelling of Polymers from Oligomers

    OpenAIRE

    Glanzmann, Livia N.; Mowbray, Duncan J.; Rubio, Angel

    2014-01-01

    Due to their exeptional physical properties, single walled carbon nanotubes (SWNTs) embedded in organic polymers (polymer-SWNT hybrid systems) are promising materials for organic photovoltaic (OPV) devices. Already at the SWNT sorting and debundling step, polymers such as the copolymer of 9,9-dioctylfluorenyl-2,7-diyl and bipyridine (PFO-BPy) are used as solubilizers. However, to model polymer-SWNT hybrid systems, we must first determine the smallest oligomer needed to sufficiently describe t...

  6. Single-molecule studies of oligomer extraction and uptake of dyes in poly(dimethylsiloxane) films.

    Science.gov (United States)

    Lange, Jeffrey J; Collinson, Maryanne M; Culbertson, Christopher T; Higgins, Daniel A

    2009-12-15

    Single-molecule microscopic methods were used to probe the uptake, mobility, and entrapment of dye molecules in cured poly(dimethylsiloxane) (PDMS) films as a function of oligomer extraction. The results are relevant to the use of PDMS in microfluidic separations, pervaporation, solid-phase microextraction, and nanofiltration. PDMS films were prepared by spin-casting dilute solutions of Sylgard 184 onto glass coverslips, yielding approximately 1.4 microm thick films after curing. Residual oligomers were subsequently extracted from the films by "spin extraction". In this procedure, 200 microL aliquots of isopropyl alcohol were repeatedly dropped onto the film surface and spun off at 2000 rpm. Samples extracted 5, 10, 20, and 40 times were investigated. Dye molecules were loaded into these films by spin-casting nanomolar dye solutions onto the films. Both neutral perylene diimide (N,N'-bis(butoxypropyl)perylene-3,4,9,10-tetracarboxylic diimide) and cationic rhodamine 6G (R6G) dyes were employed. The films were imaged by confocal fluorescence microscopy. The images obtained depict nonzero populations of fixed and mobile molecules in all films. Cross-correlation methods were used to quantitatively determine the population of fixed molecules in a given region, while a Bayesian burst analysis was used to obtain the total population of molecules. The results show that the total amount of dye loaded increases with increased oligomer extraction, while the relative populations of fixed and mobile molecules decrease and increase, respectively. Bulk R6G data also show greater dye loading with increased oligomer extraction.

  7. New strategy for stable-isotope-aided, multidimensional NMR spectroscopy of DNA oligomers

    Energy Technology Data Exchange (ETDEWEB)

    Ono, Okira; Tate, Shin-Ichi; Kainosho, Masatsune [Tokyo Metropolitan Univ., Tokyo (Japan)

    1994-12-01

    Nuclear Magnetic Resonance (NMR) is the most efficient method for determining the solution structures of biomolecules. By applying multidimensional heteronuclear NMR techniques to {sup 13}C/{sup 15}N-labeled proteins, we can determine the solution structures of proteins with molecular mass of 20 to 30kDa at an accuracy similar to that of x-ray crystallography. Improvements in NMR instrumentation and techniques as well as the development of protein engineering methods for labeling proteins have rapidly advanced multidimensional heteronuclear NMR of proteins. In contrast, multidimensional heteronuclear NMR studies of nucleic acids is less advanced because there were no efficient methods for preparing large amounts of labeled DNA/RNA oligomers. In this report, we focused on the chemical synthesis of DNA oligomers labeled at specific residue(s). RNA oligomers with specific labels, which are difficult to synthesize by the enzyme method, can be synthesized by the chemical method. The specific labels are useful for conformational analysis of larger molecules such as protein-nucleic acid complexes.

  8. Simulation of tethered oligomers in nanochannels using multi-particle collision dynamics.

    Science.gov (United States)

    Raghu, Riyad Chetram; Schofield, Jeremy

    2012-07-01

    The effect of a high Reynold's number, pressure-driven flow of a compressible gas on the conformation of an oligomer tethered to the wall of a square channel is studied under both ideal solvent and poor solvent conditions using a hybrid multiparticle collision dynamics and molecular dynamics algorithm. Unlike previous studies, the flow field contains an elongational component in addition to a shear component as well as fluid slip near the walls and results in a Schmidt number for the polymer beads that is less than unity. In both solvent regimes the oligomer is found to extend in the direction of flow. Under the ideal solvent conditions, torsional twisting of the chain and aperiodic cyclical dynamics are observed for the end of the oligomer. Under poor solvent conditions, a metastable helix forms in the end of the chain despite the lack of any attractive potential between beads in the oligomeric chain. The formation of the helix is postulated to be the result of a solvent induced chain collapse that has been confined to a single dimension by a strong flow field. PMID:22779677

  9. Panchromatic Light Capture and Efficient Excitation Transfer Leading to Near-IR Emission of BODIPY Oligomers.

    Science.gov (United States)

    Sharma, Ritambhara; Gobeze, Habtom B; D'Souza, Francis; Ravikanth, Mangalampalli

    2016-08-18

    All-BODIPY-based (BODIPY=boron-dipyrromethene) donor-acceptor systems capable of wide-band absorbance leading to efficient energy transfer in the near-IR region are reported. A covalently linked 3-pyrrolyl BODIPY-BODIPY dimer building block bearing an ethynyl group at the meso-aryl position is synthesized and coupled with three different monomeric BODIPY/pyrrolyl BODIPY building blocks with a bromo/iodo group under Pd(0) coupling conditions to obtain three covalently linked 3-pyrrolyl-BODIPY-based donor-acceptor oligomers in 19-29 % yield. The oligomers are characterized in detail by 1D and 2D NMR spectroscopy, high-resolution mass spectrometry, and optical spectroscopy. Due to the presence of different functionalized BODIPY derivatives in the oligomers, panchromatic light capture (300-725 nm) is witnessed. Fluorescence studies reveal singlet-singlet energy transfer from BODIPY monomer to BODIPY dimer leading to emission in the 700-800 nm range. Theoretical modeling according to the Förster mechanism predicts ultrafast energy transfer due to good spectral overlap of the donor and acceptor entities. Femtosecond transient absorption studies confirm this to be the case and thus show the relevance of the currently developed all-BODIPY-based energy-funneling supramolecular sytems with near-IR emission to solar-energy harvesting applications. PMID:27168532

  10. Structural Properties of HIV Integrase. Lens Epithelium-derived Growth Factor Oligomers

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, K.; Diamond, T; Hwang, Y; Bushman, F; Van Duyne, G

    2010-01-01

    Integrase (IN) is the catalytic component of the preintegration complex, a large nucleoprotein assembly critical for the integration of the retroviral genome into a host chromosome. Although partial crystal structures of human immunodeficiency virus IN alone and its complex with the integrase binding domain of the host factor PSIP1/lens epithelium-derived growth factor (LEDGF)/p75 are available, many questions remain regarding the properties and structures of LEDGF-bound IN oligomers. Using analytical ultracentrifugation, multiangle light scattering, and small angle x-ray scattering, we have established the oligomeric state, stoichiometry, and molecular shapes of IN {center_dot} LEDGF complexes in solution. Analyses of intact IN tetramers bound to two different LEDGF truncations allow for placement of the integrase binding domain by difference analysis. Modeling of the small angle x-ray scattering envelopes using existing structural data suggests domain arrangements in the IN oligomers that support and extend existing biochemical data for IN {center_dot} LEDGF complexes and lend new insights into the quaternary structure of LEDGF-bound IN tetramers. These IN oligomers may be involved in stages of the viral life cycle other than integration, including assembly, budding, and early replication.

  11. Comparison of automated pre-column and post-column analysis of amino acid oligomers

    Science.gov (United States)

    Chow, J.; Orenberg, J. B.; Nugent, K. D.

    1987-01-01

    It has been shown that various amino acids will polymerize under plausible prebiotic conditions on mineral surfaces, such as clays and soluble salts, to form varying amounts of oligomers (n = 2-6). The investigations of these surface reactions required a quantitative method for the separation and detection of these amino acid oligomers at the picomole level in the presence of nanomole levels of the parent amino acid. In initial high-performance liquid chromatography (HPLC) studies using a classical postcolumn o-phthalaldehyde (OPA) derivatization ion-exchange HPLC procedure with fluorescence detection, problems encountered included lengthy analysis time, inadequate separation and large relative differences in sensitivity for the separated species, expressed as a variable fluorescent yield, which contributed to poor quantitation. We have compared a simple, automated, pre-column OPA derivatization and reversed-phase HPLC method with the classical post-column OPA derivatization and ion-exchange HPLC procedure. A comparison of UV and fluorescent detection of the amino acid oligomers is also presented. The conclusion reached is that the pre-column OPA derivatization, reversed-phase HPLC and UV detection produces enhanced separation, improved sensitivity and faster analysis than post-column OPA derivatization, ion-exchange HPLC and fluorescence detection.

  12. NMR studies of DNA oligomers and their interactions with minor groove binding ligands

    Energy Technology Data Exchange (ETDEWEB)

    Fagan, P A [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry

    1996-05-01

    The cationic peptide ligands distamycin and netropsin bind noncovalently to the minor groove of DNA. The binding site, orientation, stoichiometry, and qualitative affinity of distamycin binding to several short DNA oligomers were investigated by NMR spectroscopy. The oligomers studied contain A,T-rich or I,C-rich binding sites, where I = 2-desaminodeoxyguanosine. I{center_dot}C base pairs are functional analogs of A{center_dot}T base pairs in the minor groove. The different behaviors exhibited by distamycin and netropsin binding to various DNA sequences suggested that these ligands are sensitive probes of DNA structure. For sites of five or more base pairs, distamycin can form 1:1 or 2:1 ligand:DNA complexes. Cooperativity in distamycin binding is low in sites such as AAAAA which has narrow minor grooves, and is higher in sites with wider minor grooves such as ATATAT. The distamycin binding and base pair opening lifetimes of I,C-containing DNA oligomers suggest that the I,C minor groove is structurally different from the A,T minor groove. Molecules which direct chemistry to a specific DNA sequence could be used as antiviral compounds, diagnostic probes, or molecular biology tools. The author studied two ligands in which reactive groups were tethered to a distamycin to increase the sequence specificity of the reactive agent.

  13. Calcium dysregulation and membrane disruption as a ubiquitous neurotoxic mechanism of soluble amyloid oligomers.

    Science.gov (United States)

    Demuro, Angelo; Mina, Erene; Kayed, Rakez; Milton, Saskia C; Parker, Ian; Glabe, Charles G

    2005-04-29

    Increasing evidence suggests that amyloid peptides associated with a variety of degenerative diseases induce neurotoxicity in their intermediate oligomeric state, rather than as monomers or fibrils. To test this hypothesis and investigate the possible involvement of Ca2+ signaling disruptions in amyloid-induced cytotoxicity, we made homogeneous preparations of disease-related amyloids (Abeta, prion, islet amyloid polypeptide, polyglutamine, and lysozyme) in various aggregation states and tested their actions on fluo-3-loaded SH-SY5Y cells. Application of oligomeric forms of all amyloids tested (0.6-6 microg ml-1) rapidly (approximately 5 s) elevated intracellular Ca2+, whereas equivalent amounts of monomers and fibrils did not. Ca2+ signals evoked by Abeta42 oligomers persisted after depletion of intracellular Ca2+ stores, and small signals remained in Ca2+-free medium, indicating contributions from both extracellular and intracellular Ca2+ sources. The increased membrane permeability to Ca2+ cannot be attributed to activation of endogenous Ca2+ channels, because responses were unaffected by the potent Ca2+-channel blocker cobalt (20 microm). Instead, observations that Abeta42 and other oligomers caused rapid cellular leakage of anionic fluorescent dyes point to a generalized increase in membrane permeability. The resulting unregulated flux of ions and molecules may provide a common mechanism for oligomer-mediated toxicity in many amyloidogenic diseases, with dysregulation of Ca2+ ions playing a crucial role because of their strong trans-membrane concentration gradient and involvement in cell dysfunction and death. PMID:15722360

  14. Aβ1-42 monomers or oligomers have different effects on autophagy and apoptosis.

    Science.gov (United States)

    Guglielmotto, Michela; Monteleone, Debora; Piras, Antonio; Valsecchi, Valeria; Tropiano, Marta; Ariano, Stefania; Fornaro, Michele; Vercelli, Alessandro; Puyal, Julien; Arancio, Ottavio; Tabaton, Massimo; Tamagno, Elena

    2014-10-01

    The role of autophagy and its relationship with apoptosis in Alzheimer disease (AD) pathogenesis is poorly understood. Disruption of autophagy leads to buildup of incompletely digested substrates, amyloid-β (Aβ) peptide accumulation in vacuoles and cell death. Aβ, in turn, has been found to affect autophagy. Thus, Aβ might be part of a loop in which it is both the substrate of altered autophagy and its cause. Given the relevance of different soluble forms of Aβ1-42 in AD, we have investigated whether monomers and oligomers of the peptide have a differential role in causing altered autophagy and cell death. Using differentiated SK-N-BE neuroblastoma cells, we found that monomers hamper the formation of the autophagic BCL2-BECN1/Beclin 1 complex and activate the MAPK8/JNK1-MAPK9/JNK2 pathway phosphorylating BCL2. Monomers also inhibit apoptosis and allow autophagy with intracellular accumulation of autophagosomes and elevation of levels of BECN1 and LC3-II, resulting in an inhibition of substrate degradation due to an inhibitory action on lysosomal activity. Oligomers, in turn, favor the formation of the BCL2-BECN1 complex favoring apoptosis. In addition, they cause a less profound increase in BECN1 and LC3-II levels than monomers without affecting the autophagic flux. Thus, data presented in this work show a link for autophagy and apoptosis with monomers and oligomers, respectively. These studies are likely to help the design of novel disease modifying therapies.

  15. Enzymatic generation of galactose-rich oligosaccharides/oligomers from potato rhamnogalacturonan I pectic polysaccharides.

    Science.gov (United States)

    Khodaei, Nastaran; Karboune, Salwa

    2016-04-15

    Potato pulp by-product rich in galactan-rich rhamnogalacturonan I (RG I) was investigated as a new source of oligosaccharides with potential prebiotic properties. The efficiency of selected monocomponent enzymes and multi-enzymatic preparations to generate oligosaccharides/oligomers from potato RG I was evaluated. These overall results of yield were dependent on the activity profile of the multi-enzymatic preparations. Highest oligo-RG I yield of 93.9% was achieved using multi-enzymatic preparation (Depol 670L) with higher hydrolytic activity toward side chains of RG I as compared to its backbone. Main oligo-RG I products were oligosaccharides with DP of 2-12 (79.8-100%), while the oligomers with DP of 13-70 comprised smaller proportion (0.0-20.2%). Galactose (58.9-91.2%, w/w) was the main monosaccharide of oligo-RG I, while arabinose represented 0.0-12.1%. An understanding of the relationship between the activity profile of multi-enzymatic preparations and the yield/DP of oligo-RG I was achieved. This is expected to provide the capability to generate galacto- and galacto(arabino) oligosaccharides and their corresponding oligomers from an abundant by-product. PMID:26616968

  16. Lysosomal Enzyme Glucocerebrosidase Protects against Aβ1-42 Oligomer-Induced Neurotoxicity.

    Directory of Open Access Journals (Sweden)

    Seulah Choi

    Full Text Available Glucocerebrosidase (GCase functions as a lysosomal enzyme and its mutations are known to be related to many neurodegenerative diseases, including Gaucher's disease (GD, Parkinson's disease (PD, and Dementia with Lewy Bodies (DLB. However, there is little information about the role of GCase in the pathogenesis of Alzheimer's disease (AD. Here we demonstrate that GCase protein levels and enzyme activity are significantly decreased in sporadic AD. Moreover, Aβ1-42 oligomer treatment results in neuronal cell death that is concomitant with decreased GCase protein levels and enzyme activity, as well as impairment in lysosomal biogenesis and acidification. Importantly, overexpression of GCase promotes the lysosomal degradation of Aβ1-42 oligomers, restores the lysosomal impairment, and protects against the toxicity in neurons treated with Aβ1-42 oligomers. Our findings indicate that a deficiency of GCase could be involved in progression of AD pathology and suggest that augmentation of GCase activity may be a potential therapeutic option for the treatment of AD.

  17. NEXAFS characterization of DNA components and molecular-orientation of surface-bound DNA oligomers

    Energy Technology Data Exchange (ETDEWEB)

    Samuel, Newton T. [National ESCA and Surface Analysis Center for Biomedical Problems, Department of Chemical Engineering, University of Washington, Box 351750, Seattle, WA 98195 (United States); Lee, C.-Y. [National ESCA and Surface Analysis Center for Biomedical Problems, Department of Chemical Engineering, University of Washington, Box 351750, Seattle, WA 98195 (United States); Gamble, Lara J. [National ESCA and Surface Analysis Center for Biomedical Problems, Department of Bioengineering, University of Washington, Box 351750, Seattle, WA 98195 (United States); Fischer, Daniel A. [National Institute of Standards and Technology, Gaithersburg, MD 20899 (United States); Castner, David G. [National ESCA and Surface Analysis Center for Biomedical Problems, Department of Chemical Engineering, University of Washington, Box 351750, Seattle, WA 98195 (United States) and National ESCA and Surface Analysis Center for Biomedical Problems, Department of Bioengineering, University of Washington, Box 351750, Seattle, WA 98195 (United States)]. E-mail: castner@nb.engr.washington.edu

    2006-07-15

    Single stranded DNA oligomers (ssDNA) immobilized onto solid surfaces forms the basis for several biotechnological applications such as DNA microarrays, affinity separations, and biosensors. Surface structure of Surface-bound oligomers is expected to significantly influence their biological activity and interactions with the environment. In this study near-edge X-ray absorption fine structure spectroscopy (NEXAFS) is used to characterize the components of DNA (nucleobases, nucleotides and nucleosides) and the orientation information of surface-bound ssDNA. The K-edges of carbon, nitrogen and oxygen have spectra with features that are characteristic of the different chemical species present in the nucleobases of DNA. The effect of addition of the DNA sugar and phosphate components on the NEXAFS K-edge spectra was also investigated. The polarization-dependent nitrogen K-edge NEXAFS data show significant changes for different orientations of surface bound ssDNA. These results establish NEXAFS as a powerful technique for chemical and structural characterization of surface-bound DNA oligomers.

  18. Dynamics in coarse-grained models for oligomer-grafted silica nanoparticles

    KAUST Repository

    Hong, Bingbing

    2012-01-01

    Coarse-grained models of poly(ethylene oxide) oligomer-grafted nanoparticles are established by matching their structural distribution functions to atomistic simulation data. Coarse-grained force fields for bulk oligomer chains show excellent transferability with respect to chain lengths and temperature, but structure and dynamics of grafted nanoparticle systems exhibit a strong dependence on the core-core interactions. This leads to poor transferability of the core potential to conditions different from the state point at which the potential was optimized. Remarkably, coarse graining of grafted nanoparticles can either accelerate or slowdown the core motions, depending on the length of the grafted chains. This stands in sharp contrast to linear polymer systems, for which coarse graining always accelerates the dynamics. Diffusivity data suggest that the grafting topology is one cause of slower motions of the cores for short-chain oligomer-grafted nanoparticles; an estimation based on transition-state theory shows the coarse-grained core-core potential also has a slowing-down effect on the nanoparticle organic hybrid materials motions; both effects diminish as grafted chains become longer. © 2012 American Institute of Physics.

  19. Preparation and properties of poly(acrylic acid) oligomer stabilized superparamagnetic ferrofluid.

    Science.gov (United States)

    Lin, Chia-Lung; Lee, Chia-Fen; Chiu, Wen-Yen

    2005-11-15

    Ferrofluids, which are stable dispersions of magnetic particles, behave as liquids that have strong magnetic properties. Nanoparticles of magnetite with a mean diameter of 10-15 nm, which are in the range of superparamagnetism, are usually prepared by the traditional method of co-precipitation from ferrous and ferric electrolyte solution. When diluted, the ferrofluid dispersions are not stable if anionic or cationic surfactants are used as the stabilizer. This work presents an efficient way to prepare a stable aqueous nanomagnetite dispersion. A stable ferrofluid containing Fe3O4 nanoparticles was synthesized via co-precipitation in the presence of poly(acrylic acid) oligomer. The mechanism, microstructure, and properties of the ferrofluid were investigated. The results indicate that the PAA oligomers promoted the nucleation and inhibited the growth of the magnetic iron oxide, and the average diameter of each individual Fe3O4 particle was smaller than 10 nm. In addition, the PAA oligomers provided both electrostatic and steric repulsion against particle aggregation, and the stability of dispersions could be controlled by adjusting the pH value of solution. A small amount of Fe2O3 was found in the nanoparticles but the superparamagnetic behavior of the nanoparticles was not affected. PMID:16009367

  20. Aβ42-oligomer Interacting Peptide (AIP) neutralizes toxic amyloid-β42 species and protects synaptic structure and function.

    Science.gov (United States)

    Barucker, Christian; Bittner, Heiko J; Chang, Philip K-Y; Cameron, Scott; Hancock, Mark A; Liebsch, Filip; Hossain, Shireen; Harmeier, Anja; Shaw, Hunter; Charron, François M; Gensler, Manuel; Dembny, Paul; Zhuang, Wei; Schmitz, Dietmar; Rabe, Jürgen P; Rao, Yong; Lurz, Rudi; Hildebrand, Peter W; McKinney, R Anne; Multhaup, Gerhard

    2015-01-01

    The amyloid-β42 (Aβ42) peptide is believed to be the main culprit in the pathogenesis of Alzheimer disease (AD), impairing synaptic function and initiating neuronal degeneration. Soluble Aβ42 oligomers are highly toxic and contribute to progressive neuronal dysfunction, loss of synaptic spine density, and affect long-term potentiation (LTP). We have characterized a short, L-amino acid Aβ-oligomer Interacting Peptide (AIP) that targets a relatively well-defined population of low-n Aβ42 oligomers, rather than simply inhibiting the aggregation of Aβ monomers into oligomers. Our data show that AIP diminishes the loss of Aβ42-induced synaptic spine density and rescues LTP in organotypic hippocampal slice cultures. Notably, the AIP enantiomer (comprised of D-amino acids) attenuated the rough-eye phenotype in a transgenic Aβ42 fly model and significantly improved the function of photoreceptors of these flies in electroretinography tests. Overall, our results indicate that specifically "trapping" low-n oligomers provides a novel strategy for toxic Aβ42-oligomer recognition and removal. PMID:26510576

  1. Characterization of oligomers from methylglyoxal under dark conditions: a pathway to produce secondary organic aerosol through cloud processing during nighttime

    Science.gov (United States)

    Yasmeen, F.; Sauret, N.; Gal, J.-F.; Maria, P.-C.; Massi, L.; Maenhaut, W.; Claeys, M.

    2010-04-01

    Aqueous-phase oligomer formation from methylglyoxal, a major atmospheric photooxidation product, has been investigated in a simulated cloud matrix under dark conditions. The aim of this study was to explore an additional pathway producing secondary organic aerosol (SOA) through cloud processes without participation of photochemistry during nighttime. Indeed, atmospheric models still underestimate SOA formation, as field measurements have revealed more SOA than predicted. Soluble oligomers (n = 1-8) formed in the course of acid-catalyzed aldol condensation and acid-catalyzed hydration followed by acetal formation have been detected and characterized by positive and negative ion electrospray ionization mass spectrometry. Aldol condensation proved to be a favorable mechanism under simulated cloud conditions, while hydration/acetal formation was found to strongly depend on the pH of the system and only occurred at a pHaldol oligomer series starts with a β-hydroxy ketone via aldol condensation, where oligomers are formed by multiple additions of C3H4O2 units (72 Da) to the parent β-hydroxy ketone. Ion trap mass spectrometry experiments were performed to structurally characterize the major oligomer species. A mechanistic pathway for the growth of oligomers under cloud conditions and in the absence of UV-light and OH radicals, which could substantially enhance in-cloud SOA yields, is proposed here for the first time.

  2. Regioselective Preparation of Diethyl 3,4-Disubstituted 1,5-Dihydro-5-oxo-2H-pyrrol-2-ylphosphonates and Their Coupling with Aldehydes. Application to the Synthesis of C/D-Rings Component of Phycocyanobilin

    OpenAIRE

    Ngwe, Hla; Kinoshita, Hideki; Inomata, Katsuhiko

    1994-01-01

    Diethyl 3,4-disubstituted 1,5-dihydro-5-oxo-2H-pyrrol-2-ylphosphonates were regioselectively prepared by acidic hydrolysis of diethyl 3,4-disubstituted 5-bromo-2-pyrrolylphosphonates. The resulting 1,5-dihydro-2H-pyrrol-2-ones readily underwent the coupling reaction with various aldehydes to afford the corresponding 1,5-dihydro-5-methylene-2H-pyrrol-2-ones including pyrromethenone derivatives in good yields. A series of these reactions was successfully applied to the synthesis of C/D-rings co...

  3. Highly Sensitive Bisphenol-A Electrochemical Aptasensor Based on Poly(Pyrrole-Nitrilotriacetic Acid)-Aptamer Film.

    Science.gov (United States)

    Kazane, Imen; Gorgy, Karine; Gondran, Chantal; Spinelli, Nicolas; Zazoua, Ali; Defrancq, E; Cosnier, Serge

    2016-07-19

    An electrochemical highly sensitive aptasensor was developed based on electropolymerized poly(pyrrole-nitrilotriacetic) acid film and a new aptamer functionalized by a pentahistidine peptide for the quantification of bisphenol A. A surface coverage of antibisphenol A aptamer of 1.84 × 10(-10) mol cm(-2) was estimated from the electrochemical signal of the [Ru(III)(NH3)6](3+) complex bound by electrostatic interactions onto the aptamer-modified electrode. The binding of bisphenol A onto the polymer film was successfully characterized by electrochemical methods as square wave voltammetry and electrochemical impedance spectroscopy measurements. The designed label-free impedimetric aptasensor displayed a wide linear range from 10(-11) to 10(-6) mol L(-1) with a sensitivity of 372 Ω per unit of log of concentration and an excellent specificity toward interfering agents such as 4,4'-dihydroxybiphenyl and bisphenol P. PMID:27332710

  4. Hemispherand-Strapped Calix[4]pyrrole: An Ion-pair Receptor for the Recognition and Extraction of Lithium Nitrite.

    Science.gov (United States)

    He, Qing; Zhang, Zhan; Brewster, James T; Lynch, Vincent M; Kim, Sung Kuk; Sessler, Jonathan L

    2016-08-10

    The hemispherand-strapped calix[4]pyrrole (1) acts as an ion pair receptor that exhibits selectivity for lithium salts. In organic media (CD2Cl2 and CD3OD, v/v, 9:1), receptor 1 binds LiCl with high preference relative to NaCl, KCl, and RbCl. DFT calculations provided support for the observed selectivity. Single crystal structures of five different lithium ion-pair complexes of 1 were obtained. In the case of LiCl, a single bridging water molecule between the lithium cation and chloride anion was observed, while tight contact ion pairs were observed in the case of the LiBr, LiI, LiNO3, and LiNO2 salts. Receptor 1 proved effective as an extractant for LiNO2 under both model solid-liquid and liquid-liquid extraction conditions. PMID:27442768

  5. Large area in situ fabrication of poly(pyrrole)-nanowires on flexible thermoplastic films using nanocontact printing

    Science.gov (United States)

    Garcia-Cruz, Alvaro; Lee, Michael; Marote, Pedro; Zine, Nadia; Sigaud, Monique; Bonhomme, Anne; Pruna, Raquel; Lopez, Manuel; Bausells, Joan; Jaffrezic, Nicole; Errachid, Abdelhamid

    2016-08-01

    Highly efficient nano-engineering tools will certainly revolutionize the biomedical and sensing devices research and development in the years to come. Here, we present a novel high performance conducting poly(pyrrole) nanowires (PPy-NW) patterning technology on thermoplastic surfaces (poly(ethylene terephthalate (PETE), poly(ethylene 2,6-naphthalate (PEN), polyimide (PI), and cyclic olefin copolymer) using nanocontact printing and controlled chemical polymerization (nCP-CCP) technique. The technique uses a commercial compact disk as a template to produce nanopatterned polydimethylsiloxane (PDMS) stamps. The PDMS nanopatterned stamp was applied to print the PPy-NWs and the developed technology of nCP-CCP produced 3D conducting nanostructures. This new and very promising nanopatterning technology was achieved in a single step and with a low cost of fabrication over large areas.

  6. Excited state non-adiabatic dynamics of pyrrole: A time-resolved photoelectron spectroscopy and quantum dynamics study

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Guorong [National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023 (China); Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China); Neville, Simon P.; Worth, Graham A., E-mail: g.a.worth@bham.ac.uk [School of Chemistry, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom); Schalk, Oliver [National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); Department of Physics, AlbaNova University Center, Stockholm University, Roslagstullsbacken 21, 109 61 Stockholm (Sweden); Sekikawa, Taro [National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); Department of Applied Physics, Hokkaido University, Kita-13 Nishi-8, Kita-ku, Sapporo 060-8628 (Japan); Ashfold, Michael N. R. [School of Chemistry, University of Bristol, Bristol BS8 1TS (United Kingdom); Stolow, Albert, E-mail: astolow@uottawa.ca [National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario K1A 0R6 (Canada); Departments of Chemistry and Physics, University of Ottawa, 10 Marie Curie, Ottawa, Ontario K1N 6N5 (Canada)

    2015-02-21

    The dynamics of pyrrole excited at wavelengths in the range 242-217 nm are studied using a combination of time-resolved photoelectron spectroscopy and wavepacket propagations performed using the multi-configurational time-dependent Hartree method. Excitation close to the origin of pyrrole’s electronic spectrum, at 242 and 236 nm, is found to result in an ultrafast decay of the system from the ionization window on a single timescale of less than 20 fs. This behaviour is explained fully by assuming the system to be excited to the A{sub 2}(πσ{sup ∗}) state, in accord with previous experimental and theoretical studies. Excitation at shorter wavelengths has previously been assumed to result predominantly in population of the bright A{sub 1}(ππ{sup ∗}) and B{sub 2}(ππ{sup ∗}) states. We here present time-resolved photoelectron spectra at a pump wavelength of 217 nm alongside detailed quantum dynamics calculations that, together with a recent reinterpretation of pyrrole’s electronic spectrum [S. P. Neville and G. A. Worth, J. Chem. Phys. 140, 034317 (2014)], suggest that population of the B{sub 1}(πσ{sup ∗}) state (hitherto assumed to be optically dark) may occur directly when pyrrole is excited at energies in the near UV part of its electronic spectrum. The B{sub 1}(πσ{sup ∗}) state is found to decay on a timescale of less than 20 fs by both N-H dissociation and internal conversion to the A{sub 2}(πσ{sup ∗}) state.

  7. Synthesis, characterization, molecular docking and biological studies of self assembled transition metal dithiocarbamates of substituted pyrrole-2-carboxaldehyde.

    Science.gov (United States)

    Nami, Shahab A A; Ullah, Irfan; Alam, Mahboob; Lee, Dong-Ung; Sarikavakli, Nursabah

    2016-07-01

    A series of self assembled 3d transition metal dithiocarbamate, M(pdtc) [where M=Mn(II), Fe(II), Co(II), Ni(II) and Cu(II)] have been synthesized and spectroscopically characterized. The bidentate dithiocarbamate ligand Na2pdtc (Disodium-1,4-phenyldiaminobis (pyrrole-1-sulfino)dithioate) was prepared by insertion reaction of carbondisulfide with Schiff base, N,N'-bis-(1H-pyrrol-2-ylmethylene)-benzene-1,4-diamine (L1) in basic medium. The simple substitution reaction between the metal halide and Na2pdtc yielded the title complexes in moderate yields. However, the in situ procedure gives high yield with the formation of single product as evident by TLC. Elemental analysis, IR, (1)H and (13)C NMR spectra, UV-vis., magnetic susceptibility and conductance measurements were done to characterize the complexes, M(pdtc). All the evidences suggest that the complexes have tetrahedral geometry excepting Cu(II) which is found to be square planar. A symmetrical bidentate coordination of the dithiocarbamato moiety has been observed in all the complexes. The conductivity data show that the complexes are non-electrolyte in nature. The anti-oxidant activity of the ligand, Na2pdtc and its transition metal complexes, M(pdtc) have been carried out using DPPH and Cu(pdtc) was found to be most effective. The anti-microbial activity of the Na2pdtc and M(pdtc) complexes have been carried out and on this basis the molecular docking study of the most effective complex, Cu(pdtc) has also been reported. PMID:27197060

  8. A Monte Carlo approach for assessing the specificity of protein oligomers observed in nano-electrospray mass spectra

    Science.gov (United States)

    Lane, Laura A.; Ruotolo, Brandon T.; Robinson, Carol V.; Favrin, Giorgio; Benesch, Justin L. P.

    2009-06-01

    Nano-electrospray mass spectrometry is an emerging approach for studying the architecture and dynamics of complex oligomeric proteins. The analysis of such species can, however, be hindered by [`]non-specific' protein-protein associations which arise as a result of the electrospray method. To understand the formation of specific versus non-specific protein oligomers detected by mass spectrometry we have developed a simple and rapid computational approach. This Monte Carlo algorithm characterizes the occupancy of protein species in the last offspring droplets created by the nano-electrospray process. As such it enables us to assess whether oligomers detected in mass spectra reflect solution populations, or instead are the result of associations during droplet fission and evaporation. We have trained and validated this method on three model protein complexes which are not known to form higher order oligomers, and one which has a tendency to self-associate in solution in a concentration dependent manner. We have then compared predictions of droplet occupancy to abundances obtained from mass spectra for the tetrameric amyloid-related protein transthyretin, which can cause cardiomyopathy and polyneuropathy in humans. Interestingly, when such comparisons were made for wild-type transthyretin we were able to observe a propensity for the protein to form specific oligomers larger than the tetramer. In contrast, the tendency for the leucine-55-proline variant to form such oligomers was considerably reduced. We contemplate the significance of these specific higher order wild-type oligomers, and absence of such species in the variant, on the pathway of amyloid formation in transthyretin. More generally this easy-to-implement computational approach promises to improve our ability to identify oligomers of biological significance within the mass spectra of heterogenous protein complexes.

  9. Laser-induced charge separation in organic nanofibers

    DEFF Research Database (Denmark)

    Tavares, Luciana; Behn, Dino; Kjelstrup-Hansen, Jakob;

    Organic semiconductors have unique properties that can be tailored via synthetic chemistry for specific applications, which combined with their low price and straight-forward processing over large areas make them interesting materials for future devices. Certain oligomers can self-assemble into c......Organic semiconductors have unique properties that can be tailored via synthetic chemistry for specific applications, which combined with their low price and straight-forward processing over large areas make them interesting materials for future devices. Certain oligomers can self......-assemble into crystalline nanofibers by vapor deposition onto muscovite mica substrates, and we have recently shown that such nanofibers can be transferred to different substrates by roll-printing and used as the active material in e.g. organic field-effect transistors (OFETs), organic light-emitting transistors (OLETs......), and organic phototransistors (OPTs). However, several device-related issues incl. charge-separation and local band structure remain poorly understood. In this work, we use electrostatic force microscopy (EFM) combined with optical microscopy to study the local surface charge of an individual organic nanofiber...

  10. CHARGE Association

    Directory of Open Access Journals (Sweden)

    Semanti Chakraborty

    2012-01-01

    Full Text Available We present here a case of 17-year-old boy from Kolkata presenting with obesity, bilateral gynecomastia, mental retardation, and hypogonadotrophic hypogonadism. The patient weighed 70 kg and was of 153 cm height. Facial asymmetry (unilateral facial palsy, gynecomastia, decreased pubic and axillary hair, small penis, decreased right testicular volume, non-palpable left testis, and right-sided congenital inguinal hernia was present. The patient also had disc coloboma, convergent squint, microcornea, microphthalmia, pseudohypertelorism, low set ears, short neck, and choanalatresia. He had h/o VSD repaired with patch. Laboratory examination revealed haemoglobin 9.9 mg/dl, urea 24 mg/dl, creatinine 0.68 mg/dl. IGF1 77.80 ng/ml (decreased for age, GH <0.05 ng/ml, testosterone 0.25 ng/ml, FSH-0.95 ΅IU/ml, LH 0.60 ΅IU/ml. ACTH, 8:00 A.M cortisol, FT3, FT4, TSH, estradiol, DHEA-S, lipid profile, and LFT was within normal limits. Prolactin was elevated at 38.50 ng/ml. The patient′s karyotype was 46XY. Echocardiography revealed ventricularseptal defect closed with patch, grade 1 aortic regurgitation, and ejection fraction 67%. Ultrasound testis showed small right testis within scrotal sac and undescended left testis within left inguinal canal. CT scan paranasal sinuses revealed choanalatresia and deviation of nasal septum to the right. Sonomammography revealed bilateral proliferation of fibroglandular elements predominantly in subareoalar region of breasts. MRI of brain and pituitary region revealed markedly atrophic pituitary gland parenchyma with preserved infundibulum and hypothalamus and widened suprasellar cistern. The CHARGE association is an increasingly recognized non-random pattern of congenital anomalies comprising of coloboma, heart defect, choanal atresia, retarded growth and development, genital hypoplasia, ear abnormalities, and/or deafness. [1] These anomalies have a higher probability of occurring together. In this report, we have

  11. Post Hartree–Fock and DFT Studies on Pyrrole···Nitrogen and Pyrrole···Carbon Monoxide Molecules

    Directory of Open Access Journals (Sweden)

    P. Kolandaivel

    2002-07-01

    Full Text Available Abstract: The hydrogen bonded and van der Waals isomers of pyrrole···nitrogen and pyrrole···carbon monoxide have been studied using ab initio and density functional theory methods. Complex geometries and total energies of the isomers have been determined at HF, MP2, B3LYP and B3PW91 levels of theory employing 6-31G* basis set. For pyrrole···nitrogen complex, only two isomers have stable structure and the more stable one is found to be the hydrogen bonded isomer. Among the five isomers of pyrrole···carbon monoxide complex, the hydrogen bonded isomer is found to be the most stable form. The interaction energy for all these isomers have been calculated after eliminating the basis set superposition errors by using the full counterpoise correction method. Chemical hardness, chemical potential have been calculated and are used to study the stability of the molecules.

  12. Following the TRMC Trail: Optimization of Photovoltaic Efficiency and Structure-Property Correlation of Thiophene Oligomers.

    Science.gov (United States)

    Ghosh, Tanwistha; Gopal, Anesh; Nagasawa, Shinji; Mohan, Nila; Saeki, Akinori; Nair, Vijayakumar C

    2016-09-28

    Semiconducting conjugated oligomers having same end group (N-ethylrhodanine) but different central core (thiophene: OT-T, bithiophene: OT-BT, thienothiophene: OT-TT) connected through thiophene pi-linker (alkylated terthiophene) were synthesized for solution processable bulk-heterojunction solar cells. The effect of the incorporation of an extra thiophene to the central thiophene unit either through C-C bond linkage to form bithiophene or by fusing two thiophenes together to form thienothiophene on the optoelectronic properties and photovoltaic performances of the oligomers were studied in detail. Flash photolysis time-resolved microwave conductivity (FP-TRMC) technique shows OT-TT has significantly higher photoconductivity than OT-T and OT-BT implying that the former can outperform the latter two derivatives by a wide margin under identical conditions in a bulk-heterojunction solar cell device. However, the initial photovoltaic devices fabricated from all three oligomers (with PC71BM as the acceptor) gave power conversion efficiencies (PCEs) of about 0.7%, which was counterintuitive to the TRMC observation. By using TRMC results as a guiding tool, solution engineering was carried out; no remarkable changes were seen in the PCE of OT-T and OT-BT. On the other hand, 5-fold enhancement in the device efficiency was achieved in OT-TT (PCE: 3.52%, VOC: 0.80 V, JSC: 8.74 mA cm(-2), FF: 0.50), which was in correlation with the TRMC results. The structure-property correlation and the fundamental reasons for the improvement in device performance upon solvent engineering were deduced through UV-vis absorption, atomic force microscopy, bright-field transmission electron microscopy, photoluminescence quenching analysis and two-dimensional grazing incidence X-ray diffraction studies.

  13. ENVIRONMENTAL ENRICHMENT STRENGTHENS CORTICOCORTICAL INTERACTIONS AND REDUCES AMYLOID-β OLIGOMERS IN AGED MICE

    Directory of Open Access Journals (Sweden)

    Marco eMainardi

    2014-01-01

    Full Text Available Brain aging is characterized by global changes which are thought to underlie age-related cognitive decline. These include variations in brain activity and the progressive increase in the concentration of soluble amyloid-β (Aβ oligomers, directly impairing synaptic function and plasticity even in the absence of any neurodegenerative disorder. Considering the high social impact of the decline in brain performance associated to aging, there is an urgent need to better understand how it can be prevented or contrasted. Lifestyle components, such as social interaction, motor exercise and cognitive activity, are thought to modulate brain physiology and its susceptibility to age-related pathologies. However, the precise functional and molecular factors that respond to environmental stimuli and might mediate their protective action again pathological aging still need to be clearly identified. To address this issue, we exploited environmental enrichment (EE, a reliable model for studying the effect of experience on the brain based on the enhancement of cognitive, social and motor experience, in aged wild-type mice. We analyzed the functional consequences of EE on aged brain physiology by performing in vivo local field potential (LFP recordings with chronic implants. In addition, we also investigated changes induced by EE on molecular markers of neural plasticity and on the levels of soluble Aβ oligomers. We report that EE induced profound changes in the activity of the primary visual and auditory cortices and in their functional interaction. At the molecular level, EE enhanced plasticity by an upward shift of the cortical excitation/inhibition balance. In addition, EE reduced brain Aβ oligomers and increased synthesis of the Aβ-degrading enzyme neprilysin. Our findings strengthen the potential of EE procedures as a non-invasive paradigm for counteracting brain aging processes.

  14. Following the TRMC Trail: Optimization of Photovoltaic Efficiency and Structure-Property Correlation of Thiophene Oligomers.

    Science.gov (United States)

    Ghosh, Tanwistha; Gopal, Anesh; Nagasawa, Shinji; Mohan, Nila; Saeki, Akinori; Nair, Vijayakumar C

    2016-09-28

    Semiconducting conjugated oligomers having same end group (N-ethylrhodanine) but different central core (thiophene: OT-T, bithiophene: OT-BT, thienothiophene: OT-TT) connected through thiophene pi-linker (alkylated terthiophene) were synthesized for solution processable bulk-heterojunction solar cells. The effect of the incorporation of an extra thiophene to the central thiophene unit either through C-C bond linkage to form bithiophene or by fusing two thiophenes together to form thienothiophene on the optoelectronic properties and photovoltaic performances of the oligomers were studied in detail. Flash photolysis time-resolved microwave conductivity (FP-TRMC) technique shows OT-TT has significantly higher photoconductivity than OT-T and OT-BT implying that the former can outperform the latter two derivatives by a wide margin under identical conditions in a bulk-heterojunction solar cell device. However, the initial photovoltaic devices fabricated from all three oligomers (with PC71BM as the acceptor) gave power conversion efficiencies (PCEs) of about 0.7%, which was counterintuitive to the TRMC observation. By using TRMC results as a guiding tool, solution engineering was carried out; no remarkable changes were seen in the PCE of OT-T and OT-BT. On the other hand, 5-fold enhancement in the device efficiency was achieved in OT-TT (PCE: 3.52%, VOC: 0.80 V, JSC: 8.74 mA cm(-2), FF: 0.50), which was in correlation with the TRMC results. The structure-property correlation and the fundamental reasons for the improvement in device performance upon solvent engineering were deduced through UV-vis absorption, atomic force microscopy, bright-field transmission electron microscopy, photoluminescence quenching analysis and two-dimensional grazing incidence X-ray diffraction studies. PMID:27598737

  15. Ligation of RNA Oligomers by the Schistosoma mansoni Hammerhead Ribozyme in Frozen Solution.

    Science.gov (United States)

    Lie, Lively; Biliya, Shweta; Vannberg, Fredrik; Wartell, Roger M

    2016-03-01

    The interstitial liquid phase within frozen aqueous solutions is an environment that minimizes RNA degradation and facilitates reactions that may have relevance to the RNA World hypothesis. Previous work has shown that frozen solutions support condensation of activated nucleotides into RNA oligomers, RNA ligation by the hairpin ribozyme, and RNA synthesis by a RNA polymerase ribozyme. In the current study, we examined the activity of a hammerhead ribozyme (HHR) in frozen solution. The Schistosoma mansoni hammerhead ribozyme, which predominantly cleaves RNA, can ligate its cleaved products (P1 and P2) with yields up to ~23 % in single turnover experiments at 25 °C in the presence of Mg(2+). Our studies show that this HHR ligates RNA oligomers in frozen solution in the absence of divalent cations. Citrate and other anions that exhibit strong ion-water affinity enhanced ligation. Yields up to 43 % were observed in one freeze-thaw cycle and a maximum of 60 % was obtained after several freeze-thaw cycles using wild-type P1 and P2. Truncated and mutated P1 substrates were ligated to P2 with yields of 14-24 % in one freeze-thaw cycle. A pool of P2 substrates with mixtures of all four bases at five positions were ligated with P1 in frozen solution. High-throughput sequencing indicated that 70 of the 1024 possible P2 sequences were represented in ligated products at 1000 or more read counts per million reads. The results indicate that the HHR can ligate a range of short RNA oligomers into an ensemble of diverse sequences in ice.

  16. Assembly of Heterometallic Rigid-Rod Complexes and Coordination Oligomers from Gold(I) Metalloligands.

    Science.gov (United States)

    Cámara, Verónica; Barquero, Natalia; Bautista, Delia; Gil-Rubio, Juan; Vicente, José

    2015-07-01

    The reactions of TpylC6H4C≡CAuL (Tpyl = 2,2':6',2″-terpyridin-4'-yl; L = PPh3, CNXy; Xy = 2,6-dimethylphenyl) with MX2·nH2O (M = Fe, X = ClO4; M = Co, X = BF4; M = Zn, X = TfO, ClO4) in a 2:1 molar ratio give complexes [M(TpylC6H4C≡CAuL)2]X2. Similarly, the reactions of PPN[(TpylC6H4C≡C)2Au] (PPN = (Ph3P)2N) with an equimolar amount of MX2·nH2O give coordination oligomers [M{(TpylC6H4C≡C)2Au}]nXn (M = Fe, Zn, X = ClO4; M = Co, X = BF4). The complexes and oligomers have been isolated and characterized. The crystal structures of [Fe(TpylC6H4C≡CAuCNXy)2](ClO4)2 and [Co(TpylC6H4C≡CAuPPh3)2](BF4)2 have been determined by X-ray diffraction. The hydrodynamic sizes of complexes [M(TpylC6H4C≡CAuPPh3)2]X2 and coordination oligomers [M{(TpylC6H4C≡C)2Au}]nXn have been studied by NMR diffusion spectroscopy and dynamic light scattering measurements. PMID:26087239

  17. Trp RNA-binding attenuation protein: modifying symmetry and stability of a circular oligomer.

    Directory of Open Access Journals (Sweden)

    Oliver W Bayfield

    Full Text Available BACKGROUND: Subunit number is amongst the most important structural parameters that determine size, symmetry and geometry of a circular protein oligomer. The L-tryptophan biosynthesis regulator, TRAP, present in several Bacilli, is a good model system for investigating determinants of the oligomeric state. A short segment of C-terminal residues defines whether TRAP forms an 11-mer or 12-mer assembly. To understand which oligomeric state is more stable, we examine the stability of several wild type and mutant TRAP proteins. METHODOLOGY/PRINCIPAL FINDINGS: Among the wild type B. stearothermophilus, B. halodurans and B. subtilis TRAP, we find that the former is the most stable whilst the latter is the least. Thermal stability of all TRAP is shown to increase with L-tryptophan concentration. We also find that mutant TRAP molecules that are truncated at the C-terminus - and hence induced to form 12-mers, distinct from their 11-mer wild type counterparts--have increased melting temperatures. We show that the same effect can be achieved by a point mutation S72N at a subunit interface, which leads to exclusion of C-terminal residues from the interface. Our findings are supported by dye-based scanning fluorimetry, CD spectroscopy, and by crystal structure and mass spectrometry analysis of the B. subtilis S72N TRAP. CONCLUSIONS/SIGNIFICANCE: We conclude that the oligomeric state of a circular protein can be changed by introducing a point mutation at a subunit interface. Exclusion (or deletion of the C-terminus from the subunit interface has a major impact on properties of TRAP oligomers, making them more stable, and we argue that the cause of these changes is the altered oligomeric state. The more stable TRAP oligomers could be used in potential applications of TRAP in bionanotechnology.

  18. Selective amyloid β oligomer assay based on abasic site-containing molecular beacon and enzyme-free amplification.

    Science.gov (United States)

    Zhu, Linling; Zhang, Junying; Wang, Fengyang; Wang, Ya; Lu, Linlin; Feng, Chongchong; Xu, Zhiai; Zhang, Wen

    2016-04-15

    Amyloid-beta (Aβ) oligomers are highly toxic species in the process of Aβ aggregation and are regarded as potent therapeutic targets and diagnostic markers for Alzheimer's disease (AD). Herein, a label-free molecular beacon (MB) system integrated with enzyme-free amplification strategy was developed for simple and highly selective assay of Aβ oligomers. The MB system was constructed with abasic site (AP site)-containing stem-loop DNA and a fluorescent ligand 2-amino-5,6,7-trimethyl-1,8-naphyridine (ATMND), of which the fluorescence was quenched upon binding to the AP site in DNA stem. Enzyme-free amplification was realized by target-triggered continuous opening of two delicately designed MBs (MB1 and MB2). Target DNA hybridization with MB1 and then MB2 resulted in the release of two ATMND molecules in one binding event. Subsequent target recycling could greatly amplify the detection sensitivity due to the greatly enhanced turn-on emission of ATMND fluorescence. Combining with Aβ oligomers aptamers, the strategy was applied to analyze Aβ oligomers and the results showed that it could quantify Aβ oligomers with high selectivity and monitor the Aβ aggregation process. This novel method may be conducive to improve the diagnosis and pathogenic study of Alzheimer's disease. PMID:26613510

  19. Resveratrol oligomers isolated from Carex species inhibit growth of human colon tumorigenic cells mediated by cell cycle arrest.

    Science.gov (United States)

    González-Sarrías, Antonio; Gromek, Samantha; Niesen, Daniel; Seeram, Navindra P; Henry, Geneive E

    2011-08-24

    Research has shown that members of the Carex genus produce biologically active stilbenoids including resveratrol oligomers. This is of great interest to the nutraceutical industry given that resveratrol, a constituent of grape and red wine, has attracted immense research attention due to its potential human health benefits. In the current study, five resveratrol oligomers (isolated from Carex folliculata and Carex gynandra ), along with resveratrol, were evaluated for antiproliferative effects against human colon cancer (HCT-116, HT-29, Caco-2) and normal human colon (CCD-18Co) cells. The resveratrol oligomers included one dimer, two trimers, and two tetramers: pallidol (1); α-viniferin (2) and trans-miyabenol C (3); and kobophenols A (4) and B (5), respectively. Although not cytotoxic, the resveratrol oligomers (1-5), as well as resveratrol, inhibited growth of the human colon cancer cells. Among the six stilbenoids, α-viniferin (2) was most active against the colon cancer cells with IC(50) values of 6-32 μM (>2-fold compared to normal colon cells). Moreover, α-viniferin (at 20 μM) did not induce apoptosis but arrested cell cycle (in the S-phase) for the colon cancer but not the normal colon cells. This study adds to the growing body of knowledge supporting the anticancer effects of resveratrol and its oligomers. Furthermore, Carex species should be investigated for their nutraceutical potential given that they produce biologically active stilbenoids such as α-viniferin. PMID:21761862

  20. Selective amyloid β oligomer assay based on abasic site-containing molecular beacon and enzyme-free amplification.

    Science.gov (United States)

    Zhu, Linling; Zhang, Junying; Wang, Fengyang; Wang, Ya; Lu, Linlin; Feng, Chongchong; Xu, Zhiai; Zhang, Wen

    2016-04-15

    Amyloid-beta (Aβ) oligomers are highly toxic species in the process of Aβ aggregation and are regarded as potent therapeutic targets and diagnostic markers for Alzheimer's disease (AD). Herein, a label-free molecular beacon (MB) system integrated with enzyme-free amplification strategy was developed for simple and highly selective assay of Aβ oligomers. The MB system was constructed with abasic site (AP site)-containing stem-loop DNA and a fluorescent ligand 2-amino-5,6,7-trimethyl-1,8-naphyridine (ATMND), of which the fluorescence was quenched upon binding to the AP site in DNA stem. Enzyme-free amplification was realized by target-triggered continuous opening of two delicately designed MBs (MB1 and MB2). Target DNA hybridization with MB1 and then MB2 resulted in the release of two ATMND molecules in one binding event. Subsequent target recycling could greatly amplify the detection sensitivity due to the greatly enhanced turn-on emission of ATMND fluorescence. Combining with Aβ oligomers aptamers, the strategy was applied to analyze Aβ oligomers and the results showed that it could quantify Aβ oligomers with high selectivity and monitor the Aβ aggregation process. This novel method may be conducive to improve the diagnosis and pathogenic study of Alzheimer's disease.

  1. Synthesis of Citric-Acrylate Oligomer and its in-Situ Reaction with Chrome Tanned Collagen (hide powder)

    International Nuclear Information System (INIS)

    The purpose of this study was to formulate the new combined system of acrylic and citric acids, which has been prepared by free radical polymerization and esterification reaction at the same time to form citric acrylate (CAC) oligomer through ester linkage and low molecular weight (Mw 2241), in compared with polyacrylic acid. The chemical structure and the reaction mechanism of this oligomer were confirmed by different spectroscopic tools (1H, 13C-NMR, ATR-IR), gel permeation chromatography and thermogravimetric analysis (TGA/DTA). The problem of the effect of the masking agents in the chrome tanning of the collagen and the pickling of the hide has been approached from the study of the hydrothermal and mechanical properties, using this new eco-friendly oligomer, which was carried out in-situ treated/grafted chrome tanned collagen (hide powder), and pickled hide. The microemulsion grafting copolymerization of (CAC) using 2.2-azo-bis isobutyronitrile (ABIN), via direct coupling reaction, onto the chrome tanned collagen showed that the free amino groups of the collagen were considered to be a potential site for the in-situ reaction with (CAC) oligomer. Also, using of citric-acrylate (CAC) oligomer, during chrome tanning of leather, instead of the traditional strong acids (sulfuric, hydrochloric and formic) resulted in significant improvement in chrome exhaustion and physical properties

  2. Investigation of intermolecular interactions between single walled nanotubes and conjugated oligomers using the dispersion-corrected DFT methods

    Science.gov (United States)

    Lagowski, Jolanta B.; Aljohani, Suad; Khan, M. Zahidul H.; Zhao, Yuming

    The area of carbon nanotubes (CNT)-polymer composites has been progressing rapidly in recent years. Pure CNT and CNT-polymer composites have many useful (industry related) properties: ranging from electronic electrical conductivity to superior strength. However the full potential of using CNTs as reinforcements (in say a polymer matrix) has been severely limited because of complications associated with the dispersion of CNTs. CNTs tend to entangle with each other forming materials that have properties that fall short of the expectations. The goal of this work is to identify the type of conjugated oligomers that are best suited for the dispersion of single walled CNT (SWCNT). For this purpose, various methods of dispersion corrected density functional theory (DFT-D/B97D, /WB97XD, /CAM-B3LYP) have been used to investigate the interaction between the SWCNT and the organic conjugated oligomers with different end groups (aldehyde (ALD) and dithiafulvenyl (DTF)). We investigate the effect of intermolecular interactions on the structure, polarity and energetics of the oligomers and SWCNT combinations. The comparison of results obtained using different DFT approximations is made. Our results show that DFT-endcapped oligomer interact more strongly with CNT than ALD-endcapped oligomer. The financial support from NSERC, SACBC and Memorial University and the computational resources from Compute Canada were received.

  3. Isolation and Quantification of Polyamide Cyclic Oligomers in Kitchen Utensils and Their Migration into Various Food Simulants.

    Science.gov (United States)

    Abe, Yutaka; Mutsuga, Motoh; Ohno, Hiroyuki; Kawamura, Yoko; Akiyama, Hiroshi

    2016-01-01

    Small amounts of cyclic monomers and oligomers are present in polyamide (PA)-based kitchen utensils. In this study, we isolated eight PA-based cyclic monomers and oligomers from kitchen utensils made from PA6 (a polymer of ε-caprolactam) and PA66 (a polymer of 1,6-diaminohexane and adipic acid). Their structures were identified using high-resolution mass spectrometry and 1H- and 13C-nuclear magnetic resonance spectroscopy, and their residual levels in PA-based kitchen utensils and degree of migration into food simulants were quantified by high-performance liquid chromatography/mass spectrometry using purchased PA6 monomer and isolated PA66 monomers, and isolated PA6 and PA66 oligomers as calibration standards. Their total residual levels among 23 PA-based kitchen utensils made from PA6, PA66, and copolymers of PA6 and PA66 (PA6/66) ranged from 7.8 to 20 mg/g. Using water, 20% ethanol, and olive oil as food simulants, the total migration levels of the PA monomers and oligomers ranged from 0.66 to 100 μg/cm2 under most examined conditions. However, the total migration levels of the PA66 monomer and oligomers from PA66 and PA6/66 kitchen utensils into 20% ethanol at 95°C were very high (1,700 and 2,200 μg/cm2, respectively) due to swelling by high-temperature ethanol. PMID:27453976

  4. Mechanisms leading to oligomers and SOA through aqueous photooxidation: insights from OH radical oxidation of acetic acid and methylglyoxal

    Directory of Open Access Journals (Sweden)

    Y. Tan

    2012-01-01

    Full Text Available Previous experiments have demonstrated that the aqueous OH radical oxidation of methylglyoxal produces low volatility products including pyruvate, oxalate and oligomers. These products are found predominantly in the particle phase in the atmosphere, suggesting that methylglyoxal is a precursor of secondary organic aerosol (SOA. Acetic acid plays a central role in the aqueous oxidation of methylglyoxal and it is a ubiquitous product of gas phase photochemistry, making it a potential "aqueous" SOA precursor in its own right. However, the fate of acetic acid upon aqueous-phase oxidation is not well understood. In this research, acetic acid (20 μM–10 mM was oxidized by OH radicals, and pyruvic acid and methylglyoxal experimental samples were analyzed using new analytical methods, in order to better understand the formation of SOA from acetic acid and methylglyoxal. Glyoxylic, glycolic, and oxalic acids formed from acetic acid and OH radicals. In contrast to the aqueous OH radical oxidation of methylglyoxal, the aqueous OH radical oxidation of acetic acid did not produce succinic acid and oligomers. This suggests that the methylgloxal-derived oligomers do not form through the acid catalyzed esterification pathway proposed previously. Using results from these experiments, radical mechanisms responsible for oligomer formation from methylglyoxal oxidation in clouds and wet aerosols are proposed. The importance of acetic acid/acetate as an SOA precursor is also discussed. We hypothesize that this and similar chemistry is central to the daytime formation of oligomers in wet aerosols.

  5. Ferrocene-Functionalized 4-(2,5-Di(thiophen-2-yl-1H-pyrrol-1-ylaniline: A Novel Design in Conducting Polymer-Based Electrochemical Biosensors

    Directory of Open Access Journals (Sweden)

    Rukiye Ayranci

    2015-01-01

    Full Text Available Herein, we report a novel ferrocenyldithiophosphonate functional conducting polymer and its use as an immobilization matrix in amperometric biosensor applications. Initially, 4-(2,5-di(thiophen-2-yl-1H-pyrrol-1-ylamidoferrocenyldithiophosphonate was synthesized and copolymerized with 4-(2,5-di(thiophen-2-yl-1H-pyrrol-1-ylbenzenamine at graphite electrodes. The amino groups on the polymer were utilized for covalent attachment of the enzyme glucose oxidase. Besides, ferrocene on the backbone was used as a redox mediator during the electrochemical measurements. Prior to the analytical characterization, optimization studies were carried out. The changes in current signals at +0.45 V were proportional to glucose concentration from 0.5 to 5.0 mM. Finally, the resulting biosensor was applied for glucose analysis in real samples and the data were compared with the spectrophotometric Trinder method.

  6. Silica sulfuric acid: a reusable solid catalyst for one pot synthesis of densely substituted pyrrole-fused isocoumarins under solvent-free conditions

    Directory of Open Access Journals (Sweden)

    Sudipta Pathak

    2013-11-01

    Full Text Available A convenient and efficient methodology for the synthesis of densely substituted pyrrole-fused isocoumarins, which employs solid-supported silica sulfuric acid (SSA as catalyst, has been developed. When the mixture of ninhydrin adducts of acetylacetone/ethyl acetoacetate and primary amines was heated on the solid surface of SSA under solvent-free conditions, the pyrrole-fused isocoumarins were formed in good yields. This synthetic method has several advantages such as the employment of solvent-free reaction conditions without the use of any toxic reagents and metal catalysts, the ease of product isolation, the use of a recyclable catalyst, the low cost, the easy availability of the starting materials, and the excellent yields of products.

  7. Electrochemical dechlorination of chloroform in neutral aqueous solution on palladium/foam-nickel and palladium/polymeric pyrrole film/foam-nickel electrodes

    Institute of Scientific and Technical Information of China (English)

    SUN Zhirong; LI Baohua; HU Xiang; SHI Min; HOU Qingnan; PENG Yongzhen

    2008-01-01

    Electrochemical dechlonnafion of chloroform in neutral aqueous solution was investigated using palladium-loaded electrodes at ambient temperature.Palladium/foam-nickel (Pd/foam-Ni) and palladium/polymeric pyrrole film/foam-nickel (Pd/PPy/foam-Ni)composite electrodes which provided catalytic surface for reductive dechiorination of chloroform in aqueous solution were prepared using an electrodepositing method.Scanning electron microscope (SEM) micrographs showed that polymeric pyrrole film modified the electrode-surface characteristics and resulted in the uniform dispersion of needle-shaped palladium particles on foam-Ni supporting electrode.The experimental results of dechlorination indicated that the removal efficiency of chloroform and current efficiency in neutral aqueous solution on Pd/PPy/foam-Ni electrode could be up to 36.8% and 33.0% at dechlorination current of 0.1 mA and dechlorination time of 180 rain,which is much higher than that of Pd/foam-Ni electrode.

  8. 3-(Dicyanomethylidene)indan-1-one-Functionalized Calix[4]arene-Calix[4]pyrrole Hybrid: An Ion-Pair Sensor for Cesium Salts.

    Science.gov (United States)

    Yeon, Yerim; Leem, Soojung; Wagen, Corin; Lynch, Vincent M; Kim, Sung Kuk; Sessler, Jonathan L

    2016-09-01

    A chromogenic calix[4]arene-calix[4]pyrrole hybrid ion pair receptor bearing an indane substituent at a β-pyrrolic position has been prepared. On the basis of solution-phase UV-vis spectroscopic analysis and (1)H NMR spectroscopic studies carried out in 10% methanol in chloroform, receptor 1 is able to bind only cesium ion pairs (e.g., CsF, CsCl, and CsNO3) but not the constituent cesium cation (as its perchlorate salt) or the F(-), Cl(-), or NO3(-) anions (as the tetrabutylammonium salts). It thus displays rudimentary AND logic gate behavior. Receptor 1 shows a colorimetric response to cesium ion pairs under conditions of solid-liquid (nitrobenzene) and liquid-liquid (D2O-nitrobenzene-d5) extraction. PMID:27533478

  9. Flavonoid oligomers from Chinese dragon’s blood, the red resins of Dracaena cochinchinensis

    OpenAIRE

    Zheng, Qing-An; Xu, Min; Yang, Chong-Ren; Dong WANG; Li, Hai-Zhou; Zhu, Hong-Tao; Zhang, Ying-Jun

    2012-01-01

    A detailed chemical investigation of the red resins from Dracaena cochinchinensis (Chinese dragon’s blood) yielded five new flavonoid oligomers, named cochinchinenins D-H (1–5), together with a known biflavonoid, cinnabarone (6), and a mixture of two known biflavonoids, socotrin-4′-ol (7) and homoisosocotrin-4′-ol (8). Of these new compounds, 1–3 were biflavonoids and 4 and 5 were triflavonoids. Their structures were determined on the basis of spectroscopic analysis. The isolated compounds we...

  10. Synthetic oligomer analysis using atmospheric pressure photoionization mass spectrometry at different photon energies

    Energy Technology Data Exchange (ETDEWEB)

    Desmazières, Bernard [Global Bioenergies, 5 rue Henri Desbruyeres, 91030 Evry (France); Legros, Véronique [CNRS, UMR8587, Université d’Evry-Val-d’Essonne, Laboratoire Analyse et Modélisation pour la Biologie et l’Environnement, F-91025 Evry (France); Giuliani, Alexandre [Synchrotron SOLEIL, L’Orme des Merisiers, Saint-Aubin, 91192 Gif-sur-Yvette (France); UAR1008, CEPIA, INRA, Rue de la Geraudiere, F-44316 Nantes (France); Buchmann, William, E-mail: william.buchmann@univ-evry.fr [CNRS, UMR8587, Université d’Evry-Val-d’Essonne, Laboratoire Analyse et Modélisation pour la Biologie et l’Environnement, F-91025 Evry (France)

    2014-01-15

    Graphical abstract: Atmospheric pressure photoIonization mass spectra of synthetic oligomers were recorded in the negative mode by varying the photon energy using synchrotron radiation. Photon energy required for an efficient ionization of the polymer was correlated to ionization potential of the solvent (for example 9.4 eV for tetrahydrofuran). -- Highlights: •Atmospheric pressure photoionization was performed using synchrotron radiation. •Photoionization of oligomers in THF with 10% CH{sub 2}Cl{sub 2} produces intact [M + Cl]{sup −} ions. •The photon energy required corresponds to ionization potential of the solvent. •Polymer distributions depend on source parameters such T °C and applied voltages. •Liquid chromatography was coupled to MS using an APPI interface for polymer analysis. -- Abstract: Atmospheric pressure photoionization (APPI) followed by mass spectrometric detection was used to ionize a variety of polymers: polyethylene glycol, polymethyl methacrylate, polystyrene, and polysiloxane. In most cases, whatever the polymer or the solvent used (dichloromethane, tetrahydrofuran, hexane, acetone or toluene), only negative ion mode produced intact ions such as chlorinated adducts, with no or few fragmentations, in contrast to the positive ion mode that frequently led to important in-source fragmentations. In addition, it was shown that optimal detection of polymer distributions require a fine tuning of other source parameters such as temperature and ion transfer voltage. Series of mass spectra were recorded in the negative mode, in various solvents (dichloromethane, tetrahydrofuran, hexane, toluene, and acetone), by varying the photon energy from 8 eV up to 10.6 eV using synchrotron radiation. To these solvents, addition of a classical APPI dopant (toluene or acetone) was not necessary. Courtesy of the synchrotron radiation, it was demonstrated that the photon energy required for an efficient ionization of the polymer was correlated to the

  11. SYNTHESES OF POLYSTYRENE RESINS CONTAINING POLYETHER OLIGOMERS AND THEIR EXTRACTION FOR GOLD (Ⅲ)

    Institute of Scientific and Technical Information of China (English)

    DONG Shihua; LIU Shi; XU Yuwu

    1994-01-01

    Three polystyrene resins containing polyether oligomers as extractants were synthesized and their extraction properties were studied. Gold (Ⅲ) ion could be extracted rapidly by the resins (T1/2<1min.)with high efficiency and capacity (for LS-B resin that were 99.8% and 95.8mg/gR respectively) from aqueous solution but most of the co-existing metal ions such as Pd (Ⅱ),Cu(Ⅱ), Zn (Ⅱ), Pb (Ⅱ) and Cd (Ⅱ) were remained. The extraction capacity and stripping percentage for gold (Ⅲ) remained unchanged in four extraction-stripping cycles. The resins also showed good column extraction-elution properties.

  12. Inhibition of Gene Expression in Escherichia coli by Antisense Phosphorodiamidate Morpholino Oligomers

    OpenAIRE

    Geller, B L; Deere, J. D.; Stein, D A; Kroeker, A. D.; Moulton, H. M.; Iversen, P. L.

    2003-01-01

    Antisense phosphorodiamidate morpholino oligomers (PMOs) were tested for the ability to inhibit gene expression in Escherichia coli. PMOs targeted to either a myc-luciferase reporter gene product or 16S rRNA did not inhibit luciferase expression or growth. However, in a strain with defective lipopolysaccharide (lpxA mutant), which has a leaky outer membrane, PMOs targeted to the myc-luciferase or acyl carrier protein (acpP) mRNA significantly inhibited their targets in a dose-dependent respon...

  13. Immunosuppressive Effects of A-Type Procyanidin Oligomers from Cinnamomum tamala

    OpenAIRE

    Liang Chen; Yang Yang; Pulong Yuan; Yifu Yang; Kaixian Chen; Qi Jia; Yiming Li

    2014-01-01

    Cinnamon barks extracts have been reported to regulate immune function; however, the component(s) in cinnamon barks responsible for this effect is/are not yet clear. The aim of this study is to find out the possible component(s) that can be used as therapeutic agents for immune-related diseases from cinnamon bark. In this study, the immunosuppressive effects of fraction (named CT-F) and five procyanidin oligomers compounds, cinnamtannin B1, cinnamtannin D1 (CTD-1), parameritannin A1, procyani...

  14. B=N Units as Part of Extended π-Conjugated Oligomers and Polymers.

    Science.gov (United States)

    Helten, Holger

    2016-09-01

    The replacement of C=C units by their isoelectronic and isosteric B=N units (BN/CC isosterism) in π-conjugated organic compounds, as a strategy to produce novel organic-inorganic hybrid materials, has recently been successfully transferred to π-conjugated polymers. This Concept provides an overview of the recent advances in this quickly evolving field, with a focus on synthesis, photophysical and electrochemical properties of the new polymers and related oligomers, as well as possible future applications in organic electronics and optoelectronics.

  15. π-CONJUGATED OLIGOMERS IN SUPRAMOLECULAR CRYSTALS AND THEIR OPTOELECTRONIC FUNCTIONS

    Institute of Scientific and Technical Information of China (English)

    Zeng-qi Xie; Bing Yang; Yu-guang Ma; Jia-cong Shen

    2007-01-01

    Functional organic molecular materials and conjugated oligomers or polymers now allow the low-cost fabrication of thin films for insertion into new generations of electronic and optoelectronic devices. The performance of these devices relies on the understanding and optimization of several complementary processes. Our goal is to discuss the relationship between the molecular stacking structures and their optoelectronic properties that are of importance in all these areas. The concept of intermolecular interaction should be taken here in the special sense that is inter-dipole coupling. Specifically, we will address the impact of inter-dipole interaction between adjacent molecules in aggregate state on the solid-state emission properties.

  16. A Convenient Method for the Preparation of 1,5-Diaryl-3-(arylamino)-I H-pyrrol-2(5 H)-ones

    Institute of Scientific and Technical Information of China (English)

    Ghashang, Majid; Shaterian, Hamid Reza~

    2011-01-01

    A simple and eco-friendly method for the preparation of 1,5-diaryl-3-(arylamino)-lH-pyrrol-2(5H)-ones via the cyclo-condensation reaction of aldehydes, amines and ethyl pyruvate in the presence of silica supported ferric chlo- ride (SiO2-FeCl3) as reusable heterogeneous catalyst is described. The present methodology offers several advantages such as excellent yields, simple procedure and short reaction times.

  17. Synthesis, characterization and computational study on ethyl 4-(3-Furan-2yl-acryloyl)-3,5-dimethyl-1H-pyrrole-2-carboxylate

    Science.gov (United States)

    Singh, R. N.; Rawat, Poonam; Sahu, Sangeeta

    2014-11-01

    As part of study on pyrrole derivatives, we have synthesized a pyrrole chalcone derivative: ethyl 4-(3-Furan-2yl-acryloyl)-3,5-dimethyl-1H-pyrrole-2-carboxylate (EFADPC) by aldol condensation of ethyl 3, 5-dimethyl-4-actyl-1H-pyrrole-2-carboxylate with furan-2-carbaldehyde in the presence of strong hydroxyl base as catalyst. The product EFADPC has been confirmed by spectroscopic (FT-IR, 1H NMR, and UV-visible) analyses. Quantum chemical calculation also provides good correlation with experimental data. The molecular electrostatic potential surface (MEP), natural bond orbital interactions (NBO), electronic descriptors, quantum theory of atoms' in molecules (QTAIM) and experimental FT-IR spectrum have been used to predict the sites and nature of interactions which indicate that the dimer formation with multiple interactions through Nsbnd H···O and Csbnd H···O. The vibrational analysis shows red shifts in νNsbnd H and νCdbnd O as result of dimer formation. The binding energy of dimer is calculated as 13.82, 15.24 kcal/mol using DFT, QTAIM analysis, respectively. The result of ellipticity confirms the existence of resonance assisted hydrogen bonds (RAHB) in dimer. The MEP and local reactivity descriptors analyses have been performed and the results indicate that carbonyl carbon and β-carbon of chalcone frame have been prone to nucleophilic attack and lead to large number of heterocyclic compounds such as oxirane, oxazoles, pyrazoles, pyridines, pyrimidines, and pyran.

  18. 2,2′,5,5′-Tetramethyl-1,1′-(hexane-1,6-diyldi-1H-pyrrole

    Directory of Open Access Journals (Sweden)

    Ana C. Santos

    2009-07-01

    Full Text Available The molecule of the title compound, C18H28N2, composed of two 2,5-dimethylpyrrole groups linked by a hexane chain, lies across a crystallographic inversion centre. The mean plane of the pyrrole ring is almost perpendicular to the mean plane of the central chain, making a dihedral angle of 89.09 (8°. The crystal structure is stabilized by intermolecular C—H...π interactions.

  19. Electrochromic properties of multicolored novel polymer synthesized via combination of benzotriazole and N-functionalized 2,5-di(2-thienyl)-1H-pyrrole units

    International Nuclear Information System (INIS)

    Synthesis of new conducting polymers is desired since their electrochemical and optical properties enable them to be used as active layers in many device applications. Benzotriazole and N-functionalized 2,5-di(2-thienyl)-1H-pyrrole (SNS Series) containing polymers showed very promising results as electrochromic materials. In order to observe the effect of the combination of these two units, three new monomers; 2-(6-(2,5-bis(5-methylthiophen-2-yl)-1H-pyrrol-1-yl)hexyl)-4,7-di (thiophen-2-yl)-2H benzo[d][1,2,3]triazole (M1), 2-(6-(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl)hexyl)-4,7-di(thiophen-2-yl) -2H-benzo[d][1,2,3]triazole (M2) and 2-(6-(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl)hexyl)-4,7-bis (5-methylthiophen-2-yl)-2H-benzo[d][1,2,3]triazole (M3) were synthesized. To better characterize the electronic and spectroscopic properties of the monomers, density functional theory (DFT) and its time-dependent generalization (TD-DFT) were used to calculate their vertical ionization potentials, vertical electron affinity and to simulate and interpret their infrared and UV-vis spectra. The monomers were electrochemically polymerized and the resultant polymers were characterized with cyclic voltammetry and UV-vis-NIR spectroscopy techniques. An electrochromic device was constructed with electrochemical polymer of M2. The device switched between red and blue colors and showed exceptional optical memory

  20. Stereoselective self-sorting in the self-assembly of a Phe-Phe extended guanidiniocarbonyl pyrrole carboxylate zwitterion: formation of two diastereomeric dimers with significantly different stabilities.

    Science.gov (United States)

    Rodler, Fabian; Sicking, Wilhelm; Schmuck, Carsten

    2011-07-28

    The 'dipeptide extended' guanidiniocarbonyl pyrrole carboxylate zwitterion GCP-Phe-Phe 1 forms stable dimers in DMSO. However, dimerization is highly stereoselective. Only homochiral dimers are formed and the (L,L)·(L,L) dimer (K(dim) > 10(5) M(-1)) is significantly more stable by a factor of 10(3) than the diastereomeric (D,L)·(D,L) dimer (K(dim) = 120 M(-1)). PMID:21670799

  1. Photocatalytic Degradation of Eosin Yellow Using Poly(pyrrole-co-aniline)-Coated TiO2/Nanocellulose Composite under Solar Light Irradiation

    OpenAIRE

    Anirudhan, T. S.; Rejeena, S. R.

    2015-01-01

    The present study describes the feasibility of a novel adsorbent cum photocatalyst, poly(pyrrole-co-aniline)-coated TiO2/nanocellulose composite (P(Py-co-An)-TiO2/NCC), to remove eosin yellow (EY) from aqueous solutions. The removal of EY was investigated by batch adsorption followed by photocatalysis. The effect of various adsorption parameters like adsorbent dose, pH, contact time, initial concentration, and ionic strength has been optimized for treating effluents from the dye industry. Ads...

  2. Interaction of derived polymers from pyrrole with biocompatible solutions; Interaccion de polimeros derivados de pirrol con soluciones biocompatibles

    Energy Technology Data Exchange (ETDEWEB)

    Lopez G, O. G.

    2010-07-01

    This work presents a study about the synthesis by plasma, the electric properties and superficial interaction of polymers derived from pyrrole doped with Iodine with potential use as bio material. Poly-pyrrole is a semiconductor and biocompatible polymer with potential application in the development of artificial muscles and implants where the electric interaction between cells and material is an important variable. The syntheses were made at 13.5 MHz in a glass tubular reactor of 1500 cm{sup 3} with electrodes of 6.5 cm diameter and stainless steel flanges. An electrode was connected to the RF terminal of the power supply that is combined with a matching coupling resistance. The monomer and dopant used in this work were pyrrole and Iodine respectively, in closed containers. They were vaporized and injected separately into the reactor at room temperature and 0.1 mbar. The vapors of the reagents mixed freely in the reactor. The synthesis time was 240 min at 40, 60, 80 and 100 W. The polymers were obtained as thin films adhered to the reactor walls. The films were washed and swollen with distilled water and removed from the reactor walls with a small spatula. The polymers were irradiated with gamma rays at 18 and 22 KGy. Due to the fact that the doses are cumulative, the final dose applied was 40 KGy. The polymers characterization was carried out by Fourier Transform Infrared Spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy, contact angle, electrical conductivity and X-ray diffraction. The analyses indicates that the polymers have very similar structure in almost the entire power range, showing C-O, C=C, C-H, O-H, N-H bonds with a predominantly amorphous structure. The TGA analyses showed that the material has 4 or 5 loses of material. The first one starts after that 115 C except for the material irradiated at 40 KGy, this one begins in 87 C, the second one is in the interval of 196 and 295 C, the third one between 311 and 500 C, and the

  3. Antitumor Activity of a 5-Hydroxy-1H-Pyrrol-2-(5H-One-Based Synthetic Small Molecule In Vitro and In Vivo.

    Directory of Open Access Journals (Sweden)

    Yunyun Geng

    Full Text Available Alternative chemo-reagents are in great demand because chemotherapy resistance is one of the major challenges in current cancer treatment. 5-hydoxy-1H-pyrrol-2-(5H-one is an important N-heterocyclic scaffold that is present in natural products and medicinal chemistry. However, its antitumor activity has not been systematically explored. In this study, we screened a panel of 5-hydoxy-1H-pyrrol-2-(5H-one derivatives and identified compound 1d as possessing strong anti-proliferative activity in multiple cancer cell lines. Cell cycle analysis revealed that 1d can induce S-phase cell cycle arrest and that HCT116 was sensitive to 1d-induced apoptosis. Further analysis indicated that 1d preferentially induced DNA damage and p53 activation in HCT116 cells and that 1d-induced apoptosis is partly dependent on p53. Furthermore, we showed that 1d significantly suppressed tumor growth in xenograft tumor models in vivo. Taken together, our results suggest that 5-hydoxy-1H-pyrrol-2-(5H-one derivatives bear potential antitumor activity and that 1d is an effective agent for cancer treatment.

  4. A mixed experimental and DFT study on ethyl 4-[3-(4-dimethylamino-phenyl)-acryloyl]-3,5-dimethyl-1H-pyrrole-2-carboxylate

    Science.gov (United States)

    Singh, R. N.; Rawat, Poonam; Sahu, Sangeeta

    2014-05-01

    A new pyrrole containing chalcone, ethyl 4-[3-(4-dimethylamino-phenyl)-acryloyl]-3,5-dimethyl-1H-pyrrole-2-carboxylate (EDPADPC) derived from ethyl 4-acetyl-3,5-dimethyl-1H-pyrrole-2-carboxylate and 4-dimethylamino-benzaldehyde has been characterized by spectroscopic techniques (1H NMR, UV-Visible, FT-IR) and results have been compared by means of theoretical findings. A combined experimental and theoretical vibrational analysis identified red shifts in vNH and vCO indicating the formation of dimer in the solid state. The binding energy of dimer has been evaluated as 9.89 kcal/mol and the strength and nature of hydrogen bonding have also been analyzed in detail. The DFT derived reactivity descriptors indicate that EDPADPC is suitable for the formation of new heterocyclic compounds. The first hyperpolarizability (β0) of EDPADPC has been computed and found to be 62.0226 × 10-30 indicating its use as non-linear optical (NLO) material.

  5. Orange to black electrochromic behaviour in poly(2-(2-thienyl)-1H-pyrrole) thin films

    International Nuclear Information System (INIS)

    We have studied an electrochromic precursor, 2-(2-thienyl)-1H-pyrrole (1), using two improved procedures of the Trofimov reaction. Optimised stereochemical calculations at the B3LYP/6-311G* level showed almost equal s-cis and s-trans conformational populations in 1 with marked out-of-plane deviations of ca. 30o. Model calculations suggest that the predominant rotational conformation in undoped poly(1) would be s-trans with the essential out-of-plane deviations around the all three interheterocyclic bonds of ca. 25-30o. Monomer 1 exhibited two irreversible oxidation processes at +0.86 and +1.3 V corresponding to the oxidation of the pyrrole and thiophene rings, respectively. Orange to black electrochromic behaviour was found in ClO4- doped poly(1) thin films with colouring and bleaching times of 1.8 and 1.3 s, respectively. The colouration efficiency during the bleaching process was 233 cm2/C. The optical contrast at 450 nm was 19% and in the near-IR was 36%. The band-gap of poly(1) (1.6-1.7 eV) was found to be significantly lower than that of polypyrrole (2.85 eV) and polythiophene (2.3 eV) as a consequence of increased electron delocalisation in the system. Important differences in the morphology of doped and dedoped poly(1) films were observed by atomic-force microscopy (AFM). Doped poly(1) films showed a granular morphology with primary particles of 45-60 nm in size and an average surface roughness of 3.5 nm. On the other hand, dedoped poly(1) films showed interconnected aggregates of 65-90 nm in size as a consequence of particle fusion, with a surface roughness of 9.2 nm. In summary, poly(1) is a promising material for emerging flexible electrochromic devices such as displays and variable optical attenuators

  6. Estimate Secondary Oil Migration Distance Using Pyrrolic Nitrogen Compounds in Petroleum

    Institute of Scientific and Technical Information of China (English)

    Li Maowen

    1997-01-01

    @@ Secondary oil migration represents one of the most important, yet least understood, geological processes responsible for the petroleum accumulation in a sedimentary basin. During secondary migration, petroleum moves updip as high-petroleum saturation rivers driven largely by buoyancy over migration distances ranging from millimeters to hundreds of kilometers. Mass balance calculations indicate that the oil-saturated portions of the carrier bed are in the order of 1%~10% of the carrier bed volume. In most cases, however, the actual dimensions of migration conduits cannot be defined by direct observation,thus preventing useful volumetric estimates of oil charges to structures, or prospect-scale deterministic modeling of secondary migration for predictive purpose.

  7. Synthesis and structural characterization of anion complexes with azacalix[2]dipyrrolylmethane: effect of anion charge on the conformation of the macrocycle.

    Science.gov (United States)

    Guchhait, Tapas; Mani, Ganesan; Schulzke, Carola

    2016-08-01

    Tetrahomodiazacalix[2]dipyrrolylmethane 1, [-CH2(C4H3N)CR2(C4H3N)CH2N(Me)-]2 an expanded version of the calix[4]pyrrole system, has the tendency to change its ring conformation (1,3-alternate) upon anion binding analogous to calix[4]pyrrole. However, owing to its tertiary amine nitrogen atoms in the ring, it can be protonated and becomes a powerful cationic receptor for anions, besides its inherent hydrogen bonding features. Macrocycle 1 binds with a series of monoanions BF4(-), Cl(-), PhCOO(-) and ClO4(-), and their X-ray structures showed that the ring conformation constitutes the 1,2-alternate form. Upon binding with dianions SO4(2-), CrO4(2-), SiF6(2-) and S2O3(2-), the ring conformation changes to the cone conformation. The intermediate partial cone conformation results for complexes with NO3(-) and Cr2O7(2-) ions. The change in the orientation of the pyrrole NH groups depending on the charge of the anion demonstrates the flexibility of the macrocycle and the dicationic macrocycle stabilizes the anions via both hydrogen bonding and electrostatic interactions. PMID:27356484

  8. Characterization of oligomers from methylglyoxal under dark conditions: a pathway to produce secondary organic aerosol through cloud processing during nighttime

    Directory of Open Access Journals (Sweden)

    F. Yasmeen

    2010-04-01

    Full Text Available Aqueous-phase oligomer formation from methylglyoxal, a major atmospheric photooxidation product, has been investigated in a simulated cloud matrix under dark conditions. The aim of this study was to explore an additional pathway producing secondary organic aerosol (SOA through cloud processes without participation of photochemistry during nighttime. Indeed, atmospheric models still underestimate SOA formation, as field measurements have revealed more SOA than predicted. Soluble oligomers (n = 1–8 formed in the course of acid-catalyzed aldol condensation and acid-catalyzed hydration followed by acetal formation have been detected and characterized by positive and negative ion electrospray ionization mass spectrometry. Aldol condensation proved to be a favorable mechanism under simulated cloud conditions, while hydration/acetal formation was found to strongly depend on the pH of the system and only occurred at a pH<3.5. No evidence was found for formation of organosulfates. The aldol oligomer series starts with a β-hydroxy ketone via aldol condensation, where oligomers are formed by multiple additions of C3H4O2 units (72 Da to the parent β-hydroxy ketone. Ion trap mass spectrometry experiments were performed to structurally characterize the major oligomer species. A mechanistic pathway for the growth of oligomers under cloud conditions and in the absence of UV-light and OH radicals, which could substantially enhance in-cloud SOA yields, is proposed here for the first time.

  9. SYNTHESIS, CHARACTERIZATION, THERMAL DEGRADATION AND ELECTRICAL CONDUCTIVITY OF OLIGO[2-(2-HYDROXYPHENYLIMINOMETHYLBENZYLIDENE)AMINOPHENOL]AND OLIGOMER-METAL COMPLEXES

    Institute of Scientific and Technical Information of China (English)

    (I)smet Kaya; S(u)leyman Culhao(g)lu

    2008-01-01

    The oxidative polycondensation reaction conditions of 2-[(2-hydroxyphenyliminomethylbenzylidene)amino-phenol] (2-HPIMBAP) has been accomplished by using air O2 and NaOCl oxidants in an aqueous alkaline medium between50-90℃. The optimum reaction conditions of the oxidative polycondensation and the main parameters of the process wereestablished. At the optimum reaction conditions, yield of the products were found to be 67.72% and 61.49% for air O2 andNaOCl oxidants respectively. The structures of the monomer and oligomer were confirmed by FT-IR, UV-Vis, 1H-NMR and13C-NMR and elemental analysis. Also, TGA-DTA, SEC techniques and solubility tests were applied for characterization.1H-NMR and 13C-NMR data show that the polymerization proceeded by the C-C and C-O-C coupling systems of orthoand para positions and oxyphenylene according to-OH group of 2-HPIMBAP. The number-average molecular weight(Mn), weight-average molecular weight (Mw) and polydispersity index (PDI) values of oligo[2-(2-hydroxyphenyliminomethylbenzylidene)aminophenol] (oligo(2-HPIMBAP)) were determined. Thermal analyses of oligomer-metal complexeswere investigated in N2 atmosphere between 15-1000℃. Electrical conductivities of oligo(2-HPIMBAP) and oligomer-metalcomplexes measured with four point technique. Electrical conductivity of the oligo(2-HPIMBAP) was measured, showingthat the oligomer is a typical semiconductor. Optical band gaps (Eg) of 2-HPIMBAP, oligo(2-HPIMBAP) and oligomer-metal complex compounds were determined by UV-Vis measurements. The monomer and oligomer were screened forantibacterial activities.

  10. Heterogeneous reactions of glyoxal on mineral particles: A new avenue for oligomers and organosulfate formation

    Science.gov (United States)

    Shen, Xiaoli; Wu, Huihui; Zhao, Yue; Huang, Dao; Huang, Liubin; Chen, Zhongming

    2016-04-01

    Glyoxal (GL) plays a crucial role in the formation of secondary organic aerosols (SOA), because it is highly water soluble and capable of oligomerization. This is the first study to describe irreversible heterogeneous reactions of GL on clean and acidic gas-aged SiO2, α-Al2O3, and CaCO3 particles, as models of real mineral particles, at various relative humidity and without irradiation and gas phase oxidants. A series of products, including oligomers, organosulfates, and organic acids, which contribute to SOA formation, were produced. GL uptake on SO2-aged α-Al2O3 enabled the oxidation of surface S(IV) to S(VI). The presence of adsorbed water on particles favored GL uptake and the formation of oligomers and organosulfate, but it suppressed organic acid formation. In addition, the aging process enhanced the positive effect of adsorbed water on GL uptake. These findings will further our understanding of the GL sink and SOA sources in the atmosphere.

  11. Oligomer formation in the troposphere: from experimental knowledge to 3-D modeling

    Science.gov (United States)

    Lemaire, Vincent; Coll, Isabelle; Couvidat, Florian; Mouchel-Vallon, Camille; Seigneur, Christian; Siour, Guillaume

    2016-04-01

    The organic fraction of atmospheric aerosols has proven to be a critical element of air quality and climate issues. However, its composition and the aging processes it undergoes remain insufficiently understood. This work builds on laboratory knowledge to simulate the formation of oligomers from biogenic secondary organic aerosol (BSOA) in the troposphere at the continental scale. We compare the results of two different modeling approaches, a first-order kinetic process and a pH-dependent parameterization, both implemented in the CHIMERE air quality model (AQM) (www.lmd.polytechnique.fr/chimere), to simulate the spatial and temporal distribution of oligomerized secondary organic aerosol (SOA) over western Europe. We also included a comparison of organic carbon (OC) concentrations at two EMEP (European Monitoring and Evaluation Programme) stations. Our results show that there is a strong dependence of the results on the selected modeling approach: while the irreversible kinetic process leads to the oligomerization of about 50 % of the total BSOA mass, the pH-dependent approach shows a broader range of impacts, with a strong dependency on environmental parameters (pH and nature of aerosol) and the possibility for the process to be reversible. In parallel, we investigated the sensitivity of each modeling approach to the representation of SOA precursor solubility (Henry's law constant values). Finally, the pros and cons of each approach for the representation of SOA aging are discussed and recommendations are provided to improve current representations of oligomer formation in AQMs.

  12. Atomistic simulation of CO 2 solubility in poly(ethylene oxide) oligomers

    KAUST Repository

    Hong, Bingbing

    2013-10-02

    We have performed atomistic molecular dynamics simulations coupled with thermodynamic integration to obtain the excess chemical potential and pressure-composition phase diagrams for CO2 in poly(ethylene oxide) oligomers. Poly(ethylene oxide) dimethyl ether, CH3O(CH 2CH2O)nCH3 (PEO for short) is a widely applied physical solvent that forms the major organic constituent of a class of novel nanoparticle-based absorbents. Good predictions were obtained for pressure-composition-density relations for CO2 + PEO oligomers (2 ≤ n ≤ 12), using the Potoff force field for PEO [J. Chem. Phys. 136, 044514 (2012)] together with the TraPPE model for CO2 [AIChE J. 47, 1676 (2001)]. Water effects on Henrys constant of CO2 in PEO have also been investigated. Addition of modest amounts of water in PEO produces a relatively small increase in Henrys constant. Dependence of the calculated Henrys constant on the weight percentage of water falls on a temperature-dependent master curve, irrespective of PEO chain length. © 2013 Taylor & Francis.

  13. Ring-like oligomers of Synaptotagmins and related C2 domain proteins

    Science.gov (United States)

    Zanetti, Maria N; Bello, Oscar D; Wang, Jing; Coleman, Jeff; Cai, Yiying; Sindelar, Charles V; Rothman, James E; Krishnakumar, Shyam S

    2016-01-01

    We recently reported that the C2AB portion of Synaptotagmin 1 (Syt1) could self-assemble into Ca2+-sensitive ring-like oligomers on membranes, which could potentially regulate neurotransmitter release. Here we report that analogous ring-like oligomers assemble from the C2AB domains of other Syt isoforms (Syt2, Syt7, Syt9) as well as related C2 domain containing protein, Doc2B and extended Synaptotagmins (E-Syts). Evidently, circular oligomerization is a general and conserved structural aspect of many C2 domain proteins, including Synaptotagmins. Further, using electron microscopy combined with targeted mutations, we show that under physiologically relevant conditions, both the Syt1 ring assembly and its rapid disruption by Ca2+ involve the well-established functional surfaces on the C2B domain that are important for synaptic transmission. Our data suggests that ring formation may be triggered at an early step in synaptic vesicle docking and positions Syt1 to synchronize neurotransmitter release to Ca2+ influx. DOI: http://dx.doi.org/10.7554/eLife.17262.001 PMID:27434670

  14. Design and evaluation of nonfluorous CO2-soluble oligomers and polymers.

    Science.gov (United States)

    Wang, Yang; Hong, Lei; Tapriyal, Deepak; Kim, In Chul; Paik, Ik-Hyeon; Crosthwaite, Jacob M; Hamilton, Andrew D; Thies, Mark C; Beckman, Eric J; Enick, Robert M; Johnson, J Karl

    2009-11-12

    Ab initio molecular modeling is used to design nonfluorous polymers that are potentially soluble in liquid CO2. We have used calculations to design three nonfluorous compounds meant to model the monomeric repeat units of polymers that exhibit multiple favorable binding sites for CO2. These compounds are methoxy isopropyl acetate, 2-methoxy ethoxy-propane, and 2-methoxy methoxy-propane. We have synthesized oligomers or polymers based on these small compounds and have tested their solubility in CO2. All three of these exhibit appreciable solubility in CO2. At 25 degrees C, oligo(3-acetoxy oxetane)6 is 5 wt % soluble at 25 MPa, the random copolymer (vinyl methoxymethyl ether30-co-vinyl acetate9) is 5 wt % soluble at 70 MPa and random copolymer (vinyl 1-methoxyethyl ether30-co-vinyl acetate9) is 3 wt % soluble at 120 MPa. These oligomers and polymers represent new additions to the very short list of nonfluorous CO2-soluble polymers. However, none of these are more soluble than poly(vinyl acetate), which exhibits the highest CO2 solubility of any known polymer containing only the elements C, H, and O.

  15. Immunosuppressive Effects of A-Type Procyanidin Oligomers from Cinnamomum tamala

    Directory of Open Access Journals (Sweden)

    Liang Chen

    2014-01-01

    Full Text Available Cinnamon barks extracts have been reported to regulate immune function; however, the component(s in cinnamon barks responsible for this effect is/are not yet clear. The aim of this study is to find out the possible component(s that can be used as therapeutic agents for immune-related diseases from cinnamon bark. In this study, the immunosuppressive effects of fraction (named CT-F and five procyanidin oligomers compounds, cinnamtannin B1, cinnamtannin D1 (CTD-1, parameritannin A1, procyanidin B2, and procyanidin C1, from Cinnamomum tamala or Cinnamomum cassia bark were examined on splenocytes proliferation model induced by ConA or LPS. Then, the effects of activated compound CTD-1 on cytokine production and 2,4-dinitrofluorobenzene (DNFB induced delayed-type hypersensitivity (DTH response were detected to evaluate the immunosuppressive activity of CTD-1. It was found that CT-F and CTD-1 significantly inhibited the splenocyte proliferation induced by ConA or LPS. CTD-1 dose-dependently reduced the level of IFN-γ and IL-2 and intensively suppressed DNFB-induced DTH responses. These findings suggest that the immunosuppressive activities of cinnamon bark are in part due to procyanidin oligomers. CTD-1 may be a potential therapeutic agent for immune-related diseases.

  16. TAU OLIGOMERS AS DIRECT TARGETS FOR ALZHEIMER´S DIAGNOSIS AND NOVEL DRUGS

    Directory of Open Access Journals (Sweden)

    Leonardo eGuzman-Martinez

    2013-10-01

    Full Text Available A cumulative number of approaches have been carried out to elucidate the pathogenesis of Alzheimer´s disease (AD. Tangle formation has been identified as a major event involved in the neurodegenerative process, due to the conversion of either soluble peptides or oligomers into insoluble filaments. Most of recent studies share in common the observation that formation of tau oligomers and the subsequent pathological filaments arrays is a critical step in AD etiopathogenesis. Oligomeric tau species appear to be neurotoxic for neuronal cells, and therefore appear as an appropriate target for the design of molecules that may control morphological and functional alterations leading to cognitive impairment. Thus, current therapeutic strategies are aimed at three major types of molecules: 1 Inhibitors of protein kinases and phosphatases that may control neuronal degeneration, 2 Methylene blue, and 3 Natural phytocomplexes and polyphenolics compounds able to either inhibit the formation of tau filaments or disaggregate them. Only a few polyphenolic molecules have emerged to prevent tau aggregation. Fulvic acid, a humic substance, has a potential activity to protect cognitive impairment. In fact, formation of paired helical filaments (PHFs in vitro, is inhibited by fulvic acid affecting the length of fibrils and their morphology.

  17. Theoretical study of the structure and electronic spectra of fully protonated emeraldine oligomers

    Science.gov (United States)

    Zhekova, H.; Tadjer, A.; Ivanova, A.; Petrova, J.; Gospodinova, N.

    Polyaniline (PANI) is one of the most studied conducting polymers. Obtained in its conducting form (known as ?emeraldine salt?) by chemical or electrochemical oxidation of aniline in aqueous acidic medium, this polymer manifests an array of attractive properties. Nevertheless, these properties still need to be described at the molecular level. Intense theoretical investigations during the past few years aim at explaining the chain organization, conductivity mechanism, and other structural and spectral characteristics. Most studies adopt simplified models in which hydration effect is underestimated, since all simulations are performed either in vacuum or in the presence of a limited number of water molecules. The present computational study sheds light on the molecular organization of a number of model PANI hydrated clusters with different alignment and multiplicity, which can explain the experimentally recorded UV/VIS spectra. The influence of hydration and interaction with adjacent oligomers is estimated. Short-chain doubly protonated emeraldine oligomers are used as model systems. The calculations are performed at the semi-empirical (AM1) and/or molecular mechanics (AMBER96) level. Proper configurations of the clusters are selected using Monte Carlo simulations. Electron correlation (CIS) is accounted for upon evaluation of the absorption spectra of the clusters. The relative strength of the interchain coupling is estimated by simulation of PANI clusters consisting of two PANI tetramers in water. Comparison to experimental results is made.

  18. Oligomer formation in the troposphere: from experimental knowledge to 3-D modeling

    Directory of Open Access Journals (Sweden)

    V. Lemaire

    2015-10-01

    Full Text Available The organic fraction of atmospheric aerosols has proven to be a critical element of air quality and climate issues. However, its composition and the aging processes it undergoes remain insufficiently understood. This work builds on laboratory knowledge to simulate the formation of oligomers from biogenic secondary organic aerosol (BSOA in the troposphere at the continental scale. We compare the results of two different modeling approaches, a 1st-order kinetic process and a pH-dependent parameterization, both implemented in the CHIMERE air quality model (AQM, to simulate the spatial and temporal distribution of oligomerized SOA over western Europe. Our results show that there is a strong dependence of the results on the selected modeling approach: while the irreversible kinetic process leads to the oligomerization of about 50 % of the total BSOA mass, the pH-dependent approach shows a broader range of impacts, with a strong dependency on environmental parameters (pH and nature of aerosol and the possibility for the process to be reversible. In parallel, we investigated the sensitivity of each modeling approach to the representation of SOA precursor solubility (Henry's law constant values. Finally, the pros and cons of each approach for the representation of SOA aging are discussed and recommendations are provided to improve current representations of oligomer formation in AQMs.

  19. Workplace Charging. Charging Up University Campuses

    Energy Technology Data Exchange (ETDEWEB)

    Giles, Carrie [ICF International, Fairfax, VA (United States); Ryder, Carrie [ICF International, Fairfax, VA (United States); Lommele, Stephen [National Renewable Energy Lab. (NREL), Golden, CO (United States)

    2016-03-01

    This case study features the experiences of university partners in the U.S. Department of Energy's (DOE) Workplace Charging Challenge with the installation and management of plug-in electric vehicle (PEV) charging stations.

  20. Crystallization and preliminary crystallographic study of oligomers of the haemolytic lectin CEL-III from the sea cucumber Cucumaria echinata

    OpenAIRE

    Unno, Hideaki; Hisamatsu, Keigo; Nagao, Tomonao; Tateya, Yuki; Matsumoto, Naoki; Goda, Shuichiro; Hatakeyama, Tomomitsu

    2013-01-01

    CEL-III is a Ca2+-dependent haemolytic lectin isolated from the marine invertebrate Cucumaria echinata. This lectin binds to Gal/GalNAc-containing carbohydrate chains on the cell surface and, after conformational changes, oligomerizes to form ion-permeable pores in cell membranes. CEL-III also forms soluble oligomers similar to those formed in cell membranes upon binding of specific carbohydrates in high-pH and high-salt solutions. These soluble and membrane CEL-III oligomers were crystallize...

  1. CRP and Adiponectin and Its Oligomers in the Metabolic Syndrome: Evaluation of New Laboratory-Based Biomarkers

    OpenAIRE

    Devaraj, Sridevi; Swarbrick, Michael M.; Singh, Uma; Adams-Huet, Beverley; Havel, Peter J.; Jialal, Ishwarlal

    2008-01-01

    The metabolic syndrome (MetS) confers an increased risk for diabetes and cardiovascular disease. Although high-sensitive C-reactive protein (hsCRP) concentrations are higher and adiponectin concentrations lower in MetS, there is no reliable biochemical measure that can capture its various features. We evaluated whether hsCRP, adiponectin, or the ratio of adiponectin or its oligomers, especially the high-molecular-weight (HMW) oligomer, to hsCRP predict MetS in 123 subjects with MetS compared ...

  2. Steady State and Time-Resolved Fluorescence Dynamics of Triphenylamine Based Oligomers with Phenylene/Thiophene/Furan in Solvents

    Institute of Scientific and Technical Information of China (English)

    ZENG Qi; LIU Ying-Liang; MENG Kang; ZHAO Xiang-Jie; WANG Shu-Feng; GONG Qi-Huang

    2009-01-01

    We investigate the photo-physical properties of a series of triphenylamine-based oligomers by steady-state and picosecond transient fluorescence measurements in solvents. The oligomers are composed alternatively with triph-enylamine and phenylene/thiophene/furan group, bridged by vinyl group (PNB/PNT/PNF). Their fluorescence spectra show bathochromic phenomenon with solvent polarity and viscosity increasing. The fluorescence decays are bi-exponential for PNB and PNT, and tri-exponential for PNF in THF and aniline. The strong viscosity dependence suggests conformational relaxation along the PNF chain after photo excitation.

  3. Comparative neurotoxicity and pyrrole-forming potential of 2,5-hexanedione and perdeuterio-2,5-hexanedione in the rat

    Energy Technology Data Exchange (ETDEWEB)

    DeCaprio, A.P.; Briggs, R.G.; Jackowski, S.J.; Kim, J.C.

    1988-01-01

    2,5-Hexanedione (2,5-HD), the neurotoxic metabolite of n-hexane, reacts with protein amines to form alkylpyrrole adducts. Pyrrolylation of neurofilament protein may be the initiating molecular event in 2,5-HD neuropathy. The present study compares the neurotoxic and pyrrole-forming potentials of 2,5-HD with those of perdeuterio-2,5-HD ((D10)-2,5-HD) in the rat. Due to a requirement for C-H bond breaking in the reaction mechanism, the latter derivative was expected to exhibit a primary isotope effect, thus forming the pyrrole at a slower rate. In vitro studies confirmed that (D10)-2,5-HD pyrrolylated protein at only one-third of the initial rate seen with native 2,5-HD. Prolonged incubation resulted in similar pyrrole concentrations with both derivatives. Adult, male Wistar rats were administered daily (5 days/week) ip doses of either 3.5 mmol 2,5-HD or (D10)-2,5-HD/kg/day for 17 days or 2.5 mmol/kg/day for 38 days. At termination, animals administered 2,5-HD and (D10)-2,5-HD exhibited 27 and 8% body weight loss, respectively. Moderate to severe hindlimb paralysis was present in the 2,5-HD groups while only mild effects were seen in (D10)-2,5-HD-dosed rats. Neuropathological changes were prominent in spinal cord sections from 2,5-HD-treated animals, while no effects were present in rats given the deuterated derivative. Pyrrole adduct concentrations in serum and axonal cytoskeletal proteins from 2,5-HD-treated animals were two- to threefold higher than in rats given equimolar doses of (D10)-2,5-HD. Levels of covalent crosslinking of axonal cytoskeletal proteins (assessed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis) appeared to correlate with pyrrole concentrations. Tissue concentrations of each diketone isomer were not significantly different, indicating similar uptake of native and deuterated 2,5-HD.

  4. A pyrrole quinoline quinone glucose dehydrogenase biosensor based on screen-printed carbon paste electrodes modified by carbon nanotubes

    International Nuclear Information System (INIS)

    A carbon nanotube (CNT) modified biosensor based on oxygen-independent, pyrrole quinoline quinone glucose dehydrogenase (PQQ-GDH) for monitoring glucose was studied. The disposable amperometric biosensors based on screen-printed carbon paste electrodes are low cost and suitable for mass production. Potassium ferricyanide was immobilized on the surface of the electrodes as an electron mediator, which decreased the work potential. The biosensor showed a linear amperometric response to glucose from 1 to 35 mM, with a sensitivity of 31.0 µA mM−1 cm−2. Experimentally, the compositions of PQQ-GDH, potassium ferricyanide, CNTs and other components were evaluated and optimized. Only 2 µl of sample are needed for one test, and the response time of the sensor is 20 s. The characteristics of the biosensor were studied through cyclic voltammetry, and experimental results showed that the CNTs could facilitate the electron transfer between the enzyme and electrode surface significantly. Compared with the biosensor without carbon nanotube modification, the CNTs improved the sensitivity of the biosensor up to five times

  5. Characterization of poly pyrrole/montmorillonite electro polymerised onto Pt; Caracterizacao de filmes PPy/montmorilonita eletropolimerizados sobre Pt

    Energy Technology Data Exchange (ETDEWEB)

    Castagno, K.R.L., E-mail: katiarlc@pelotas.ifsul.edu.b [Instituto Federal Sul-rio-grandense (IFSul), RS (Brazil). Dept. de Quimica; Azambuja, D.S.; Dalmoro, V.; Mauller, R.S. [Universidade Federal do Rio Grande do Sul (UFRGS), Pelotas, RS (Brazil). Inst. de Quimica

    2010-07-01

    In this study films of polypyrrole/montmorillonite (PPy/MT) were electropolymerized on platinum in order to evaluate the performance of this technique in the preparation of nanocomposite materials and to determine the thermal properties and conductivity of the composites. The films were synthesized from a solution containing pyrrole, dodecylbenzene sulfonate, acid and two types of clays: montmorillonite-Na + (MT-Na) and montmorillonite-30B (MT-M). The characterization of the films we have used FT-IR, TEM, XRD, TGA, DSC and resistivity measurement by the four-point van der Pauw method. The study showed that the adopted method of exfoliation and the electropolymerization method used, allows obtaining nanocomposite materials. Analyses of FT-IR, TEM and XRD show that the clays are exfoliated in the polymer matrix. Thermal analysis of the films indicates that the addition of clay reflects an enhancement in the thermal properties of the matrix of PPy, but decreases the conductivity of the same. (author)

  6. Electrochemical synthesis of Poly[3, 4-Propylenedioxythiophene-co-N-Phenylsulfonyl Pyrrole]: Morphological, electrochemical and spectroscopic characterization

    Directory of Open Access Journals (Sweden)

    2011-06-01

    Full Text Available Electroactive random copolymers of 3,4-Propylenedioxythiophene (ProDOT and N-Phenylsulfonyl Pyrrole (PSP were electrochemically synthesized on single carbon fiber microelectrode (SCFME by cyclic voltammetry (CV. Fourier Transform Infrared-Attenuated Total Reflectance (FTIR-ATR measurements indicate the inclusion of PSP into the copolymer structure. The influence of feed ratios on the copolymers was studied by CV and electrochemical impedance spectroscopy (EIS and equivalent circuit modelling (ECM. The morphologies and film thicknesses of copolymers were characterized by scanning electron microscopy (SEM and atomic force microscopy (AFM. The results have shown that the principal changes in morphology, conductivity, porous nature and thickness of Poly(ProDOT-co-PSP film depend on the concentration of PSP. The strong electron-withdrawing sulfonyl group substitution on PSP significantly inhibited electrochemical copolymerization. Semicircular characteristics at Nyquist plots reflected an increasing trend with the increase of PSP concentration in the feed at high frequency. The semicircular characteristic of the copolymer film is useful for the bioelectrochemical sensor applications.

  7. One electron vs. two electron electrochemical and chemical oxidation of electron-donor substituted diketo-pyrrolo-pyrroles

    International Nuclear Information System (INIS)

    Electrochemical and chemical (using FeCl3) oxidation reactions of a series of eight N,N′-dialkylated soluble diketo-pyrrolo-pyrrole dyes (DPPs) substituted by electron donating and/or electron withdrawing groups were investigated electrochemically and by UV–vis spectrometry and the results were rationalized by DFT calculations. Influence of substituents on HOMO and LUMO energies as well as on the electron transfer mechanism was followed. Destabilization of HOMO by two piperidino-substituents in 3,6-diphenyl-DPP 5 enabled to observe a potential inversion in electrochemical oxidation of this derivative, when a two-electron oxidation occurs leading directly to a dication, whereas other DPPs are oxidized first in a one-electron transfer to a radical cation. In chemical oxidation with FeCl3 the radical cation is produced by two mechanisms: either directly (standard reaction) or in the case of 5 by a comproportionation reaction of neutral molecule and its dication. Using mutual comparison of oxidation potentials and HOMO/LUMO energies a quite realistic limit of FeCl3 oxidation ability in acetonitrile was found

  8. A soluble conducting polymer: 1-Phenyl-2,5-di(2-thienyl)-1H-pyrrole and its electrochromic application

    Energy Technology Data Exchange (ETDEWEB)

    Tarkuc, S. [Department of Chemistry, Middle East Technical University, 06531 Ankara (Turkey); Sahmetlioglu, E. [Department of Chemistry, Middle East Technical University, 06531 Ankara (Turkey); Department of Chemistry, Nigde University, 51100 Nigde (Turkey); Tanyeli, C. [Department of Chemistry, Middle East Technical University, 06531 Ankara (Turkey); Akhmedov, I.M. [Department of Chemistry, Middle East Technical University, 06531 Ankara (Turkey); Toppare, L. [Department of Chemistry, Middle East Technical University, 06531 Ankara (Turkey)]. E-mail: toppare@metu.edu.tr

    2006-07-28

    A thiophene-functionalized monomer 1-phenyl-2,5-di(2-thienyl)-1H-pyrrole (PTP) was synthesized. The chemical polymerization of PTP (CPTP) was realized by using FeCl{sub 3} as the oxidant. The structures of both the monomer and the soluble polymer (CPTP) were investigated by Nuclear Magnetic Resonance ({sup 1}H and {sup 13}C NMR) and Fourier Transform Infrared (FTIR). The average molecular weight of the chemically synthesized polymer was determined by gel permeation chromatography (GPC) as Mn = 7.2 x 10{sup 3}. The electrochemical oxidative polymerization of PTP was carried out via constant-potential electrolysis. Characterizations of the resulting polymer were done by cyclic voltammetry (CV), FTIR, Scanning Electron Microscopy (SEM) and UV-vis Spectroscopy. The conductivity of sample was measured by four-probe technique. Moreover, the spectroelectrochemical and electrochromic properties of the polymer film were investigated. Spectroelectrochemical analysis of P(PTP) revealed electronic transitions at 413, 577 and 884 nm corresponding to {pi}-{pi}* transition, polaron, and bipolaron band formations, respectively. Kinetic studies evaluated the switching ability of the P(PTP); the percent transmittance T% was found as 27%. The homopolymer of PTP was used to construct dual-type polymer electrochromic devices (ECDs) against poly(3,4-ethylenedioxythiophene) (PEDOT). Spectroelectrochemistry, electrochromic switching and open circuit stability of the devices were investiga0009t.

  9. A soluble conducting polymer: 1-Phenyl-2,5-di(2-thienyl)-1H-pyrrole and its electrochromic application

    International Nuclear Information System (INIS)

    A thiophene-functionalized monomer 1-phenyl-2,5-di(2-thienyl)-1H-pyrrole (PTP) was synthesized. The chemical polymerization of PTP (CPTP) was realized by using FeCl3 as the oxidant. The structures of both the monomer and the soluble polymer (CPTP) were investigated by Nuclear Magnetic Resonance (1H and 13C NMR) and Fourier Transform Infrared (FTIR). The average molecular weight of the chemically synthesized polymer was determined by gel permeation chromatography (GPC) as Mn = 7.2 x 103. The electrochemical oxidative polymerization of PTP was carried out via constant-potential electrolysis. Characterizations of the resulting polymer were done by cyclic voltammetry (CV), FTIR, Scanning Electron Microscopy (SEM) and UV-vis Spectroscopy. The conductivity of sample was measured by four-probe technique. Moreover, the spectroelectrochemical and electrochromic properties of the polymer film were investigated. Spectroelectrochemical analysis of P(PTP) revealed electronic transitions at 413, 577 and 884 nm corresponding to π-π* transition, polaron, and bipolaron band formations, respectively. Kinetic studies evaluated the switching ability of the P(PTP); the percent transmittance T% was found as 27%. The homopolymer of PTP was used to construct dual-type polymer electrochromic devices (ECDs) against poly(3,4-ethylenedioxythiophene) (PEDOT). Spectroelectrochemistry, electrochromic switching and open circuit stability of the devices were investigated

  10. Effect of non-electroactive additives on the early stage pyrrole electropolymerization on indium tin oxide electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Castro-Beltran, A. [Facultad de Ingeniería Mecánica y Eléctrica, Universidad Autónoma de Nuevo León, Ave. Pedro de Alba s/n, Ciudad Universitaria, C.P. 66451 San Nicolás de los Garza, N.L. (Mexico); Centro de Innovación Investigación y Desarrollo en Ingeniería y Tecnología (CIIDIT), Universidad Autónoma de Nuevo León, PIIT-Monterrey C.P. 66600 Apodaca, N.L. (Mexico); Dominguez, C.; Bahena-Uribe, D. [Centro Investigación en Ingeniería y Ciencias Aplicadas (CIICAp), Universidad Autónoma del Estado de Morelos, Av. Universidad 1001, Col. Chamilpa, C.P. 62209 Cuernavaca, Mor. (Mexico); Sepulveda-Guzman, S., E-mail: selene.sepulvedagz@uanl.edu.mx [Facultad de Ingeniería Mecánica y Eléctrica, Universidad Autónoma de Nuevo León, Ave. Pedro de Alba s/n, Ciudad Universitaria, C.P. 66451 San Nicolás de los Garza, N.L. (Mexico); Centro de Innovación Investigación y Desarrollo en Ingeniería y Tecnología (CIIDIT), Universidad Autónoma de Nuevo León, PIIT-Monterrey C.P. 66600 Apodaca, N.L. (Mexico); Cruz-Silva, R. [Research Center for Exotic NanoCarbon, Shinshu University, 4-17-1 Wakasato, Nagano 380-8553 (Japan)

    2014-09-01

    The use of non-electroactive additives during electrodeposition of conducting polymers has long been used to modify the properties of deposited films. These additives can improve the adhesion, and not only change the morphology and deposition rate but also modify the chemical composition of the electrodeposited polymer. Several compounds have been used to modify deposition of polypyrrole; however, there is no systematic study of these compounds. In this work, we comparatively studied several water soluble chemical compounds, a cationic polymer, an anionic polymer, a cationic surfactant, and an anionic surfactant during potentiostatic electrodeposition of polypyrrole. In order to study the effect of these compounds on the interface, where the electrochemical polymerization takes place, we used electrochemical impedance spectroscopy. The morphology during the initial stage of growth was studied by atomic force microscopy, whereas the resulting polypyrrole films were observed by scanning electron microscopy. - Highlights: • Early-stage polymerization polypyrrole particles on indium tin oxide (ITO). • Anionic additives promote pyrrole oxidation and polypyrrole film growth on ITO. • Cationic polyelectrolyte promotes adhesion between ITO and polypyrrole film. • Non-electroactive additives strongly influence polypyrrole nucleation on ITO.

  11. Biofabrication Using Pyrrole Electropolymerization for the Immobilization of Glucose Oxidase and Lactate Oxidase on Implanted Microfabricated Biotransducers

    Directory of Open Access Journals (Sweden)

    Christian N. Kotanen

    2014-03-01

    Full Text Available The dual responsive Electrochemical Cell-on-a-Chip Microdisc Electrode Array (ECC MDEA 5037 is a recently developed electrochemical transducer for use in a wireless, implantable biosensor system for the continuous measurement of interstitial glucose and lactate. Fabrication of the biorecognition membrane via pyrrole electropolymerization and both in vitro and in vivo characterization of the resulting biotransducer is described. The influence of EDC-NHS covalent conjugation of glucose oxidase with 4-(3-pyrrolyl butyric acid (monomerization and with 4-sulfobenzoic acid (sulfonization on biosensor performance was examined. As the extent of enzyme conjugation was increased sensitivity decreased for monomerized enzymes but increased for sulfonized enzymes. Implanted biotransducers were examined in a Sprague-Dawley rat hemorrhage model. Resection after 4 h and subsequent in vitro re-characterization showed a decreased sensitivity from 0.68 (±0.40 to 0.22 (±0.17 µA·cm−2·mM−1, an increase in the limit of detection from 0.05 (±0.03 to 0.27 (±0.27 mM and a six-fold increase in the response time from 41 (±18 to 244 (±193 s. This evidence reconfirms the importance of biofouling at the bio-abio interface and the need for mitigation strategies to address the foreign body response.

  12. Sub-10 nm Platinum Nanocrystals with Size and Shape Control: Catalytic Study for Ethylene and Pyrrole Hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Tsung, Chia-Kuang; Kuhn, John N.; Huang, Wenyu; Aliaga, Cesar; Hung, Ling-I; Somorjai, Gabor A.; Yang, Peidong

    2009-03-02

    Platinum nanocubes and nanopolyhedra with tunable size from 5 to 9 nm were synthesized by controlling the reducing rate of metal precursor ions in a one-pot polyol synthesis. A two-stage process is proposed for the simultaneous control of size and shape. In the first stage, the oxidation state of the metal ion precursors determined the nucleation rate and consequently the number of nuclei. The reaction temperature controlled the shape in the second stage by regulation of the growth kinetics. These well-defined nanocrystals were loaded into MCF-17 mesoporous silica for examination of catalytic properties. Pt loadings and dispersions of the supported catalysts were determined by elemental analysis (ICP-MS) and H2 chemisorption isotherms, respectively. Ethylene hydrogenation rates over the Pt nanocrystals were independent of both size and shape and comparable to Pt single crystals. For pyrrole hydrogenation, the nanocubes enhanced ring-opening ability and thus showed a higher selectivity to n-butylamine as compared to nanopolyhedra.

  13. Characterization of electro-conductive fabrics prepared by in situ chemical and electrochemical polymerization of pyrrole onto polyester fabric

    Energy Technology Data Exchange (ETDEWEB)

    Maiti, Syamal; Das, Dipayan; Sen, Kushal, E-mail: kushal@textile.iitd.ernet.in

    2014-09-15

    Highlights: • Surface resistivity of the fabrics decreased rapidly with an increase in add-on. • Add-on and resistivity were not correlated below a resistivity value of about 200 Ω. • Higher add-on but lower surface roughness resulted in lower surface resistivity. • The voltage–current and voltage–temperature behaviours were found to be non-linear. • Electro-conductive fabric exhibited 98% electromagnetic shielding efficiency. - Abstract: This paper reports a study on electro-conductive fabrics prepared by a combined in situ chemical and electrochemical polymerization of pyrrole. Specific observations are made to establish the roles of add-on and surface roughness on the surface resistivity of the electro-conductive fabrics. The performance characteristics of the fabrics are reported in terms of electrical conductivity, voltage–current and voltage–temperature characteristics and electromagnetic interference (EMI) shielding capability. The surface resistivity of the fabric was found to be as low as 11.79 Ω. The voltage–current profile of the fabric is observed to be non-ohmic as well as the voltage–temperature curve is found to be exponential. The EMI shielding efficiency of the fabric was found to be about 98%.

  14. Co-existence of Two Different α-Synuclein Oligomers with Different Core Structures Determined by Hydrogen/Deuterium Exchange Mass Spectrometry

    DEFF Research Database (Denmark)

    Paslawski, Wojciech; Mysling, Simon; Thomsen, Karen;

    2014-01-01

    and structure. Hydrogen/deuterium exchange (HDX) monitored by mass spectrometry is used to analyze oligomers formed by wild-type (wt) αSN and also three familial αSN mutants (A30P, E46K, and A53T). All four variants show co-existence of two different oligomers. The backbone amides of oligomer type I...... are protected from exchange with D2 O until they dissociate into monomeric αSN by EX1 exchange kinetics. Fewer residues are protected against exchange in oligomer type II, but this type does not revert to αSN monomers. Both oligomers are protected in the core sequence Y39-A89. Based on incubation studies...

  15. Oligomer Formation of Amyloid-β(29-42) from Its Monomers Using the Hamiltonian Replica-Permutation Molecular Dynamics Simulation.

    Science.gov (United States)

    Itoh, Satoru G; Okumura, Hisashi

    2016-07-14

    Oligomers of amyloid-β peptides (Aβ) are formed during the early stage of the amyloidogenesis process and exhibit neurotoxicity. The oligomer formation process of Aβ and even that of Aβ fragments are still poorly understood, though understanding of these processes is essential for remedying Alzheimer's disease. In order to better understand the oligomerization process of the C-terminal Aβ fragment Aβ(29-42) at the atomic level, we performed the Hamiltonian replica-permutation molecular dynamics simulation with Aβ(29-42) molecules using the explicit water solvent model. We observed that oligomers increased in size through the sequential addition of monomers to the oligomer, rather than through the assembly of small oligomers. Moreover, solvent effects played an important role in this oligomerization process. PMID:27281682

  16. A DFT Study of Pyrrole-Isoxazole Derivatives as Chemosensors for Fluoride Anion

    Directory of Open Access Journals (Sweden)

    Shanshan Tang

    2012-09-01

    Full Text Available The interactions between chemosensors, 3-amino-5-(4,5,6,7-tetrahydro-1H-indol-2-ylisoxazole-4-carboxamide (AIC derivatives, and different anions (F Cl, Br, AcO, and H2PO4 have been theoretically investigated using DFT approaches. It turned out that the unique selectivity of AIC derivatives for F is ascribed to their ability of deprotonating the host sensors. Frontier molecular orbital (FMO analyses have shown that the vertical electronic transitions of absorption and emission for the sensing signals are characterized as intramolecular charge transfer (ICT. The study of substituent effects suggests that all the substituted derivatives are expected to be promising candidates for fluoride chemosensors both in UV-vis and fluorescence spectra except for derivative with benzo[d]thieno[3,2-b]thiophene fragment that can serve as ratiometric fluorescent fluoride chemosensor only.

  17. Vaccination with a non-human random sequence amyloid oligomer mimic results in improved cognitive function and reduced plaque deposition and micro hemorrhage in Tg2576 mice

    Directory of Open Access Journals (Sweden)

    Rasool Suhail

    2012-08-01

    Full Text Available Abstract Background It is well established that vaccination of humans and transgenic animals against fibrillar Aβ prevents amyloid accumulation in plaques and preserves cognitive function in transgenic mouse models. However, autoimmune side effects have halted the development of vaccines based on full length human Aβ. Further development of an effective vaccine depends on overcoming these side effects while maintaining an effective immune response. Results We have previously reported that the immune response to amyloid oligomers is largely directed against generic epitopes that are common to amyloid oligomers of many different proteins and independent of a specific amino acid sequence. Here we have examined whether we can exploit this generic immune response to develop a vaccine that targets amyloid oligomers using a non-human random sequence amyloid oligomer. In order to study the effect of vaccination against generic oligomer epitopes, a random sequence oligomer (3A was selected as it forms oligomers that react with the oligomer specific A11 antibody. Oligomer mimics from 3A peptide, Aβ, islet amyloid polypeptide (IAPP, and Aβ fibrils were used to vaccinate Tg2576 mice, which develop a progressive accumulation of plaques and cognitive impairment. Vaccination with the 3A random sequence antigen was just as effective as vaccination with the other antigens in improving cognitive function and reducing total plaque load (Aβ burden in the Tg2576 mouse brains, but was associated with a much lower incidence of micro hemorrhage than Aβ antigens. Conclusion These results shows that the amyloid Aβ sequence is not necessary to produce a protective immune response that specifically targets generic amyloid oligomers. Using a non-human, random sequence antigen may facilitate the development of a vaccine that avoids autoimmune side effects.

  18. Mechanisms of hybrid oligomer formation in the pathogenesis of combined Alzheimer's and Parkinson's diseases.

    Directory of Open Access Journals (Sweden)

    Igor F Tsigelny

    Full Text Available BACKGROUND: Misfolding and pathological aggregation of neuronal proteins has been proposed to play a critical role in the pathogenesis of neurodegenerative disorders. Alzheimer's disease (AD and Parkinson's disease (PD are frequent neurodegenerative diseases of the aging population. While progressive accumulation of amyloid beta protein (Abeta oligomers has been identified as one of the central toxic events in AD, accumulation of alpha-synuclein (alpha-syn resulting in the formation of oligomers and protofibrils has been linked to PD and Lewy body Disease (LBD. We have recently shown that Abeta promotes alpha-syn aggregation and toxic conversion in vivo, suggesting that abnormal interactions between misfolded proteins might contribute to disease pathogenesis. However the molecular characteristics and consequences of these interactions are not completely clear. METHODOLOGY/PRINCIPAL FINDINGS: In order to understand the molecular mechanisms involved in potential Abeta/alpha-syn interactions, immunoblot, molecular modeling, and in vitro studies with alpha-syn and Abeta were performed. We showed in vivo in the brains of patients with AD/PD and in transgenic mice, Abeta and alpha-synuclein co-immunoprecipitate and form complexes. Molecular modeling and simulations showed that Abeta binds alpha-syn monomers, homodimers, and trimers, forming hybrid ring-like pentamers. Interactions occurred between the N-terminus of Abeta and the N-terminus and C-terminus of alpha-syn. Interacting alpha-syn and Abeta dimers that dock on the membrane incorporated additional alpha-syn molecules, leading to the formation of more stable pentamers and hexamers that adopt a ring-like structure. Consistent with the simulations, under in vitro cell-free conditions, Abeta interacted with alpha-syn, forming hybrid pore-like oligomers. Moreover, cells expressing alpha-syn and treated with Abeta displayed increased current amplitudes and calcium influx consistent with the

  19. Characterization of radiation modified κ-carrageenan oligomers for bio-based materials development

    International Nuclear Information System (INIS)

    κ-carrageenan oligomers are known to have several biological activities such as anti-HIV, anti-herpes, antitumor and antioxidant properties. Recent progress in the development of radiation modified κ-carrageenan has resulted in new applications such as plant growth promoter, radiation dose indicator and hydrogels for wound dressing. This presentation would touch on the changes in chemical structure, gelation and conformational transition behavior and molecular size of κ-carrageenan at doses from 0 to 200 kGy and would be correlated to these functions for the development of bio-based materials. Chemical and spectral analyses were carried out using UV-Vis spectroscopy, FT-IR spectroscopy, NMR spectroscopy, reducing sugar analysis, free sulfate and carboxylic acid analysis. The chemical and spectral analyses of the radiolytic products indicated increasing reducing sugars, carbonyl, carboxylic acids, and sulfates with increasing doses which reached a maximum level at a certain dose depending on the irradiation condition. Values were very much lower in solid irradiation (in vacuum and in air) as compared to aqueous irradiation. NMR data also revealed an intact structure of the oligomer irradiated at 100 kGy in the specific fraction that contains an Mw = (3-10) kDa. κ-carrageenan oligomers exhibited antioxidant properties as determined by hydroxyl radical scavenging activity, reducing power and DPPH radical scavenging capacity assay. The degree of oxidative inhibition increased with increasing dose which can be attributed to higher reducing sugar. Dynamic light scattering (DLS) experiments showed that a dose of up to 50 kGy, sol-gelation transition was still observed. Beyond 50 kGy, no gelation took place, instead appearance of fast relax-carrageenan mode in characteristic decay time function was observed at doses of (75-150) kGy. Optimum peak intensity was found at 100 kGy (mol wt. 5-10 kDa) which coincides with the optimum plant growth promoter effect in κ

  20. Mechanisms leading to oligomers and SOA through aqueous photooxidation: insights from OH radical oxidation of acetic acid

    Directory of Open Access Journals (Sweden)

    Y. Tan

    2011-06-01

    Full Text Available Previous experiments have demonstrated that the aqueous OH radical oxidation of methylglyoxal produces low volatility products including oxalate and oligomers. These products are found predominantly in the particle phase in the atmosphere, suggesting that methylglyoxal is a precursor of secondary organic aerosol (SOA. Acetic acid is an important intermediate in aqueous methylglyoxal oxidation and a ubiquitous product of gas phase photochemistry, making it a potential "aqueous" SOA precursor in its own right. Altieri et al. (2008 proposed that acetic acid was the precursor of oligoesters observed in methylglyoxal oxidation. However, the fate of acetic acid upon aqueous-phase oxidation is not well understood. In this research, acetic acid at concentrations relevant to atmospheric waters (20 μM–10 mM was oxidized by OH radical. Products were analyzed by ion chromatography (IC, electrospray ionization mass spectrometry (ESI-MS, and IC-ESI-MS. The formation of glyoxylic, glycolic, and oxalic acids were observed. In contrast to methylglyoxal oxidation, succinic acid and oligomers were not detected. Using results from these and methylglyoxal + OH radical experiments, radical mechanisms responsible for oligomer formation from methylglyoxal oxidation in clouds and wet aerosols are proposed. The importance of acetic acid/acetate as an SOA precursor is also discussed. We hypothesize that this and similar chemistry is central to the daytime formation of oligomers in wet aerosols.

  1. The Slowly Aggregating Salmon Calcitonin: A Useful Tool for the Study of the Amyloid Oligomers Structure and Activity

    Directory of Open Access Journals (Sweden)

    Marco Diociaiuti

    2011-12-01

    Full Text Available Amyloid proteins of different aminoacidic composition share the tendency to misfold and aggregate in a similar way, following common aggregation steps. The process includes the formation of dimers, trimers, and low molecular weight prefibrillar oligomers, characterized by the typical morphology of globules less than 10 nm diameter. The globules spontaneously form linear or annular structures and, eventually, mature fibers. The rate of this process depends on characteristics intrinsic to the different proteins and to environmental conditions (i.e., pH, ionic strength, solvent composition, temperature. In the case of neurodegenerative diseases, it is now generally agreed that the pathogenic aggregates are not the mature fibrils, but the intermediate, soluble oligomers. However, the molecular mechanism by which these oligomers trigger neuronal damage is still unclear. Inparticular, it is not clear if there is a peculiar structure at the basis of the neurotoxic effect and how this structure interacts with neurons. This review will focus on the results we obtained using salmon Calcitonin, an amyloid protein characterized by a very slow aggregation rate, which allowed us to closely monitor the aggregation process. We used it as a tool to investigate the characteristics of amyloid oligomers formation and their interactions with neuronal cells. Our results indicate that small globules of about 6 nm could be the responsible for the neurotoxic effects. Moreover, our data suggest that the rich content in lipid rafts of neuronal cell plasma membrane may render neurons particularly vulnerable to the amyloid protein toxic effect.

  2. Identification and quantification of oligomers as potential migrants in plastics food contact materials with a focus in polycondensates - A review

    NARCIS (Netherlands)

    M. Hoppe; P. de Voogt; R. Franz

    2016-01-01

    Background: Over the last years the variety of food and beverage packaging has increased with the development of new plastic materials and (co)polymer modifications. Oligomers which are always present in polymers evoke attention as potential migrants, from a qualitatively and quantitatively viewpoin

  3. Lifetimes of organic photovoltaics: Design and synthesis of single oligomer molecules in order to study chemical degradation mechanisms

    DEFF Research Database (Denmark)

    Alstrup, J.; Norrman, K.; Jørgensen, M.;

    2006-01-01

    Degradation mechanisms in organic and polymer photovoltaics are addressed through the study of an organic photovoltaic molecule based on a single phenylene-vinylene-type oligomer molecule. The synthesis of such a model compound with different end-groups is presented that allows for assignment...

  4. Amyloid-β Oligomers May Impair SNARE-Mediated Exocytosis by Direct Binding to Syntaxin 1a

    Directory of Open Access Journals (Sweden)

    Yoosoo Yang

    2015-08-01

    Full Text Available Alzheimer’s disease (AD is closely associated with synaptic dysfunction, and thus current treatments often aim to stimulate neurotransmission to improve cognitive impairment. Whereas the formation of the soluble N-ethylmaleimide-sensitive factor attachment protein receptor (SNARE complex is essential for synaptic transmission, the correlation between SNAREs and AD neuropathology is unknown. Here, we report that intracellular amyloid-β (Aβ oligomers directly inhibit SNARE-mediated exocytosis by impairing SNARE complex formation. We observe abnormal reduction of SNARE complex levels in the brains of APP/PS1 transgenic (TG mice compared to age-matched wild-types. We demonstrate that Aβ oligomers block SNARE complex assembly through the direct interaction with a target membrane (t-SNARE syntaxin 1a in vitro. Furthermore, the results of the in vitro single-vesicle content-mixing assay reveal that Aβ oligomers inhibit SNARE-mediated fusion pores. Thus, our study identifies a potential molecular mechanism by which intracellular Aβ oligomers hamper SNARE-mediated exocytosis, likely leading to AD-associated synaptic dysfunctions.

  5. Correlation hole effect in comblike copolymer systems obtained by hydrogen bonding between homopolymers and end-functionalized oligomers

    NARCIS (Netherlands)

    Huh, J; Ikkala, O; tenBrinke, G

    1997-01-01

    This paper addresses concentration fluctuations in comblike copolymer systems obtained by hydrogen bonding between polymers and end-functionalized oligomers. Monodisperse block copolymer systems in the homogeneous melt exhibit small-angle X-ray scattering peaks at finite nonzero angle due to charact

  6. Binding affinity of amyloid oligomers to cellular membranes is a generic indicator of cellular dysfunction in protein misfolding diseases

    Science.gov (United States)

    Evangelisti, Elisa; Cascella, Roberta; Becatti, Matteo; Marrazza, Giovanna; Dobson, Christopher M.; Chiti, Fabrizio; Stefani, Massimo; Cecchi, Cristina

    2016-01-01

    The conversion of peptides or proteins from their soluble native states into intractable amyloid deposits is associated with a wide range of human disorders. Misfolded protein oligomers formed during the process of aggregation have been identified as the primary pathogenic agents in many such conditions. Here, we show the existence of a quantitative relationship between the degree of binding to neuronal cells of different types of oligomers formed from a model protein, HypF-N, and the GM1 content of the plasma membranes. In addition, remarkably similar behavior is observed for oligomers of the Aβ42 peptide associated with Alzheimer’s disease. Further analysis has revealed the existence of a linear correlation between the level of the influx of Ca2+ across neuronal membranes that triggers cellular damage, and the fraction of oligomeric species bound to the membrane. Our findings indicate that the susceptibility of neuronal cells to different types of misfolded oligomeric assemblies is directly related to the extent of binding of such oligomers to the cellular membrane. PMID:27619987

  7. Kinetic properties of two Rhizopus exo-polygalacturonase enzymes hydrolyzing galacturonic acid oligomers using isothermal titration calorimetry

    Science.gov (United States)

    The kinetic characteristics of two Rhizopus oryzae exo-polygalacturonases acting on galacturonic acid oligomers (GalpA) were determined using isothermal titration calorimetry (ITC). RPG15 hydrolyzing (GalpA)2 demonstrated a Km of 55 uM and kcat of 10.3 s^-1^ while RPG16 was shown to have greater af...

  8. Tuning of the excited state properties of phenylenevinylene oligomers : A time-dependent density functional theory study

    NARCIS (Netherlands)

    Grozema, FC; Telesca, R; Snijders, JG; Siebbeles, LDA

    2003-01-01

    This paper discusses a time-dependent density functional theory study of the effect of molecular structure on the excited state polarizability of conjugated molecules. A short phenylenevinylene oligomer containing three phenyl rings (PV2, distyryl benzene) is taken as a model system. Introduction of

  9. Linear and cyclic ester Oligomers of succinic acid and 1,4-butanediol: Biocatalytic synthesis and characterization

    NARCIS (Netherlands)

    Habeych Narvaez, D.I.; Eggink, G.; Boeriu, C.G.

    2011-01-01

    The lipase-catalyzed synthesis of cyclic ester oligomers from non-activated succinic acid (A) and 1,4-butanediol (B) in the presence of immobilized Candida antarctica lipase B was investigated. Batch and pulse fed-batch systems were implemented to increase the formation of cyclic ester products. The

  10. Photo-Crosslinked Biodegradable Hydrogels Prepared From Fumaric Acid Monoethyl Ester-Functionalized Oligomers for Protein Delivery

    NARCIS (Netherlands)

    Jansen, Janine; Mihov, George; Feijen, Jan; Grijpma, Dirk W.

    2012-01-01

    Photo-crosslinkable, fumaric acid monoethyl ester-functionalized triblock oligomers are synthesized and copolymerized with N-vinyl-2-pyrrolidone to form biodegradable photo-crosslinked hydrogels. Poly(ethylene glycol) is used as the middle hydrophilic segment and the hydrophobic segments are based o

  11. Pyrrole Hydrogenation over Rh(111) and Pt(111) Single-Crystal Surfaces and Hydrogenation Promotion Mediated by 1-Methylpyrrole: A Kinetic and Sum-Frequency Generation Vibrational Spectroscopy Study

    Energy Technology Data Exchange (ETDEWEB)

    Kliewer, Christopher J.; Bieri, Marco; Somorjai, Gabor A.

    2008-03-04

    Sum-frequency generation (SFG) surface vibrational spectroscopy and kinetic measurements using gas chromatography have been used to study the adsorption and hydrogenation of pyrrole over both Pt(111) and Rh(111) single-crystal surfaces at Torr pressures (3 Torr pyrrole, 30 Torr H{sub 2}) to form pyrrolidine and the minor product butylamine. Over Pt(111) at 298 K it was found that pyrrole adsorbs in an upright geometry cleaving the N-H bond to bind through the nitrogen evidenced by SFG data. Over Rh(111) at 298 K pyrrole adsorbs in a tilted geometry relative to the surface through the p-aromatic system. A pyrroline surface reaction intermediate, which was not detected in the gas phase, was seen by SFG during the hydrogenation over both surfaces. Significant enhancement of the reaction rate was achieved over both metal surfaces by adsorbing 1-methylpyrrole before reaction. SFG vibrational spectroscopic results indicate that reaction promotion is achieved by weakening the bonding between the N-containing products and the metal surface because of lateral interactions on the surface between 1-methylpyrrole and the reaction species, reducing the desorption energy of the products. It was found that the ring-opening product butylamine was a reaction poison over both surfaces, but this effect can be minimized by treating the catalyst surfaces with 1-methylpyrrole before reaction. The reaction rate was not enhanced with elevated temperatures, and SFG suggests desorption of pyrrole at elevated temperatures.

  12. Interchain tube pressure effect in extensional flows of oligomer diluted nearly monodisperse polystyrene melts

    DEFF Research Database (Denmark)

    Rasmussen, Henrik K.; Huang, Qian

    2014-01-01

    , if the solvent has less than two Kuhn steps, e.g. is not a chain. The constitutive equation is based on a phenomenological tube-based model within the methodology of the molecular stress function approach. The nonlinear dynamics have been explained as a consequence of a constant thermal interchain pressure......We have derived a constitutive equation to explain the extensional dynamics of oligomer-diluted monodisperse polymers, if the length of the diluent has at least two Kuhn steps. These polymer systems have a flow dynamics which distinguish from pure monodisperse melts and solutions thereof...... times and entanglements have been established based on published extensional experiments on nearly monodisperse polystyrene melts. The constitutive equation has shown agreement with the experimental startup of and steady extension data from Huang et al. (Macromolecules 46:5026–5035, 2013a) based on 285...

  13. Single Molecule Characterization of Conjugated Oligomers Formed through Radical Cyclization at a Surface

    Science.gov (United States)

    Tsai, Hsin-Zon; Riss, Alexander; Wickenburg, Sebastian; Tan, Liang; Gorman, Patrick; Oteyza, Dimas; Chen, Yen-Chia; Bradley, Aaron; Ugeda, Miguel; Etkin, Grisha; Louie, Steven; Fischer, Felix; Crommie, Michael

    2014-03-01

    Conjugated polymers have gained considerable attention due to their potential industrial applications and interesting fundamental properties. Real-space imaging their chemical bonds and understanding their electronic structures at the nanoscale could lead to enhanced control in the synthesis of these polymers for the potential applications in the nanoelectronics. Here, we present the synthesis and characterization of poly-acetylene derivatives resulting from cyclizations of enediyne molecules on an Au(111) surface. We performed non-contact atomic force microscopy (nc-AFM) with sub-molecular resolution to determine the precise chemical structure of cyclized monomers and chemically linked molecular chains. Additionally, STM measurements provide insight into the corresponding electronic structure and reveal a 1D conducting channel along the backbone of the conjugated oligomers, consistent with theoretical predictions. This work demonstrates the unique insight that can be gained by combining nc-AFM and STM to study the chemical and electronic structure of molecular assemblies at surfaces.

  14. γ-ray degradation of chitosan to prepare water-soluble oligomers

    International Nuclear Information System (INIS)

    Water-soluble chitosan oligomers with different molecular weight were prepared by a γ-ray degradation method. Effects of irradiation conditions on the chitosan degradation, molecular weight of the irradiated chitosan and yield of the water-soluble products were studied. Gd value of the chitosan radiation degradiation was calculated, and mechanisms of the degradation were discussed. Gel permeation chromatography, Fourier transform infrared spectroscopy and ultraviolet-visible spectrometry (UV-VIS) were applied to characterized and analyzed the degradation products. The results indicated that molecular weight of the degraded chitosan decreased remarkably and its chemical structure changed. It was considered that OH radical is vital to the radiation degradation of chitosan. (authors)

  15. SELECTIVE TRANSPORT OF GOLD(Ⅱ) THROUGH THE LIQUID MEMBRANE CONTAINING POLYTHIOETHER OLIGOMER AS CARRIER

    Institute of Scientific and Technical Information of China (English)

    XUYuwu; WANGYing; 等

    1993-01-01

    This paper deals with the transport properties of oligomer of polythioether PSA used as moble carrier in bulk liquid membrane for gold(Ⅲ).It was found that Au(Ⅲ) can be transported by PSA from source phase to receiving phase completely under appropriate conditions and only Au(Ⅲ) can be transferred through the liquid membrane to receiving phase from a mixture of Na(I)-Cu(Ⅱ)-Au(Ⅲ)-Fe(Ⅲ)-Pt(Ⅳ) in the following system:HAuCl4-HCl(aq.)/PSA-ClCH2-CH2Cl/(NH2)2CS-HCl(aq.).The transport rate of Au(Ⅲ) depended on the concentration of carrier,the thickness of liquid membrane,the concentration of Au(Ⅲ) in source phase and the acidity of the media.

  16. Synthesis of Kappa-carrageenan oligomers via synergistic action of gamma radiation and hydrogen peroxide

    International Nuclear Information System (INIS)

    In this study, the synthesis of k-carrageenan oligometers with the simultaneous action of gamma radiation and hydrogen peroxide was carried out. Effects on molecular weight and structure of k-carrageenan were assessed using GPC, UV-VIS and FT-IR. Radiation degradation yield (G(s)) and reaction rate constants (k) based on Mn values were also determined. The results showed that k-carrageenan oligomers with Mw of less than 10 kDa can be prepared easily at low doses (2.5-5 kGy) in the presence of low concentrations of hydrogen peroxide (0.25-0.5%). The G(s)) and k values increased significantly with the presence of H2O2. Structural changes in k-carrageenan treated by the degradation agents were accompanied by appearance of UV peak at 260 nm and characteristic FT-IR band at 1728 cm-1. (Author)

  17. Structure of ring-shaped Aβ42 oligomers determined by conformational selection

    Science.gov (United States)

    Tran, Linh; Basdevant, Nathalie; Prévost, Chantal; Ha-Duong, Tâp

    2016-02-01

    The oligomerization of amyloid beta (Aβ) peptides into soluble non-fibrillar species plays a critical role in the pathogenesis of Alzheimer’s disease. However, it has been challenging to characterize the tertiary and quaternary structures of Aβ peptides due to their disordered nature and high aggregation propensity. In this work, replica exchange molecular dynamics simulations were used to explore the conformational space of Aβ42 monomer. Among the most populated transient states, we identified a particular conformation which was able to generate ring-shaped pentamers and hexamers, when docked onto itself. The structures of these aggregates were stable during microsecond all-atom MD simulations in explicit solvent. In addition to high resolution models of these oligomers, this study provides support for the conformational selection mechanism of Aβ peptide self-assembly.

  18. On the effect of electron correlation on the static second hyperpolarizability of π conjugated oligomer chains.

    Science.gov (United States)

    Limacher, Peter A; Li, Qingxu; Lüthi, Hans P

    2011-07-01

    In this article, we report on the ab initio calculation of the static longitudinal second hyperpolarizability (γ) of π conjugated unsaturated oligomer chains using polyacetylene and polyyne as model compounds. The common observation is that the electron correlation enhances γ in these systems. The present study reveals that for extended chain lengths the opposite appears to be true: Electron correlation may have a damping effect on this property. For double-zeta basis sets, a negative contribution from electron correlation to γ is found within the range of chain lengths investigated. For triple-zeta basis sets, the same behavior must be anticipated at larger chain lengths based on extrapolation schemes. The analysis of the excitation energies and transition moments shows that transition moments between excited states as predicted by the Hartree-Fock and coupled cluster methods have a different response to chain length extension. There also are indications that higher order correlation effects will enhance γ. PMID:21744892

  19. Gene-Specific Countermeasures against Ebola Virus Based on Antisense Phosphorodiamidate Morpholino Oligomers.

    Directory of Open Access Journals (Sweden)

    2006-01-01

    Full Text Available The filoviruses Marburg virus and Ebola virus (EBOV quickly outpace host immune responses and cause hemorrhagic fever, resulting in case fatality rates as high as 90% in humans and nearly 100% in nonhuman primates. The development of an effective therapeutic for EBOV is a daunting public health challenge and is hampered by a paucity of knowledge regarding filovirus pathogenesis. This report describes a successful strategy for interfering with EBOV infection using antisense phosphorodiamidate morpholino oligomers (PMOs. A combination of EBOV-specific PMOs targeting sequences of viral mRNAs for the viral proteins (VPs VP24, VP35, and RNA polymerase L protected rodents in both pre- and post-exposure therapeutic regimens. In a prophylactic proof-of-principal trial, the PMOs also protected 75% of rhesus macaques from lethal EBOV infection. The work described here may contribute to development of designer, "druggable" countermeasures for filoviruses and other microbial pathogens.

  20. Gene-specific countermeasures against Ebola virus based on antisense phosphorodiamidate morpholino oligomers.

    Directory of Open Access Journals (Sweden)

    Kelly L Warfield

    2006-01-01

    Full Text Available The filoviruses Marburg virus and Ebola virus (EBOV quickly outpace host immune responses and cause hemorrhagic fever, resulting in case fatality rates as high as 90% in humans and nearly 100% in nonhuman primates. The development of an effective therapeutic for EBOV is a daunting public health challenge and is hampered by a paucity of knowledge regarding filovirus pathogenesis. This report describes a successful strategy for interfering with EBOV infection using antisense phosphorodiamidate morpholino oligomers (PMOs. A combination of EBOV-specific PMOs targeting sequences of viral mRNAs for the viral proteins (VPs VP24, VP35, and RNA polymerase L protected rodents in both pre- and post-exposure therapeutic regimens. In a prophylactic proof-of-principal trial, the PMOs also protected 75% of rhesus macaques from lethal EBOV infection. The work described here may contribute to development of designer, "druggable" countermeasures for filoviruses and other microbial pathogens.

  1. Oligomer stability of Amyloid- β (A β) 25-35: A Dissipative Particle Dynamics study

    Science.gov (United States)

    Pivkin, Igor; Peter, Emanuel

    Alzheimer's disease is strongly associated with an accumulation of Amyloid- β (A β) peptide plaques in the human brain. A β is a 43 residues long intrinsically disordered peptide and has a strong tendency to form aggregates. Evidence accumulates that A β acts toxic to the neurons in the brain through the formation of small soluble oligomers. A β 25-35 is the smallest fragment of A β which still retains its toxicity and its ability to form extended fibrils. In this talk we will present the results from simulations of aggregation of up to 100 A β 25-35 peptides using a novel polarizable coarse-grained protein model in combination with Dissipative Particle Dynamics.

  2. Optical magnetism and plasmonic Fano resonances in metal-insulator-metal oligomers.

    Science.gov (United States)

    Verre, R; Yang, Z J; Shegai, T; Käll, M

    2015-03-11

    The possibility of achieving optical magnetism at visible frequencies using plasmonic nanostructures has recently been a subject of great interest. The concept is based on designing structures that support plasmon modes with electron oscillation patterns that imitate current loops, that is, magnetic dipoles. However, the magnetic resonances are typically spectrally narrow, thereby limiting their applicability in, for example, metamaterial designs. We show that a significantly broader magnetic response can be realized in plasmonic pentamers constructed from metal-insulator-metal (MIM) sandwich particles. Each MIM unit acts as a magnetic meta-atom and the optical magnetism is rendered quasi-broadband through hybridization of the in-plane modes. We demonstrate that scattering spectra of individual MIM pentamers exhibit multiple Fano resonances and a broad subradiant spectral window that signals the magnetic interaction and a hierarchy of coupling effects in these intricate three-dimensional nanoparticle oligomers.

  3. Synergistic effects of atmospheric pressure plasma-emitted components on DNA oligomers: a Raman spectroscopic study.

    Science.gov (United States)

    Edengeiser, Eugen; Lackmann, Jan-Wilm; Bründermann, Erik; Schneider, Simon; Benedikt, Jan; Bandow, Julia E; Havenith, Martina

    2015-11-01

    Cold atmospheric-pressure plasmas have become of increasing importance in sterilization processes especially with the growing prevalence of multi-resistant bacteria. Albeit the potential for technological application is obvious, much less is known about the molecular mechanisms underlying bacterial inactivation. X-jet technology separates plasma-generated reactive particles and photons, thus allowing the investigation of their individual and joint effects on DNA. Raman spectroscopy shows that particles and photons cause different modifications in DNA single and double strands. The treatment with the combination of particles and photons does not only result in cumulative, but in synergistic effects. Profilometry confirms that etching is a minor contributor to the observed DNA damage in vitro. Schematics of DNA oligomer treatment with cold atmospheric-pressure plasma.

  4. Preparation and Property of Bisphenol A Bis(diphenyl phosphate) Oligomer

    Institute of Scientific and Technical Information of China (English)

    LI Bing-hai; OU Yu-xiang; XIN Fei

    2007-01-01

    Bisphenol A bis(diphenyl phosphate) oligomer(BDP) is prepared successfully from the reactants consisting of phosphorus oxychloride (POCl3), bisphenol A and phenol with a Friedel-Crafts catalyst. The resultant products were examined with thermo-gravimetric analysis (TGA) and high performance liquid chromatography(HPLC). Thermogravimetry data shows that BDP decomposes at 375℃ when 5% weight lost. Experiments results show that catalyst is preferably AlCl3 and the amount of it is preferably 1% relative to bisphenol A by mole. POCl3/bisphenol A mole ratio is preferably about 5∶1 to 6∶1. Experiments unclosed that a seal apparatus is very important to the properties of product.

  5. Investigation of ferroelectric domains in thin films of vinylidene fluoride oligomers

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, Pankaj, E-mail: psharma@huskers.unl.edu; Poddar, Shashi; Ducharme, Stephen; Gruverman, Alexei, E-mail: alexei-gruverman@unl.edu [Department of Physics and Astronomy, and Nebraska Center for Materials and Nanoscience, University of Nebraska-Lincoln, Nebraska 68588 (United States); Korlacki, Rafal [Department of Electrical Engineering and Center for Nanohybrid Functional Materials, University of Nebraska-Lincoln, Nebraska 68588 (United States)

    2014-07-14

    High-resolution vector piezoresponse force microscopy (PFM) has been used to investigate ferroelectric domains in thin vinylidene fluoride oligomer films fabricated by the Langmuir-Blodgett deposition technique. Molecular chains are found to be preferentially oriented normal to the substrate, and PFM imaging shows that the films are in ferroelectric β-phase with a predominantly in-plane polarization, in agreement with infrared spectroscopic ellipsometry and X-ray diffraction measurements. The fractal analysis of domain structure has yielded the Hausdorff dimension (D) in the range of ∼1.3–1.5 indicating a random-bond nature of the disorder potential, with domain size exhibiting Landau-Lifshitz-Kittel scaling.

  6. Synthesis and bioactivity of MSH4 oligomers prepared by an A2 + B2 strategy

    Science.gov (United States)

    Dehigaspitiya, Dilani Chathurika; Navath, Suryakiran; Weber, Craig S.; Lynch, Ronald M.; Mash, Eugene A.

    2014-01-01

    Oligomers incorporating the tetrapeptide MSH4, the minimum active sequence of melanocyte stimulating hormone, were synthesized by an A2 + B2 strategy involving microwave-assisted copper-catalyzed azide-alkyne cycloaddition. A2 contained an MSH4 core while B2 contained a (Pro-Gly)3 spacer. Soluble mixtures containing compounds with up to eight MSH4 units were obtained from oligomerizations at high monomer concentrations. The avidities of several oligomeric mixtures were evaluated by means of a competitive binding assay using HEK293 cells engineered to overexpress the melanocortin 4 receptor. When based on total MSH4 concentrations, avidities were only minimally enhanced compared with a monovalent control. The lack of variation in the effect of ligands on probe binding is consistent with high off rates for MSH4 in both monovalent and oligomeric constructs relative to that of the competing probe. PMID:26120211

  7. Progress in conducting/semiconducting and redox-active oligomers and polymers of arylamines

    Directory of Open Access Journals (Sweden)

    Janošević Aleksandra

    2013-01-01

    Full Text Available Recent advances in synthesis, characterization and application of the selected conducting/semiconducting and redox-active oligomers and polymers of arylamines are reviewed. A brief historical background of the selected topics is given. The overview of the preparation, structure and properties of polyaniline, substituted polyanilines, especially those obtained by the oxidative polymerization of p-substituted anilines, poly(1-aminonaphthalene and its derivatives, carbocyclic and heterocyclic polyaryldiamines such as poly(p-phenylenediamine and polydiaminoacridines, is presented. The mechanism of formation of polyaniline nanostructures is discussed. Recent approaches to the preparation of one-dimensional polyaniline nanostructures are concisely reviewed, with special attention paid to the template-free falling-pH method. Current and potential future applications of oligo/polyarylamines are briefly discussed. [Projekat Ministarstva nauke Republike Srbije, br. OI 172043

  8. Catalytic production of biofuels (butene oligomers) and biochemicals (tetrahydrofurfuryl alcohol) from corn stover.

    Science.gov (United States)

    Byun, Jaewon; Han, Jeehoon

    2016-07-01

    A strategy is presented that produces liquid hydrocarbon fuels (butene oligomers (BO)) from cellulose (C6) fraction and commodity chemicals (tetrahydrofurfuryl alcohol (THFA)) from hemicellulose (C5) of corn stover based on catalytic conversion technologies using 2-sec-butylphenol (SBP) solvents. This strategy integrates the conversion subsystems based on experimental studies and separation subsystems for recovery of biomass derivatives and SBP solvents. Moreover, a heat exchanger network is designed to reduce total heating requirements to the lowest level, which is satisfied from combustion of biomass residues (lignin and humins). Based on the strategy, this work offers two possible process designs (design A: generating electricity internally vs. design B: purchasing electricity externally), and performs an economic feasibility study for both the designs based on a comparison of the minimum selling price (MSP) of THFA. This strategy with the design B leads to a better MSP of $1.93 per kg THFA. PMID:27030955

  9. Preparation and characterization of galactosylated alginate-chitosan oligomer microcapsule for hepatocytes microencapsulation.

    Science.gov (United States)

    Tian, Meng; Han, Bo; Tan, Hong; You, Chao

    2014-11-01

    Galactosylated alginate (GA)-chitosan oligomer microcapsule was prepared to provide a sufficient mechanical stability, a selective permeability and an appropriate three-dimensional (3D) microenvironment for hepatocytes microencapsulation. The microcapsule has a unique asymmetric membrane structure, with a dense layer located in the inner surface and gradually decreasing toward the outside surface. The stable microcapsule was obtained when GA lower than 50%, while the permeability was increased with increasing of GA. A balance between mechanical stability and permeability was achieved through modulating membrane porosity and thickness. The optimal microcapsule displays a selective permeability allowing efficient transport of human serum albumin while effectively blocking immunoglobulin G. Hepatocytes exhibited high and long term viability (>92%), proliferability, multicellular spheroid morphology, and enhancement of liver-specific functions in the microcapsule wherein galactose moieties present chemical cues to support cell-matrix interactions while the 3D structure of the microcapsule behaves physical cues to facilitate cell-cell interactions.

  10. Cross-linking of glycoprotein oligomers during herpes simplex virus type 1 entry.

    OpenAIRE

    Handler, C G; Cohen, G H; Eisenberg, R J

    1996-01-01

    Herpes simplex virus (HSV) has 10 glycoproteins in its envelope. Glycoprotein B (gB), gC, gD, gH, and gL have been implicated in virus entry. We previously used chemical cross-linking to show that these five glycoproteins were close enough to each other to be cross-linked into homodimeric and hetero-oligomeric forms; hetero-oligomers of gB-gC, gC-gD, gD-gB, gH-gL, gC-gL and gD-gL were found in purified virions. To better understand the roles of these glycoproteins in viral entry, we have modi...

  11. Effective anti-Alzheimer Aβ therapy involves depletion of specific Aβ oligomer subtypes

    Science.gov (United States)

    Knight, Elysse M.; Kim, Soong Ho; Kottwitz, Jessica C.; Hatami, Asa; Albay, Ricardo; Suzuki, Akinobu; Lublin, Alex; Alberini, Cristina M.; Klein, William L.; Szabo, Paul; Relkin, Norman R.; Ehrlich, Michelle; Glabe, Charles G.; Steele, John W.

    2016-01-01

    Background: Recent studies have implicated specific assembly subtypes of β-amyloid (Aβ) peptide, specifically soluble oligomers (soAβ) as disease-relevant structures that may underlie memory loss in Alzheimer disease. Removing existing soluble and insoluble Aβ assemblies is thought to be essential for any attempt at stabilizing brain function and slowing cognitive decline in Alzheimer disease. IV immunoglobulin (IVIg) therapies have been shown to contain naturally occurring polyclonal antibodies that recognize conformational neoepitopes of soluble or insoluble Aβ assemblies including soAβ. These naturally occurring polyclonal antibodies have been suggested to underlie the apparent clinical benefits of IVIg. However, direct evidence linking anti-Aβ antibodies to the clinical bioactivity of IVIg has been lacking. Methods: Five-month-old female Dutch APP E693Q mice were treated for 3 months with neat IVIg or with IVIg that had been affinity-depleted over immobilized Aβ conformers in 1 of 2 assembly states. Memory was assessed in a battery of tests followed by quantification of brain soAβ levels using standard anti-soAβ antibodies. Results: We provide evidence that NU4-type soAβ (NU4-soAβ) assemblies accumulate in the brains of Dutch APP E693Q mice and are associated with defects in memory, even in the absence of insoluble Aβ plaques. Memory benefits were associated with depletion from APP E693Q mouse brain of NU4-soAβ and A11-soAβ but not OC-type fibrillar Aβ oligomers. Conclusions: We propose that targeting of specific soAβ assembly subtypes may be an important consideration in the therapeutic and/or prophylactic benefit of anti-Aβ antibody drugs. PMID:27218118

  12. Identification and bioactivities of resveratrol oligomers and flavonoids from Carex folliculata seeds.

    Science.gov (United States)

    Li, Liya; Henry, Geneive E; Seeram, Navindra P

    2009-08-26

    Plants of the Carex genus (Family: Cyperaceae) have attracted recent attention as potential food additives because they contain high levels of bioactive polyphenols commonly found in plant foods. Seven compounds, which included two resveratrol oligomers and five flavonoids, were isolated from seeds of Carex folliculata L. (northern long sedge), a forage prevalent in the northern United States. The compounds were identified by (1)H and (13)C nuclear magnetic resonance and mass spectrometry data. The resveratrol oligomers were pallidol (1), a resveratrol dimer reported to be present in levels equivalent to those of resveratrol in red wine, and kobophenol A (2), a resveratrol tetramer with a unique 2,3,4,5-tetraaryltetrahydrofuran skeleton. The flavonoids were isoorientin (3), luteolin (4), quercetin (5), 3-O-methylquercetin (6), and rutin (7). Compounds were evaluated for antioxidant activity in the diphenylpicrylhydrazyl (DPPH) radical scavenging assay; cytotoxicity activity against human colon (HCT116, HT29) and breast (MCF7, MDA-MB-231) tumor cell lines; and antibacterial activity against methicillin-resistant Staphylococcus aureus (MRSA). The antioxidant activities of the flavonoids (3-7; IC(50) values ranging from 50 to 200 microM) were comparable to that of ascorbic acid (IC(50) = 60 microM) and superior to those of the resveratrol derivatives (1 and 2; IC(50) > 1000 microM) and butylated hydroxytoluene (BHT; IC(50) = 1500 microM), a commercial antioxidant. In the cytotoxicity and antibacterial bioassays, compounds 4 (IC(50) for HCT116 = 45 microM) and 6 (IC(50) for MRSA = 6.4 microM) were the most active, respectively. Therefore, given the wide availability and underutilization of C. folliculata, this forage may provide a source of bioactive compounds useful for nutraceutical purposes. Also, this is the first reported phytochemical investigation of C. folliculata.

  13. Nonoxynol-9: in vivo disposition, metabolism and in vitro spermicidal assessment of selected oligomers

    Energy Technology Data Exchange (ETDEWEB)

    Walter, B.A.

    1988-01-01

    The disposition of nonoxynol-9 labelled with carbon-14 at the ethylene oxide units was studied following an i.v. or vaginal administration to female Sprague Dawley rats. The results from the vaginal administration studies indicate 12.8% absorption of (C-14) radioactivity in 6.0h and 37.7% in 24 h. Tissue distribution studies showed that the small and large intestines, including their contents, had the highest C-14 activity by either route of administration. Radiomonitored HPLC of bile collected at 6.0h and urine at 6.0, 24.0 and 48.0h following an i.v. injection of (C-14) nonoxynol-9 showed that the compound was completely metabolized in the body of the rat. Pharmacokinetics of the most abundant oligomer (E.O.8) following an i.v. administration indicated a rapid distribution to a peripheral compartment followed by a slower elimination (half-life = 196min) of the E.O.8 from the plasma. The in vitro spermicidal activity of various molecular weight N-9 oligomers was compared to N-9 with rabbit spermatozoa. When HPLC purified fractions of N-9 were formulated with PVP and evaluated in equimolar concentrations the order of spermicidal activity was: middle MW fraction (E.O. = 6-8) > N-9 > high MW fraction (E.O. = 11-13) > low MW fraction (E.O. = 1-4). Also the N-9 - PVP complex was more effective in immobilizing spermatozoa than N-9 alone.

  14. Conformation of chromatin oligomers. A new argument for a change with the hexanucleosome.

    Science.gov (United States)

    Marion, C; Bezot, P; Hesse-Bezot, C; Roux, B; Bernengo, J C

    1981-11-01

    Quasielastic laser light scattering measurements have been made on chromatin oligomers to obtain information on the transition in their electrooptical properties, previously observed for the hexameric structures [Marion, C. and Roux, B. (1978) Nucleic Acids Res. 5, 4431-4449]. Translational diffusion coefficients were determined for mononucleosomes to octanucleosomes containing histone H1 over a range of ionic strength. At high ionic strength, oligomers show a linear dependence of the logarithm of diffusion coefficient upon the logarithm of number of nucleosomes. At low ionic strength a change occurs between hexamer and heptamer. Our results agree well with the recent sedimentation data of Osipova et al. [Eur. J. Biochem. (1980) 113, 183-188] and of Butler and Thomas [J. Mol. Biol. (1980) 140, 505-529] showing a change in stability with hexamer. Various models for the arrangements of nucleosomes in the superstructure of chromatin are discussed. All calculations clearly indicate a conformational change with the hexanucleosome and the results suggest that, at low ionic strength, the chromatin adopts a loosely helical structure of 28-nm diameter and 22-nm pitch. These results are also consistent with a discontinuity every sixth nucleosome, corresponding to a turn of the helix. This discontinuity may explain the recent electric dichroism data of Lee et al. [Biochemistry (1981) 20, 1438-1445]. The hexanucleosome structure which we have previously suggested, with the faces of nucleosomes arranged radially to the helical axis has been recently confirmed by Mc Ghee et al. [Cell (1980) 22, 87-96]. With an increase of ionic strength, the helix becomes more regular and compact with a slightly reduced outer diameter and a decreased pitch, the dimensions resembling those proposed for solenoid models. PMID:7308214

  15. Characterization of glycidyl methacrylate - crosslinked hyaluronan hydrogel scaffolds incorporating elastogenic hyaluronan oligomers.

    Science.gov (United States)

    Ibrahim, S; Kothapalli, C R; Kang, Q K; Ramamurthi, A

    2011-02-01

    Prior studies on two-dimensional cell cultures suggest that hyaluronic acid (HA) stimulates cell-mediated regeneration of extracellular matrix structures, specifically those containing elastin, though such biologic effects are dependent on HA fragment size. Towards being able to regenerate three-dimensional (3-D) elastic tissue constructs, the present paper studies photo-crosslinked hydrogels containing glycidyl methacrylate (GM)-derivatized bio-inert high molecular weight (HMW) HA (1 × 10(6)Da) and a bioactive HA oligomer mixture (HA-o: MW ∼0.75 kDa). The mechanical (rheology, degradation) and physical (apparent crosslinking density, swelling ratio) properties of the gels varied as a function of incorporated HA oligomer content; however, overall, the mechanics of these hydrogels were too weak for vascular applications as stand-alone materials. Upon in vivo subcutaneous implantation, only a few inflammatory cells were evident around GM-HA gels, however their number increased as HA-o content within the gels increased, and the collagen I distribution was uniform. Smooth muscle cells (SMC) were encapsulated into GM hydrogels, and calcein acetoxymethyl detection revealed that the cells were able to endure twofold the level of UV exposure used to crosslink the gels. After 21 days of culture, SMC elastin production, measured by immunofluorescence quantification, showed HA-o to increase cellular deposition of elastic matrix twofold relative to HA-o-free GM-HA gels. These results demonstrate that cell response to HA/HA-o is not altered by their methacrylation and photo-crosslinking into a hydrogel, and that HA-o incorporation into cell-encapsulating hydrogel scaffolds can be useful for enhancing their production of elastic matrix structures in a 3-D space, important for regenerating elastic tissues. PMID:20709199

  16. Quantitative monitoring of dermal and inhalation exposure to 1,6-hexamethylene diisocyanate monomer and oligomers.

    Science.gov (United States)

    Fent, Kenneth W; Jayaraj, Karupiah; Ball, Louise M; Nylander-French, Leena A

    2008-04-01

    Respiratory sensitization and occupational asthma are associated with exposure to 1,6-hexamethylene diisocyanate (HDI) in both monomeric and oligomeric forms. The monomer and polymers of diisocyanates differ significantly in their rates of absorption into tissue and their toxicity, and hence may differ in their contribution to sensitization. We have developed and evaluated a liquid chromatography/mass spectrometry (LC-MS) method capable of quantifying HDI and its oligomers (uretidone, biuret, and isocyanurate) in air, tape-stripped skin, and paint samples collected in the automotive refinishing industry. To generate analytical standards, urea derivatives of HDI, biuret, and isocyanurate were synthesized by reaction with 1-(2-methoxyphenyl)piperazine and purified. The urea derivatives were shown to degrade on average by less than 2% per week at -20 degrees C over a 2 month period in occupational samples. The average recovery of HDI and its oligomers from tape was 100% and the limits of detection were 2 and 8 fmol microl(-1), respectively. Exposure assessments were performed on 13 automotive spray painters to evaluate the LC-MS method and the sampling methods under field conditions. Isocyanurate was the most abundant component measured in paint tasks, with median air and skin concentrations of 2.4 mg m(-3) and 4.6 microg mm(-3), respectively. Log-transformed concentrations of HDI (r = 0.79, p < 0.0001) and of isocyanurate (r = 0.71, p < 0.0001) in the skin of workers were correlated with the log-transformed product of air concentration and painting time. The other polyisocyanates were detected on skin for less than 25% of the paint tasks. This LC-MS method provides a valuable tool to investigate inhalation and dermal exposures to specific polyisocyanates and to explore relative differences in the exposure pathways. PMID:18385871

  17. Molecular Dynamics Simulations of Silica Nanoparticles Grafted with Poly(ethylene oxide) Oligomer Chains

    KAUST Repository

    Hong, Bingbing

    2012-03-01

    A molecular model of silica nanoparticles grafted with poly(ethylene oxide) oligomers has been developed for predicting the transport properties of nanoparticle organic-hybrid materials (NOHMs). Ungrafted silica nanoparticles in a medium of poly(ethylene oxide) oligomers were also simulated to clarify the effect of grafting on the dynamics of nanoparticles and chains. The model approximates nanoparticles as solid spheres and uses a united-atom representation for chains, including torsional and bond-bending interactions. The calculated viscosities from Green-Kubo relationships and temperature extrapolation are of the same order of magnitude as experimental data but show a smaller activation energy relative to real NOHMs systems. Grafted systems have higher viscosities, smaller diffusion coefficients, and slower chain dynamics than the ungrafted ones at high temperatures. At lower temperatures, grafted systems exhibit faster dynamics for both nanoparticles and chains relative to ungrafted systems, because of lower aggregation of particles and enhanced correlations between nanoparticles and chains. This agrees with the experimental observation that NOHMs have liquidlike behavior in the absence of a solvent. For both grafted and ungrafted systems at low temperatures, increasing chain length reduces the volume fraction of nanoparticles and accelerates the dynamics. However, at high temperatures, longer chains slow down nanoparticle diffusion. From the Stokes-Einstein relationship, it was determined that the coarse-grained treatment of nanoparticles leads to slip on the nanoparticle surfaces. Grafted systems obey the Stokes-Einstein relationship over the temperature range simulated, but ungrafted systems display deviations from it. © 2012 American Chemical Society.

  18. Comprehensive analysis of fragment orbital interactions to build highly π-conjugated thienylene-substituted phenylene oligomers.

    Science.gov (United States)

    Florès, Jean-Charles; Lacour, Marie-Agnès; Sallenave, Xavier; Serein-Spirau, Françoise; Lère-Porte, Jean-Pierre; Moreau, Joël J E; Miqueu, Karinne; Sotiropoulos, Jean-Marc; Flot, David

    2013-06-01

    π-Conjugated thienylene-phenylene oligomers with fluorinated and dialkoxylated phenylene fragments have been designed and prepared to understand the interactions in fragment orbitals, the influence of the substituents (F, OMe) on the HOMO-LUMO gap, and the role of intramolecular non-covalent cumulative interactions in the construction of π-conjugated nanostructures. Their strong conjugation was also evidenced in the gas phase by UV photoelectron spectroscopy and theoretical calculations. These results can be explained by the crucial role of the relative energetic positions of the π orbitals of the dimethoxyphenylene, which was used to model the dialkoxyphenylene entity, in determining the π/π(*) orbital levels of the fluorinated phenylene entity. Dialkoxyphenylenes raise the HOMO orbitals, whereas fluorinated phenylenes lower the LUMO orbitals in the oligomers. In addition, the presence of S⋅⋅⋅F and H⋅⋅⋅F interactions in the fluorinated phenylene-thienylene compounds add to the S⋅⋅⋅O interactions in the mixed targets and contribute to the full conjugation in the oligomer, inducing weak inter-ring angles between the involved aromatic cycles. These results, which showed extended conjugation of the π system, were corroborated by a narrow HOMO-LUMO gap (according to DFT calculations) and by a relatively strong maximum wavelength (as obtained by TD-DFT calculations and experimental UV/Vis measurements). The crystallographic data of two mixed thienylene-(fluorinated and dialkoxylated phenylene) five-ring oligomers agree with the above results and show the formation of quasi-planar conformations with non-covalent S⋅⋅⋅O, H⋅⋅⋅F, and S⋅⋅⋅F interactions. These studies in the solid and gas phases show the relevance of associating dialkoxyphenylene and fluorinated phenylene fragments with thiophene to lead to oligomers with improved electronic delocalization for electronic or optoelectronic devices. PMID:23576222

  19. Transient EPR Reveals Triplet State Delocalization in a Series of Cyclic and Linear π-Conjugated Porphyrin Oligomers.

    Science.gov (United States)

    Tait, Claudia E; Neuhaus, Patrik; Peeks, Martin D; Anderson, Harry L; Timmel, Christiane R

    2015-07-01

    The photoexcited triplet states of a series of linear and cyclic butadiyne-linked porphyrin oligomers were investigated by transient Electron Paramagnetic Resonance (EPR) and Electron Nuclear DOuble Resonance (ENDOR). The spatial delocalization of the triplet state wave function in systems with different numbers of porphyrin units and different geometries was analyzed in terms of zero-field splitting parameters and proton hyperfine couplings. Even though no significant change in the zero-field splitting parameters (D and E) is observed for linear oligomers with two to six porphyrin units, the spin polarization of the transient EPR spectra is particularly sensitive to the number of porphyrin units, implying a change of the mechanism of intersystem crossing. Analysis of the proton hyperfine couplings in linear oligomers with more than two porphyrin units, in combination with density functional theory calculations, indicates that the spin density is localized mainly on two to three porphyrin units rather than being distributed evenly over the whole π-system. The sensitivity of the zero-field splitting parameters to changes in geometry was investigated by comparing free linear oligomers with oligomers bound to a hexapyridyl template. Significant changes in the zero-field splitting parameter D were observed, while the proton hyperfine couplings show no change in the extent of triplet state delocalization. The triplet state of the cyclic porphyrin hexamer has a much decreased zero-field splitting parameter D and much smaller proton hyperfine couplings with respect to the monomeric unit, indicating complete delocalization over six porphyrin units in this symmetric system. This surprising result provides the first evidence for extensive triplet state delocalization in an artificial supramolecular assembly of porphyrins. PMID:26035477

  20. Polyalanine and Abeta Aggregation Kinetics: Probing Intermediate Oligomer Formation and Structure Using Computer Simulations

    Science.gov (United States)

    Phelps, Erin Melissa

    2011-12-01

    The aggregation of proteins into stable, well-ordered structures known as amyloid fibrils has been associated with many neurodegenerative diseases. Amyloid fibrils are long straight, and un-branched structures containing several proto-filaments, each of which exhibits "cross beta structure," -- ribbon-like layers of large beta sheets whose strands run perpendicular to the fibril axis. It has been suggested in the literature that the pathway to fibril formation has the following steps: unfolded monomers associate into transient unstable oligomers, the oligomers undergo a rearrangement into the cross-beta structure and form into proto-filaments, these proto-filaments then associate and grow into fully formed fibrils. Recent experimental studies have determined that the unstable intermediate structures are toxic to cells and that their presence may play a key role in the pathogenesis of the amyloid diseases. Many efforts have been made to determine the structure of intermediate oligomer aggregates that form during the fibrillization process. The goal of this work is to provide details about the structure and formation kinetics of the unstable oligomers that appear in the fibril formation pathway. The specific aims of this work are to determine the steps in the fibril formation pathway and how the kinetics of fibrillization changes with variations in temperature and concentration. The method used is the application of discontinuous molecular dynamics to large systems of peptides represented with an intermediate resolution model, PRIME, that was previously developed in our group. Three different peptide sequences are simulated: polyalanine (KA14K), Abeta17-40, and Abeta17-42; the latter two are truncated sequences of the Alzheimer's peptide. We simulate the spontaneous assembly of these peptide chains from a random initial configuration of random coils. We investigate aggregation kinetics and oligomer formation of a system of 192 polyalanine (KA14K) chains over a

  1. Right- and Left-Handed Helices, What is in between? Interconversion of Helical Structures of Alternating Pyridinedicarboxamide/m-(phenylazo)azobenzene Oligomers.

    Science.gov (United States)

    Tao, Peng; Parquette, Jon R; Hadad, Christopher M

    2012-12-11

    Some unnatural polymers/oligomers have been designed to adopt a well-defined, compact, three-dimensional folding capability. Azobenzene units are common linkages in these oligomer designs. Two alternating pyridinedicarboxamide/m-(phenylazo)azobenzene oligomers that can fold into both right- and left-handed helices were studied computationally in order to understand their dynamical properties. Helical structures were shown to be the global minima among the many different conformations generated from the Monte Carlo simulations, and extended conformations have higher potential energies than compact ones. To understand the interconversion process between right- and left-handed helices, replica-exchange molecular dynamic (REMD) simulations were performed on both oligomers, and with this method, both right- and left-handed helices were successfully sampled during the simulations. REMD trajectories revealed twisted conformations as intermediate structures in the interconversion pathway between the two helical forms of these azobenzene oligomers. This mechanism was observed in both oligomers in current study and occurred locally in the larger oligomer. This discovery indicates that the interconversion between helical structures with different handedness goes through a compact and partially folded structure instead of globally unfold and extended structure. This is also verified by the nudged elastic band (NEB) calculations. The temperature weighted histogram analysis method (T-WHAM) was applied on the REMD results to generate contour maps of the potential of mean force (PMF). Analysis showed that right- and left-handed helices are equally sampled in these REMD simulations. In large oligomers, both right- and left-handed helices can be adopted by different parts of the molecule simultaneously. The interconversion between two helical forms can occur in the middle of the helical structure and not necessarily at the termini of the oligomer.

  2. Structure and spectroscopic properties of N,S-coordinating 2-methylsulfanyl-N-[(1H-pyrrol-2-ylmethylidene]aniline methanol monosolvate

    Directory of Open Access Journals (Sweden)

    D. Douglas Richards

    2015-10-01

    Full Text Available The reaction of pyrrole-2-carboxaldehyde and 2-(methylsulfanylaniline in refluxing methanol gave an olive-green residue in which yellow crystals of the title compound, C12H12N2S·CH3OH, were grown from slow evaporation of methanol at 263 K. In the crystal, hydrogen-bonding interactions link the aniline molecule and a nearby methanol solvent molecule. These units are linked by a pair of weak C—H...Omethanol interactions, forming inversion dimers consisting of two main molecules and two solvent molecules.

  3. 1-Benzoyl-3-[3-cyano-8-methyl-4-(1-methyl-1H-pyrrol-2-yl-5,6,7,8-tetrahydroquinolin-2-yl]thiourea

    Directory of Open Access Journals (Sweden)

    Abdullah M. Asiri

    2011-09-01

    Full Text Available In the N-substituted benzoylthiourea, C24H23N5OS, the benzoylthiourea unit is non-planar (r.m.s. deviation = 0.126 Å. The aliphatic part of the tetrahydroquinoline fused-ring system is disordered over two positions in a 0.592 (5:0.408 (5 ratio. The pyridine and pyrrole rings are twisted by 55.2 (1° in order to avoid crowding of their respective substituents. Pairs of molecules are linked by N—H...N hydrogen bonds, forming centrosymmetric dimers. Furthermore, an intramolecular N—H...O hydrogen bond stabilizes the molecular conformation.

  4. Magnetic charge quantisation and fractionally charged quarks

    NARCIS (Netherlands)

    Hooft, G. 't

    1976-01-01

    If magnetic monopoles with Schwinger's value of the magnetic charge would exist then that would pose serious restrictions on theories with fractionally charged quarks, even if they are confined. Weak and electromagnetic interactions must be unified with color, leading to a Weinberg angle w close to

  5. Multistep Charge Method by Charge Arrays

    Science.gov (United States)

    Segami, Go; Kusawake, Hiroaki; Shimizu, Yasuhiro; Iwasa, Minoru; Kibe, Koichi

    2008-09-01

    We studied reduction of the size and weight of the Power Control Unit (PCU). In this study, we specifically examined the weight of the Battery Charge Regulator (BCR), which accounts for half of the PCU weight for a low earth orbit (LEO) satellite. We found a multistep charge method by charge arrays and adopted a similar method for GEO satellites, thereby enabling the BCR reduction. We found the possibility of reducing the size and weight of PCU through more detailed design than that for a conventional PCU.BCRC1R1batterySAPower Control UnitBCRC1R1batterySAPower UnitHowever, this method decreases the state of charge (SOC) of the battery. Battery tests, a battery simulator test, and numerical analysis were used to evaluate the SOC decrease. We also studied effects of this method on the battery lifetime. The multistep charge method by charge arrays enabled charging to the same level of SOC as the conventional constant current/ constant voltage (CC/CV) charge method for a LEO satellite.

  6. Ferrocene-Functionalized 4-(2,5-Di(thiophen-2-yl)-1H-pyrrol-1-yl)aniline: A Novel Design in Conducting Polymer-Based Electrochemical Biosensors

    OpenAIRE

    Rukiye Ayranci; Dilek Odaci Demirkol; Metin Ak; Suna Timur

    2015-01-01

    Herein, we report a novel ferrocenyldithiophosphonate functional conducting polymer and its use as an immobilization matrix in amperometric biosensor applications. Initially, 4-(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl)amidoferrocenyldithiophosphonate was synthesized and copolymerized with 4-(2,5-di(thiophen-2-yl)-1H-pyrrol-1-yl)benzenamine at graphite electrodes. The amino groups on the polymer were utilized for covalent attachment of the enzyme glucose oxidase. Besides, ferrocene on the backbon...

  7. Preparation and analysis of styrene oligomers containing migrates from various polystyrenes used in food packaging.

    Science.gov (United States)

    Klärner, P; Klenz, R; Eder, R; Volz, W E; Schnell, H W; Leyendecker, D; Güntner, A; Niessner, N; Morris, C R; Christian, M S

    1998-01-01

    An oligostyrene-like product (F2L5250) was reported to have estrogen-like activity (statistically significant increases in means for absolute uterine weight and the ratios of the uterine weight to terminal body weight) in juvenile female rats provided a dietary concentration of 100 ppm F2L5250 for four consecutive days. The highest no-effect-level (NOEL) for estrogenic activity was 80 ppm in the diet, corresponding to a daily intake of 13.3 mg F2L5250/kg. Although it is unlikely that such estrogenic tetramers would occur in commercial polystyrene, the Styrene Steering Committee (SSC) of the European Chemical Industry Council (CEFIC) sponsored the current extensive project to address any concern that human consumption of styrene oligomers migrating from polystyrene containers into food, e.g., from packaged yoghurt, or from the use of EPS coffee cups and related products, might affect human health. To ensure confidentiality and compliance with the highest scientific and regulatory standards, the entire project was conducted without knowledge of the oligomer migrates tested, and all activities were managed and audited under a contract between the SSC and a third party, Argus International. This paper describes the preparation and analyses of the 23 representative polystyrenes [9 general purpose polystyrenes (GPPS), 8 high impact polystyrenes (HIPS) and 6 expandable polystyrenes (EPS)] evaluated for estrogenicity in an in vivo uterotrophic assay in immature female rats. The polystyrene samples were chosen to represent food packaging applications. They were obtained from participating European Polystyrene Manufacturers, coded at the TNO Nutrition and Food Research Institute, Utrecht, The Netherlands (TNO) and sent to BASF, Ludwigshafen, Germany for preparation of test bars (GPPS and HIPS) or test foam parts (EPS). The prepared polystyrene test bars or test foam parts were submitted to elution with 50% aqueous (v/v) ethanol for 10 days at 40 degrees C, a procedure which

  8. On Dust Charging Equation

    OpenAIRE

    Tsintsadze, Nodar L.; Tsintsadze, Levan N.

    2008-01-01

    A general derivation of the charging equation of a dust grain is presented, and indicated where and when it can be used. A problem of linear fluctuations of charges on the surface of the dust grain is discussed.

  9. Green Synthesis of Ag and Pd Nanospheres, Nanowires, and Nanorods Using Vitamin B2: Catalytic Polymerisation of Aniline and Pyrrole

    Directory of Open Access Journals (Sweden)

    Mallikarjuna N. Nadagouda

    2008-01-01

    Full Text Available For the first time, we report green chemistry approach using vitamin B2 in the synthesis of silver (Ag and palladium (Pd, nanospheres, nanowires, and nanorods at room temperature without using any harmful reducing agents, such as sodium borohydride (NaBH4 or hydroxylamine hydrochloride and any special capping or dispersing agent. Vitamin B2 was used as reducing agent as well as capping agent due to its high-water solubility, biodegradability, and low-toxicity compared with other reducing agents. The average particle size of nanoprticle was found to be Ag (average size 6.1±0.1 nm and Pd (average size 4.1±0.1 nm nanoparticles in ethylene glycol and Ag (average size 5.9±0.1 nm, and average size 6.1±0.1 nanoparticles in acetic acid and NMP, respectively. The formation of noble multiple shape nanostructures and their self assembly were dependent on the solvent employed for the preparation. When water was used as solvent media, Ag and Pd nanoparticles started to self-assemble into rod-like structures and in isopropanol Ag and Pd nanoparticles yielded wire-like structures with a thickness in the range of 10 to 20 nm and several hundred microns in length. In acetone and acetonitrile medium, the Ag and Pd nanoparticles are self-assembled into a regular pattern making nanorod structures with thicknesses ranging from 100 to 200 nm and lengths of a few microns. The so-synthesized nanostructures were characterized using scanning electron microscopy (SEM, transmission electron microscopy (TEM, energy dispersive X-ray (EDX analysis, and UV spectroscopy. The ensuing Ag and Pd nanoparticles catalyzed the reactions of aniline and pyrrole to generate polyaniline and polypyrrole nanofibers and may find various technological and biological applications. This single-step greener approach is general and can be extended to other noble metals and transition metal oxides.

  10. High content of pyridinic- and pyrrolic-nitrogen-modified carbon nanotubes derived from blood biomass for the electrocatalysis of oxygen reduction reaction in alkaline medium

    International Nuclear Information System (INIS)

    Graphical abstract: Display Omitted -- Highlights: •An ORR electrocatalyst was fabricated from blood biomass and carbon nanotube. •The N-CNT catalyst exhibits good ORR activity, methanol resistance and stability. •The pyrolysis process produces high contents of pyridinic and pyrrolic N species. •The pyridinic-N group may play more important role in the active sites for ORR. -- Abstract: Here we present a facile synthetic route to design nitrogen-doped nanostructured carbon-based electrocatalyst for oxygen reduction reaction (ORR) by the copyrolysis of blood biomass from pig and carbon nanotubes (CNTs) at high temperatures. The nitrogen-doped CNTs obtained at 800 °C not only results in excellent ORR activity with four-electron transfer selectivity in alkaline medium, but also exhibits superior methanol-tolerant property and long-term stability. It is confirmed that high-temperature pyrolysis processes can facilitate to produce higher contents of pyridinic- and pyrrolic-N binding groups in electrocatalysts, contributing to the enhancement of ORR performance in terms of onset potential, half-wave potential, and limited current density. We also propose that the planar-N configuration may be the active site that is responsible for the improved ORR electrocatalytic performance. The straight-forward and cheap synthesis of the active and stable electrocatalyst makes it a promising candidate for electrochemical power sources such as fuel cells or metal-air batteries

  11. Conjugated and fluorescent polymer based on dansyl-substituted pyrrole prepared by electrochemical polymerization in acetonitrile containing boron trifluoride diethyl etherate

    International Nuclear Information System (INIS)

    Graphical abstract: - Highlights: • A fluorescent pyrrole derivative bearing a dansyl substituent (PyPDG) was synthesized. • PyPDG was electropolymerized onto ITO in (C4H9)4NBF4/CH3CN/BFEE mixed electrolyte. • The resulting polymer (PPyPDG) films displayed electrochromic behavior. • PPyPDG is a good green light emitter material. - Abstract: A fluorescent pyrrole derivative bearing a dansyl substituent was prepared by a simple synthetic route and electropolymerized onto Indium Tin Oxide (ITO) electrodes. The presence of the dansyl group in the monomer precursor prevents the electropolymerization in usual systems, such as (C4H9)4NBF4 in acetonitrile (CH3CN). For this reason, it was added 20% boron trifluoride diethyl etherate (BFEE) to this system, to achieve electropolymerization. The resulting poly[3-(N-pyrrolyl)propyl dansylglycinate] (PPyPDG) films displayed electrochromic behavior. Their color varied from greenish-yellow, in the neutral state, to greyish-green, in the oxidized state; moreover PPyPDG is a good green light emitter material. Therefore, PPyPDG films might be potentially applicable in displays and optoelectronic devices

  12. Strikingly different luminescent properties arising from single crystals grown from solution or from the vapor phase in a diketo-pyrrolo-pyrrole analog

    Science.gov (United States)

    Imoda, Tomohiko; Mizuguchi, Jin

    2007-10-01

    The title compound di-cyano-pyrrolo-pyrrole (DCPP) is an analog of diketo-pyrrolo-pyrrole (DPP) known as a red pigment on the market. Brilliant orange photoluminescence has been observed in crystals of DCPP recrystallized from solution (crystal I); whereas the luminescence was quite weak in single crystals grown from the vapor phase (crystal II). To elucidate the difference in luminescent properties, a series of structural analysis together with thermal analysis has been carried out on crystals I and II at -180 °C, RT, 150 °C, and 200 °C. However, no difference in structure is recognized between crystals I and II within the precision of the x-ray analysis. Nevertheless, a slight difference in sublimation temperature of about 5° is observed between crystals I and II. Since the sublimation temperature depends on the cohesion in the solid state and the cohesion, in turn, governs the extent of lattice vibration (i.e., nonradiative process), a slight difference in sublimation temperature appears to determine the fraction between the radiative and nonradiative processes in crystals I and II.

  13. Concentrations of oligomers and polymers of proanthocyanidins in red and purple rice bran and their relationships to total phenolics, flavonoids, antioxidant capacity and whole grain color

    Science.gov (United States)

    Proanthocyanidins, a flavonoids subgroup, are proposed to have chronic disease modulation properties. With the eventual goal of enhancing rice phytonutrient concentrations, we investigated the genotypic variation of the concentrations of individual oligomers and polymers of proanthocyanidins in dark...

  14. Induced Charge Capacitive Deionization

    OpenAIRE

    Rubin, S.; Suss, M. E.; Biesheuvel, P. M.; Bercovici, M.

    2016-01-01

    We demonstrate the phenomenon of induced-charge capacitive deionization (ICCDI) that occurs around a porous and conducting particle immersed in an electrolyte, under the action of an external electrostatic field. The external electric field induces an electric dipole in the porous particle, leading to capacitive charging of its volume by both cations and anions at opposite poles. This regime is characterized both by a large RC charging time and a small electrochemical charge relaxation time, ...

  15. Parametrization of coarse grained force fields for dynamic property of ethylene glycol oligomers/water binary mixtures

    CERN Document Server

    Yamazaki, Tamio

    2011-01-01

    To evaluate shear viscosity of ehylene glycol oligomers (EGO)/water binary mixture by means of coarse-grained molecular dynamics (CG-MD) simulations, we proposed the self-diffusion-coefficient-based parameterization of non-bonded interactions among CG particles. Our parameterization procedure consists of three steps: 1)determination of bonded potentials, 2)scaling for time and solvent diffusivity, and 3)optimization of Lennard-Jones parameters to reproduce experimental self-diffusion coefficient data. With the determined parameters and the scaling relations, we evaluated shear viscosities of EGO/water binary mixtures, which are in close agreement with the experimental data, without any further fitting procedure. The largest simulation in this article corresponds to a 1.2 microseconds atomistic simulation for 100,000 atoms. Our CG model with the parameterization scheme for CG particles may be useful to study the dynamic properties of a liquid which contains relatively low molecular weight polymers or oligomers...

  16. ENTROPIC CONTRIBUTION TO THE INTERACTION PARAMETER x IN THE POLYMER/OLIGOMER SYSTEM: A LATTICE CLUSTER THEORY CONSIDERATION

    Institute of Scientific and Technical Information of China (English)

    Dong-shan Zhou; Xiao-liang Wang; Bo Che; Liang Li; Jin-lu Chen; Gi Xue

    2005-01-01

    Entropic contribution to the interaction parameter xeff in the model incompressible polymer/oligomer system is calculated by the lattice cluster theory (LCT). It is found that in the oligomer solvent, there exists a wide concentration range that the non-combinatorial "entropic interaction" term xeff φ1φ2 perceptibly counteracts the mean field combinary entropy △SMF. With the increase of the solvent size, both xeff and the ratio xeff φ1φ2/ASMF first reach their maximum and finally become trivially to zero. It is worth noting that no any demixing was found in the current calculation. This makes the controversial idea "entropically driven demixing" even elusive. However, we propose that further work on compressible

  17. Inhibitory effect of oatmeal extract oligomer on vasoactive intestinal peptide-induced inflammation in surviving human skin.

    Science.gov (United States)

    Boisnic, S; Branchet-Gumila, M C; Coutanceau, C

    2003-01-01

    The aim of this study was to evaluate the antiinflammatory effect of oatmeal extract oligomer on skin fragments stimulated by a neuromediator, vasoactive intestinal peptide (VIP). Skin fragments (from plastic surgery) were maintained in survival conditions for 6 h. To induce inflammation, VIP was placed in contact with dermis by culture medium. Histological analysis was then performed on hematoxylin- and eosin-stained slides. Edema was evaluated with semiquantitative scores. Vasodilation was studied by quantifying the percentage of dilated vessels according to scores and by measuring their surface by morphometrical image analysis. TNF-alpha dosage was made on culture supernatants. Vasodilation was significantly increased after application of VIP. After treatment with oatmeal extract oligomer, the mean surface of dilated vessels and edema were significantly decreased compared with VIP-treated skin. Moreover, treatment with this extract decreased TNF-alpha.

  18. Charge exchange system

    Science.gov (United States)

    Anderson, Oscar A.

    1978-01-01

    An improved charge exchange system for substantially reducing pumping requirements of excess gas in a controlled thermonuclear reactor high energy neutral beam injector. The charge exchange system utilizes a jet-type blanket which acts simultaneously as the charge exchange medium and as a shield for reflecting excess gas.

  19. Charge-transfer excitons in DNA.

    Science.gov (United States)

    Conwell, E M; McLaughlin, P M; Bloch, S M

    2008-02-21

    There have been a number of theoretical treatments of excitons in DNA, most neglecting both the intrachain and interchain wavefunction overlaps of the electron and hole, treating them as Frenkel excitons. Recently, the importance of the intrachain and interchain coupling has been highlighted. Experiments have shown that in (dA)n oligomers and in duplex (dA)n.(dT)n, to be abbreviated (A/T), where A is adenine and T is thymine, the exciton wavefunction is delocalized over several bases. In duplexes it is possible to have charge-transfer (CT) excitons. Theoretical calculations have suggested that CT excitons in DNA may have lower energy than single chain excitons. In all the calculations of excitons in DNA, the polarization of the surrounding water has been neglected. Calculations have shown, however, that polarization of the water by an excess electron or a hole in DNA lowers its energy by approximately 1/2 eV, causing it to become a polaron. It is therefore to be expected that polarization charge induced in the surrounding water has a significant effect on the properties of the exciton. In what follows, we present calculations of some properties CT excitons would have in an A/T duplex taking into account the wavefunction overlaps, the effect of the surrounding water, which results in the electron and hole becoming polarons, and the ions in the water. As expected, the CT exciton has lowest energy when the electron and hole polarons are directly opposite each other. By appropriate choice of the dielectric constant, we can obtain a CT exciton delocalized over the number of sites found in photoinduced absorption experiments. The absorption threshold that we then calculate for CT exciton creation in A/T is in reasonable agreement with the lowest singlet absorption deduced from available data. PMID:18232682

  20. Characterization of non-photochemically formed oligomers from methylglyoxal: a pathway to produce secondary organic aerosol through cloud processing during night-time

    OpenAIRE

    F. Yasmeen; N. Sauret; J. F. Gal; P.-C. Maria; Massi, L.; W. Maenhaut; Claeys, M.

    2009-01-01

    Aqueous-phase oligomer formation from methylglyoxal, a major atmospheric photooxidation product, has been investigated in a simulated cloud matrix under dark conditions. The aim of this study was to explore an additional path producing secondary organic aerosol (SOA) through cloud processes without photochemistry during night-time. Indeed, atmospheric models still underestimate SOA formation, as field measurements have revealed more SOA than predicted. Soluble oligomers (n=...